In this article, based on progressively type-II censored schemes, the maximum likelihood, Bayes, and two parametric bootstrap methods are used for estimating the unknown parameters of the Weibull Fréchet distribution and some lifetime indices as reliability and hazard rate functions. Moreover, approximate confidence intervals and asymptotic variance-covariance matrix have been obtained. Markov chain Monte Carlo technique based on Gibbs sampler within Metropolis–Hasting algorithm is used to generate samples from the posterior density functions. Furthermore, Bayesian estimate is computed under both balanced square error loss and balanced linear exponential loss functions. Simulation results have been implemented to obtain the accuracy of the estimators. Finally, application on the survival times in years of a group of patients given chemotherapy and radiation treatment is presented for illustrating all the inferential procedures developed here. T and number of failures m, respectively. For more details and applications, see Lawless  − 1)b−). Thus, the samples of a can be generated by using any gamma routine. From Eqs. a(0), b(0), α(0), β(0))Start with ((2)k = 1Set (3)ak)(exp[(αk − 1)(/yj)βk − 1)(] − 1)bk − 1)(−)Generate (4)b∗ from N(bk − 1)), α∗ from N(αk − 1)), and β∗ from N(βk − 1))Generate Evaluate the acceptance probabilitiesUsing M-Hr1, r2, and r3 from a Uniform distribution(c) Generate r1 < ψ1, accept the proposal, and set bk)( = bk − 1)((d) If r2 < ψ2, set αk)( = αk − 1)((e) If r3 < ψ3, set βk)( = βk − 1)((f) If r(t) and h(t)(5) Evaluate the reliability characteristics k = k + 1(6) Set N times(7) Repeat Steps 3-6 From Eq. , the fulrom Eqs. , 19), a, aa is Grom Eqs. , the posM simulated values. Then, the selected samples are ak)((t), and hk)((t), k = M + 1, ⋯, N; for large N, the Bayes estimate of ν = a, b, α, β, r(t), or h(t) is given byHence, to guarantee the convergence and to remove the affection of the selection of initial value, we remove the first a, b, α, β, r(t), and h(t), make ak)((t), and hk)((t), k = 1, 2, ⋯, N in ascending order as {a(1)<⋯<aN)<⋯<bN)<⋯<αN)<⋯<βN)(t)<⋯<rN)((t)}, and {h(1)(t)<⋯<hN)((t)}; hence, (1 − δ)100% CI of a, b, α, β, r(t), or h(t) is given byTo compute the credible intervals of δ be an estimator of the unknown parameter ψ. ψ under BSE and BLINEX loss functions, where w and q are both nonzero real numbers.In this subsection, two loss functions have been considered: (i) balanced squared error loss function and (ii) balanced-LINEX loss function are introduced by Jozani et al. . Let δ ba = 0.5, b = 0.5, α = 2.0, and β = 3.5. The true values of r(t) and h(t) at t = 0.5 are r(0.5) = 0.9879 and h(0.5) = 0.1. We also computed the Bayes estimates based on 10000 MCMC samples with respect to the BSE and BLINEX loss function are computed for two distinct values of ω, equal 0 and 0.6.To compare the parameter estimators, we perform Monte Carlo simulations 1000 prog. type-II censored samples for each simulations. MATHEMATICA ver. 12 has been used for all computations, with parameters We use the following scheme (CS)in our study:a, b, α, β, r(t), and h(t) has been considered in terms of mean square error (MSE), which is computed by k = 1, 2, ⋯, 6 and ψ1 = a, ψ2 = b, ψ3 = α, ψ4 = β, ψ5 = r(t), and ψ6 = h(t). All results are shown in Tables 2The performance of the resulting estimators of a, b, α, β) with the parameters , using progressive censoring scheme CS: m = 15 which generated randomly of sample size n = 30 with censoring scheme R = 7, 1, 2, 4, 1, 0, 0, 0, 0, 0, 0, 0, 0, 0, 0. The progressive type-II censored sample isIn this subsection, we present a simulation example to check the estimation procedures. By using the algorithm described in Balakrishnan and Sandhu , we gener(t) and h(t) are 0.9435 and 0.3013, respectively, for t = 0.5. a, b, α, β, r(t), and h(t) using MLE, Bootstrap-p, Bootstrap-t, and MCMC methodsa, b, α, β, r(t), and h(t) using MLE, Bootstrap-p, Bootstrap-t, and MCMC methodsa, b, α, β, r(t), and h(t)q = −0.5,0, 0.5 shape parameter of LINEX loss function and various values of ω = 0,0.3,0.6,0.9 for unknown parameters a, b, α, β, r(t), and h(t)From Eqs.  and 4),,4), the p value is 0.826301. Hence, p value is quite large; we accept the null hypothesis that the data is coming from the WFr distribution. n = 46, the failure sample size m = 26, by using the algorithm described in Balakrishnan and Sandhu [p = 0.4) R = {7, 7, 1, 1, 1, 0, 1, 2, 0, 0, 0, 0, 0, 0, 0, 0, 0, 0, 0, 0, 0, 0, 0, 0, 0, 0}. Based on these data, we compute the proposed estimates for the unknown parameters, reliability, and hazard rate functions by various methods . (2)a, b, α, β, r(t), and h(t)(3)(4)In this subsection, we study an application of a real data set. This data set represents the life data regarding gastric cancer survival times in years for a group of patients given chemotherapy and radiation treatment. This data set reported by Stablein et al.  and usedn, m) and different CSs  for the comparison of the proposed estimates. From the results, we observe the following:a, b, α, β, r(t), and h(t). So, Bayes estimates perform better than the MLEs and bootstrap methods in all cases consideredTables 2It is clear that the bootstrap-t is better than MLE and bootstrap-p from (2–7)ω = 0, Bayes estimates are giving better estimates for the unknown parameters and the reliability characteristics in the sense of having smaller MSEsWhen q = 0.5 provides better estimation in the sense of having smaller MSEs when ω = 0 and 0.6Bayes estimation under BLINEX with For the same sample size, SC I performs better than SC II and SC III in the sense of having smaller MSEsIn this paper, we estimated the parameters, reliability, and hazard rate function of the Weibull Fréchet distribution under progressive type-II censored sample using several methods as MLE, parametric bootstrap, and Bayes estimate. Furthermore, the approximately confidence intervals for these parameters were constructed by using the asymptotic normality of MLE as well as the delta method is used to construct the CIs for the reliability and hazard functions, parametric bootstrap, and Bayes methods. It is clear that the Bayes estimators cannot be obtained in explicit forms, and they can be obtained by using the numerical integration. Because of that, MCMC techniques have been used, and it is observed that the Bayes estimate with respect to informative prior works quite well in this case. Also, the Bayes estimates have been computed with respect to two loss functions. Also, we considered a real life data set for illustrative purpose. Finally, an elaborate simulation study was conducted for different sample sizes (


However, it has very low solubility in water. The formulation of this compound requires high amounts of solubilizers, which limits its clinical application. In addition, its low solubility in water is a barrier to the distribution of this drug, thus affecting its potency. Cyclodextrin (CD) is widely used as a solubility enhancer of poorly soluble drugs. This study aimed to increase the solubility of α-M in water through complex formation with CD. The complex of α-Mangostin and γ-Cyclodextrin (α-M/γ-CD CX) was prepared by the solubilization method, resulting in a solubility improvement of α-M in water. Characterization of α-M/γ-CD CX by using FTIR-Spectrometry, XRD, H-, C-, and HMBC-NMR showed that α-M was able to form an inclusion complex with γ-CD. The complex yielded an entrapment efficiency of 84.25 and the thermodynamic study showed that the α-M/γ-CD CX was formed spontaneously, based on the negative values of Gibbs energy and ΔH. Interestingly, the solubility of α-M/γ-CD CX significantly increased by 31.74-fold compared with α-M. These results suggest that α-M/γ-CD CX has the potential in the formulation of water-based preparation for clinical applications. Garcinia mangostana pericarp extract  -9H-xanthen-9-one] (α-M) is a major compound in  extract  [1]. α-MCyclodextrin (CD) is an oligosaccharide molecule that has a unique cavity structure: it has a hydrophobic property in the inner cavity but is hydrophilic in the outer cavity. The conical truncated structure of CDs proposed to include the hydrophobic molecule in the cavity, resulting in their improved water solubility. CD molecules are formed by glucopyranose units via α-1,4-glycosidic linkages. The type of CDs correlated with the number of glucopyranose units. α-, β-, and γ-CD contain six, seven, and eight units, respectively . Some neIn this study, the inclusion complexes of α-M and γ-CD were prepared by solubilization method to improve the solubility of α-M in water. The phase solubility study was implemented to display the solubility enhancement of α-M in several concentrations of γ-CD and a Job plot predict the molar ratio of the complex formation. Several characterizations such as FTIR-Spectrometry, XRD, SEM, H-, C-, and HMBC-NMR were performed to study the configuration of the inclusion complex. The termodynamic studies were implemented to study the complex formation process. α-M could be more widely used both in formulation and several pharmacological applications due to the increased solubility of α-M in the inclusion complex.α-Mangostin was purchased from Chengdu Pharmaceutical Industries, China. γ-CD was a kind gift from Kumamoto University, Kumamoto, Japan. Ethanol 95% and aqua deionized to a high purity were purchased from Sigma Aldrich, St. Louis, MO, USA. All the reagents were of analytical grade and were used without any further purification.α-M and γ-cyclodextrin were weighed in a 1:2 molar ratio and mixed for 1 min using a vortex mixer ,21.The stoichiometry of the α-M/γ-CD complex (α-M/γ-CD CX) formation was determined using the continuous variation method (Job plot). Each concentration (0–1 mM) of the α-M and γ-CD solution was mixed in a constant molar fraction. All the mixtures were stored at room temperature for 24 h. After equilibration, the solution was filtered using a 0.45 μm filter membrane ,22. The This study was performed according to The Higuchi and Connors Method . An exceThe solubility improvement of α-M/γ-CD CX in water was investigated by dispersing 0.1–0.3 g of α-M, α-M/γ-CD PM, and α-M/γ-CD CX in 10 mL of distilled water. The mixtures were shaken for 24 h at 25 °C. The mixtures were then filtered with 0.45 μm filter membrane. The concentration of α-M was measured using an Analytic Jena Specord 200 at 316 nm .The complex was prepared by the solubility method. A total amount of 1 mM of α-M solution in ethanol 95% and 2 mM of γ-CD solution in water was made in a separated volumetric flask. α-M solution was gradually added into γ-CD solution and mixed for about 24 h at room temperature. Then, the solution was evaporated at 60 °C to yield the complex powder. The entrapment efficiency of the complex was measured by an Analytic Jena Specord 200 at 316 nm ,9,22,26.−1. About 2 mg of sample was blended with 200 mg KBr powder. The mixture was pressed into a disc and analyzed at 400–4000 cm−1 [The samples of the complex were analyzed using IR Prestige-21 Spectrometry at 400–4000 cm000 cm−1 ,26.The XRD pattern of α-M, γ-CD, the physical mixture (α-M/γ-CD PM), and the inclusion complex (α-M/γ-CD CX) were analyzed using a XRD Bruker D8 Advance 3 kW with LynxEye XE-T detector and radiation source CuK alfa. Each sample was scanned at 2θ from 5–50 ,19,26.The morphology surface of α-M, γ-CD, α-M/γ-CD PM, and α-M/γ-CD CX were assessed by scanning electron microscopy (SEM) JEOL JSM 6510 LA. The sample was placed in a sample holder, sprayed to remove impurities, and coated with gold. The analyses were carried out at an acceleration voltage of 15 kV, and each sample was observed at 250 and 3000 magnification ,26.The structure of α-M, γ-CD, α-M/γ-CD PM and α-M/γ-CD CX were analyzed using NMR spectrometry 500 Hz JEOL, JNM ECA 500 ,27.sK) was calculated by using the slope value from the solubility phase diagram, utilizing the following equation:An excess of α-M (±25 mg) was added into 5 mL γ-CD solution . Each mixture was shaken continuously in an incubator shaker at 24 °C for 96 h until equilibrium was reached ,21,24. TS0 is the solubility of α-M without the presence of cyclodextrin, and slope is the gradient of the solubility phase diagram [ diagram ,24.H), and Gibbs energy (∆G) of α-M/γ-CD CX formation were determined using the stability constant (Ks) vs. temperature, following the Van’t Hoff equation:The change of enthalpy , R is the gas constant (8.314 J/mL/K), and ∆H  is calculated using the slope value from the sK vs. 1/T graph [/T graph ,24.G was calculated by the following equation:Furthermore, the value of ∆p-Value ≤ 0.05 is considered as statistically significant between-group population.Statistical comparison was performed by using Scheffe’s test. A phase solubility study was undertaken to analyze the molar ratio of α-M and γ-CD in the complex α-M/γ-CD CX was prepared by the solubilization method: α-M was dissolved in ethanol, while γ-CD was dissolved in water. Both of the solutions were mixed for 24 h and evaporated at around 60 °C. The entrapment efficiency of this complex was 84.25 ± 6.80%.L type of solubility diagram, indicated that α-M solubility was reached linearly with γ-CD [The phase solubility study can be seen in ith γ-CD ,28. At tith γ-CD .The number of α-M to form the complex results in the improvement of its solubility in water. The high percentage of artemisinin complexed with γ-CD was higher than α- and β-CD . MoleculThe stoichiometry of complex formation was established using a Job plot. A gradient concentration of α-M was mixed with a gradient concentration of γ-CD in a constant mole fraction, and the mixture was allowed to stand overnight. The mixture was filtered by 0.45 μm membrane, and the α-M in the filtrate was measured at 316 nm. In max value at 0.4, corresponding with the stoichiometry ratio of the complex formation at 1:1. This ratio implies the inclusion of a single guest molecule entrapped with one molecule of the host [The toroidal structure of γ-CD can entrap α-M in its cavity . The stothe host ,33.−1. The FTIR spectra of α-M, γ-CD, α-M/γ-CD PM, and α-M/γ-CD CX are shown in −1 corresponds to the hydrogen bond of the hydroxyl groups, and the weak absorption near 2900 cm−1 is related with sp3 hybridization of aliphatic carbon. The bend absorption at 1300–1000 cm−1 is the absorption of C-O groups, and the slight absorption at wavenumber 1600–1700 cm−1 is the vibration of C=C groups.The functional group analysis of α-M, γ-CD, α-M/γ-CD PM, and α-M/γ-CD CX was carried out using FTIR spectrophotometry at wavenumber 4500–500 cm−1. For interpretation, in the first graph (α-M), the stretching vibration at 3410 and 3252 cm−1 corresponds with the –OH in α-M. The band at 2970 and 2931 cm−1 is given by the asymmetric stretching vibration of sp3 hybridization of the aliphatic carbons of the α-M methyl (CH3) and methylene (CH2) groups. The absorption bands at 1580 cm−1, 1645 cm−1, and 1630 cm−1 are the stretching vibrations of unconjugated C=C in α-M. The band at 1470 cm−1 is given by the unconjugated carbonyl group (C=O) on the B ring of α-M; 1362 cm−1 is given by CH3 bending; 1083 cm−1 and 1051 cm−1 correspond with the stretching vibration of C-O; and 1011 cm−1, 862 cm−1, 804 cm−1, 772 cm−1, and 598 cm−1 are given by C-OH stretching, –CH=CH- (trans), –CH=CH- (cis), CH2, and –CH=CH- bending, respectively [The FTIR spectra of α-M, γ-CD, α-M/γ-CD PM, and α-M/γ-CD CX are shown in −1 with a maximum absorption at 3395 cm−1. This band is related to the stretching vibration of the –OH groups in the glucose ring. The band at 2930 cm−1 comes from the stretching vibrations of the C-H bonds in the CH2. The high-intensity bands at 1030 cm−1 and 999 cm−1 are related to the C-H out-of-plane bending vibrations and the C-O stretching vibration modes, respectively [The second graph (γ-CD) shows a broad absorption around 3000–3600 cmectively .−1 corresponds to the hydrogen bond of the hydroxyl groups. The weak absorption 2930 cm−1 corresponds with the methylene (CH2) groups, 1640 cm−1 is given by CH3 bending, 998 cm−1 is the bend absorption of C-OH stretching vibration, and 598 cm−1 indicates –CH=CH- bending [The same absorption-type can be seen for the α-M/γ-CD PM (the third graph). The strong band at 3000–3500 cm bending ,35.−1 with the maximum absorption at 3346 cm−1 is given by the stretching vibration of the –OH groups in the glucose ring of γ-CD. The maximum band at 2930 cm−1 comes from the stretching vibrations of the C-H bonds in the CH2. A high-intensity doublet, with maximum absorption at 1030 cm−1 and 1000 cm−1, is assigned to the C-H out-of-plane bending vibrations and the C-OH stretching vibration modes, respectively. The band at 598 cm−1 is given by –CH=CH- bending [The last graph is the spectra for α-M/γ-CD CX. The broad band around 3000–3600 cm bending .The crystallinity of intact α-M was 91.1% with the specific peak at 5.890. The crystallinity of intact γ-CD was 62.6% with the specific peak at 5.19. These peaks still remain in α-M/γ-CD PM at 5.14 and 5.95. In contrast, both of the peaks disappeared, and the crystallinity of α-M was decreased into 28.2% in α-M/γ-CD CX; the peak was seen around 16–18 with an intensity of about 1000. This indicates that α-M formed a complex with γ-CD .The crystallinity of α-M, γ-CD, α-M/γ-CD PM, and α-M/γ-CD CX was examined using PXRD . Intact SEM was performed to analyze the morphology of each sample . The surThe surface of α-M was rough, and the particle size was around 150 μm . The surThe NMR spectra of α-M, γ-CD, α-M/γ-CD PM, and α-M/γ-CD CX were obtained using NMR Spectrometry 500 Hz JEOL, JNM ECA 500. The analysis was performed for proton (H-NMR), C-NMR, and HMBC.1H NMR spectra of α-M, γ-CD, α-M/γ-CD PM, and α-M/γ-CD CX are shown in The signal of a,b,c,d and e, given by the proton in glucopyranose monomer of γ-CD at a,b,c,d and e position. The integration of the overlapped peaks was used to calculate the molar ratio of α-M and γ-CD in the complex. The result emphasized the Job plot, which showed the molar ratio of this complex is 1:1. The chemical shift of α-M/γ-CD CX was influenced by the guest molecule (α-M) entering into the hydrophobic cavity. This phenomenon indicates that the complex of α-M/γ-CD CX was formed ,17,18.The study continued by using C-NMR and HMBC to investigate the molecular interaction of α-M and γ-CD. The HMBC spectrum of α-M/γ-CD CX is given in A hydrogen bond was found at the hydroxyl group of α-M, which interacted with the hydrogen ion of the γ-CD molecule. The signal of a, b, c, d and e, given by the proton in glucopyranose monomer of γ-CD at a, b, c, d and e position. The signal 1, 3, 4a, 6 and 7 given by the carbon of α-M molecule at the same postion. The interaction of α-M and γ-CD shows the interaction between the proton (H) from the hydroxyl groups with the C of the methoxy groups. The hydrogen bond was found at the hydroxy group at the A and C ring of α-M, which interacted with the hydrogen ion at a, b, c, and d of the γ-CD molecule. The interaction occurred at C 4a of α-M with a hydrogen atom at the d position of γ-CD. Two other signals appear at C7 of α-M, with hydrogen at the a and d position of γ-CD. This interaction describes the successful complex formation of α-M and γ-CD ,25.sK) in each temperature was calculated by using Equation (1) by using the slope of the graph in each temperature  and ∆H is the slope of the diagram in Thermodynamic studies of α-M/γ-CD CX formation were undertaken to study the complex formation process. This procedure was carried out at temperatures of 25 °C, 31 °C, and 37 °C. The stability constant  yielded an energy of complexation of −5.68 kcal/mol, while the parameterization method 7 (PM7) gave an energy of complexation of 5.29 kcal/mmol [The thermodynamic study of α-M/γ-CD CX formation gave an energy of complexation of about −5.019 ± 0.224 kcal/mol and ΔH of −5.520 kcal/mol. The in silico study using PM6 yielded an energy of complexation of −5.68 kcal/mol, while the PM7 method gave an energy of complexation of 5.29 kcal/mmol [The in silico study showed that α-M molecules were included in the inclusion complex with γ-CD. In the latest study, PM6 molecular docking indicated that the O4 of γ-CD attached with the hydroxyl groups at C3 and C6 in α-M, while PM7 resulted in the interaction of hydroxyl groups in γ-CD with the methoxy groups at the C ring and the carbonyl group at the B ring of α-M .α-M is able to form an inclusion complex with α-, β-, and γ-CD. The in silico study using PM7 found that the inclusion complex of α-M with γ-CD is the most favorable, because this complex has the lowest negative value of free binding energy (ΔG), −5.68 kcal/mol, while a higher energy was needed for α- and β-cyclodextrin inclusion complexes  . The calThe Job plot diagram and H-NMR revealed that α-M/γ-CD CX has formed as an inclusion complex at a stoichiometry ratio of 1:1. Analysis by FTIR, XRD, and NMR  corroborates that the complex was formed by the molecular interaction of α-M and γ-CD, resulting in an amorphous complex with the solubility improvement and different physical properties compared with α-M. Furthermore, the thermodynamic study exhibited that the Gibbs energy of the complex formation was negative, indicating that this complex was formed spontaneously.


Analysis and characterization of the samples were performed using standard physicochemical techniques, elemental analysis, nuclear magnetic resonance, Fourier transform infrared spectroscopy, and UV-vis spectroscopy. Single-crystal X-ray crystallography revealed the formation of a pentacoordinate complex in 1 and a hexacoordinate complex in 2, in which the anionic ligand HL− has undergone monodentate coordination through the tetrazole unit. Furthermore, the crystal structure of H2L·MeOH is also discussed. The potential application of compounds 1 and 2 in bioinorganic chemistry was addressed by investigating their radical scavenging activity with the 2,2-diphenyl-1-picrylhydrazyl radical (DPPH) and the results were supported also by theoretical calculations.Two mononuclear Cu(II) complexes, [Cu(phen) Indole  in 2015 . New com−1. The 1H, 13C, and 2D NMR spectra of the ligand were measured on a 400 MHz Varian spectrometer. UV/Vis spectra were measured on Cintra 3030 (GBC Scientific Instruments) double beam spectrometer.All solvents and chemicals were purchased from various commercial sources and used without further purification. Elemental analysis was performed on the Thermo Scientific Flash 2000 analyzer. The infrared spectra of the complexes were measured on a Jasco FT/IR-4700 using ATR technique with a diamond plate in the range of 400–4000 cmH-indole-2-carboxylic acid in 25 ml of chloroform was mixed with 5 ml of thionyl chloride (SOCl2) and three drops of dimethylformamide (DMF). The reaction mixture was then refluxed for 2 hours. The cooled solution was then poured into a slurry of 20 ml of aqueous ammonia and 20 g of ice. The mixture was then stirred for 2 hours at room temperature, during which a large amount of yellow precipitate appeared. The solid product was filtered off, washed with water, and dried in a vacuum desiccator. The product, 1H-indole-2-carboxamide, was used in the next step without further purification (yield: 4.4 g (89%)).The solution of 5 g (31 mmol) of 1H-indole-2-carboxamide was added to 50 ml of phosphoryl chloride (POCl3). This mixture was refluxed for 30 minutes and subsequently it was poured onto 100 g of ice. The pH of the mixture was then adjusted to 8 by aqueous ammonia during which light brown product precipitated. This suspension was extracted 3 times with 50 ml of diethyl ether. The organic phase was dried over Na2SO4 and filtered and the solvent was removed to dryness on a rotatory evaporator. The light brown product, 1H-indole-2-carbonitrile, was dried in a vacuum desiccator and used in the next step without further purification (yield: 4.12 g (74%)).6.3 g (39 mmol) of the previously prepared 1H-indole-2-carbonitrile was dissolved in 25 ml of DMF. To this was then added 3.77 g (58 mmol) of NaN3 and 1.55 g (29 mmol) of NH4Cl. This suspension was heated at 120°C for 18 hours. After it was cooled to room temperature, this mixture was poured into 100 ml of distilled water. The pH was adjusted to 1–2 with 2M HCl and the solution was extracted 3 times with 50 ml of ethyl acetate. The organic phase was washed with brine and dried over Na2SO4. After filtration, the solvent was removed on a rotatory evaporator to dryness. The resulting brown powder was recrystallized from methanol with a spoon of activated charcoal. The resulting off-white crystals of 2-(1H-tetrazol-5-yl)-1H-indole (H2L) were suitable for X-ray diffraction analysis (yield: 2.84 g (45%)).4.12 g (29 mmol) of 110H11N5O (Mr = 217.1) corresponding to H2L.MeOH: C, 55.3; H, 5.1; N, 32.2. Found: C, 54.9; H, 4.9; N, 32.3. FT-IR : 438w, 525w, 709w, 742s, 801m, 892w, 923m, 1005w, 1023w, 1083m, 1118w, 1137w, 1233m, 1249w, 1277w, 1338s, 1378s, 1414w, 1455w, 1509w, 1573w, 1618s, 2640w, 2687w, 2775w, 2832w, 2894w, 2964w, 3034w, 3111w, 3223s, 3362w, 3478w. 1H NMR (DMSO-d6) δ (ppm.): 7.04 , 7.14 , 7.19 , 7.47 , 7.64 , 12.13 . 13C NMR (DMSO-d6) δ (ppm.): 104.05, 112.66, 120.55, 121.58, 122.38, 124.01, 127.88, 137.82, 150.48.Anal. Calcd. (%) for Cμmol) of Cu(ClO4)2.6H2O was dissolved in 5 ml of DMF together with 45.6 mg (230 μmol) of 1,10-phenanthroline monohydrate and 25 mg (115 μmol) of H2L. Subsequently, 115 μl of 1M aq. NaOH solution was added to deprotonate the ligand. The formation of green crystals suitable for an XRD analysis was observed upon diethyl ether vapors diffusion into the solution. The product was filtered off, washed with diethyl ether, and dried in a vacuum desiccator (yield: 56.8 mg (56%)).42.7 mg (115 39H38ClCuN11O7 (Mr = 871.8) corresponding to [Cu(phen)2(HL)]ClO4·H2O.2DMF: C, 53.7; H, 4.4; N, 17.7. Found: C, 53.6; H, 4.2; N, 17.3. FT-IR : 427w, 521w, 620m, 660w, 721m, 755w, 847m, 1084s, 1145w, 1193w, 1223w, 1254w, 1308w, 1339w, 1362w, 1387w, 1424m, 1496w, 1518m, 1585w, 1604w, 1655s, 2924w, 3159w, 3380w.Anal. Calcd. (%) for Cμmol) of Cu(OAc)2.H2O was added to 10 ml of ethanol together with 91.2 mg (460 μmol) of 1,10-phenanthroline monohydrate. After everything was dissolved, 50 mg (230 μmol) of H2L was added to the reaction mixture. The solution was mixed to complete dissolution of the ligand and the clear solution was left to evaporate at room temperature, leading to the formation of green crystals suitable for an X-ray diffraction analysis. The resulting product was filtered off, washed with diethyl ether, and dried in a vacuum desiccator (yield: 67 mg (35%)).46 mg (230 44H34CuN14O (Mr = 838.4) corresponding to [Cu(phen)2(HL)2]·EtOH: C, 63.0; H, 4.1; N, 23.4. Found: C, 62.6; H, 3.8; N, 23.1. FT-IR : 419w, 446w, 520w, 582w, 662w, 723s, 750m, 808w, 840m, 863w, 930w, 1035w, 1100w, 1143w, 1222w, 1306w, 1335s, 1363w, 1409m, 1423m, 1496w, 1514w, 1590w, 1625w, 3057w, 3345m.Anal. Calcd. (%) for C2L·MeOH (CSD number 2114450), 1 (CSD number 2114451), and 2 (CSD number 2114452) was carried out on SuperNova diffractometer from Rigaku OD equipped with Atlas2 CCD detector and Cu Kα sealed tube as source. CrysAlisPro version 1.171.41.93a was used for the data collection and for the cell refinement, data reduction, and absorption correction ClO4·H2O.2DMF (1) and [Cu(phen)2(HL)2]·EtOH (2) were prepared by mixing the components CuII : phen : H2L in a molar ratio of 1 : 2 : 1, where copper perchlorate or copper acetate salts were utilized. In the synthesis of compound 1, it was necessary to deprotonate the ligand H2L by adding an equimolar amount of 1 M aq. NaOH solution, while in the synthesis of compound 2, anion of acetic acid originating from copper acetate acts as a base. The formation of suitable single crystals of 1 and 2 for the X-ray analysis was achieved either by diffusion of diethyl ether into the solution or by slow evaporation of the solvent. Also, it is worth mentioning that changing the molar ratio of CuII : phen : H2L in 1 : 1 : 1 resulted in products insoluble in common polar solvents. Infrared spectrum of H2L·MeOH comprises ν(O-H) and ν(N-H) stretching vibrations of methanol and H2L within 3100–3500 cm−1 range, while the aromatic ν(C-H) are observed around 3030 cm−1  stretching vibration of the indole of H2L in the range of 3300–3400 cm−1. Also, the different ratio of HL : phen in 1 and 2 is reflected in different relative transmittance of in-plane C/N-H and ring vibrations in 1655–1000 cm−1 region. The coordination of the heterocycles ligands is generally confirmed by shifting of characteristic vibrations. Thus, strong C=C/C=N vibrations of H2L at 1618 cm−1 have been significantly shifted downfield in both complexes 1 and 2 to 1518 and 1514 cm−1, respectively. Characteristic peaks of 1,10-phenanthroline can be found in spectra of both complexes at 736 and 850 cm−1, as well as around 1344, 1421, and 1503 cm−1 1 Figure . The aro Figures –S9. Neve503 cm−1  26]. Th. Th2(HL)084 cm−1 .2L·MeOH is discussed (2L molecules formed between indole and tetrazole units with d(N5⋯N4) = 2.9466 (23) Å  Å . The det1 crystallized in a triclinic crystal system with a space group P – 1 (1 contains a [Cu(phen)2(HL)] complex, perchlorate anion, two molecules of DMF, and one molecule of water. The copper atom is coordinated by two phen ligands in bidentate fashion, and the anionic HL− ligand is coordinated through the nitrogen atom of the tetrazole unit, with the respective Cu-N distances listed in 5} chromophore, and the Addison parameter  and a molecule of ethanol 2] of 2 shows elongated square-bipyramidal geometry, in which the axial positions are occupied by nitrogen atoms of two phen ligands (2. These supramolecular dimers are stabilized by hydrogen bonds between nitrogen atom of tetrazole ring and protonated nitrogen of indole of the second complex with following donor-acceptor distances: d(N54⋯N23) = 3.098 (2) Å  Å  Å . Further6 (12) Å . Lastly,6 (12) Å .˙ radical.Spectroscopic determination of DPPH radical quenching is one of the most widely used methods which readily and reliably provide information about the radical scavenging activity of studied compounds. In our case, this represents a measure of the ability of studied complexes to scavenge detrimental radicals present in the intracellular environment, such as the aforementioned OH1 and 2 was measured by UV-Vis spectroscopy at 517 nm in triplicate and the values were averaged for each concentration 2(HL)]+ of 1 and [Cu(phen)2(HL)2] of 2. Herein, ORCA 5.0 computation package + ↔ [Cu(phen)2(L)]+· + H·   [Cu(phen)2(HL)2] ↔ [Cu(phen)2(HL) (L)]· + H·   + + CH3OH ↔ [Cu(phen)2(L)]2+ + CH3OH·−   [Cu(phen)2(HL)2] + CH3OH ↔ [Cu(phen)2(HL)2]+ + CH3OH·−   [Cu(phen)2(HL)]+ + CH3OH·− ↔ [Cu(phen)2(L)] + CH3OH   [Cu(phen)2(HL)2] + CH3OH·− ↔ [Cu(phen)2(HL)2]− + CH3OH   + + CH3OH ↔ [Cu(phen)2(L)] + CH3OH2+   [Cu(phen)2(HL)2] + CH3OH ↔ [Cu(phen)2(HL)(L)]− + CH3OH2+   + of 1 and the value of ΔrG = −81.58 kcal/mol for [Cu(phen)2(HL)2] of 2 are similar in agreement with the comparable radical scavenging activity of these compounds.Evidently, the only spontaneous reaction (exergonic reactions) is attributed to SET in which the electron is donated to the complexes, which resulted in the reduction of CuH-tetrazol-5-yl)-1H-indole ligand (H2L) was investigated. The single-crystal X-ray analysis confirmed formation of pentacoordinate [Cu(phen)2(HL)]ClO4·H2O·2DMF (1) and hexacoordinate [Cu(phen)2(HL)2]·EtOH (2) compounds. In both compounds, the anionic HL− ligand acts as a monodentate N-donor ligand attached to the central atom through the tetrazole unit. The investigation of the interaction of these complexes with DPPH radical in their methanolic solution revealed moderate radical scavenging activity. The subsequent theoretical DFT calculations proposed that the dominant mechanism is the single electron transfer to the studied complexes.The impact of different copper salts on the preparation of metal complexes with 2-(1


Anoxybacillus strains were isolated from sediment and water samples from a Karvachar hot spring located in the northern part of Nagorno-Karabakh. Based on phenotypic, chemotaxonomic and phylogenetic characteristics, one of the isolates, designated strain K1T, was studied in detail. The cells are straight, motile rods that are 0.2–0.4×2.3–7.2 µm in size. The strain is a Gram-stain-positive, moderately thermophilic facultative anaerobe with an optimum growth temperature of 60–65 °C and a growth temperature range of 45–70 °C. Growth of strain K1T was observed at pH 6–11  and was inhibited in the presence of NaCl concentrations above 2.5 % . The isolate could utilize a wide variety of carbon sources, including d-arabinose, d-ribose, d-galactose, d-fructose, d-mannitol, maltose, aesculin, melibiose, sucrose, trehalose, raffinose, amidone, glycogen, turanose, d-lyxose, d-tagatose, potassium gluconate and 2-keto-gluconate. The strain was able to hydrolyse starch, casein and gelatin, was positive for oxidase and catalase, and reduced nitrate to nitrite, but was negative for H2S production. Production of urease and indole was not observed. The major cellular fatty acids were C15 : 0 iso, C16 : 0 and C17 : 0 iso . Strain K1T shares >99 % 16S rRNA sequence similarity and a genomic average nucleotide identity value of 94.5 % with its closest relative, Anoxybacillus flavithermus DSM 2641T, suggesting that it represents a separate and novel species, for which the name Anoxybacillus karvacharensis sp. nov. is proposed. The type strain of Anoxybacillus karvacharensis is K1T (=DSM 106524T=KCTC 15807T).Twelve thermophilic  Anoxybacillus are frequently isolated from terrestrial high-temperature habitats. The type species of the genus Anoxybacillus, Anoxybacillus pushchinoensis DSM 12423T, was first described by Pikuta et al. in 2000 .d-arabinose, d-ribose, d-galactose, d-fructose, d-mannitol, maltose, aesculin, melibiose, sucrose, trehalose, raffinose, amidone, glycogen, turanose, d-lyxose, d-tagatose, potassium gluconate and 2-keto-gluconate. Starch, casein and gelatin are hydrolysed by the strain, but Tween 40 is not. Nitrate is reduced to nitrite, but the strain is negative for H2S production. The strain is negative in the VP test. Urease, dihydroxyacetone and indole are not produced. Arginine di-hydrolase, lysine decarboxylase, ornithine decarboxylase and tryptophan deaminase tests are negative, but the β-galactosidase test is positive. The fatty acid profile contains C15 : 0 iso, C16 : 0 and C17 : 0 iso as major components. Growth is inhibited in the presence of ciprofloxacin (5 µg), doxycycline (30 µg), erythromycin (15 µg), ampicillin (10 µg), kanamycin (30 µg), gentamycin (10 µg), tetracycline (30 µg), streptomycin (10 µg), penicillin (6 µg), trimethoprim (5 µg), imipenem (10 µg), furadonin (300 µg), ceftriaxone (30 µg), cefoxitin (30 µg), amoxicillin/clavulanic acid (20/10 µg) and sulfamethoxazole (100 µg).Cells are Gram-stain-positive, rod-shaped, occurring singly or in short chains, motile and 0.2–0.4×2.3–7.2 µm in size. Subterminal ellipsoidal endospores were formed. Colonies are 2–3 mm in diameter, cream-coloured, and regular in shape with round edges. The strain is moderately thermophilic, facultatively anaerobic and alkali-tolerant. The temperature range for growth is 45–70 °C, with an optimum temperature range of 60–65 °C. The pH range for growth is pH 6.0–11.0, with an optimal pH of 8.0–9.0. Growth occurs at NaCl concentrations of up to 2.5 %. The strain is catalase- and oxidase-positive. The isolate is able to utilize a wide variety of carbon sources including T is 41.6 mol%. The type strain, K1T (=DSM 106524T=KCTC 15807T), was isolated from the Karvachar geothermal spring, Nagorno Karabakh.The genomic G+C content of K1Click here for additional data file.


The π···π interactions appear in C-∗-C, H-∗-H, and C-∗-H, with the asterisks indicating the existence of bond critical points (BCPs) on the interactions. The interactions of 3–12 are all predicted to have a p-CS/vdW nature (vdW nature of the pure closed-shell interaction), except for 2Cbay-∗-7Cbay of 10, which has a p-CS/t-HBnc nature . (See the text for definition of the numbers of C and the bay and cape areas). The natures of the interactions are similarly elucidated between the components of helicene dimers 6:6 and 7:7 with QTAIM-DFA, which have a p-CS/vdW nature. The characteristic electronic structures of helicenes are clarified through the natures predicted with QTAIM-DFA. Some bond paths (BPs) in helicenes appeared or disappeared, depending on the calculation methods. The static nature of Ccape-∗-Ccape is very similar to that of Cbay-∗-Cbay in 9–12, whereas the dynamic nature of Ccape-∗-Ccape appears to be very different from that of Cbay-∗-Cbay. The results will be a guide to design the helicene-containing materials of high functionality.The intrinsic dynamic and static nature of the π···π interactions between the phenyl groups in proximity of helicenes  Helicenes, which are ortho-fused polycyclic aromatic or heteroaromatic compounds with all rings angularly arranged to form helically shaped molecules, are of current and continuing interest. Helicenes are chiral; as a result, they are expected to have specific functionalities. Recently, helicenes have been widely applied in various fields ,2,3,4,5,The noncovalent distances between the aromatic planes in close proximity to the helicenes were determined as the total effect of the attractive and repulsive forces between the atoms on the planes. The restoring forces from the deviated planarity in the helicenes should be a main factor for the attractive and repulsive forces due to π-orbital overlapping in the helicenes. The noncovalent distances between the planes in close proximity to the helicenes are defined as the balanced distances of the two factors. The noncovalent intramolecular distances between atoms in close proximity to the helicenes must be (much) shorter than the noncovalent intermolecular distances between the unrestricted nonhelical aromatic species. The shorter distances in helicenes result from the π···π interactions between the planes in close proximity in space, which operate under very severe conditions. Clarifying the nature of the π···π interactions in helicenes under such severe conditions will enable us to understand the factors that control the structures and the nature of the interactions. The results will also provide a starting point for understanding the nature of π···π interactions and will hint at designs for materials with high functionality based on the interactions.1–12 and concave-type dimers 6:6–8:8 and 10:10, where 1–3 are analyzed as helicenes in this paper, although they are usually not. 1–12, dimers 6:6–8:8, 10:10, and [n]phenacenes p1–p12, where p1–p12 are the comparative compounds and p stands for phenacenes. The bay and cape areas used in this paper are also illustrated. We have previously reported the nature of the benzene π···π interactions in cyclophanes phenacene, a nonhelical species, evaluated with M06-2X/6-311+G. The energy profiles will be discussed based on the energy differences, ΔE(n) = E(n) − E(n − 1) for helicenes (1–12) and ΔE(np) = E(np) − E(np − 1) for [n]phenacenes (p1–p12). The ΔE(n) values correspond to the energy differences in the formation of n from n − 1, and the ΔE(np) values similarly correspond to np from (np− 1). The E(n), E(np), ΔE(n), and ΔE(np) values were calculated on the energy surface, which are described by EES(n), EES(np), ΔEES(n), and ΔEES(np), respectively. The values were also calculated with the zero-point energies, which are described by EZP(n), EZP(np), ΔEZP(n), and ΔEZP(np). The values calculated with M06-2X/6-311+G are collected in EZP(n) versus ΔEES(n) revealed an excellent correlation  can be used to analyze the energy terms.How can the behaviour of the energies of the helicenes be explained? The energies of the helicenes were compared with the energies of [EES(n) and ΔEES(np) versus n. Both the ΔEES(n) and ΔEES(np) values ) decrease when n increases from 2 to 3. The extension of the π system appears to contribute more to the formation of phenanthrene from naphthalene than the repulsive noncovalent H···H interaction. The ΔEES values are less than the ΔEES values; however, the ΔEES values increase from 3; p3 to 4; p4. In the case of ΔEES(np), the ΔEES(p4) value is somewhat larger than ΔEES(p3) but slightly smaller than ΔEES(p2). The ΔEES(np) value decreases again slightly from p4 to p5. Then, the values are nearly constant for np ≥ p5. The results show that the repulsive energy from the noncovalent H···H interaction does not appear to be as severe as the stabilization factor from the extended π systems in p1–p12. Namely, the np system stabilizes almost constantly as the size of the species increase, especially for np ≥ p5, although a change in ΔEES(np) is detected for p2 ≤ np < p5.EES(n) appear to be greater than those for ΔEES(np) when n ≥ 4. The observations must be due to the severe steric repulsion in ΔEES(n ≥ 4), where the plot for ΔEES(np) corresponds to that without such severe steric repulsion. The ΔEES(4) value is much larger than those of ΔEES(2) and ΔEES(3). The results can be explained by considering the much larger contribution from the repulsive noncovalent H···H interaction in 4 than in 3. This consideration is supported by the optimized structure of 4, drawn in EES(n) values decrease in the following order: ΔEES(4) > ΔEES(5) > ΔEES(6) > ΔEES(7) > ΔEES(8). The contribution of steric repulsion to ΔEES(n) due to noncovalent interactions is expected to increase as n increases in this process. However, the observed results are the opposite of what was expected. Therefore, the observed trend should be attributed to the increased energy-lowering effect by the extended π systems in 4–8 relative to the repulsive interactions.The data points for ΔEES(n) value becomes somewhat larger again from n = 8 to 9 and 9 to 10, and then decreases again from 10 to 11 and 11 to 12. The subtle conditions in the steric repulsion contribute to the complex behaviour of ΔEES(n) (8 ≤ n ≤ 12). The behaviour of ΔEES(2)–ΔEES(12) shown in EES(4) value is the largest among ΔEES(2)–ΔEES(12). The results are of great interest since the repulsive noncovalent H···H interaction in 4 from 3 appears to be very large among 2–12 when evaluated by ΔEES(n). The trend in ΔEES(n) seems to be in good agreement with those reported by Rulíšek et al., calculated with PBE-D/TZVP//PBE-D/6-31G(d), except for ΔEES(8) and ΔEES(9) [The Δ ΔEES(9) .y = 0.964x + 0.042; Rc2 = 0.981), whereas the correlations of the plots for acenes versus helicenes were very poor . The very good correlation of the former demonstrates that the aromaticities of the helicenes appear to be very similar to those of the phenacenes, irrespective of the very severe steric deformations in the structures of helicenes. However, the very poor correlations with the negative correlation constants show that the aromaticities of the helicenes are very different from those of acenes.It is also instructive to analyze the aromaticities of acenes, phenacenes, and helicenes after investigating the energy profiles. The structures of acenes, phenacenes, and helicenes are illustrated in 4, 7, 9, 11, and 12. Many BPs with BCPs are detected in the π···π interactions between the phenyl rings in close proximity to the helicenes. The molecular graphs for helicenes 3–12, except for 4, 7, 9, 11, and 12, are shown in rBP) were calculated for all X-∗-Y of 3–12, along with the corresponding straight-line distances (RSL). The values are collected in rBP = rBP – RSL). The averaged values of ΔrBP were 0.2040, 0.4006, 0.0588, and 0.1451 Å for Hbay-∗-Hbay, Cbay-∗-Hbay, Cbay-∗-Cbay, and Ccape-∗-Ccape, respectively. As a result, ΔrBP for Hbay-∗-Hbay and Cbay-∗-Hbay were larger than 0.20 Å, while those for Cbay-∗-Cbay and Ccape-∗-Ccape were less than 0.15 Å. Therefore, the BPs corresponding to Cbay-∗-Cbay and Ccape-∗-Ccape can be roughly approximated as straight lines since the ΔrBP values are less than 0.20 Å  appear almost straight, as shown in see also .3–12 with M06-2X/6-311+G. ρb(rc), Hb(rc) − Vb(rc)/2, and Hb(rc) values for one of the X-∗-Y if it is doubly degenerated due to the C2 symmetry of the optimized structures. Hb(rc) versus Hb(rc) – Vb(rc)/2 for each X-∗-Y, exemplified by 3–6, 8, 10, and 12, where H-∗-H was detected in 3 and 4 and C-∗-H and C-∗-C were detected in 8, 10, and 12. .The QTAIM functions were calculated at BCPs on X-∗-Y of R, θ) and  for each X-∗-Y of 3–12, along with the iiC values corresponding to the interactions in question. The  values, evaluated with CIV, should be denoted by , respectively. However,  will be used in place of  to simplify the notation. The QTAIM functions and QTAIM-DFA parameters calculated with M06-2X/6-311+G and LC-ωPBE/6-311+G are collected in The plots were analyzed according to θ < 90° should be classified as pure closed-shell (p-CS) interactions. In the p-CS region of 45° < θ < 90°, the character of the interactions will be the vdW type for 45° < θp < 90° (45° < θ < 75°), whereas the character of the interactions will be the typical hydrogen bond type (t-HB) with no covalency (t-HBnc) for 90° < θp < 125° (75° < θ < 90°), where θ = 75° and θp = 125° are tentatively given for θp = 90° and θ = 90°, respectively.The criteria shown in 3–12 were subdivided into Cbay and Ccape based on the positions of the atoms in the species, as were the H atoms into Hbay and Hcape. The bay and cape areas (positions) in the species are illustrated in bay and Ccape atoms of 3–12 participate in the interactions as BPs, only Hbay atoms participate as BPs. The θ and θp values for H-∗-H, C-∗-H, and C-∗-C of 3–12, collected in θp of 2Cbay-∗-7Cbay in 10, where  = . The 2Cbay-∗-7Cbay interaction in 10 is denoted by 10 (2Cbay-∗-7Cbay) , which is predicted to have a p-CS/t-HBnc nature.The C atoms in helicenes see also . Therefoθ, θp) values are  and  for 3 (1Hbay-∗-4Hbay) and 4 (1Hbay-∗-5Hbay), respectively. The θ values for 3 (1Hbay-∗-4Hbay) and 4 (1Hbay-∗-5Hbay) are larger than those of A-∗-HF  = ), whereas the θp values are larger than those of A-∗-HF (A = He and Ar). The interaction in 4 is estimated to be slightly stronger than that in 3, although the real image of 3 (1Hbay-∗-4Hbay) has been much debated [3 (1Hbay-∗-4Hbay) would not show enough strength for the interaction. It could be the mathematical results of the treatment. Nevertheless, 3 (1Hbay-∗-4Hbay) and 4 (1Hbay-∗-5Hbay) are discussed as very weak interactions in this work because the  values are larger than those of A-∗-HF . Double Hbay-∗-Cbay interactions are detected for each of 5–12, with  values of . The  values are very close to those of A-∗-HF . The BP (Hbay-∗-Cbay) in 6 and 9 connect the Hbay and Cbay atoms. However, they are not located at the nearest positions, as shown in bay-∗-Cbay) in 6 and 9 should be analyzed carefully.Next, the interactions were individually examined. The  values for C-∗-C in 7–12 are . It appears better to separately examine the values for two groups of Cbay-∗-Cbay and Ccape-∗-Ccape. While the  values of Cbay-∗-Cbay in 7–12 are , the values are  for Ccape-∗-Ccape. The θ values for Ccape-∗-Ccape are slightly smaller than those of Cbay-∗-Cbay (by 0.5–2.2°), but the θp values for Ccape-∗-Ccape are much smaller than those of Cbay-∗-Cbay (by 13.2–24.5°). In this case, θp < θ for Ccape-∗-Ccape, whereas θp > θ for Cbay-∗-Cbay. Interactions with θp > θ are usually observed, but interactions with θp < θ are rare.One, one, four, four, seven, and eight different types of C-∗-C interactions are detected for θ > θp occur under some specific conditions. To examine the behaviour of θ and θp in 7–12, the Δθp (=θp – θ) values are plotted versus θp for C-∗-C, H-∗-H and C-∗-H in 3–12. y = 0.918x – 64.88: Rc2 = 0.995). . The two areas for C-∗-C interactions with Δθp > 0 and Δθp < 0 are clearly illustrated by the green dotted lines in θp values for the interactions are positive if the θp values are larger than 70.7°, whereas Δθp < 0 if θp < 70.7°. bay-∗-Cbay and Ccape-∗-Ccape in 9–12 belong to the areas where Δθp > 0 and Δθp < 0, respectively.Interactions with θ should be a measure of the strength of the interactions. If so, the steric compression on Ccape-∗-Ccape in 9–12 appears to be similar to that on Cbay-∗-Cbay in fully optimized structures. Namely, the Ccape-∗-Ccape and Cbay-∗-Cbay interactions in the fully optimized structures of 9–12 would be affected similarly to steric compression, according to the θ values. On the other hand, the dynamic nature of the interactions is defined by θp based on the behaviour of the interactions in the perturbed structures. The Cbay-∗-Cbay interactions in the perturbed structures will be affected by steric compression, similar to the usual cases of interactions, whereas the Ccape-∗-Ccape interactions will be inversely affected compared with the usual cases when measured by the θp values at the BCPs of the interactions.It seems difficult to clearly explain the results shown in 6:6 (Ci) and 7:7 (Ci) with M06-2X/6-311+G. 6:6 and 7:7. Five and four independent BPs with BCPs were detected in 6:6 and 7:7, respectively, between the components of H-∗-H and C-∗-H, as well as two independent BPs with BCPs for the intramolecular C-∗-H interactions in each component of 6:6 and 7:7. The behaviour of the interactions was also investigated for 7:7 (Ci), 8:8 (Ci), and/or 10:10 (Ci) with M06-2X/6-311+G and LC-ωPBE/6-311+G. The results are collected in 6:6 and 7:7 with M06-2X/6-311+G.What is the behaviour of the interactions when the helicenes form concave-type dimers? The behaviour was elucidated, exemplified by ρb(rc), Hb(rc) − Vb(rc)/2, and Hb(rc) values for one of the doubly degenerate interactions due to the Ci symmetry of the optimized structures. Hb(rc) versus Hb(rc) − Vb(rc)/2 for each interaction between the components at 6:6 and 7:7.  and  for the intermolecular interactions in question at 6:6 and 7:7, together with the iiC values corresponding to the interactions in question. The  values for the three H-∗-H and two C-∗-C intermolecular independent interactions of 6:6 are  and , respectively. The  values for the couple of H-∗-H and two C-∗-H intermolecular independent interactions at 7:7 are  and , respectively. The θ and θp values for the intermolecular H-∗-H, C-∗-H, and C-∗-C interactions at 6:6 and 7:7 are all less than 90°; therefore, the interactions are all predicted to have a p-CS/vdW nature  values. However,  =  for 6:6 (1Hbay-∗-17’Hcape), of which nature seems close to p-CS/t-HBnc.The plots were analyzed similarly to the case of ture see . The int1Hbay-∗-5Cbay and 3Cbay-∗-7Hbay were detected at 6:6. The former was also observed in 6, whereas the latter was newly detected in 6:6. The new appearance of 6 (3Cbay-∗-7Hbay) may be due to a structural change at 6:6 relative to 6. Similarly, 1Hbay-∗-6Cbay and 3Cbay-∗-8Hbay were detected at 7:7. The former was observed in 7, while 3Cbay-∗-8Hbay in 7:7 appeared in place of 2Cbay-∗-7Cbay in 7. The change in the optimized structures between 7 and 7:7 would again be responsible for the results. However, clarifying the reason for the appearance/disappearance of BPs is very complex and difficult in helicenes, and it is beyond the scope of this work.In the case of intramolecular interactions, Vxc term is the largest among several possibilities, where Vxc stands for a quantum-mechanical correction coming from the exchange correlation second-order density [Highly theoretical treatment must be necessary to clarify the reason for the appearance and disappearance of BPs/BCPs. Pendás and coworkers discussed BPs as privileged exchange channels, using the interacting quantum atom (IQA) framework . They ha density . It has  density . Moreove density . Similar density . The rea density .θ, θp) values for the intramolecular interactions at 6:6 and 7:7 are . As a result, the interactions are all predicted to have a p-CS/vdW nature  and  and the iiC values, calculated with M06-2X/6-311+G, M06-2X/6-311+G, and LC-ωPBE/6-311+G. nν corresponding to the interactions in question, which are closely related to . ν1 of 7 and 7:7 calculated with M06-2X/6-311+G, M06-2X/6-311+G, and LC-ωPBE/6-311+G.  and r(2Cbay···7Cbay) distances were 2.590 Å and 2.975 Å, respectively, for 7, when calculated with M06-2X/6-311+, while the values were 2.590 Å and 3.003 Å, respectively, when calculated with M06-2X/6-311+. The differences are less than 0.001 Å for r(1Hbay···6Cbay) and 0.028 Å for r(2Cbay···7Cbay). The results show that the structure of 7 optimized with M06-2X/6-311+ appears to be nearly identical to that optimized with M06-2X/6-311+. On the other hand, the r(1Hbay···6Cbay) and r(2Cbay···7Cbay) of 7 were 2.561 Å and 3.227 Å, respectively, if calculated with LC-ωPBE/6-311+. The difference was −0.029 Å for the former but 0.224 Å for the latter relative to the corresponding values calculated with M06-2X/6-311+. The structure of 7 optimized with LC-ωPBE/6-311+ appears to be (very) different from that optimized with M06-2X/6-311+, especially around r(2Cbay···7Cbay). In the case of 1Hbay···5Cbay, the distance was optimized to be 2.468 Å with LC-ωPBE/6-311+, which is shorter than the r(1Hbay···6Cbay) distance optimized with M06-2X/6-311+ (2.590 Å) by 0.122 Å. BPs (with BCPs) were detected for 1Hbay-∗-6Cbay and 2Cbay-∗-7Cbay in 7 if calculated with M06-2X/6-311+ and M06-2X/6-311+, while a BP was detected for 1Hbay-∗-5Cbay if calculated with LC-ωPBE/6-311+. The 2Cbay-∗-7Cbay and 1Hbay-∗-5Cbay distances in 7, optimized with LC-ωPBE/6-311+, were (much) longer and shorter than those optimized with M06-2X/6-311+, respectively.The calculated ν1 appears to be very similar when calculated at both the M06-2X and LC-ωPBE levels, indicating that ν1 is a good measure for imaging the dynamic nature of the π···π interactions in 7 among the internal vibrations. Small differences in the dynamic nature of the interactions predicted at both the M06-2X and LC-ωPBE levels result from the (very) similar motion of ν1. The magnitudes of the displacements in the cape area seem (much) larger than those in the bay area in ν1. This will be instructive if the relationship is clarified for that between the magnitudes of the displacements and the Δθp values. This issue will be investigated in a future work. The very low energy of ν1 in 7 suggests the basis set and level dependence can easily change the optimized structure.The differences in the optimized distances appear to be the main factor for the appearance/disappearance of the BPs, although predicting the appearance/disappearance of the BPs is very difficult and complex. Despite such different results, the motion of 7:7, the r(20Hcape···18’Hcape), r(20Hcape···20’Hbay), r(20Hcape···2’Ccape), and r(8Hcape···3’Ccape) distances were 2.543 Å, 2.716 Å, 2.677 Å, and 2.964 Å, respectively, when calculated with M06-2X/6-311+, while the values were 2.564 Å, 2.729 Å, 2.688 Å, and 2.986 Å, respectively, when calculated with M06-2X/6-311+. The differences are 0.011–0.022 Å, which are less than approximately 0.02 Å. The results show that the optimized structures of 7:7 are very similar with both M06-2X/6-311+ and M06-2X/6-311+. On the other hand, the distances are optimized to be 2.947 Å, 3.015 Å, 3.066 Å, and 3.659 Å with LC-ωPBE/6-311+. The differences with the corresponding values of M06-2X/6-311+ are 0.286–0.674 Å. Namely, the structure of 7:7 optimized with LC-ωPBE/6-311+ appears to be very different from that optimized with M06-2X/6-311+, similar to the case of 7.In the case of 20Ccape-∗-18’Hcape distance was optimized to be 3.236 Å, which is longer than r(20Hcape···18’Hcape) (2.947 Å) by 0.288 Å with LC-ωPBE/6-311+. However, a BP was detected for 20Ccape-∗-18’Hcape but not for 20Hcape-∗-18’Hcape. The difference in the atomic size between C and H, such as the van der Waals radii, may be responsible for the predicted results, in this case. The 20Ccape-∗-18’Hcape, 20Hcape-∗-20’Hbay, 20Hcape-∗-2’Ccape, and 8Hcape-∗-3’Ccape distances at 7:7, optimized with LC-ωPBE/6-311+, were much longer than the corresponding distances, optimized with M06-2X/6-311+. BPs were detected for 20Hcape-∗-18’Hcape, 20Hcape-∗-20’Hbay, 20Hcape-∗-2’Ccape, and 18Hcape-∗-3’Ccape when calculated with M06-2X/6-311+, while they were detected for 20Ccape-∗-18’Hcape, 20Hcape-∗-20’Hbay, 20Hcape-∗-2’Ccape, and 8Hcape-∗-3’Ccape when calculated with LC-ωPBE/6-311+. The differences in the optimized distances appear to be the main factor for the appearance/disappearance of the BPs, similar to the case of 7.The ν1 values for 7 and 7:7, calculated with M06-2X/6-311+, M06-2X/6-311+, and LC-ωPBE/6-311+. 7:7, where most candidates were found to be less than νn of ν20. The ν1 values for 7 were 48.4 cm−1, 46.6 cm−1, and 40.2 cm−1 when calculated with the three methods, respectively. The ν1 motion of 7 appears to be very similar when calculated with the three methods. In the case of 7:7, the frequencies of ν1 calculated with M06-2X/6-311+G and M06-2X/6-311+G were 14.0 cm−1 and 13.1 cm−1, respectively, while the value calculated with LC-ωPBE was 2.1 cm−1. Very large differences are predicted for ν1 at 7:7 when calculated at the M06-2X and LC-ωPBE levels. The ν1 value with the motion should correspond to the strength of the interactions in the direction of the perturbed structures.θ, θp) values of 7:7 are  and  with M06-2X/6-311+ and LC-ωPBE/6-311+, respectively. The differences seem large relative to the case of 7, with  values of  and  when calculated with M06-2X/6-311+ and LC-ωPBE/6-311+, respectively, although 7 (1Hbay-∗-6Cbay) was detected with M06-2X/6-311+ and 7 (1Hbay-∗-5Cbay) was detected with LC-ωPBE/6-311+. The (optimized) structures of 7:7 would be affected more easily by surroundings containing the calculation methods than the case of 7. The basis set and level dependence of the interactions in 7 and 7:7 can help us to better understand the interactions in helicenes.The , M06-2X/6-311+, and LC-ωPBE/6-311+, respectively. This consideration explains the above results.The unit of 1–12, as well as in dimers 6:6 and 7:7, were analyzed with QTAIM-DFA after clarifying the structural features and the energy profile. Hb(rc) was plotted versus Hb(rc) − Vb(rc)/2, and the data from the fully optimized structures and the perturbed structures around the fully optimized structures were used in QTAIM-DFA. Data from the fully optimized structures in the plots correspond to the static nature of the interactions, which are analyzed using polar coordinate  representation. Data from both the perturbed and fully optimized structures are expressed by , where θp corresponds to the tangent line and κp is the curvature of the plot. The concept of the dynamic nature of the interactions was proposed based on .It is challenging to clarify the natures of π···π interactions in helicenes since the interactions are factors that control the fine details of structures and are expected to give rise to specific functionalities for the species. The repulsive interactions between the benzene rings in helicenes must be very strong; therefore, the π···π interactions would be considered strong. The π···π interactions in the helicenes are described by the H-∗-H, C-∗-H, and C-∗-C forms with BPs and BCPs. The π···π interactions in helicenes 3–12 into Cbay and Ccape and the H atoms into Hbay and Hcape. While both Cbay and Ccape atoms of 3–12 take part in the interactions, only Hbay atoms participate as BPs. The θ and θp values for H-∗-H, C-∗-H, and C-∗-C of 3–12 are all less than 90°, except for 10 (2Cbay-∗-7Cbay), where  = . Therefore, the H-∗-H, C-∗-H, and C-∗-C interactions of 3–12 are all predicted to have a p-CS/vdW nature, except for 10 (2Cbay-∗-7Cbay), which is predicted to have a p-CS/t-HBnc nature. While the  values of Cbay-∗-Cbay in 7–12 are , the values are  for Ccape-∗-Ccape. The θ values for Ccape-∗-Ccape are slightly smaller than those of Cbay-∗-Cbay (by 0.5–2.2°), but the θp values for Ccape-∗-Ccape are much smaller than those of Cbay-∗-Cbay (by 13.2–24.5°). In this case, θ < θp for Cbay-∗-Cbay, whereas θ > θp for Ccape-∗-Ccape. Interactions with θ < θp are usually observed, whereas interactions with θ > θp are rare.The interactions were analyzed by dividing the C atoms of 6:6 and 7:7 were similarly analyzed. The interactions were predicted to have a p-CS/vdW nature, although 6:6 (1Hbay-∗-17’Hcape) has a nature close to p-CS/t-HBnc, since  = . The interactions at 3–12 and 6:6 and 7:7 were predicted to be much weaker than expected. The very low energy of ν1 of 7:7 supports the very weak nature predicted for interactions and the easy dependence of the levels on the nature of the interactions. The strength of the interactions can also be estimated by the iiC−1 values. Detecting the interactions and predicting the nature of helicenes will provide a solid basis for investigating and applying the interactions in helicenes.The H-∗-H, C-∗-H, and C-∗-C interactions of dimers


In the title compound, one of the fused pyrazole rings adopts an envelope conformation while the other displays a twisted conformation. In the crystal, the molecules are linked by C—H⋯O hydrogen bonds and aromatic π–π interactions. 17H17BrN2O5, resulted from the 1,3-dipolar cycloaddition reaction between dimethyl acetylenedicarboxylate and (3-bromobenzylidene)-4-methyl-5-oxopyrazolidin-2-ium-1-ide in CHCl3. The dihedral angle between the pyrazole rings  is 32.91 (10)°; the oxo-pyrazole ring displays an envelope conformation whereas the other pyrazole ring adopts a twisted conformation. The bromophenyl ring subtends a dihedral angle of 88.95 (9)° with the mean plane of its attached pyrazole ring. In the crystal, the molecules are linked by C—H⋯O hydrogen bonds and aromatic π–π interactions with an inter-centroid distance of 3.8369 (10) Å. The Hirshfeld surface analysis and fingerprint plots reveal that the molecular packing is governed by H⋯H (37.1%), O⋯H/H⋯O (31.3%), Br⋯H/H⋯Br (13.5%) and C⋯H/H⋯C (10.6%) contacts. The energy framework indicates that dispersion energy is the major contributor to the molecular packing.The title compound, C Moreover, the mean plane passing through the oxo-pyrazole ring subtends a dihedral angle of 61.15 (10)° with the C12–C17 bromophenyl ring, which is practically perpendicular to the other pyrazole ring as indicated by the dihedral angle of 88.95 (9)°. The non-H atoms of the ester groups are virtually coplanar, the maximum deviations from the mean planes being 0.017 (2) Å at C10 for the O2/O3/C10/C11 grouping and 0.013 (1) Å at O5 for the O4/O5/C8/C9 grouping. The dihedral angle between these two planes is 62.15 (12)°.The molecular structure of the the title compound is shown in Fig. 1In the crystal, the molecules are linked by C—H⋯O hydrogen bonds: O1 accepts two such bonds and O2 and O3 accept one each Table 1. The broet al., 2016tert-butylamino)-7-phenyl-5-oxo-1H,5H-pyrazolopyrazole-1,2-dicarboxylate ° in the title compound. It may be noted that the phenyl substituent is linked to the oxo-pyrazole ring and the two carboxylate groups to the other pyrazole ring in RICFUF, while in the title compound the phenyl and both carboxylate groups are linked to the same pyrazole ring.A search of the Cambridge Structural Database , while blue regions indicate atoms with positive electrostatic potential (hydrogen-bond donors)  analyses  , contributing 37.6% to the overall crystal packing, which is reflected as widely scattered points of high density due to the large hydrogen content of the molecule. The contribution from the O⋯H/H⋯O contacts (31.4%), corresponding to C—H⋯O interactions, is represented by a pair of sharp spikes characteristic of a strong hydrogen-bond interaction . The reciprocal H⋯Br/Br⋯H interactions (12.8%) are present as two symmetrical broad wings with di + de = 3.10 Å . The C⋯H/H⋯C contacts contribute 10.8% to the Hirshfeld surface, featuring a wide region with di + de = 2.95 Å . The smaller percentage contributions of other types of contact are listed in Table 2Two-dimensional fingerprint plots for the H⋯H, H⋯O/O⋯H, H⋯Br/Br⋯H and H⋯C/C⋯H contacts are presented in Fig. 4Å) Fig. 4b, contr Å Fig. 4d. The C Å Fig. 4e. The sInteraction energy calculationsCrystal Explorer 17.5  is the sum of electrostatic (Eele), polarization (Epol), dispersion (Edis), and exchange-repulsion (Erep) energies. The energy frameworks, which provide a view of the supramolecular architecture of crystals, are represented by cylinders joining the centroids of molecular pairs using red, green and, blue colour codes for the Eele, Edis, and Etot energy components, respectively, with a cut-off value of 5 kJ mol−1 and a scale factor of 80 to all energy components  having a major electrostatic contribution (–21.9 kJ mol−1). The next most significant contribution, with a total energy of −34.9 kJ mol−1, arises from the C11—H11B⋯O2 hydrogen bond. Lower energies, compared to the above interactions, are calculated for the Br1A⋯O4, C9—H9A⋯O1 and C14—H14⋯O1 contacts.The intermolecular interaction energies between molecules in the title compound computed using a B3LYP/6–31G  energy model available in ts Fig. 5. The benFrontier molecular orbital (FMO) calculationsGAUSSIAN 09 . The HOMO–LUMO gap of the molecule is calculated to be about 4.16 eV.The optimized structure of the title compound was established in the gas phase using density functional theory (DFT) using the B3LYP exchange correlation functional and basis-set calculations , (3-bromobenzylidene)-4-methyl-5-oxopyrazolidin-2-ium-1-ide  was added . After completion of the reaction, the residue was concentrated in vacuo. The crude product was purified by column chromatography on silica gel using hexane:ethyl acetate (2/8 v:v) as eluent. The title compound was recrystallized from ethanol solution in the form of colourless blocks .To a solution of DMAD  in 10 ml of CHCled Fig. 6. The mixUiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C). The Br atom was modelled as disordered over adjacent sites in a 0.5862:0.4138 ratio.Crystal data, data collection and structure refinement details are summarized in Table 410.1107/S2056989021013621/hb8006sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021013621/hb8006Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021013621/hb8006Isup3.cmlSupporting information file. DOI: 2131209CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:


The objective of this study was to evaluate the biodistribution and radiation dosimetry of [18F]PR04.MZ by serial PET imaging.PR04.MZ. After rigid co-registration, volumes of interest were outlined either on CT or PET images. Time-integrated activity coefficients were calculated for selected source organs. Organ absorbed doses, and the effective dose were calculated using IDAC-Dose 2.1.Six healthy subjects , urinary bladder wall (27.2 ± 4.5 µGy/MBq), red marrow (26.5 ± 1.4 µGy/MBq), cortical bone surface (26.3 ± 2.5 µGy/MBq), liver (22.5 ± 1.8 µGy/MBq) and kidneys (21.8 ± 1.1 µGy/MBq). The effective dose according to ICRP 60 and 103 was 16.3 ± 1.1 and 16.6 ± 1.5 µSv/MBq, respectively.Physiological uptake of [18F]PR04.MZ has a favourable dosimetry profile, comparable to those of other 18F-labelled PET tracers, and is suitable for larger clinical applications.[Trial registration CEC SSM Oriente, Santiago, Chile, permit 20140520. The presynaptic dopamine transporter (DAT) modulates the extracellular dopamine concentration in the brain. DAT availability is an important imaging biomarker of different disease states, such as movement disorders, attention deficit hyperactivity disorder (ADHD) and drug addiction , 2. PartFor disease management, DAT imaging is used to differentiate essential tremor from tremor due to PS for which the Single Photon Emission Computed Tomography (SPECT) tracer DaTscan™ (Ioflupane I-123), approved by the FDA and EMA, is the standard of care . Althoug18F-labelled tracers such as [18F]FP-CIT, [18F]FE-CNT, [18F]FE-PE2I, [18F]LBT-999 is a viable alternative when precise quantification for clinical research is necessary or where DaTscan™ is not available [DAT PET imaging with vailable –10.18F]PR04.MZ is a new, innovative PET imaging agent with an improved affinity and selectivity profile, which further allows for quantification of extra-striatal DAT, for example in the substantia nigra pars compacta [18F]PR04.MZ showed very high specific uptake in striatal and midbrain regions, excellent imaging contrast and robust quantification outcomes PR04.MZ PET/CT in healthy controls to support clinical application in larger groups of patients.The aim of this study was to evaluate the long-term biodistribution and dosimetry of [18F]PR04.MZ was produced under GMP-compliant conditions as previously described PR04.MZ was 200 ± 11 MBq , there were no adverse or clinically detectable pharmacologic effects (injected mass was < 1.0 ug) in any of the six subjects and no significant changes in vital signs were observed.The administered activity of [18F]PR04.MZ was observed in the striatum, brain, heart, parotid and submaxillary glands, thyroid, liver, gall bladder, intestine, red marrow and cortical bone , urinary bladder wall (27.2 ± 4.5 µGy/MBq), red marrow (26.5 ± 1.4 µGy/MBq), cortical bone surface (26.3 ± 2.5 µGy/MBq) and liver (22.5 ± 1.8 µGy/MBq) in 5/6 subjects. The subject which underwent cholecystectomy prior to study inclusion still showed activity uptake in the biliary ductus. Due to a significant contribution of the liver to the gall bladder dose, the absorbed dose to the gall bladder wall was only 40% lower than the median dose across all subjects without relevant impact on effective dose calculation.18F]FP-CIT and [18F]FE-PE2I, the urinary bladder wall had the highest absorbed dose with mean values of 58.6 µGy/MBq [18F]PR04.MZ provides a higher selectivity for DAT [18F]Fluoride have been described for [18F]PR04.MZ which would be primarily cleared via the kidneys and bladder Fluoride to the absorbed dose to bone surface since the dose contribution from red marrow tissue as source organ to bone is only 12%.It can further be assumed that the absorbed dose to bone surface was higher in the current study because cortical and trabecular bone were explicitly used as source organs compared to other der body , 23. It 18F]FE-PE2I [18F]FP-CIT [18F]FE-PE2I with 25 µGy/MBq [18F]PR04.MZ. In both cases, red marrow was included as a source organ and in addition, both used IDAC  FP-CIT . A simil µGy/MBq  comparede 2.0 in  and IDACµGy/MBq) .123I]FP-CIT. The effective dose of [18F]PR04.MZ calculated with IDAC-Dose 2.1 according to ICRP 60 and 103 was 16.3 ± 1.1 µSv/MBq and 16.6 ± 1.5 µSv/MBq, respectively, which is within the standard range of 15–30 µSv/MBq observed for the vast majority of 18F-labelled PET tracers [18F]FE-PE2I, calculated with IDAC 2.0 according to ICRP 60, was higher with 23 µSv/MBq [18F]FP-CIT, the effective dose equivalent according to ICRP 26 [123I]FP-CIT, the widely used DaTscan™ SPECT tracer, is also in that range with 23.5 µSv/MBq PR04.MZ would result in an effective dose of approximately 3 mSv, far below the most strict dose limit of 10 mSv used in some European countries PR04.MZ has a favourable dosimetry profile which is comparable to other 18F-labelled PET tracers and would result in an average effective dose of 16.3 ± 1.1 µSv/MBq. This is within the standard range of 15–30 µSv/MBq observed for the majority of 18F-labelled PET tracers and a standard injection of 185 MBq [18F]PR04.MZ would result in an effective dose of approximately 3 mSv. In addition, [18F]PR04.MZ showed high specific uptake in striatal and midbrain regions [18F]PR04.MZ supports clinical applications in larger groups of patients being evaluated for movement disorders.[ regions  and show regions  PS 15]..18F]PR04


Ir-dfpMepy-CN) bearing tridentate bis-N-heterocyclic carbene (NHC) chelate , bidentate chelates 2--4-methylpyridine (dfpMepy), and monodentate ligand (-CN) has been designed and synthesized. The tridentate bis-NHC ligand enhances molecular stability by forming strong bonds with the center iridium atom. The electron-withdrawing groups in the bidentate ligand (dfpMepy) and monodentate ligand (-CN) ameliorate the stability of the HOMO levels. Ir-dfpMepy-CN shows photoluminescence peaks of 440 and 466 nm with a high quantum efficiency of 84 ± 5%. Additionally, the HATCN (10 nm)/TAPC (40 nm)/TcTa (10 nm)/10 wt% Ir-dfpMepy-CN in DPEPO (10 nm)/TmPyPB (40 nm)/Liq (2.5 nm)/Al (100 nm) OLED device employing the complex shows a CIE coordinate of , reaching a deeper blue emission. The high quantum efficiency is attributed to rapid singlet to triplet charge transfer transition of 0.9–1.2 ps. The successful synthesis of Ir-dfpMepy-CN has opened a new window to develop advanced blue emitters and dopant alternatives for future efficient blue PhOLEDs.Cyclometalated iridium (III) complexes are indispensable in the field of phosphorescent organic light-emitting diodes (PhOLEDs), while the improvement of blue iridium (III) complexes is as yet limited and challenging. More diversified blue emitters are needed to break through the bottleneck of the industry. Hence, a novel [3+2+1] coordinated iridium (III) complex (noted as  Howeverum yield .d6 electron configuration of iridium ion (The blue iridium (III) complexes generally feature an octahedral conformation with three bidentate or two tridentate ligands  due to the dium ion . [2+2+2]dium ion , and onedium ion . As showdium ion  [3+3]. Cdium ion . Scheme dium ion . Multi-sIn this work, a novel [3+2+1] coordinated iridium (III) complex, bearing tridentate bis-N-heterocyclic carbene (NHC) chelate , bidentate chelates 2--4-methylpyridine (dfpMepy), and monodentate ligand (-CN), has been designed and synthesized. The tridentate ligand improves the molecular stability with the similar function of the [3+3] conformation and sufficient bidentate ligands are available to tune the emission wavelength. Additionally, monodentate ligand (-CN) is a strong electron-withdrawing group, facilitating the stability of the HOMO levels. The designed [3+2+1] iridium (III) complex shows emission peaks of 440 and 466 nm with a high quantum efficiency of 84 ± 5%. Furthermore, the femtosecond transient absorption spectrum further reveals the singlet transition to triplet state with a time constant of 0.9–1.2 ps. This work exhibits a novel cyclometalated iridium (III) complex configuration that will help develop more dopant options for blue PHOLEDs.4, yielding an oily organic layer. The crude product was concentrated and purified by column chromatography  to obtain light yellow powder . 1H NMR : δ = 8.58 , 7.98 , 7.58 , 7.13–7.07 , 7.01 , 6.93 , 2.43  ppm.2-bromo-4-methylpyridine , potassium carbonate  and tetrakis (triphenylphosphine) palladium  were added into a 250 ml round-bottomed flask.  boronic acid , ethanol (20 ml) and tetrahydrofuran (20 ml) were slowly added into the flask under stirring conditions. The mixture was then heated to reflux for 20 h under a nitrogen atmosphere. After cooled to room temperature, the resulting solution was firstly washed by water for three times and then filtered, extracted with dichloromethane, and dried with MgSO1H NMR : δ = 7.93 , 7.63 , 7.45 , 7.42 , 7.35 , 7.27  ppm.1,3-Dibromobenzene , imidazole , potassium carbonate , cupric oxide  and DMSO (60 ml) were added into a 250 ml flask. The mixture was heated to 150°C for 48 h. After cooling to room temperature, the resulting solution was filtered under reduced pressure and washed by water for three times. DMSO was then removed from the solution by vacuum distillation. The crude product was concentrated and purified by column chromatography to obtain a white powder . 1H NMR : δ = 10.29 , 8.59 , 8.53 , 8.19–8.13 , 8.07 , 7.96 , 4.33 , 1.93 , 1.36 , 0.95  ppm.1,3-Bis(imidazolyl)benzene , n-butyl bromide  and acetonitrile (30 ml) were added to a 100 ml round-bottomed flask. The mixture was heated to 85°C for 3 h. After cooled to room temperature, the solution was concentrated and purified by vacuum distillation to obtain a white powder . 2  and compound 2  were added into a 25 ml Schlenk tube. Triethylamine (2 ml) and acetonitrile (10 ml) were slowly added into the Schlenk tube under the protection of N2. The mixture was heated to 90°C for 12 h. After cooled to room temperature, the resulting solution was concentrated by vacuum distillation to get a yellow sticky solid. Then dfpMepy  and propionic acid (10 ml) were added for next step reaction with the residual. The mixture was heated to 150°C under N2 atmosphere for 24 h. After cooled to room temperature, the resulting solution was purified by vacuum distillation, column chromatography to get crude product Ir-dfpMepy-Br . 1H NMR : δ = 10.13 , 8.16 , 8.04 , 7.47 , 7.40 , 7.23 , 7.18 , 6.50 , 5.27 , 2.59 , 1.36–1.27 , 0.95 , 0.81 , 0.65  ppm.[Ir(COD)Cl]2 atmosphere. After cooled to room temperature, the resulting solution was further filtered through kieselguhr, evaporated under reduced pressure and purified by silica gel column to get a white powder . 1H NMR : δ = 9.98 , 8.24 , 7.50 , 7.26 , 7.16 , 6.80 , 6.32–6.22 , 5.49 , 3.27 , 2.61 , 1.40 , 1.15 , 0.94 , 0.80 , 0.77  ppm.Ir-dfpMepy-Br  and Silver cyanide  were dissolved in N. N-dimethylformamide (10 ml) in Schlenk tube. The mixture was then heated to 120°C under N1H-NMR spectrometer (Bruker AV400) and referenced to tetramethylsilane (TMS) as a standard benchmark at 0.00 ppm. The ultra-violate absorption spectra was performed by Cary 5000 UV-vis-NIR spectrophotometer in degassed dichloromethane at a diluted concentration (2 × 10−5 M) of the iridium (III) complex. The photoluminescence (PL) spectra was obtained by spectrofluorometer of Edinburgh Instruments Ltd FS5. The femtosecond transient absorption (fs-TA) measurements were obtained on a Helios pump-probe system (Ultrafast Systems LLC) with an amplified femtosecond laser system . The 320 nm pump pulses were achieved by the optical parametric amplifier (TOPAS-800-fs). The 380–680 nm probe pulses were gained by focusing the tiny portion of the 800 nm laser beams onto a sapphire plate. The fs-TA curves were collected and further analyzed by Surface Xplorer software. Thermogravimetric analysis (TGA) of Ir-dfpMepy-CN was recorded by the Mettler TGA2 thermogravimeter. The weight loss of the iridium complex was initially measured from 25 to 100°C at a speed of 10°C/min under a nitrogen atmosphere. Before continuing to heat to 500°C, the sample was kept for 15 min at 100°C. Electrochemical characterization of the iridium complex was measured by PalmSens4 electrochemical workstation, using platinum wire as the counter electrode, platinum-carbon as a working electrode and a saturated calomel electrode (SCE) in a saturated KCl aqueous solution as the reference electrode. The cyclic voltammogram of Ir-dfpMepy-CN was referenced to the ferrocene/ferrocenium couple at the scanning rate of 100 mV s−1.All the reagents were purchased from Leyan, General Reagent and Aldrich and all the reactants and solvents were used without further purification unless otherwise specified. The key reaction products are characterized by a 400 MHz Ir-dfpMepy-CN and DPEPO were thermally deposited together at the speed of 0.1 Å s−1 and 0.9 Å s−1 separately, while the other organic functional layers were evaporated at the same rate of 1.0 Å s−1 at a pressure of ca. 3.5 × 10–7 Torr. A 2.5 nm Liq layer was deposited on Al cathode and the two materials are deposited at the rate of 0.1 and 1 Å s−1. The organic diode was assembled on an active area of 3 × 3 mm2 on the substrates. The device performance, including electroluminescence (EL) spectra, Commission Internationale de L’Eclairage (CIE) and current density-voltage-luminance (J-V-L) curves, were measured by a Keithley 2400 semiconductor characterization system with PR-788 photometer and BM-7A luminance colorimeter.The indium-tin-oxide (ITO) coated glass substrates were initially cleaned sequentially by deionized water, ethanol, dichloromethane for 5 min separately and then treated with plasma for 1 min. The dopant material The structures were optimized with dispersion density functional theory at the PBE0-D3/def2-SVP level by Gaussian 09. In order to investigate the photophysical properties, the excited electronic structures of these molecules were calculated at the PBE0-D3/def2-TZVP level with the time-dependent density functional theory (TDDFT) method. The electron transition characterization was obtained by electron excitation analysis performed using Multiwfn program from the transition density matrix of TDDFT calculation.Ir-dfpMepy-CN with [3+2+1] conformation was depicted in 1H NMR spectrometry for further study, as shown in The synthetic route of the Ir-dfpMepy-CN were recorded in degassed CH2Cl2 (DCM) solution at a concentration of 2 × 10−5 M. The strong absorption at 250–280 nm in the ultraviolet region (ε > 2.5 × 104 M−1 cm−1) was assigned to the ligand-centered (1π→π*) transitions (1π→π*) transition and metal to ligand charge transfer (1MLCT) transitions. The weak absorptions bands (ε ≈ 0.3 × 104 M−1 cm−1) lying in the visible light region at 350–400 nm were related to the spin-orbit coupling enhanced 3π→π* states and spin-forbidden metal to ligand charge transfer (3MLCT) transitions  complex were investigated. As shown in nsitions . The absnsitions . The PL ox) of 0.80–1.16 V (vs. Fc+/0) due to the electron-deficient property of the pyridine group and reduction peak (E_red) around −2.50 V. The HOMO and LUMO energy of Ir-dfpMepy-CN were calculated by Ir-dfpMepy-CN is −5.2 and −2.0 eV. Thermogravimetric analysis (TGA) experiments revealed the thermal stability of Ir-dfpMepy-CN  surfaces and their corresponding energy levels were given in Ir-dfpMepy-CN. The phenyl unit of bis-NHC pincer moiety is suggested to dominate the HOMO, while the difluoro-phenyl unit of dfppy dominates a major contribution in its HOMO-1. The participation of the bis-NHC carbene pincer moiety and monodentate ancillaries in HOMOs keep synergistically. The N-heterocyclic phenyl unit in dfpMepy almost dominates LUMO and LUMO+1. The T1 optical transition state were calculated by TD-DFT. As shown in 1 transition state is contributed by HOMO-3, HOMO-2, HOMO-1 and LUMO. 1 geometries, indicating the T1 transition state is mixing MLCT, ligand centered (LC) or intra-ligand charge transfer (ILCT) excited state.The density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculation were implemented to gain a deeper insight into the ground and excited electronic states of the Ir-dfpMepy-CN are studied by the femtosecond transient absorption spectroscopy. The iridium complex in DCM solution was pumped by a flash laser at 320 nm, resulting a broad absorption ranging from 340 to 480 nm. Monitoring the kinetics of two absorption peaks at 350 and 370 nm gives two growth lifetimes of 0.9 and 1.2 picoseconds (ps), respectively, and this species has a long lifetime beyond 1,000 ps from fs-TA analysis, revealing the generation of triplet from singlet occurs in 1.2 ps. The non-decaying signal of the absorption spectra indicates the overlap of excited singlet and triplet states of the iridium complex, which adversely influences the relaxation between two energy states and leads to an almost constant transient absorbance /TmpypB (40 nm)/Liq (2.5 nm)/Al (100 nm). The electroluminescence spectrum is depicted in The effectiveness of A novel [3+2+1] coordinated iridium (III) complex was designed and synthesized. The complex shows good stability due to the strong bonds formed by the center iridium atom and tridentate bis-NHC ligand. The designed [3+2+1] iridium (III) complex shows high photoluminescence peaks of 440 and 466 nm as both the bidentate (dfpMepy) and monodentate cyanide (-CN) ligand are strong electron-withdrawing groups, facilitating the stability of the HOMO levels. Notably, the complex shows a high PLQY of 84 ± 5% due to the rapid transition between singlet and triplet state with a time constant of 0.9–1.2 ps. The thermally evaporated device employed the [3+2+1] complex shows a CIE coordinate , reaching deeper blue emission. This work provides a highly efficient blue cyclometalated iridium (III) complex configuration that will help develop more blue emitters and provide more dopant options for blue PhOLEDs.


Correction to: Rice 14, 53 (2021)https://doi.org/10.1186/s12284-021-00493-wIt was highlighted that in the original article . C. Deletion of functional domains shown by modeling the three-dimensional protein structures of wild-type PSL50 and ΔPSL50. The three-dimensional model structures were predicted using Swiss-model (https://swissmodel.expasy.org/interactive). Figure S2. Leaf phenotypes and H2O2 content of wild-type and psl50 at 40 d after transplanting. L1-L4 represent four leaves from top to bottom, respectively. Data are means ± SD (n = 3), *P < 0.05 by Student’s t test. Figure S3.PSL50 expression in different leaves at the mature stage. a Phenotypes of different leaves at the mature stage. L1-L5 represent five leaves from top to bottom, respectively. bPSL50 expression in different leaves shown in a. Data are means ± SD (n = 3). Figure S4. Effects of light intensity on WT and psl50 seedlings under heat stress. a Phenotypes of WT and psl50 seedlings under heat stress and different light intensity. NL, normal light intensity (200 μmol m-2 s-1); HL, High light intensity (500 μmol m-2 s-1); HT, heat stress at 45°C. 2-week-old hydroponic plants at 26°C with 14 h light/10 h dark cycles (200 μmol m-2 s-1) were used for the treatment. Scale bars = 5 cm. b Photochemical efficiency of PSII (Fv/Fm ) of WT and psl50 plants shown in a. ND, not detected. Data are means ± SD (n = 5). c Survival rate of WT and psl50 plants shown in a following a 7 d recovery at 26°C with 14 h light/10 h dark cycles (200 μmol m-2 s-1). Data are means ± SD for three biological replicates (n = 48 for each replicate). Asterisks indicate significant difference by Student’s t test (*P < 0.05).


The Jahn-Teller distortion in MoO6 octahedra due to the doubly degenerate ground state of Mo5+, which can be continuously strengthened by oxygen vacancies, triggers the phase transformation of α-MoO3 bulk belts (up to 30 μm long and 500 nm wide). The optimized fibrous electrode exhibits among the highest volumetric performance with a specific capacitance (CV) of 921.5 F cm−3 under 0.3 A cm−3, endowing the fiber-based weaveable supercapacitor superior CV and EV (energy density) of 107.0 F cm−3 and 9.5 mWh cm−3, respectively, together with excellent cyclic stability, mechanical robustness, and rate capability. This work demonstrates a promising strategy for synthesizing nanosized amorphous materials in a scalable, cost-effective, and controllable manner.Amorphous pseudocapacitive nanomaterials are highly desired in energy storage applications for their disordered crystal structures, fast electrochemical dynamics, and outstanding cyclic stability, yet hardly achievable using the state-of-the-art synthetic strategies. Herein, for the first time, high capacitive fiber electrodes embedded with nanosized amorphous molybdenum trioxide (A-MoO Our calculation shows that α-MoO3 has a strong affinity towards C-OH groups rather than C=O, and the energy barrier for the linkage between Mo atom and -OH is 0.25 eV  at the scan rate of 2 mV s−1 were measured in a three-electrode configuration within the potential window between 0 and 0.8 V using Ag/AgCl (saturated KCl) as the reference electrode and H2SO4 (1 M) as the acidic electrolyte, respectively. As expected, moderate amount of oxygen vacancies, uniform loading of amorphous nanoparticles, and the mild reduction of GO nanosheets together endow the resultant A-MoO3-x/rGO fiber the maximum current density in CV curves at 2 mV s−1 and longest discharge time in GCD  profiles at 1.4 A cm−3  for A-MoO3-x/rGO fiber obtained at 6.0 h hydrothermal reaction with the feeding ratio of 2 : 1 between GO and α-MoO3  [3-x nanopaper (652 F cm−3) [xMoO3−y (350 F cm−3) [2/HGO fiber (448 F cm−3) [2-rGO fiber (491.1 F cm−3) [3-x/rGO fiber electrode was further characterized using electrochemical impedance spectroscopy (EIS). The EIS slope of hybrid fiber electrode at low-frequency range is slightly lower than that of bare rGO fiber electrode, indicating compromised ion diffusion for hybrid fibers  , MoO3-x  F cm−3) , HxMoO3− F cm−3) , MoS2/HG F cm−3) , and MoS F cm−3)  reporteds Figure . In addiO fiber 4 F cm−3 [s Figure .3-x/rGO and rGO fibers as electrodes, symmetric FSCs were assembled. CV profiles in H2SO4/PVA gel electrolyte were obtained under 2 mV s−1. The FSC based on rGO fiber exhibits an almost rectangular CV curve, indicating a typical EDLC behavior. Comparably, A-MoO3-x/rGO FSC  at 0.14 A cm−3 (−3 for MnO2-MWCNT fiber device (0.1 A cm−3), 28.1 F cm−3 for Ni(OH)2/CNT fiber device (0.4 A cm−3), and 53.5 F cm−3 for MoO3/rGO-based asymmetric device (0.1 A cm−3) [−3, the capacitance decreases to 55.3 F cm−3 with 51.7% retention. In contrast, only 26.9% of the initial capacitance (63.1 F cm−3) was retained for the rGO-based device when the current density increased from 0.14 to 1.4 A cm−3. According to the equations of EV = 1/2 × CV × V2 and PV = EV/tdischarge , EV of the A-MoO3-x/rGO FSC increases from 4.5 to 9.5 mWh cm−3 with the corresponding PV varying between 0.84 and 0.06 W cm−3. As shown in −3) [2O3/PPy (0.22 mWh cm−3) [−3) [−3) [−3) [−3) [−3) [−3) [3-x/rGO FSC exhibits excellent flexibility and cycling stability. 98.6% capacitance was sustained after bending-unbending for 5000 cycles  –51. At 1n in −3) , Fe2O3/P−3) [−3) , CNT/N-r−3) [−3)  and comp−3) [−3) , PPy@nan−3) [−3) , and PAN−3) [−3) . In addi0 cycles , and 90.cles , and concentrated H2SO4 (46 mL) were mixed and placed in an ice bath under stirring. KMnO4 (5.0 g) was slowly added to keep the reaction temperature below 20°C. Then, the mixture was heated to 35 ± 1°C and maintained for 8.0 h before adding deionized water (46 mL). 4 mL H2O2 (30 wt%) was subsequently added to the resultant suspension; then, GO nanosheets were collected and washed thoroughly.A modified Hummers' method was employed to synthesize GO nanosheets . Briefly2O2 (20 wt%) to obtain a light yellow solution. The mixture was hydrothermally heated at 220°C for 15.0 h, and the precipitate was collected.Typically, 1.0 g Mo powder was firstly dissolved in 15 mL H−1) was mixed with α-MoO3 belts and the mass ratio was controlled 2 : 1. After violently shaking, the mixture became homogeneous and subsequently was injected into a glass capillary with an inner diameter of ~1.0 mm. After being sealed at both ends using a welding torch, the glass capillaries were heated in an electric oven at 160°C for 6.0 h. The obtained hydrogel fibers (self-assembled) were then thoroughly washed using deionized water and dried at 60°C in a vacuum oven.Typically, GO aqueous solution  was used for identifying crystal structure. The confocal micro-Raman system (WITEC Alpha 300 M+) was performed using a diode laser of 633 nm at ambient conditions. X-ray photoelectron spectroscopy (XPS) was carried out on a PHI Quantera spectrometer. Tensile tester (HY-0350) and Keithley 2400 were used for measuring the failure strength and electrical conductivity of fibers.Field-emission scanning electron microscope  and transmission electron microscope  were employed for morphology characterizations. X-ray diffraction  method [Vienna Ab initio Simulation Package (VASP) was adopted for theoretical calculations based on a gradient approximation described by Perdew-Burke-Ernzerhof (PBE) –63, ab i) method .3-x/rGO hybrid fiber was tested in a three-electrode configuration with a reference electrode of Ag/AgCl (saturated KCl aqueous solution), a counter electrode of Pt plate, and the electrolyte of 1 M H2SO4. CV, and GCD measurements were performed on an electrochemical workstation . The fiber volume (Vwe) was obtained according to Vwe = L × π × (D/2)2, where L represents fiber length while D is fiber diameter. The electrochemical performance of pristine α-MoO3 was also measured in the same three-electrode system.The electrochemical performance of A-MoO3-x/rGO hybrid fibers (diameter of ~50 μm) were placed closely on a polymeric (PET) substrate, on top of which H2SO4/PVA gel was coated. Ag paste was applied on one end of fiber electrode for better electrical connection. The electrochemical characterization and capacitance calculation of FSCs are similar to that of a single electrode.Two ~1.5 cm long A-MoO