In this work, we examined how reaction conditions affect the synthesis of PLGA25 (L:G 25:75) through the ring-opening polymerisation of d-l-lactide (L) and glycolide (G), using tin 2-ethylhexanoate (Sn(Oct)2) as the catalyst and 1-dodecanol as the initiator. The effects of varying the initiator concentration, catalyst concentration, reaction time, and temperature on the molecular weight, monomer conversion, and thermal properties of PLGA25 were investigated. Increasing the reaction temperature from 130 to 205 °C significantly reduced the time required for high monomer conversions but caused greater polymer discolouration. Whilst increasing the [M]:[C] from 6500:1 to 50,000:1 reduced polymer discolouration, it also resulted in longer reaction times and higher reaction temperatures being required to achieve high conversions. High Mn and Mw values of 136,000 and 399,000 g mol−1 were achieved when polymerisations were performed in the solid state at 150 °C using low initiator concentrations. These copolymers were analysed using high temperature SEC at 80 °C, employing DMSO instead of HFIP as the eluent.The rise in demand for biodegradable plastic packaging with high barrier properties has spurred interest in poly(lactic acid- The use of biodegradable plastic packaging is regarded as an effective way to reduce the amount of plastic pollution in the natural environment. After starch blends, poly(lactic acid) (PLA) is the world’s most widely used biodegradable plastic . One facPoly(glycolic acid) (PGA) is a biodegradable aliphatic polyester that has biodegradation rates comparable to cellulose. It possesses a higher tensile strength, superior barrier properties, and higher thermal stability than most currently used packaging plastics ,12. As aco-glycolic acid) (PLGA) is a common copolymer that has found widespread commercial use in biomedical devices. PLGAs with high glycolide contents possess PGA’s high barrier properties and tensile strength, whilst having lower melting temperatures so they can be processed at lower temperatures :[I]) ratio, 0.015 mol (1.74 g) of glycolide, and 0.005 mol (0.72 g) of 2, and smashed to remove the sample.For the conversion optimisation experiments, a reaction mixture containing 0.04 mol (4.92 g) of monomer and the desired amounts of catalyst and initiator was made. A total of 0.8 g of this mixture was then added to a 15 mL sample vial, sealed, and purged with N2. The vial was then added to an oil bath at a set temperature. After the desired time, the vial was removed, placed in liquid N1H NMR spectra were recorded at 80 °C on an AV400 Bruker Avance III 400 MHz spectrometer  using DMSO-d6 as the solvent. For sample preparation, 15 mg of PLGA25 was added to 0.7 mL DMSO-d6 and stirred at 80 °C for 30 min.The 400 MHz −1 at 80 °C. Poly(methyl methacrylate) standards   were used for calibration between 2,270,000 and 1860 g mol−1 and were fitted with a 3rd order polynomial. Analyte samples were dissolved in DMSO by shaking at 100 °C for roughly 30 min and filtered. Molecular weight and dispersity values of synthesised polymers were determined by conventional calibration using Agilent GPC/SEC software.For SEC analysis performed in DMSO, SEC analysis was carried out on an Agilent PLL220 GPC  equipped with a differential refractive index detector and a viscometer. DMSO containing 0.1 M of sodium nitrate was used as the eluent at a temperature of 80 °C. Samples were run at 1 mL minFor SEC analysis performed in HFIP, HFIP containing 5 mM of sodium trifluoroacetate was used as the eluent at a temperature of 40 °C. The column was a PL-HFIP column. The detector was a differential refractive index (DRI) detector and a poly(methyl methacrylate) calibration was used to determine molecular weight values.−1. Samples of mass 6 mg were used. Td values were evaluated from 5% degradation.TGA experiments were performed on a Mettler-Toledo TGA . Samples were heated under a nitrogen atmosphere over a temperature range of 25–500 °C and at a heating rate of 10 °C min−1. Samples of a mass of 6 mg were used. gT values were reported from the second heating scans.DSC experiments were performed on a Mettler-Toledo DSC . Samples were scanned under a nitrogen atmosphere over a temperature range of 25–230 °C and at a heating rate of 10 °C minP value reduces the ingress of water into the reaction. When synthesising PLGA75, Wang et al. varied the monomer to the 1-dodecanol ratio ([M]:[I]) from 20:1 to 300:1 and observed that the Mn increased from 3400 to 99,000 g mol−1 :[I] due to side reactions, such as transesterification, occurring alongside chain propagation. Therefore, in order to examine the relationship between the initiator concentration and molecular weight in PLGA25, a series of PLGA25s were synthesised in which the [M]:[I] was varied from 30:1 to 30,000:1. These experiments were all performed at 150 °C over 2.5 h using a monomer to catalyst ratio ([M]:[C]) of 6500:1.n = 23,400 g mol−1 (Ð = 1.56) was recorded and in HFIP at 40 °C, Mn = 25,000 (Ð = 1.93) was recorded. Thus, DMSO at 80 °C is an excellent alternative eluent to HFIP for conducting SEC experiments with high glycolide PLGAs.Due to their poor solubility in common solvents, the molecular weight of high glycolide PLGAs are typically determined by SEC using hexafluoroisopropanol (HFIP) as the eluent. However, as HFIP is expensive and quite hazardous we used DMSO at 80 °C as a low-cost and safer alternative. As the only reported use of SEC in DMSO at high temperatures for similar polymers has been for PGA oligomers, PLGA25 synthesised using an [M]:[I] = 30:1 was also analysed with SEC in HFIP at 40 °C and the results from the two eluents were compared  38]. Bo. Bo38]. n and Mw values of 136,000 g mol−1 and 399,000 g mol−1 were achieved. The increase in molecular weight was accompanied by an increase in dispersity from 1.56 to 2.92, suggesting that more side reactions, such as intermolecular transesterification, occurred as higher molecular weight polymers were formed.From the SEC analysis shown in n increased from 23,400 to 136,000 g mol−1. Discolouration is a common problem encountered in the synthesis of polyesters by both polycondensation and ROP and has been reported to be influenced by the catalyst used :[I] = 3000:1–30,000:1show good linearity over a wide molecular weight range with α values of 0.55–0.59, suggesting linear polymers . The low1H NMR spectra revealed that as the [M]:[I] increased, the total monomer conversion (CLD+GD) decreased from 98.8 to 94.0%. For each polymerisation, the glycolide conversion (CGD) was high, however, the lactide conversion (CLD) decreased from 98.0% to 76.9%, indicating that the decrease in total monomer conversion was due to a decrease in the lactide conversion. It is known that glycolide has a faster rate of propagation than lactide often resulting in PLGA having a lower L:G ratio than the monomer feed :[I] = 30,000:1 was relatively low, further reaction optimisation was required. Aside from causing a poor yield, a low conversion is undesirable as it results in higher traces of a residual monomer in the polymer product. Residual lactide and glycolide increase the rate of hydrolytic degradation and result in poorer mechanical properties, decreasing the product life-time. Additionally, they cause degradation during melt-processing ,43. Ther1H NMR spectra of these polymers revealed how conversion changed with time, LD+GD = 97.6%) at 4 h, and then fell to 92.5% after 8 h due to thermal depolymerisation. Similarly, both Mn and Mw initially increased, but then started to decrease after 1 h, most likely due to random chain scission during the reaction. However, the conversion improved significantly during this time, increasing from 93.8% to 97.6% when the reaction time was increased from 1 to 4 h. Similar observations of reductions in molecular weight and conversion after certain periods of time have been reported previously for PLA and PLGA synthesised using Sn(Oct)2 :[C] = 6500:1 and [M]:[I] = 30,000:1 at times ranging from 15 min to 8 h. The Sn(Oct)2 ,29,30,31n , suggesting higher amounts of decomposition. Since these higher reaction temperatures increased PLGA25 discolouration, some polymerisation reactions were then performed at 130 °C. The resulting PLGA25 was much lighter in colour, however a longer reaction time (8 h) was required to achieve a 96.9% total monomer conversion.PLGA25 is an amorphous polymer that melts at around 180–190 °C, thus at 150 °C the reaction occurs in the solid-state. Performing PLA and PGA polymerisation at low temperatures in the solid state has been shown to be an effective way to reduce the remaining monomer content and achieve high conversions ,31,45,46n  and Mw  values achieved in each reaction. However, this increase in reaction temperature was also accompanied by increased discolouration, with the PLGA25 turning from beige to orange to dark brown as the temperature increased from 130 to 150 to 180 °C, suggesting increased polymer degradation  and significant discolouration (2 was used. Similar relationships between the Sn(Oct)2 concentration, conversion, and molecular weight have been previously reported by Avgoustakis et al., who when synthesising PLGA70 (L:G = 70:30) achieved the highest conversions and intrinsic viscosities after 4 h reactions at 190 °C using 0.03 wt.% Sn(Oct)2 and at 130 °C using 0.1 wt.% Sn(Oct)2 :[C] ratio from 6500:1 to 50,000:1 improved the dT from 262 to 280 °C 2 catalyses depolymerisation reactions.The effect of catalyst concentration on the thermal stability of PLGA25 was then examined by analysing two PLGA25 samples synthesised using different Sn(Oct)o 280 °C . This ren from 23,400 to 136,000 g mol−1. This increase in Mn was accompanied by increases in dispersity and discolouration. When using a monomer to catalyst ratio ([M]:[C]) of 6500:1, increasing the reaction temperature reduced the time required to achieve high monomer conversions (>96%), such that reactions for 8 h at 130 °C, 4 h at 150 °C and 2 h at 180 °C yielded similar conversion and Mn values. However, increasing the reaction temperature resulted in greater polymer discolouration, causing the PLGA25 to turn from beige to dark brown. Increasing the [M]:[C] from 6500:1 to 50,000:1 decreased polymer discolouration, but resulted in longer reaction times (8–16 h) and higher temperatures (150–170 °C) being required to achieve high conversions. Thermal analysis showed that increasing the molecular weight increased the gT from 31.1 to 41.6 °C and improved the dT (5%) from 238 to 267 °C. An increase in the thermal stability was also found upon reducing the catalyst concentration. These results demonstrate how reaction variables can be altered in order to achieve high molecular weights and conversions in the synthesis of high glycolide PLGAs for packaging applications.When synthesising PLGA25 by ROP at 150 °C, increasing the ratio of the monomer to 1-dodecanol ([M]:[I]) from 30:1 to 30,000:1 increased the M


Myceliophthora thermophila has been improved through N-terminal signal peptide engineering in P. pastoris. The production of newly recombinant xylanase (termed Mtxyn11C) was improved from 442.53 to 490.7 U/mL, through a replacement of α-factor signal peptide with the native xylanase signal peptide segment (MVSVKAVLLLGAAGTTLA) in P. pastoris. Scaling up of Mtxyn11C production in a 7.5 L fermentor was improved to the maximal production rate of 2503 U/mL. In this study, the degradation efficiency of Mtxyn11C was further examined. Analysis of the hydrolytic mode of action towards the birchwood xylan (BWX) revealed that Mtxyn11C was clearly more effective than commercial xylanase and degrades xylan into xylooligosaccharides . More importantly, Mtxyn11C in combination with a single multifunctional xylanolytic enzyme, improved the hydrolysis of BWX into single xylose by 40%. Altogether, this study provided strategies for improved production of xylanase together with rapid conversion of xylose from BWX, which provides sustainable, cost-effective and environmental friendly approaches to produce xylose/XOSs for biomass energy or biofuels production.Xylanases with high specific activity has been focused with great interest as a useful enzyme in biomass utilization. The production of recombinant GH11 xylanase (MYCTH_56237) from  Xylanases an integral group of hemicelluloses and offers an opportunity of best interest area for researchers on account of their insightful investigation and prospective of industrial applications, especially in the degradation of biomass into fermentable sugars . On accoPichia pastoris) for mass production.Albeit, the enzymatic hydrolysis demonstrates better results and low process energy requirements, however, the high cost of commercial enzymes and probably enzymes with low activity, creates a bottleneck for complete degradation of hemicelluloses. Therefore, more potent and efficient enzymes with high activity need to be developed for more economical purposes. Several approaches have been adopted to minimize the expenses of hydrolysis process such as improving enzyme activity and enzyme production . The genP. pastoris has been substantiated as a more successful system for recombinant proteins, due to the high cell densities and therefore yield high volumetric products  resulted in lower yield for the secretion of the xylanase xynB instead of the α-mating factor (α-MF) peptide from S. cerevisiae (products . Moreovesequence . Proteinsequence . Secretorevisiae . Similarrevisiae .M. thermophila was expressed in P. pastoris and achieved a high specific xylanase activity of 1533.71 U/mg (P. pastoris. As expected an increased production of the xylanase in (both shake flasks and 7.5 L fermentor) was achieved by substituting of the secretory α-MF with the native signal peptide. In this study, the degradation efficiency of newly improved xylanase was clearly more effective and produced xylobiose, xylotriose and xylotetrose from birchwood-xylan (BWX). This study also elucidated the improved conversion of xylan into xylose by 40%, when integrated with the multifunctional xylanloytic enzyme , and standard xylooligosaccharides  were from Megazyme (Ireland). XOSs  were provided by Aladdin (X140487), China. X2, X3, X4 and X5 were further identified on HPLC analysis.Restriction enzymes and ligases were purchased from New England Biolabs (NEB). Substrates 4-nitrophenyl β-D-xylopyranoside (pNPX), 4-nitrophenyl β-D-glucopyranoside (pNPG), 4-nitrophenyl β-D-cellobioside (pNPC), and commercial xylanase from Sigma-Aldrich (United States). Birchwood-xylan (BWX), commercial β-xylosidase ] were prepared according to the manual in the Pichia Expression Kit (Invitrogen). Other chemicals used were analytical grade unless otherwise stated.Cultivation media [Yeast extract peptone dextrose (YPD) and buffered minimal glycerol medium (BMGY)], and gene expression medium for MYCTH_56237 was amplified from pMD19-T simple vector harboring the MYCTH_56237 using specific primers  was predicted based on SignalP . The native signal peptide segment of MYCTH_56237 positioned between the C-terminus of the α-MF and the N-terminus of pPICZαA termed Mtxyn11A, and pPICZαA without native signal peptide of MYCTH_56237 termed Mtxyn11B. Similarly, the pPICZαA with native signal peptide segment of MYCTH_56237 (without α-MF) termed Mtxyn11C  by one step PCR according to the Phanta Max Super-Fidelity DNA Polymerase  and further confirmed by colony PCR with AOX-F/AOX-R primers and DNA sequencing should be inserted in editable format from the equation editor.Enzyme activity of MYCTH_56237 was improved through replacement of α-factor in Mtxyn11C . The expP. pastoris colonies were cultured in BMGY medium (5 mL tubes) at 28°C, 200 rpm until the OD600 of the culture reached to 4–6. The culture was then resuspended in BMMY medium (50 mL) containing YNB (1.34%) and biotin (4.0 μg/mL). Pure methanol was added to the culture to a final concentration of 1% every 24 h to maintain induction  equilibrated with 1 × phosphate buffer   followed by the purification through Ni-affinity column (Bio-Beadsidazole) . ProteinXylanase activity of the recombinant strains Mtxyn11A, Mtxyn11B, and Mtxyn11C was assayed by 3,5-dinitrosalicylic acid (DNS) method . The reaTrichoderma longibrachiatum , under the assay conditions as described above. Optimum temperature and pH for commercial xylanase activity were sustained as per provided information.The enzyme activity of the recombinant xylanase was compared with commercial xylanase from 4 ·7H2 O (14.9 g/L), H3 PO4 (26.7 mL/L), CaSO4 ·7H2 O (14.9 g/L), K2 SO4 (18.2 g/L). BSM was supplemented containing 17.3 mL PTM1 solution. Fermentation of MYCTH_56237 and MYCTH_49824 was applied based on the Pichia Fermentation Process Guidelines (Invitrogen). The temperature and pH were maintained at 29°C and 5.0, respectively. Growth phase of the yeast cells were continued until the glycerol utilization from the feeding medium, which was indicated by the dissolved oxygen (DO) spike. When the glycerol was fully utilized from the feeding medium containing glycerol, 12 mL/L PTM1 solution was fed to fermenter according to a pre-adjusted DO level (10%). When the DO level reached higher than 60%, the glycerol feeding was stopped and pure methanol containing 12 mL/L PTM1 solution was pumped to induce the targeted gene expression, with the DO being set to 10–20%. Culture samples were collected at different time intervals to determine the OD600 and xylanase activity.Fed-batch fermentation of xylanase was performed in a 7.5 L fermentor  with 4 L basal salts medium (BSM) (glycerol (40 g/L), KOH (4.13 g/L), MgSOHydrolytic activity of recombinant xylanase was estimated based on the hydrolysis of substrate BWX. For this purpose, reactions mixture containing 900 µL of 1% BWX (w/v) with 100 µL of appropriate diluted enzyme, in sodium phosphate buffer (pH 6.0) was prepared. The reaction mixture was then incubated at 50°C for 12 h and reducing sugars released from substrates were determined by DNS method (as above). The degradation rate  was calculated according to the following equation:5, X4, X3, X2) as standards. HPLC system was equipped with a ROA-Organic Acid H+ (8%) column (Phenomenex) and a RIDL10A refractive index detector. The HPLC column was sustained at 50°C with H2SO4 (5 mM) as the mobile phase at a flow rate of 0.6 mL/min.Hydrolysis products were analyzed by LC-20A HPLC  with xylose and XOSs , Mtxyn11B  and Mtxyn11C (without the sequence of α-MF) were constructed for the expression in P. pastoris  and further regulated by an AOX1 promoter (induced by methanol). After 120 h of cultivation in BMMY medium, significantly observed was the parameter of a single peptide involved in the secretion. The xylanase activity of the recombinant strain Mtxyn11C  was significantly 1.2-folds higher than that of Mtxyn11B , followed by Mtxyn11C  was inoculated to the medium and glycerol was supplemented after 24 h. The rate of dissolved oxygen (DO) was raised up to 50% after the termination of glycerol feeding. Methanol was then pumped into the medium to induce the xylanase production with a stepwise increasing rate. Xylanase activity in the culture supernatant was not detected until the initiation of methanol feeding. Followed by the methanol feeding for 83 h, the maximum xylanase activity in the supernatant was 2503 U/mL  Mtxyn11C was employed in 7.5 L fermentor. The recombinant strain (503 U/mL . Xylanas503 U/mL .2), xylotriose (X3) and xylotetrose (X4), among the hydrolysis product (Trichoderma longibrachiatum (according to conditions provided by the manufacturer’s) and Mtxyn11C was observed more effective than commercial endoxylanase  with 1% BWX, in sodium phosphate buffer (pH 6.0) at 50°C. The maximum degradation rate of Mtxyn11C was observed towards BWX and reached to 49% in 6 h . Moreove product  was presxylanase .2, X3, X4). The amount of xylose produced in result of both enzymes synergism was higher than that of commercial β-xylosidase . The oligosaccharides  are used in dietary supplements and used as byproducts in various chemical industries  using BWX as substrate (in pH 6.0 buffer at 50°C for 1 h), using identical reaction conditions. Consequently, Mtxyn11C liberated a notable amount of xylose, with a trace amount of XOSs (Xlosidase . Mtxyn11dustries .M. thermophila (termed Ttxy43). Ttxy43 showed multi-enzyme activities of endoxylanase (105.42 U/mg), β-xylosidase (80.8 U/mg) and α-L-arabinofuranosidase (15.81 U/mg). The catalytic mode of action of Ttxy43 towards BWX revealed that xylanase firstly degrades xylan to XOSs  as intermediates, which were then rapidly hydrolyzed into single xylose by β-xylosidase [14]. In order to improve further the xylose production, 2 U of Mtxyn11C and Ttxt43 was incubated with 1% BWX in sodium phosphate buffer (pH 6.0) at 50°C for 1 h. Consequently, the xylose production was successfully improved by 40% in short duration of 30 min  when integrated with the multifunctional xylanloytic enzyme. Altogether, these findings illustrate innovative strategies for biomass energy or biofuels production.In this study, the xylanase activity from previously identified from the


N-retinylidene-N-retinylethanolamine (A2E) plays a central role in age-related macular degeneration (AMD) by inducing angiogenesis and inflammation. A2E effects are mediated at least partly via the retinoic acid receptor (RAR)-α. Here we show that A2E binds and transactivates also peroxisome proliferator-activated receptors (PPAR) and retinoid X receptors (RXR). 9’-cis-norbixin, a di-apocarotenoid is also a ligand of these nuclear receptors (NR). Norbixin inhibits PPAR and RXR transactivation induced by A2E. Moreover, norbixin reduces protein kinase B (AKT) phosphorylation, NF-κB and AP-1 transactivation and mRNA expression of the inflammatory interleukins (IL) -6 and -8 and of vascular endothelial growth factor (VEGF) enhanced by A2E. By contrast, norbixin increases matrix metalloproteinase 9 (MMP9) and C-C motif chemokine ligand 2 (CCL2) mRNA expression in response to A2E. Selective PPAR-α, -β/δ and –γ antagonists inhibit the expression of IL-6 and IL-8 while only the antagonist of PPAR-γ inhibits the transactivation of NF-κB following A2E exposure. In addition, a cocktail of all three PPARs antagonists and also HX531, an antagonist of RXR reproduce norbixin effects on inflammation. Altogether, A2E’s deleterious biological effects could be inhibited through PPAR and RXR regulation. Moreover, the modulation of these NR by norbixin may open new avenues for the treatment of AMD. N-retinylidene-N-retinylethanolamine (A2E) is a by-product of the visual cycle  GW7647, an agonist of PPAR-α, and [3H] rosiglitazone, an agonist of PPAR-γ. We report that norbixin binds to PPAR-α with an IC50 of 16.5 × 10−6 M and a KD of 1.5 × 10−5 M (50 =1.9 × 10−6 M and KD = 1.0 × 10−6 M)  induced transactivation of the corresponding PPAR isoform  . Interes× 10−6 M . Secondl isoform  to 2C. T isoform  and GW07 isoform . Importa isoform  but this isoform . Altogetp < 0.0001)  . By cont 0.0001)  to 3D buIn conclusion, here we show that norbixin, that does not induce nor inhibit endogenous PPAR transactivation, can inhibit PPAR transactivation induced by A2E. This indicates that norbixin behaves as a neutral antagonist of PPARs, when their transactivation is stimulated by A2E, which has a low affinity for these NR.in vitro and in vivo 9-cis-retinoic acid as the natural ligand of RXR-α, [3H]GW7647 an agonist of PPAR-α and [3H]Rosiglitazone an agonist of PPAR-γ.Binding studies of A2E and norbixin to RXR-α and PPAR-α and γ were performed in vitro. For experiments aimed at measuring mRNA or protein expression in RPE, cells were trypsinized after one week in culture and transferred to 24-well or 6-well plates at a density of 1.5 × 105 cells/cm2 in DMEM2%FCS. Norbixin or agonists were added to the medium 24 h after seeding, and antagonists were added to the medium 24 h later. A2E treatment was performed during 19 h before cellular sample preparation. All the drugs used in these experiments were prepared as stock solutions in DMSO.Pig eyes were obtained from a local slaughterhouse and transported to the laboratory in ice-cold Ringer solution. After removal of the anterior segment of the eye, the vitreous and neural retina was separated from the RPE and removed. The eyecup was washed twice with phosphate buffer saline (PBS), filled with trypsin (0.25% in PBS) and incubated at 37°C for 1.5 h. RPE cells were harvested by gently pipetting, centrifuged to remove trypsin and re-suspended in Dulbecco’s Modified Eagle Medium (DMEM) supplemented with 20% (v/v) foetal-calf serum (DMEM20%FCS) and 0.1% gentamycin. Cells were seeded into 60 mm diameter Petri dishes, cultured in an atmosphere of 5% CO2/95% air at 37°C, and supplied with fresh medium after 24 hours and 4 days 4 cells/cm2 in DMEM2%FCS. The next day, cells were transfected using the Cignal Reporter Assay Kits for PPAR, RXR, AP-1 and NF-κB, according to the manufacturer’s specifications. To measure the specific activation of PPAR isoforms, cells were also co-transfected with PPAR-α, PPAR-β/δ or PPAR-γ expression vectors. Transfection was performed with Lipofectamine and Plus Reagent in serum-free medium. 3 h after the transfection, the medium was replaced and treatments with the molecules to assay were performed. Luciferase activity was measured the next day using the Dual-Luciferase Reporter Assay System. The measurements were performed with a luminometer . Firefly: Renilla activity ratios were calculated for each condition and ratios from transcription factor-responsive reporter transfections were divided by ratios from negative control transfections to obtain relative luciferase unit, as described by the manufacturer. At least 3 independent transfections were performed in triplicate for each condition.After one week in culture, cells were trypsinized and transferred to a 96-well plate at a density of 6 × 10® RNA kit according to manufacturer’s instructions. RT of 500 ng of RNA was performed using the SuperScript III Reverse Transcriptase following the manufacturer’s instructions. Five ng of cDNA were amplified using the SYBR GREEN real-time PCR method. PCR primers for target genes and housekeeping gene GAPDH were designed using Primer3Plus Bioinformatic software  prime detection kit, quantified by densitometry using Bio1D  and normalized by GAPDH levels. Each experiment was done at least 3 times.For statistical analyses one-way ANOVA followed by Dunnett’s tests were performed using Prism 7 .


The effect of Nd3+ ions substitution on the structural, optical and photo-Fenton activity of ZnNdxFe2−xO4 has been investigated. The addition of Nd3+ ions caused a decrease in the grain size of ferrites, the reduction of the optical bandgap energies and thus could be well exploited for the catalytic study. The photocatalytic activity of the ferrite samples was evaluated by the degradation of Rhodamine B (RhB) in the presence of H2O2 under visible light radiation. The results indicated that the ZnNdxFe2−xO4 samples exhibited higher removal efficiencies than the pure ZnFe2O4 ferrites. The highest degradation efficiency was 98.00%, attained after 210 min using the ZnNd0.03Fe1.97O4 sample. The enhanced photocatalytic activity of the ZnFe2O4 doped with Nd3+ is explained due to the efficient separation mechanism of photoinduced electron and holes. The effect of various factors  on the degradation of RhB dye was clarified.In this study, nanocrystalline ZnNd TiO2  sites containing iron has been shown to displace Fe3+ into (A) sites, thus altering the structure and electrical and magnetic characteristics the ferrites , iron(II) nitrate nonahydrate , and neodymium(III) nitrate hexahydrate (Nd(NO3)3·6H2O, 99.9% pure, Sigma-Aldrich) were used as oxidizer and urea  was used as a fuel additive. A number of proper ions: Zn2+ (1 mmol) combined with Fe3+ [(2−x) mol] and Nd3+ (x mol)  were dissolved in distilled water. The final pH of the solution was adjusted at 5.0, and then was heated to 100 °C for 1 h. The precipitation was collected, washed with distilled water (3 × 20 mL) to eliminate metal ion and anion traces and then calcinated up to 500 °C for 2 h (ramping rate of 10 °C/min). The product was ground and stored at a vacuum container.Firstly, urea coprecipitation method was adopted to fabricate nanocrystalline ZnNdfication . Analytiα radiation (λ = 1.5406 Å) in a 2θ angle ranging from 20° to 70° with a step of 0.03° source, FTIR Affinity-1S , Hitachi S-4800 , JEOL-JEM-1010 , JEOL JED 2300 Analysis Station  and U-4100  operating in the wavelength range of 200–800 nm.The as-synthesized particles were characterized using a number of techniques including X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscope (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX) and UV-Vis absorption spectroscopy. Respective instruments for those analyses include D8 Advance diffractometer  with CuKxFe2−xO4  nanoparticles and RhB dye under visible light irradiation . In a typical experiment, 0.1 g of catalyst was introduced into 200 mL of RhB aqueous solution (10 mg·L−1) and suspended on a shaker table at 200 rpm. The suspension was first stirred in the dark for 30 min to attain the adsorption-desorption equilibrium state between the catalyst and RhB. Afterwards, the reaction was stirred and H2O2 30% (w/w) in H2O (Sigma-Aldrich) was added to the mixture, which was then irradiated under visible light for 210 min. To determine the RhB concentration in the mixture, 5 mL of each aliquot was taken out periodically, then centrifuged to remove the solid catalyst. The effect of two factors including H2O2 concentrations  and the catalyst dosages  on the photo-degradation efficiency was studied.In this study, Rhodamine B (RhB) was used as target pollutant to assess the photocatalytic potential of as-synthesized ferrite samples. Accordingly, the RhB degradation reaction was carried out in a reactor containing the ZnNdo and Ct are the concentration of RhB (mg·L−1) at the time 0 and t. The samples were measured by scanning at the maximum wavelength λ = 553 nm.The efficient degradation of RhB (H) was calculated according to the formula Equation (1).2O4 and different ZnNdxFe2−xO4  samples synthesized at 500 °C. The formation of zinc ferrite (JCPDS number 022-1012) was evidenced by reflection peaks corresponding to the characteristic spacing between (220), (311), (400), (422), (511) and (440) planes of a cubic spinel structure. Employing Scherrer’s equation, average crystallite size of the samples could be calculated as follows:λ, k, β and θ wavelength of the X-ray (0.1504 nm), the Scherrer’s constant (k = 0.89), the full width at half maximum observed in radians and the angle of diffraction of the (311) peak with the highest intensity, respectively.3+ ions could be observed from the XRD data given in 3+ from 0 to 0.05 mol, which was in good agreement with a previous publication [3+ added increases. This outcome can be due to the difference of the radius of ferrites, or more specifically, metal ions radius . Indeed, the ionic radius of Nd3+ ion (0.98 Å) is larger than the ionic radius of Zn2+ (0.74 Å) and Fe3+ (0.67 Å); hence Nd3+ ions prefer to occupy more octahedral sites (B-sites) than Fe3+ ions [3+ ions to be distributed in the grain boundaries, thus contributing to the improvement of energy barrier of Zn2+ or Fe3+ movement [3+ showed a significant effect on the crystalline nanostructure of origin zinc ferrites.To determine the lattice constant (a) at the most intense peak (311), following formula was usedlication . Moreovee3+ ions . It is lmovement . As a removement ,39, nickmovement  and zincmovement . To sum xFe2−xO4 nanoparticles. The first band is located at 522.7−528.6 cm−1  all display a type of uniform sphere  of zinc ferrites nanoparticles with the absorption coefficient (α) obtainable from DRS spectra as Equation (4).α is the absorption coefficient and R is the reflectance. The following relationship could be used to determine the band gap energy (Eg) as shown in Equation (5).ν: energy of the photon, α: the the absorption coefficient, A: material parameter and n: transition parameter, n = 2 represent indirect transitions. The slope of plotting (αhν)2 against hν could be used to measure the band gap energy for the absorption peak, as shown in xFe2−xO4  nanoparticles are found to be 1.75, 1.57, 1.50 and 1.42 eV, respectively. This indicates that the Nd3+ ions concentration affected the band gap energy of zinc ferrites nanoparticles. The band gap energy value decreased with increasing the Nd3+ ions concentration. Due to the larger ionic radius, the crystal lattice is bound to distort leading to generation of interface defects [xFe2−xO4 samples, thus resulting in decreased band gap energy value [2O4 samples doped with La decreases from 1.35 to 1.1 eV [The band gap of the spinel nanoparticles was determined by DRS. Kubelka-Munk model was used to calculate band gaps  at the different irradiation time as shown in −1, 98.00% and 0.0189 min−1, 95.46% and 0.0163 min−1 in the presence of H2O2 and ZnNdxFe2−xO4 with x = 0.01, 0.03 and 0.05, respectively . When hydrogen peroxide presents in high concentration, •OH could be scavenged (Equations (4)–(6)) and reduced [2O2 content was 0.04 M. reduced ,26. Ther0.03Fe1.97O4 dosage increases from 0.5 g/L to 0.75 g/L, the efficient degradation of RhB increases from 62.13% to 98.01% at 180 min. However, the removal rate of RhB decreased to 93.02% when increasing the ZnNd0.03Fe1.97O4 dosage to 1.0 g/L. This outcome is because when increasing catalyst dosage, •OH radical amount increases due to the reaction of h+ in the valence of ferrite sample [The effect of the ferrite sample amount on the RhB removal rate is shown in e sample . Howevere sample . Therefo3+ substituted zinc ferrite nanoparticles were successfully synthesized via solution combustion technique. The physical and chemical characteristic of the ZnNdxFe2−xO4 samples were investigated by XRD, EDX, FT-IR, SEM and TEM. The average crystallite size and the optical band gap values reduced from 22 to 12 nm and from 1.75 to 1.42 eV, respectively, with increasing Nd3+ ions content. The substitution of Nd3+ ions on octahedral sites was confirmed by the change of ν1 and ν2 frequency. The enhanced photocatalytic activity of the zinc ferrite samples was observed with increasing Nd3+ ions concentration. The ZnNd0.03Fe1.97O4 nanoparticles have the highest efficient degradation for Rhodamine B. The removal efficiency of Rhodamine B dye was affected by the concentration of H2O2, catalyst amount. The optimal initial H2O2 content was 0.04 M and the optimal dosage of the catalyst was 0.75 g/L.Nd


Xylopia aethiopica, has shown several pharmacological properties. Traditionally, the plant is used to treat several diseases and is being used in the preparation of several local foods despite the lack of information about its safety, food-drug interaction, and other pharmacokinetic properties. This study, therefore, investigated the effect of XA on rat liver cytochrome P450 (CYP) enzymes in vivo and in vitro.  Xylopic acid (XA), the major constituent of the fruit of n = 5) animals in each group. The in vitro inhibition of CYP 3A4 was assessed by treating rat liver microsomes with XA.  Inhibition or induction of some isoforms of CYP450 enzymes: CYP 1A1/1A2, 1A2, 2B1/2B2, 3A4, 2D6, and 2C9 were investigated using microsomal fractions of the liver obtained from rats pretreated with a low dose of xylopic acid (LDT) 30 mg/kg, high dose of xylopic acid (HDT) 100 mg/kg, phenobarbitone (PC) 80 mg/kg, and ketoconazole (NC) 100 mg/kg, and a no-treatment group received distilled water, with ( Xylopic acid induced CYP 1A1/1A2, 1A2, 2D6, and 2C9, inhibited CYP 3A4, and had no effect on 2B1/2B2.  The findings would help mitigate toxicity and therapeutic failure especially in cases of coadministration of medications with food containing XA, with metabolism altered by the latter. Xylopia aethiopica. Studies have shown that the plant has anti-inflammatory, antimicrobial, analgesic, antiparasitic, and antioxidant properties [Xylopia aethiopica [The use of medicinal natural products is traced back thousands of years due to the belief that herbal drugs have fewer side effects, enhance the effects of conventional agents, and can be an alternative for the management of several disorders , 2. An eoperties –5. In Ghoperties . Some fooperties . The plaoperties , 9 whereoperties . The plaoperties . Severaloperties , 13. Conoperties . The comthiopica .Xylopia aethiopica as therapeutic agents in conditions associated with acute inflammation and some respiratory disorders [P. berghei-induced malaria in ICR mice as well as antipyretic properties [Xylopia aethiopica were found to have significant central nervous system depressant effects in mice [Research on xylopic acid has shown that it exhibits diuretic and vasorelaxant properties in rodents . Xylopicisorders . Xylopicoperties . Xylopic in mice , 19. TheGenerally, people use traditional medicine with the notion that it has little or no side effects. Hence, such herbs do not pass through rigorous tests before approval is granted compared to conventional drugs , 21. DuePhenobarbitone, ketoconazole, CYP450 isoenzymes, potassium phosphate dibasic, potassium phosphate monobasic, bovine serum albumin (BSA), nicotinamide adenine dinucleotide phosphate (NADPH), ethoxyresorufin, methoxyresorufin, pentoxyresorufin, benzyloxyresorufin, dextromethorphan, diclofenac, zinc sulphate heptahydrate, trimethylamine, and acetonitrile used to evaluate the effect of xylopic acid on CYPs were all obtained from Sigma-Aldrich Chemie GmbH (Eschenstrasse), Germany. XA was purified following the procedure described by Biney et al. .ad libitum using standard animal laboratory pellet and water. They were housed under standard laboratory conditions of 25 ± 1°C ambient temperature, 60–70% relative humidity, and 12 : 12 hour light : dark cycle to ensure acclimatization to the laboratory. The experiments were conducted following the National Institute of Health (NIH) Guidelines for Care and Use of Laboratory Animals and approved by the Scientific and Technical Committee and Institutional Animal Care and Use Committee (IACUC) of Noguchi Memorial Institute for Medical Research, University of Ghana (UG-IACUC004/18–19).Before the experiment, male Sprague–Dawley rats were purchased from the Animal Experimentation Unit of Noguchi Memorial Institute for Medical Research, Accra, Ghana and were fed in vivo and in vitro assays as earlier described [The activities of xylopic acid high dose (100 mg/kg) and xylopic acid low dose (30 mg/kg) were tested on CYP 1A1/1A2 (EROD), CYP 2B1/2B2 (PROD), CYP 3A4 (BROD), CYP 2D6, and CYP 2C9 employing escribed . Ketoconn = 5) were randomly assigned to one of the four experimental groups, being low-dose xylopic acid treatment group (LDT) 30 mg/kg, high-dose xylopic acid treatment group (HDT) 100 mg/kg, phenobarbitone (PC) 80 mg/kg, a no-treatment group that received distilled water, and finally for CYP 3A4, a control group treated with ketoconazole (KC) 100 mg/kg with (n = 5) animals in each group. The choice of dosage for XA was informed by previous studies on the interaction of XA on hepatic enzymes using pentobarbitone-induced sleep test in mice [2 inhalation to minimize suffering, then sacrificed by abdominal venesection method after which their liver was harvested, snap-frozen in liquid nitrogen, and stored at −80°C until further analysis was carried out.Male rats weighing 250–300 g  using a mortar and a pestle. The homogenate was centrifuged at 2,500 rpm for 50 minutes at 4°C and further centrifuged at 40,000 rpm for 60 minutes at 4°C. The resultant supernatant (cytosol) was then separated from the pellet (microsomes). The microsomes obtained were further homogenized in potassium phosphate buffer 20 mM (pH 7.4) and stored at −80°C , 26.μL of BSA and 200 μL of Bio-Rad reagent which was then added to each microsomal dilution in a 96-well plate in triplicate and incubated at room temperature for 5 minutes, after which the absorbance was read at a wavelength of 530 nm excitation and 586 nm emission using Tecan Infinite M200 PRO.The protocol for protein determination was adapted from the protocol described by Harwood et al. , 26. FouμL of potassium phosphate buffer at a pH of 7.4 in triplicate into a 96-well plate followed by addition of 10 μL (2 μM) of each substrate (ethoxyresorufin (EROD), methoxyresorufin (MROD), pentoxyresorufin (PROD), and benzyloxyresorufin (BROD)). Subsequently, 10 μL of the microsomal fraction obtained from each treatment group was added to each well plate and preincubated at 37°C for 5 minutes, after which, 10 μL of nicotinamide adenine dinucleotide phosphate (NADPH) with a concentration of 100 μM was added to each of the wells and incubated at 37°C for 10, 20, and 30 minutes for CYPs 1A1/1A2, 1A2, 2B1/2B2, and 3A4, respectively. Plates were gently shaken after the addition of 40 μL of stopping solution (20% 0.5 M Tris and 80% acetonitrile) to each well. Fluorescence was determined at wavelengths of 586 nm emission and 530 nm excitation proceeding optimization of the protocol. The assay was repeated, and the mean values were used for computation.The effect of xylopic acid on CYP 1A1/1A2, 1A2, 2B1/2B2, and 3A4 was determined using fluorometric assays as described previously . This waμl of 0.1 M potassium phosphate buffer (pH 7.4) which was pipetted into a 50 ml Eppendorf tube, followed by the addition of 600 μl of the substrate (benzyloxyresorufin) for CYP 3A4, and followed by the addition of 600 μl of the enzyme (microsomes). A volume of 80 μl was then pipetted from the cocktail into a 96-well plate in triplicate and then preincubated at 37°C for 5 minutes. Afterward, 10 μL of nicotinamide adenine dinucleotide phosphate (NADPH) with a concentration of (100 μM) was added to each of the wells followed by the addition of ketoconazole and xylopic acid to separate plates containing BROD. The plates were incubated at 37°C for 30 minutes for BROD. A volume of 40 μL of stopping solution (20% 0.5 M Tris and 80% acetonitrile) was finally added to each well. The plate was gently shaken, and its fluorescence read at wavelengths of 586 nm emission and 530 nm excitation [Microsomes obtained from male rats pretreated with phenobarbitone were used in this assay. The standard inhibitor used was ketoconazole for CYP 3A4 and xylopic acid as the test compound. A cocktail was prepared for seven different concentrations for each standard inhibitor. The cocktail contained 3000 citation . The assμL of potassium phosphate buffer (pH 7.4) into Eppendorf tubes in triplicate. A volume of 50 μL of 0.25 mM dextromethorphan was added, followed by 50 μL of microsomes obtained from each treatment group. The mixture was preincubated at 37°C for 5 minutes in a water bath after which 50 μL of NADPH solution 100 μM was added. The mixture was further incubated for 45 minutes, followed by the addition of 100 μL of stopping solution (300 mM zinc sulphate heptahydrate). The mixture was centrifuged at 4,000 rpm for 15 min at room temperature, and the supernatant was collected in vials. Analysis of the supernatant was done using an isocratic HPLC . The mobile phase consisted of 24% (v/v) acetonitrile and 0.1% (v/v) trimethylamine adjusted to pH 3.0 with perchloric acid. The carrier flow rate was 0.8 ml/min, and peaks were monitored at wavelengths of 280 nm excitation and 310 nm emission [The CYP 2D6-dextromethorphan-O-demethylation assay was used to determine the effect of xylopic acid on CYP 2D6. The assay was done by pipetting 350 emission . The assμL of potassium phosphate buffer (pH 7.4) into Eppendorf tubes followed by adding 50 μL of 0.05 mM diclofenac, after which 50 μL of the microsomal fraction obtained from each treatment group was added (in triplicate) and preincubated at 37°C for 5 minutes in a water bath. A volume of 50 μL of NADPH solution (100 μM) was added to each tube and further incubated in a water bath at 37°C for 10 minutes. The reaction was terminated by adding 200 μL of stopping solution (ice-cold methanol) to the mixture. The mixture was centrifuged at 12,000 rpm for 8 minutes at room temperature. The supernatants were collected in vials and analyzed using high-performance liquid chromatography [The CYP 2C9 diclofenac hydroxylation assay was used to determine the effect of xylopic acid on CYP 2C9 . This astography . The assin vivo testing, GraphPad Prism version 8 was used for all statistical analyses, and P values < 0.05 were considered statistically significant. All data obtained were expressed as a mean ± standard error of the mean. For the in vitro analysis, the column graphs were subjected to one-way ANOVA with Tukey's post hoc test. Doses for 50% of the maximal effect (IC50) for each drug were determined by using an iterative computer least squares method, with the following nonlinear regression (3-parameter logistic) equation. The fitted midpoints (IC50s) of the curves were compared statistically using the F test.For the P < 0.05) CYP 1A2 enzyme induction as shown in All the treatment groups produced significant (P < 0.05) effect on CYP 1A1/1A2, with phenobarbitone alone exhibiting the highest enzyme induction with a percentage activity of 139.9% (All the treatment groups had a significant (f 139.9% . A high P < 0.001) effect on CYP 2B1/2B2. XA low and high doses did not produce a significant effect on CYP 2B1/2B2 compared to the no treatment group. However, there was about a 2.5-fold increase in CYP 2B1/2B2 activity of phenobarbitone-treated animals compared to both doses of XA.From P < 0.001).P < 0.001) for phenobarbitone and XA high dose and a significance of (P < 0.05) in the case of XA low dose. Phenobarbitone, XA low dose, and XA high dose had activities of 48.6%, 24%, and 80.5%, respectively. XA high dose was 1.65 times more effective (P=0.0029) than the standard phenobarbitone.Effects of phenobarbitone, XA low dose, and XA high dose on CYP 2D6 are shown in in vitro. Ketoconazole was used as the positive control. The IC50 values for ketoconazole and xylopic acid were 0.091 ± 0.002 μM and 1.30 ± 0.01 μM, respectively. Thus, ketoconazole showed more potent inhibition of CYP 3A4 than xylopic acid.Figures in vitro and in vivo. Interestingly, a recent study suggested that xylopic acid has a biphasic effect on rat hepatic CYP450 enzymes at low and high doses [X. aethiopica (which contains xylopic acid) on human hepatic CYP450 enzymes although the fruits are heavily consumed as a spice in local dishes. Therefore, there are no data on the metabolism of xylopic acid or its related kaurene diterpenes in rodents or humans, hence limiting these studies to implicate any possible metabolite of xylopic acid on the effects observed in these studies. Owing to the fact that X. aethiopica is heavily consumed, xylopic acid or its possible active metabolites can reach concentrations high enough to interact with other medications when taken concurrently. It was therefore imperative to identify the specific isoenzymes induced and inhibited on the administration of xylopic acid with a focus on CYP 1A1/1A2, 1A2, 2B1/2B2, 3A4, 2D6, and 2C9.The study evaluated the ability of xylopic acid to influence the activity of hepatic CYPs in rats gh doses , but no Xylopic acid induced CYP 1A1/1A2 at high and low doses. Other substances that induce CYP 1A1/1A2 are barbiturates, tobacco, and rifampin among others .in vivo at low and high doses, like the effect seen in phenobarbitone. Studies have shown that CYP 1A2 is responsible for the primary metabolism of theophylline and propranolol amongst others [2-receptor antagonist as an inhibitor of CYP 1A2 [2-receptor antagonists may result in drug-drug interaction.Xylopic acid induced CYP 1A2 t others . A study CYP 1A2 . This suCYP 2B1/2B2 is a phenobarbital-inducible member of the P450 xenobiotic-inducible superfamily involved in the hydroxylation of decanoic and other fatty acids . The curin vivo studies were 30 and 100 mg/kg, the amount absorbed into the bloodstream was not measured, but the concentration achieved in the blood can be high enough to produce food-drug interaction since this concentration was able to inhibit the CYP 3A4 enzymes.CYP 3A4 was inhibited by low and high doses of xylopic acid. The inhibition observed was weaker than that expressed by ketoconazole, a standard inhibitor of 3A4. CYP 3A4 accounts for 30–50% of drugs metabolized through type I enzymes [Xylopic acid at low and high doses induced CYP 2C9. It is primarily expressed in the liver; a study suggests that its expression level is the second highest among CYP isoforms. It is responsible for the metabolic clearance of up to 15–20% of all drugs . Some otPatients vary widely in their response to drugs. They include individuals with no CYP 2D6 activity and individuals with genetically elevated CYP 2D6 activity, suggesting an altered response to drugs that are CYP 2D6 substrates. Drugs that inhibit CYP 2D6 activity are likely to increase the plasma concentrations of other medications, such as fluoxetine and paroxetine leading to drug toxicity .Xylopic acid induced rat liver microsomal CYP 1A1/1A2, 1A2, 2D6, and 2C9; inhibited CYP 3A4; and did not affect CYP 2B1/2B2. Since these enzymes are implicated in the metabolism of several drugs, it is expected that XA can potentially influence the metabolism of other drugs through food-drug and drug-drug interactions.


The key parameters for tailoring the morphology and chemical, surface, and interfacial properties of the heterostructure were identified for efficient and selective conversion of CO2 into valuable chemicals. Introducing MoS2 layers onto NiTiO3 NFs provided superior CO2 conversion with significantly higher yields. The optimized hybrid structure produced CO and CH4 yields of 130 and 55 μmol g−1 h−1, respectively, which are 3.8- and 3.6-times higher than those from pristine NiTiO3 nanofibers  and 3.6- and 5.5-times higher than those from pristine MoS2 . This improved performance was attributed to efficient absorption of a wider spectrum of light and efficient transfer of electrons across the heterojunction. Effective charge separation and reduced charge carrier recombination were confirmed by photoluminescence and impedance measurements. The performance may also be partly due to enhanced hydrophobicity of the hierarchical surfaces due to MoS2 growth. This strategy contributes to the rational design of perovskite-based photocatalysts for CO2 reduction.Herein, a full spectrum-induced hybrid structure consisting of one-dimensional nickel titanate (NiTiO Exhaustive research has examined sustainable technologies for CO2 reduction , a member of the Ti-based perovskite oxide group, has recently received attention due to its photocatalytic activity in visible light (2.1–2.9 eV) -active photocatalysts. Zeng et al.  . NiTiO3,g et al.  reported removal ; 2022a,  removal , and tox removal . Therefo2 evolution, water treatment, and water splitting, research on CO2 reduction performance is still in its infancy. Molybdenum disulfide  is the most frequently used TMD having a graphite-like 2D structure. Due to its facile synthesis and cost-effectiveness, MoS2 is regarded as an ideal substitute for noble metals in the context of photocatalytic H2 evolution. MoS2 has three polytypic structures, with the hexagonal 2H and octahedral 1T phases being the most common. The metastable 1T phase, which is active on basal and edge planes, unlike the 2H phase, has interesting chemical and physical properties but its synthesis is challenging  transition-metal dichalcogenides (TMDs) are another emerging group of materials that show promise because of their unique nanoflower morphology, consisting of layered structures with thin open edges . TMDs hallenging .3/gC3N4, NiTiO3/TiO2, Fe2O3/NiTiO3, mono/multilayer MoS2, MoS2 nanoflowers, 1D/2D TiO2/MoS2, MoS2/graphene, Bi2S3/MoS2, Au-MoS2, NiTiO3/MoS2, phosphated 2D/3D MoS2, CdS/MoS2, Cu/MoS2, and co-doped MoS2 nanoparticles have been reported  has therefore been extensively investigated for use as heterogeneous photocatalysts . The 1D reported  but to t3/MoS2 (1D/2D) heterostructure was synthesized using a two-step process. NiTiO3 nanofibers (NFs) were firstly synthesized via electrospinning which were later combined with 2D flower-like MoS2 via a hydrothermal process. The morphologies and optical properties of the as-synthesized photocatalysts were characterized using various techniques. The selective growth of highly reactive 1T, along with honeycomb-like 2H phases, was confirmed by X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The hybrid NiTiO3/MoS2 exhibited a redshift to the visible light region, with enhanced absorption. At the optimum loading of MoS2, NiTiO3/MoS2 exhibited the greatest CO2 reduction, producing CO and CH4 gases at 130 and 55 μmol g−1 h−1, respectively, which are 3.8- and 3.6-times higher amounts than those  of pristine NiTiO3 NFs, achieving an overall CO2 selectivity of 83%. This work could contribute to the development of efficient and stable photocatalytic materials for water splitting, H2 evolution, and other photocatalytic activities.Herein, a highly synergized NiTiO2NCSNH2), obtained from Wako Pure Chemical Industries, Ltd , were used in the synthesis of the NiTiO3 NFs. Sodium sulfate (Na2SO4) and triethanolamine (TEOA) from Samchun Pure Chemical Co., Ltd  were used in the measurement of electrochemical and photocatalytic properties. Conductive fluorine-doped tin oxide  glass with dimensions of 2 × 6 cm2, purchased from Korea Fine Chemical Co., Ltd., was used as a substrate film.All materials were of analytical grade and were used without further purification. Nickel (II) acetate tetrahydrate (98%), titanium (IV) butoxide (97%), sodium molybdate dihydrate (≥99.5%), ethanol (EtOH), and acetylacetone were purchased from Sigma–Aldrich . Polyvinylpyrrolidone K90  and thiourea  was stirred in EtOH (5 ml) until it was well-mixed. Then, the required amount of nickel (II) acetate tetrahydrate was added and the solution was continuously stirred for 3 h at room temperature. Subsequently, PVP (0.6 g) was added to the solution, which was stirred continuously for another 8 h to obtain a viscous solution. Finally, acetylacetone (0.3 ml) was added and the solution was stirred for at least 2 h until uniformly light green in color. The viscosity of the solution measured using a DV2TLVCJ0 viscometer  was 195 ± 5 cP. This solution was taken-up in a 12-ml nonpyrogenic plastic syringe and connected to a 25-gauge (0.26 mm) stainless-steel needle for electrospinning. The syringe was then mounted vertically and attached to a pump that was connected to a high-voltage power supply. The distance from the needle to the collection plate was fixed at 110 mm and the flow rate was maintained at 10 μl/min. Electrospinning was performed using an electrospinning machine  and maintained at 10 kV for the synthesis of NiTiO3 NFs. The NFs were collected every 2 h and kept in an oven at 60°C, to remove residual solvent before heat treatment in a box furnace under an air atmosphere of 600°C . These NFs were characterized without further treatment.NiTiO3/MoS2 with different loading amounts of MoS2 precursors was synthesized by a hydrothermal process. The required amounts of sodium molybdate dihydrate and thiourea were dissolved in 60 ml of deionized (DI) water under stirring for 1 h. Then, 100 mg of NiTiO3 NFs were added and mixed by a high-speed ultrasonic processor  for 15 min  to ensure uniform and complete mixing. The solution was then transferred to a 100-ml Teflon-lined autoclave to grow MoS2 nanosheets over the NiTiO3 NFs via a hydrothermal method. This mixture was maintained at 200°C for 24 h in a box furnace under an air atmosphere. Finally, the NiTiO3/MoS2 sample was collected and washed three times with DI water and EtOH to remove organic impurities. The obtained black-colored NiTiO3/MoS2 samples were dried overnight in a vacuum oven at 60°C and then characterized. 2 precursor was varied and samples were classified as NMS-01, NMS-02, NMS-03, or NMS-04 (2 was synthesized under the same process conditions without adding NiTiO3 NFs.NiTiOr NMS-04 . For com2SO4) was used during this process. Each photocatalyst (200 mg) was dissolved in 1.5 ml of EtOH and coated on the 2 × 4 cm2 area of the FTO film (2 × 6 cm2) via spin-coating at 2,500 rpm for 60 s. The as-prepared films were sintered at 150°C for 1 h to remove residual EtOH. Each coated FTO film contained ∼1.5 mg of the photocatalyst. The FTO film, Pt wire, and Ag/AgCl were used as the working, counter, and reference electrodes, respectively. The films were characterized using electrochemical impedance spectroscopy (EIS) under ultraviolet-visible (UV-vis) light irradiation at frequencies ranging from 105 to 0.1 Hz, at an AC amplitude of 10 mV. The photocurrent density was measured while 1 V bias potential was applied via the reference electrode. All photoelectrochemical analyses were conducted using a 300-W Xe lamp  under UV-vis light irradiation.A three-electrode quartz cell with a potentiostat  was used to measure the photoelectrochemical performances of the photocatalysts. Electrolyte  equipped with a 300-W Xe lamp as the light source. In a typical procedure, the required amount of sample was coated on the FTO film and used as a photocatalyst to react with CO2 and water (125 ml) inside the reactor. Triethanolamine (10 vol%) was used as a hole scavenger. Before photocatalytic experiments, the reactor cell was purged with CO2 gas  to remove air and other gases. Evolved gases were collected every hour and separated by a fused silica capillary column equipped with a pulsed discharge detector . Helium continuously flowed as carrier gas. A 300-W Xe lamp was used as a simulated sunlight source and the focused light intensity (10 mW cm−2) was measured using an 843-R USB power meter .The photocatalytic performance of all samples was measured according to the photoreduction of CO3 NFs, MoS2, and NiTiO3/MoS2  were measured by field-emission scanning electron microscopy  at 15 kV. To further investigate the structure and interaction between NiTiO3 NFs and MoS2, scanning TEM  analysis was performed at 200 kV. X-ray diffraction  was carried out using a Bruker Advanced X-ray instrument with Cu Kα radiation at a wavelength of 1.5418 Å, to analyze the crystalline phases of the samples. A Brunauer–Emmett–Teller (BET) N2 adsorption/desorption analyzer  was used to measure the specific surface area and pore size distribution of the catalysts. To study the chemical properties of the photocatalysts, XPS  with an Al Kα source was used. Optical properties were measured by UV-vis spectroscopy . Fourier transform infrared spectroscopy  was used to confirm the presence of specific surface groups  in NiTiO3 NF and NMS-02. A photoluminescence spectrophotometer  was used to study the recombination rates of the charge carriers. Contact angles (CAs) were measured at room temperature (22–25°C) and 20–30% RH using a static CA analyzer . For the analysis, 3.4 µl of DI water was used.The microstructures of pristine NiTiO. The pristine NiTiO3 NFs  had a smooth surface, with an average diameter of 540 nm and average length of a few micrometers. Pristine MoS2 had a petal-like hierarchical architecture . Hybrid structures (NiTiO3/MoS2) were synthesized via a hydrothermal method, by varying the loading amount of MoS2 precursors. Consequently, the hybrid structures appeared as high aspect ratio NiTiO3 NFs of uniform diameter, covered by flower-like MoS2 particles formed by sulfurization of MoO3. Loading amounts of MoS2 were varied and the corresponding hybrid structures were assigned the names NMS-01, NMS-02, NMS-03, and NMS-04, respectively. Growth of flower-like MoS2 increased with increasing amounts of MoS2 precursor. Optimal growth was observed for NMS-02 . Low-magnification TEM images  revealed the uniform size and long length of the pristine NFs. Characteristic interplanar spacing of 0.35 nm was confirmed by a high-magnification image of NiTiO3 NFs . Low-magnification images of NMS-02  show growth of flower-like MoS2 firmly attached to the NiTiO3 NF substrate. The high-resolution TEM image  shows lattice fringes of NiTiO3 NFs and MoS2 with d-spacings of 0.35 and 0.65 nm, respectively, indicating intimate interfacial contact. Layers (7–12) of MoS2 covered the NiTiO3 NFs. This analysis confirmed the successful formation of a 1D/2D (NiTiO3/MoS2) hybrid structure. High-resolution TEM images confirmed the coexistence of honeycomb-like 2H and well-ordered trigonal 1T phases. The 1T/2H hybrid structure was directly observed via selected area inverse fast Fourier transform (FTT) . Insertion of the 1T  phase into the 2H phase (semiconductor) enhanced the catalytically active site in the composite structure.To further investigate the microstructure, TEM analyses were performed on pristine NiTiO images  revealeiO3 NFs . Low-ma NMS-02  show grM image  shows lm (FTT) . Insert). Pristine NiTiO3 showed characteristic peaks at 2θ = 24.09°, 33.06°, 35.73°, 40.96°, 49.40°, 54.08°, 62.45°, 64.03°, and 71° that were assigned to the (012), (104), (110), (113), (024), (116), (124), (300), and (1010) planes of NiTiO3 NFs (JCPDS No. 01-076-0334). In addition to the intense peaks of the NiTiO3 NFs, a peak due to rutile TiO2 appeared at 27.37° (JCPDS No. 98-000-0375). All hybrid samples contained some additional peaks at 2θ = 14.1°, 39.41°, and 58.69°, which were attributed to the (002), (103), and (110) planes of MoS2 (JCPDS 01-075-1539). The presence of all characteristic peaks of NiTiO3 NFs and MoS2 in the XRD spectra of the composite samples confirmed successful integration of the NiTiO3/MoS2 hybrid structure, in agreement with the TEM results.The phase structures of the samples were characterized by X-ray diffraction . Pristi2 loading on the NiTiO3 NFs . Survey spectra  confirmed the presence of all essential elements  in the NiTiO3/MoS2 hybrid structure, in correspondence with SEM mapping results . The NMS-02 spectra were further analyzed to investigate the chemical states and interaction between NiTiO3 and MoS2. The Mo 3d signal  consisted of two prominent peaks related to Mo4+. High-intensity peaks at 229.3 and 232.4 eV, corresponding to Mo4+ 3d5/2 and Mo4+ 3d3/2, respectively, were attributed to the 1T MoS2 phase; two other peaks at 230.1 and 233.3 eV were assigned to the 2H phases of MoS2. A pair of peaks at 234.2 and 236.0 eV were attributed to Mo6+ of MoO3. One additional peak at 226.4 eV was assigned to S 2s. The S 2p spectrum  was deconvoluted into four peaks having energies of 162.0, 162.7, 163.3, and 164.1 eV. Peaks at 162.0 and 163.3 eV corresponding to S 2p3/2 and S 2p1/2 were attributed to 1T-MoS2 while the peaks at 162.7 and 164.1 eV corresponding to S 2p3/2 and S 2p1/2, respectively, were attributed to 2H-MoS2. The Ni 2p spectrum was deconvoluted into two major peaks corresponding to Ni 3p3/2 and Ni 2p1/2 at 855.9 and 873.7 eV, respectively . Peaks in the Ti 2p spectra appearing at 458.8 and 464.6 eV were assigned to Ti 2p2/3 and Ti 2p1/2, respectively . Four O 1s peaks  at 530.1, 530.6, 531.9, and 532.5 eV were attributed to Ti–O–Ti, Ti–O–Mo, surface water, and Ti–O–H bonds, respectively. The appearance of the peak at 530.6 eV due to the Ti–O–Mo linkage indicated a strong chemical interaction between NiTiO3 and MoS2 in NiTiO3/MoS2, which could improve photocatalytic activity.XPS was performed to investigate the chemical composition and effect of MoSiO3 NFs . Surveyspectra  confirm results . The NM signal  consistpectrum  was decctively . Peaks ctively . Four Os peaks  at 530.. Pristine NiTiO3 NFs displayed an absorption edge of 474 nm with little light absorption, especially in the visible region. The light absorption edge red-shifted from 489 nm (NMS-01) to 636 nm (NMS-04) with increasing loading of MoS2 onto the NiTiO3 NFs. The optimum sample (NMS-02), with an absorption edge of 509 nm, showed more light absorption than pristine NiTiO3 NFs, confirming the structural advantage of the composite sample. This enhanced UV-Vis light absorption could promote photocatalytic activity. The bandgap energies estimated using the Tauc method  were 2.61, 2.53, 2.43, 1.94, 1.92, and 1.6 eV for NiTiO3 NF, NMS-01, NMS-02, NMS-03, NMS-04, and pristine MoS2 photocatalysts, respectively. This steady reduction in bandgap energy was attributed to the inherent light absorption of the black MoS2.The optical properties of the as-prepared samples were measured by UV-vis spectroscopy over the range of 300–900 nm . Pristi method  were 2.2 loading on charge carrier recombination, to design an efficient heterostructure . Pristine NiTiO3 NFs showed no intense peaks, which indicated no activation in this region, while MoS2 showed high PL intensity due to high recombination rates. A remarkable reduction in charge carrier recombination was found, reflected in quenching of PL peak intensity when MoS2 was added to the NiTiO3 NFs. The lowest peak intensity for NMS-02 indicated the significance of identifying the optimum amount of MoS2, to design an efficient heterostructure to restrain charge carrier recombination. The decreased PL intensity for NMS-02 relative to all of the other photocatalysts was reflected in the highest photocatalytic performance. We performed EIS analysis under UV-vis irradiation to confirm the results obtained by PL spectroscopy, and to study the nature of the charge . A smaller semicircle radius in a Nyquist plot represents lower recombination and more efficient charge transfer across an interface. All of the composite samples showed smaller radii compared with the pristine samples, which confirmed that the growth of MoS2 on NiTiO3 NFs promoted successful electron transfer, resulting in enhanced photocatalytic performance. The radius was smallest for NMS-02, which also corroborated that it had the best CO2 reduction performance. To further confirm its effectiveness of the 1D/2D hybrid structure on the separation of photogenerated electrons and holes, transient photocurrent intensities were measured for bare and hybrid catalysts . The transient photocurrent was measured while switching the light on and off after every 60 s. The photocurrent density of pristine NiTiO3 NF and MoS2 showed the lowest values of 1.6 μA/cm2, and 1.8 μA/cm2 respectively while the hybrid structures NMS-01, NMS-02, NMS-03, and NMS-04 showed 3.6 μA/cm2, 7.6 μA/cm2, 5.9 μA/cm2, and 3.6 μA/cm2 respectively. This increase in the photocurrent density observed in the hybrid structures, is attributed to the successful formation of heterostructure between 1D NiTiO3 NFs and 2D MoS2 nanosheets.For a photocatalyst to show high performance, low rates of recombination of the charge carriers are crucial. Photoluminescence analysis was performed at an excitation wavelength of 325 nm to study the effect of MoSructure . Pristi charge . A smaltalysts . The tr. All samples were degassed overnight at 100°C prior to analysis. The N2 isotherms  for MoS2 had the smallest specific surface area due to highly densely clustered nanosheets. However, when MoS2 sheets were grown on the NiTiO3 NFs, the specific surface area significantly increased due to hierarchical “puffy” nanosheets of MoS2 dispersed over the surface of the NFs. The higher specific surface area of the composite structure could provide more adsorption and reactive sites, to enhance photocatalytic performance. The BJH pore size distribution plots  show typical adsorption-desorption isotherms for NiTiO3 and NMS-02 hybrid structures that confirmed the presence of pores, while the isotherms for pristine MoS2 indicated the absence of pores. This analysis showed that porous NiTiO3 NFs favored the growth of structurally stable vertical nanosheets of MoS2. The reduction of CO2 in the presence of water is usually in fierce competition with hydrogen evolution reaction (HER). This causes low activity and selectivity toward CO2 photoreduction. Therefore, the adsorption and activation of the CO2 on the surface of the catalyst are crucial for the subsequent reduction process. The amounts of CO2 adsorbed for the TiO2 NF, NMS-02, and MoS-02 were analyzed at 25°C . Results show a higher amount of CO2 adsorption on the surface of the NMS-02 hybrid sample (1.73 cm3/g STP) than that of pristine NiTiO3 NF (1.29 cm3/g STP) and pristine MoS2 (0.62 cm3/g STP). The epitaxial growth of MoS2 combined with the porous structure of NiTiO3 NFs provided more active sites for CO2 diffusion and adsorption. FTIR analysis showed the presence of OH groups on the surface of NiTiO3 NF and NMS-02 catalysts  pore size distributions were determined to further investigate the microstructures . All saotherms  for MoSn plots , inset sat 25°C . Resultatalysts . Surfaceeduction . The hig2 photoreduction experiments were performed in a custom-made steel reactor equipped with a quartz window. A 300-W Xe lamp was used as the UV-vis light source. Three sequential experiments were performed under the same conditions to confirm the reliability of the results. Control experiments were also performed without using CO2 and photocatalyst; no by-products were obtained, which indicated that photocatalyst and CO2 are essential to convert CO2 into useful hydrocarbon fuels . Yields decreased with further increases in MoS2 loading to NMS-03  and NMS-04 , which suggested that excess MoS2 might have induced charge carrier recombination during the reaction process. The low activity of the composite samples with higher MoS2 contents may also be partly due to fewer active sites, due to agglomerated MoS2 sheets as observed in SEM images. The CO and CH4 yields of the optimum sample of NMS-02 were 3.8- and 3.6-times those of pristine NiTiO3 NF  and 3.6- and 5.5-times those of the pristine MoS2  (3 NFs and MoS2 (2 over NiTiO3 NFs enhanced light absorption and exposed active edges. Mixed (1T/2H) phases of MoS2, enhanced CO2 adsorption, and improved charge separation might also have contributed to the significantly higher performance of the NMS-02 photocatalyst.To investigate the photocatalytic performance of the samples, COon fuels . Figure ctively) . The amoand MoS2 , because2 evolution, thereby favoring CO2 photoreduction reactions by exerting an umbrella-like effect over photocatalysts to minimize water contact  and hydrophobic (CA ≥ 90°) behavior. However, in our study, surfaces with CAs close to 90° were identified as hydrophobic while those with lower CAs were deemed hydrophilic.Hydrophobic surfaces suppress H contact . CA measand MoS2 . Here, h2 selectivity (SCO2) of each catalyst can be calculated according to n is the amount of H2, CO, and CH4 produced in units of μmol g−1 h−1 during 7 h of light irradiation. The highest selectivity, of 83%, was recorded for NMS-02, which compares with 63%, 78%, 80%, 73%, and 59% for NiTiO3 NFs, NMS-01, NMS-03, NMS-04, and MoS2, respectively . The stability of the optimum sample was determined by measuring CO2 reduction performance. The experiment was repeated for up to three cycles; after each cycle, the sample was removed from the instrument, and heated at 100°C for 4 h to remove DI water and TEOA. No significant change in performance was observed during the three consecutive experiments, which indicated good photocatalyst stability . Moreover, the sample was collected after the completion of the stability test for XRD analysis. 2 photoreduction looks almost similar. No observable change was observed according to XRD analysis, confirming that the heterostructure is highly stable.The COctively . The stability . Moreov2 reduction results confirmed that pure NiTiO3 NFs and pure MoS2 showed exceptionally lower amounts of CO and CH4 as compared to those for NiTiO3/MoS2 heterostructures. It can be inferred that the photocatalytic reduction of CO2 can be improved by light-harvesting, photogenerated carrier generating, and the CO2 adsorption capacity of the catalyst. Results of UV-Vis absorbance, PL, photocurrent density, and BET analysis show that the introduction of MoS2 nanosheets on the surface of NiTiO3 nanofibers can effectively increase the light absorption, charge separation, and CO2 adsorption and activation ability of the catalyst. As the activated CO2 is more susceptible to the reduction, the photogenerated electrons on the surface of heterostructure will react with the activated CO2 and H2O to form carbon-containing products as well as H2. NiTiO3 nanofibers decorated with flower-like MoS2, improving the selectivity of the CO, and CH4 products through the higher density of the photogenerated electrons to suppress the H2 formation on the active sides of the heterostructure. Based on the above results and discussions, a mechanism for the CO2 photocatalytic reduction process can be proposed in 3 NFs to the valence band (VB) of NiTiO3 nanofibers from where electrons migrate to CB of the MoS2 nanosheets due to good band alignment between the two components. Subsequently, the excited electrons from the CB of MoS2 nanosheets react with adsorbed CO2 and water producing CO and CH4. Meanwhile, the holes at VB-holes move from the VB of NiTiO3 NF to VB of MoS2 where they combine with TEOA to oxidize TEOA to TEOA+. The electrons enriched active sites of MoS2 in CB would be used for CO2 reduction. Thus, the synthesized hybrid structure delayed recombination of electron-hole pairs, thereby improving charge transfer at the interface.CO3 decorated with 1T/2H MoS2 were prepared via a facile one-step hydrothermal method. The key parameters for tailoring the morphology, porosity, surface, and interfacial properties of the photocatalysts were identified, with a view to efficient and selective conversion of CO2 into valuable chemicals. Introduction of MoS2 layers onto the NiTiO3 NFs increased the CO2 selectivity to 83% for the optimized hybrid structure, which compares with 63% and 59% for pristine NiTiO3 NFs and MoS2, respectively. This large improvement was attributed to the positive synergistic effect between the NiTiO3 NFs and MoS2 in the hybrid photocatalyst. High CO2 selectivity could also be attributed to enhanced light absorption, an abundance of active edges, insertion of multiphase (2H/1T) MoS2, and higher surface area, and partly to the hydrophobic nature of the composite structure. We believe that this strategy provides a new route to the design and manufacture of more energy-efficient materials having higher photocatalytic activity.Full spectrum-induced hybrid structures consisting of 1D NiTiO