Particularly, MoS2 nanosheets anchored on the two ends of CdS nanowires are identified as a reduction cocatalyst to accelerate hydrogen evolution, while RuO2 nanoparticles as an oxidation cocatalyst are deposited onto the sidewalls of CdS nanowires to facilitate oxygen evolution kinetics. The density functional theory simulations and ultrafast spectroscopic results reveal that photogenerated electrons and holes directionally migrate to MoS2 and RuO2 catalytic sites, respectively, thus achieving efficient charge carrier separation. The design of ternary dumbbell structure guarantees metal sulfides against photocorrosion and thus extends their range in solar water splitting.Solar‐driven overall water splitting based on metal sulfide semiconductor photocatalysts remains as a challenge owing to the strong charge recombination and deficient catalytic active sites. Additionally, significant inhibition of back reactions, especially the oxidation of sulfide ions during the photocatalytic water oxidation catalysis, is an arduous task that requires an efficient photogenerated hole transfer dynamics. Here, a ternary dumbbell‐shaped catalyst based on RuO 2/CdS/MoS2 photocatalyst with selective attachment of reduction and oxidation cocatalysts enables water splitting into H2 and O2. The critical aspect is the spatially separated distribution of MoS2 and RuO2 dual cocatalysts, which not only achieves photogenerated electron–hole pairs separation, but also protects CdS from photocorrosion by holes.The ternary dumbbell‐like RuO It has been regarded as a simple and cost‐effective method to produce clean hydrogen fuel by photocatalytic overall water splitting, comparable to fossil‐fuel‐derived hydrogen due to its simplicity and low cost. However, the photocatalysts for water splitting in previously reported literature still face grand challenges: 1) most of photocatalysts suffer from weak visible light response owing to their large bandgap; 2) O2 evolution from semiconductor photocatalysts is difficult due to multiple electrons and protons transfer process for the formation of O—O bond (1.23 eV). In this regard, it is vital to develop narrow‐bandgap and low‐cost photocatalysts capable of decomposing water into hydrogen and oxygen to maximize the photoconversion efficiency.The global energy demand continues to rise, which presents inextricably serious challenges to environment issues, and drives the quest for clean and renewable energy sources alternative to fossil fuels.2, 3 The structure of 1D metal chalcogenides with reduction‐cocatalyst tip possesses a few unique advantages in photocatalytic water splitting, such as fully exposed active sites, effective hole localization, and long‐distance electron transport. For instance, 1D CdS nanorods with Pt nanoparticles (NPs) at the end of nanorods can show impressive photocatalytic H2 evolution performance with a high quantum efficiency of 9.6% under the light illumination with the wavelength of 455 nm. This optimized reduction‐cocatalyst‐tipped semiconductor nanostructure fully exploits the benefits of interfacial charge separation between photogenerated electrons transferring to Pt cocatalyst and holes remaining on the CdS nanorods, thus resulting in longer electron lifetime. The improvement of the photogenerated electron lifetime is closely associated with the introduction of sacrificial electron donors. With the absence of sacrificial electron donors, the photoinduced holes accumulated on the sidewalls of 1D metal sulfide tend to oxidize lattice sulfide ions rather than involve in oxygen evolution. Consequently, an efficient hole transfer is a key step to achieve high‐efficiency solar‐to‐fuel conversion.Transitional metal chalcogenides is a promising candidate for efficient solar energy harvesting due to their simple chemical composition, narrow bandgap, and appropriate band structure.20 The Nevertheless, the metal‐based molecular cocatalysts require complicated organic synthetic process and exhibit poor stability as a result of hole‐induced ligand oxidation. Compared with metal‐based molecular cocatalysts, non‐photoresponsive metal oxides, such as RuO2 and IrO2, are alternative oxidation cocatalysts with low resistivity and high corrosion resistance. Therefore, we can expect that the deposition of metal oxides cocatalysts onto the sidewalls of 1D metal sulfide structure can effectively transfer multiple holes from sulfide to oxidation cocatalysts sites, which is indispensable for water oxidation.Recently, researchers employed metal‐based molecular cocatalysts as holes collector and investigated the effect of tunable ligand structure on water oxidation activity.31 Nev2 (electron collector) and RuO2 (hole collector) dual cocatalysts to successfully achieve simultaneous H2 and O2 evolution  simulations to investigate the coupling effect and charge transfer route at the interfaces. These two heterostructures based on CdS/MoS2 and RuO2/CdS are formed by the strong chemical bonding interactions, due to the high binding energies of —0.30 and −1.08 J m−2, respectively. Furthermore, Figure 2 and RuO2/CdS junction region, indicating the remarkable charge transfer occurs at the interfaces. Clearly, the outmost Cd atoms of CdS donate electrons to the S atoms of MoS2 at the MoS2/CdS heterostructure interface  calculated from Bader charge reveals the formation of positively charged RuO2 and negatively charged CdS at the RuO2/CdS interface, indicating the surface of RuO2 attracts holes from the adjacent CdS. Our calculations suggest that the strong interface coupling on both CdS/MoS2 and RuO2/CdS enables efficient interfacial charge carrier transfer in ternary RuO2/CdS/MoS2 structure, which is essential for high photocatalytic performance.The band structure of CdS nanowires was first investigated to analyze the possibility of photocatalytic overall water splitting . The bandgap of CdS is determined to be 2.12 eV from the Tauc plot , and its valence band (VB) potential is calculated to be 1.88 eV from X‐ray photoelectron spectroscopy (XPS) . The conduction band (CB) position is thus estimated at −0.24 eV. Electronic band structure of CdS  further shows that the reduction level for Hplitting.37 Aft2/CdS/MoS2 photocatalyst with nanodumbbells structure  by hydrothermal treatment with Na2MoO4 and thioacetamide as the MoS2 precursors in the mixture of H2O and diethylenetriamine. The SEM and TEM images  show that MoS2 NSs are selectively and symmetrically grown on the two tips of CdS nanowire to form a well‐defined nanodumbbell structure. After MoS2 NSs affixed CdS nanowire tips, the surface‐modified —NH2 groups still remain at the sidewalls of CdS nanowires, which is confirmed by Fourier transform infrared spectra . The strong coordination between Ru3+ and —NH2 groups ensures that the dispersion of Ru3+ ions on the sides of CdS/MoS2. Following a thermal treatment process, RuO2 NPs were selectively formed on the sidewalls of CdS nanowires. The morphology characterizations manifest that the prepared RuO2/CdS/MoS2 sample still maintains symmetrical tip‐coated structure  image of the sidewall of RuO2/CdS/MoS2 .We designed a synthetic strategy to fabricate the ternary RuOe Figure 2a. AmineCdS/MoS2.38 Fole Figure , and soms Figure . More cls Figure  on the ts Figure  and thei2 Figure  reveals 2 Figure , the int2/CdS/MoS2 are confirmed by XRD patterns and XPS spectra. The XRD pattern  and Ru (0.96 wt%) concentration, which is confirmed by the inductively coupled plasma mass spectrometry (ICP‐MS) . XPS survey spectrum  shows the coexistence of Cd, S, Mo, Ru, and O elements, indicating successful deposition of MoS2 and RuO2 on CdS. The high resolution XPS signal , suggesting more free electrons accumulation at CdS caused by the holes transfer from CdS to RuO2 after their combination, which is in agreement with the DFT simulation results. Similarly, the S 2p peaks for CdS/RuO2 also display negative shift in binding energy . However, an obvious shift of 0.3 eV to high binding energy region can be also observed in Cd 3d XPS spectrum of CdS/MoS2 as compared to that of CdS , and photoluminescence (PL) spectroscopy. As displayed in Figure 2/CdS/MoS2 shows the highest photocurrent intensity, suggesting enhancement of charge separation efficiency by introducing spatially separated MoS2 and RuO2 dual cocatalysts. Furthermore, the EIS spectra  demonstrate that the semicircle diameter of RuO2/CdS/MoS2 is the smallest one among all the samples, indicating the optimal interfacial charge‐carrier transfer ability on the surface of RuO2/CdS/MoS2. In addition, PL quenching experiments were conducted to investigate the electron transfer dynamics. The most significant quenching of PL is observed by the decoration of dual cocatalysts, testifying the prolonged lifetime of photogenerated charge carrier in RuO2/CdS/MoS2. To better understand the spatial separation behavior of photoinduced charge carriers in RuO2/CdS/MoS2, two photodeposition reactions, reduction of Au3+ with lactic acid as hole collectors and oxidation of Mn2+ with IO3− as electron acceptors were carried out, respectively. As indicated in Figure S11 (Supporting Information), Au NPs were selectively loaded on the MoS2 tips, suggesting that the photogenerated electrons tend to migrate to MoS2 sites for reduction reaction. By contrast, MnOx NSs derived from Mn2+ oxidation were deposited only on RuO2 part , revealing the photogenerated holes are inclined to accumulate on RuO2 sites for oxidation reaction.Ultraviolet visible (UV–vis) diffuse reflectance spectra were employed to investigate the light harvesting capability of the as‐prepared samples. As displayed in  of MoS2.45 Aft2, and RuO2/CdS/MoS2 show the distinctly negative absorption peak at 475 nm , which is attributed to photobleaching of the ground state (GS) absorption. Transient absorption (TA) kinetic decay traces of the three samples are fitted with biexponential decay, and the fitting parameters are summarized in Table S2 (Supporting Information). Upon light irradiation, photoinduced electrons can be first excited from GS to excited state (ES) followed by two fast processes involving charge recombination from ES to GS and charges trapping from ES to inactive trap states (TS). It is noted that the electrons on TS are inactive and not involved into photocatalytic reaction. For CdS nanowires, the decay observed within 10 ps  is assigned to the active charge recombination from ES to GS, while the lifetime of 350.8 ps  is attributed to the charge transfer process from ES to TS. Regarding CdS/MoS2, the fast decay component of 8.1 ps  is mainly ascribed to the charge recombination from ES to GS in CdS. The lifetime of 123.5 ps  is attributed to the charge transfer from ES of CdS to MoS2 rather than from ES to TS in CdS, because the efficient electron capture ability of MoS2 prevents photogenerated electrons from trapping into inactive TS in CdS. After the decoration of RuO2 on the sidewalls of CdS/MoS2 nanodumbbells, the lifetime  is further reduced to 40.8 ps, revealing that the introduction of RuO2 promotes electron transfer process from ES of CdS to MoS2, which accords with the PL results.To further ascertain the nature of the photoinduced charge carrier transfer interaction, femtosecond transient absorption (Fs‐TA) spectroscopy was carried out by employing pump–probe technique using 400 nm laser as a pump pulse and a white light continuum of 440–700 nm as the probe pulse. Upon 400 nm excitation, these three samples of CdS, CdS/MoSsorption.46 TraFigure 2/CdS nanowires show negligible H2 production activity, while CdS/MoS2 nanodumbbells display moderate H2 evolution activity (0.7 µmol h−1) due to the decreased charge recombination rate in terms of the electron transfer from CdS to MoS2. After further depositing of RuO2 NPs, the hydrogen evolution rate of RuO2/CdS/MoS2 nanodumbbells can be remarkably improved and reach up to 5.2 µmol h−1, and O2 evolution proceeds continuously at a rate of 1.1 µmol h−1. It should be also noted that RuO2/CdS/MoS2 achieves photocatalytic water splitting into H2 (2.7 µmol h−1) and O2 (0.6 µmol h−1) under visible light irradiation (λ>420 nm), indicating the efficient solar energy harvesting of RuO2/CdS/MoS2. Besides, control experiments show that no O2 evolution was detected by gas chromatography (GC) when CdS/MoS2 was used as photocatalyst over a 5 h reaction period, which indicates a well‐established photocorrosion reaction between S2− and the holes remaining on the sides for CdS/MoS2 nanodumbbells. The TEM observations  and XRD patterns  of CdS/MoS2 after the water‐splitting reaction further prove that photoinduced holes can readily oxidize the lattice S2− ions of CdS. Similar phenomenon is also observed for bare CdS nanowires . Furthermore, the linear sweep voltammetry (LSV) curve of the RuO2/CdS/MoS2 nanodumbbells demonstrates an obvious reduction of the S2− ions oxidation peak along with the decreased overpotential of oxygen evolution as compared to that of the CdS/MoS2 nanodumbbells . It can be observed that the nominal loading amounts of MoS2 and RuO2 were 15.52 and 1.26 wt%, respectively .The photocatalytic activity of the as‐prepared samples were evaluated by hydrogen and oxygen evolution from water‐splitting reaction under simulated solar light irradiation  without any sacrificial reagents. As indicated in s of CdS.48 Sims Figure , indicat2 and O2 evolution based on RuO2/CdS/MoS2 nanodumbbells is achieved, the H2/O2 ratio deviated from the stoichiometric value of 2. To unravel the intrinsic reason, we used an iodometric method to detect potentially produced H2O2. As expected, with the water‐splitting proceeding, a trace amount of H2O2 was observed, and the concentration of H2O2 gradually increased over 5 h , suggesting part of holes on the RuO2 sites take part in H2O2 evolution via 2‐eletrons pathway, which is supported by energy band structure . To further confirm that the detected O2 was indeed generated from H2O splitting, an isotopes labeling experiment was performed in a mixture of H2O and H218O. As shown in Figure 16–18O2, verifying that O2 is formed from photocatalytic overall water splitting. In addition, the stability experiment demonstrates negligible deterioration of photocatalytic activity for RuO2/CdS/MoS2 during 25 h irradiation  for RuO2/CdS/MoS2 during overall water splitting as a function of the incident light wavelength was displayed in Figure 2/CdS/MoS2 reach 0.32% at 365 nm, 0.23% at 425 nm, and 0.10% at 475 nm. When the light absorption at wavelengths is longer than 500 nm, the AQE value is nearly zero due to the low absorption efficiency for CdS in the visible‐light region beyond 500 nm.Although simultaneous Hn Figure . SEM and2/CdS)@MoS2 core–shell photocatalyst with randomly loaded catalytic sites as control sample. As shown in Figure S19a (Supporting Information), RuO2 NPs are first deposited on the sidewalls of CdS nanowires and subsequently the obtained RuO2/CdS nanowires are wrapped by MoS2 NSs to form (RuO2/CdS)@MoS2 core–shell structure. SEM images , TEM images , and element mapping  indicate the successful preparation of (RuO2/CdS)@MoS2 core–shell structure. Besides, there are no distinct differences in light absorption , crystal structure , and the loading amount of dual cocatalysts  between (RuO2/CdS)@MoS2 and RuO2/CdS/MoS2, eliminating the effects of these three factors on photocatalytic performance. As indicated in Figure 2/CdS)@MoS2 are almost 10 times faster than that of (RuO2/CdS)@MoS2 (0.57 µmol h−1 H2 and 0.1 µmol h−1 O2). The origin of the remarkably enhanced performance is attributed to the spatially separated catalytic sites for the H2 and O2 evolution. Basically, for RuO2/CdS/MoS2 dumbbell structure, the photogenerated electrons and holes have a remarkably tendency to locate at MoS2 and RuO2, respectively, thus facilitating charge separation. Nevertheless, regarding (RuO2/CdS)@MoS2, there are lots of contact interface between MoS2 and RuO2 due to their random loading , which leads to the recombination of photoinduced charge carriers at the interfaces.To highlight the advantages of nanodumbbell structure with spatial separated sites in photocatalysis, we prepared (RuO2/CdS/MoS2 photocatalyst with well‐defined dumbbell structure evolved H2 and O2 via a water‐splitting reaction under simulated solar light irradiation. The construction of spatially separated dual cocatalysts on CdS nanowires enables the photoexcited electrons and holes to transfer expeditiously from CdS to the MoS2 and RuO2 catalytic sites, respectively, resulting in a superior and durable photocatalytic water‐splitting activity. This work provides an efficient strategy for the design of metal‐sulfide‐based photocatalysts with high overall water‐splitting performance.In conclusion, we demonstrated that a ternary RuOThe authors declare no conflict of interest.Supporting InformationClick here for additional data file.


In this study, we evaluate sea surface pCO2 measurements collected over a 6‐year period along a fixed cruise track in the Canada Basin. The measurements show that mean pCO2 levels are significantly higher during low ice years. The pCO2 increase is likely driven by ocean surface heating and uptake of atmospheric CO2 with large interannual variability in the contributions of these processes. These findings suggest that increased ice‐free periods will further increase sea surface pCO2, reducing the Canada Basin's current role as a net sink of atmospheric CO2.Less than three decades ago only a small fraction of the Arctic Ocean (AO) was ice free and then only for short periods. The ice cover kept sea surface  The Arctic Ocean is losing ice cover at a rapid rate2, increasing sea surface CO2 levelsThe loss of ice cover is leading to heating and uptake of atmospheric CO2 will likely reduce the uptake of atmospheric CO2 in the futureContinued increase of sea surface CO St‐Laurent during 2012–2017. No pCO2 measurements were made in 2015. The starting dates for the five ~4 week cruises were 6 August 2012, 3 August 2013, 25 September 2014, 24 September 2016, and 8 September 2017. The pCO2 was recorded using an infrared‐gas equilibrator system  located in the ship's lab. The instrument uses an infrared analyzer  and gas phase equilibrator  as described in Hales et al. (2 gas standards and a zero CO2 gas sample. Temperature was measured in the equilibrator and at the seawater intake (9 m depth), assumed equal to sea surface temperature (SST), as discussed below. The infrared analyzer CO2 mole fraction was corrected to SST and converted to pCO2 using 100% humidity at SST and local barometric pressure  and the pCO2 was discarded during these periods. A flow meter was installed in 2016 to detect periods of low flow rate. The pCO2 uncertainty is estimated to be ±5 μatm based on the reproducibility of the standards and baseline zero. CTD stations showed that the seawater intake was sometimes within the halocline , and this was also evident from the salinity and temperature variability recorded by the ship's thermosalinograph. These conditions were found mostly on the continental shelf during 2012 and 2013 due to high Mackenzie River outflow. This analysis focuses on the Canada Basin bounded by 155–130°W and 72–82°N where CTD stations consistently found that mixed layer depths were greater than the ship intake depth.Underway sea surface s et al. . The equ−3  Earth System Research Laboratory (ESRL) (https://www.esrl.noaa.gov). Sea ice concentration with daily, 12 km resolution was obtained from the French Research Institute for Exploration of the Sea (IFREMER) (http://cersat.ifremer.fr/oceanography-fromspace/our-domains-of-research/sea-ice) that provides data collected by the satellite‐based Special Sensor Microwave Imager (SSM/I) and processed by the National Snow and Ice Data Center (https://nsidc.org).Air temperature, wind speed, wind direction, and barometric pressure were recorded by the ship's weather system. Mixed layer depths, defined as the depth where the density difference from the surface first exceeds 0.25 kg m2.2pCO2 levels are related to interannual variability in ice concentration and to evaluate processes that might control pCO2 under low (or no) ice conditions. To facilitate analysis of the spatially and temporally disparate shipboard pCO2 and other data, Canada Basin data were gridded by identifying 20 × 20 km grid areas that contain data, and those data were then averaged as described in Evans et al.  for each grid cell. DOR is the day when ice concentration dropped below 15% in any grid cell  mixed layer mass balance , Fgasex is the air‐sea CO2 flux , MLD is the mixed layer depth, and ρ is seawater density. Warming (increasing SST) is accounted for in the equilibrium calculation as described below. Fgasex was calculated usingk is the gas transfer velocity, K0 is the CO2 solubility, ΔpCO2 is the pCO2 difference between the sea surface and atmosphere, and f is the fraction of open water . Fgasex is negative when there is a net uptake of CO2 by the ocean from the atmosphere. We used the wind speed relationship in Wanninkhof  was calculated as opposed to wind speed averages because short‐term (<daily) variability in the winds is retained leading to higher gas transfer rates during periods of greater wind speed variability . We used values from Ji et al.  in the CO2 equilibrium program CO2sys  calculations used the Mehrbach et al. . Sea surface pCO2 was also highly variable spatially and interannually. Open water in the Canada Basin typically had higher pCO2 levels than pCO2 recorded in ice‐covered areas; for example, compare 2012 (low ice) and 2014 (more ice) in Figure The shipboard pCO2 is higher and closer to atmospheric saturation during years of low ice concentration and exceeded atmospheric pCO2 , MLD, wind speed, and NCP  differs significantly, as do data from the late September cruises (2014 and 2017). These differences are also evident in the pCO2 data in Figure The gridded sea surface y Figure . Each yepCO2 with increasing DSR and that these processes are highly variable from year to year . Also, employing DSR as a time variable in the model assumes that no air‐sea exchange or warming occurred when sea ice concentration was greater than 15% which is clearly not true  over the range of NCP reported in Ji et al. (2/argon method integrates NCP over the residence time of O2 in the mixed layer (10–30 days)  (doi:10.18739/A2R785P3X).The data are available through the U.S. National Science Foundation (NSF) Arctic Data Center (Supporting Information S1Click here for additional data file.


The benefits of this synergy are twofold for OER: highly conductive metallic Ag improves the charge transfer ability of the electrocatalysts while ultra‐small Ag2O clusters provide the centers that can uptake Fe impurities from KOH electrolyte and boost the catalytic efficiency of Co–Ag oxides. The current density of mesostructured Co3O4 at 1.7 VRHE is increased from 102 to 211 mA cm−2 with incorporation of silver spices. This work presents the dual role of silver moieties and demonstrates a simple method to increase the OER activity of Co3O4.Herein, we show that the performance of mesostructured cobalt oxide electrocatalyst for oxygen evolution reaction (OER) can be significantly enhanced by coupling of silver species. Various analysis techniques including pair distribution function and Rietveld refinement, X‐ray absorption spectroscopy at synchrotron as well as advanced electron microscopy revealed that silver exists as metallic Ag particles and well‐dispersed Ag One stone, two birds: The twofold advantages of silver coupling with ordered mesoporous Co3O4 for OER are demonstrated. Metallic silver enhances the conductivity of the structure while Ag2O nanoclusters provide centers for Fe uptake from the KOH electrolyte and boost significantly the efficiency of the electrocatalyst. The synergy of these two silver species resulted in enhanced OER performance by reaching a much lower overpotential (371 mV) at 10 mA cm−2 than that of the pristine Co3O4 (392 mV). Moreover, the overpotential further decreased 344 mV at 10 mA cm−2 after chronopotentiometry experiment, which is similar to what occurs when amorphous cobalt oxide is activated by iron impurities.2O nanoclusters provided the sites to uptake trace iron impurities from KOH electrolyte, which stimulated the kinetics in terms of lowering the activation energy barrier for water oxidation. To the best of our knowledge the present results represent the first time that the dual‐functional role of silver moieties coupled with OM Co3O4 has been elucidated.Herein, we used the ordered mesoporous (OM) structure as a model system to explore the synergistic effect between cobalt and silver in spinel cobalt oxides with the aim of developing high‐performance OER electrocatalysts. By following the hard templating approach, silver could be incorporated into mesostructured Co3O4 spinel and metallic Ag for all mixed samples. Notably, compared to Co3O4 spinel, metallic Ag exhibited much sharper diffraction patterns, suggesting its high crystallinity with a large crystallite size. During the thermal treatment, the starting precursors of cobalt and silver nitrates are converted to their oxide and metallic counterparts. Although the passivated silver and silver oxide are stable at the ambient condition, at high temperature as 550 °C, Ag2O further decomposes to Ag and oxygen .3O4 mesostructure. This can be also seen from the transmission electron microscopy (TEM) images of the nanocast oxides. As shown in Figure S1, an OM Co3O4 structure with an average crystallite size of around 7 nm (which is corresponding to the pore size of silica template) is obtained after the removal of silica template, illustrating a successful replication process. By simply tuning the composition of the starting precursor during the impregnation step, a series of cobalt–silver oxides with designed Co/Ag ratio were successfully synthesized as well. The actual ratio of Co/Ag was determined by energy‐dispersive X‐ray spectroscopy , and the results are listed in Table S1. A lower amount of Ag was always observed in the nanocast Ag‐Co oxides compared to the designed ratios. Especially for the oxide with high Ag loading, for example, the oxide with a Co/Ag ratio of 1/1, ≈36 at. % of Ag was lost during the preparation steps. This can be ascribed to: (1) limited solubility of AgNO3 in ethanol ,3 out of the silica template, followed by decomposition to form Ag on crucible during the calcination.Following a well‐developed nanocasting protocol,3O4 matrix during nanocasting. As shown in Figure S4a, a large particle of ≈100 nm was embedded within the oxide sample. High‐resolution TEM image shows the lattice fringes on the large crystal with a spacing of 0.20 nm, corresponding to the (200) plane of Ag metal . Good contact existed between the large Ag crystallites and the OM matrix. The nanoparticles of the OM matrix are Co3O4 nanoparticles, as suggested by the characteristic lattice fringes observed at different positions . As a result, the cubic symmetry of the ordered mesoporous structure is distorted with the addition of Ag, as displayed by the lower peak intensities in Figure The well‐ordered mesoporous structure of KIT‐6 silica template was replicated to some extent on the Ag–Co oxides, although the structure looks denser and coupled as seen in Figure S3. This is due to the formation of large Ag particles, which were well integrated with the OM Co3O4 matrix. The high‐resolution scanning electron microscopy (HR‐SEM) image and the EDX mapping images show the uniform distribution of O and Co  to investigate the structural information of Ag as well as its distribution in the OM Co to inves3O4 spinel can host other transition metals via the substitution on its tetrahedral and octahedral sites,3O4. First, Rietveld refinement was conducted on XRD patterns to obtain a deeper insight on the bulk crystal structure  and metallic Ag (12 wt. %). The unchanged unit cell parameter of Co3O4 in Co8Ag oxide illustrates that no significant expansion of the unit cell is observed for Co3O4 structure. Second, to better reveal the structural environment, pair distribution function (PDF) analysis was performed and demonstrated well‐resolved peaks of local bonding in Co3O4 spinel structure, as well as the distinct Ag–Ag bonding occurring in the structure of metallic Ag  to deduce the coordination number and valence state of local Co spinel structure by studying both X‐ray absorption near edge structure (XANES) and extended X‐ray absorption fine structure (EXAFS). As shown Figure 3O4 and Co8Ag oxide, demonstrating that Ag brought a negligible change in the local structure of Co coordination. No significant change on the bonding lengths between Co and neighboring atoms, as shown by EXAFS spectra in Figure S9, illustrates that the coordination environment of Co is maintained upon the addition of Ag. These results clearly support that Ag atoms were not incorporated in the Co3O4 spinel  but rather homogeneously distributed on the surface of Co3O4.Although it is well‐known that Coe Figure  a. As exllic Ag 1 wt. %. Tllic Ag 1 wt. %. T3O4 and Co8Ag oxide, X‐ray photoelectron spectroscopy (XPS) was carried out. As shown in the high‐resolution Co 2p spectra  and Co in Co3O4 (4.5 eV),3O4 matrix. As a result, this contact of the Ag/Co3O4 interface caused surface electron dislocation, as demonstrated by XPS, but not shown in bulk sensitive XAS measurement. Furthermore, high‐angle annular dark field (HAADF) image shows that Ag2O is located on the surface of Co3O4 as ultrasmall nanoclusters (<2 nm). The Ag2O nanoclusters can be distinguished from Co3O4 on the basis of the brightness variations of these nanoclusters in the HAADF‐STEM image  curves collected before and after 50 cycle voltammetry (CV) scans (0.6–1.6 VRHE), we can deduce the activation/deactivation behaviors of samples under applied potentials in KOH electrolyte. As seen in Figure S10 and S11, pristine Co3O4 shows stable OER activity, whereas a higher catalytic current is achieved on Ag‐containing oxides after 50 CV scans, suggesting the activation of samples. This can be also seen in Figure 8Ag oxide shows the highest OER activity after activation with a current density (159 mA cm−2) and an overpotential (371 mV), which are superior to pristine Co3O4 (99 mA cm−2 and 398 mV).After a detailed structural analysis, the synergy of coupling silver with cobalt is further investigated for OER in 1 8Ag oxide being the most active OER catalyst. Clearly, the addition of Ag is beneficial to the OER activity of spinel Co3O4, as shown in previous studies where Ag was employed as a conductive additive.8Ag oxide. Accordingly, relevant experiments were conducted to verify this postulation.In order to understand the electrochemical activation of Ag‐Co oxides, we conducted the same experiment in Fe‐free KOH electrolyte, since trace Fe impurities present in the electrolyte are known as a booster to enhance the OER activity in the case of nickel/cobalt based oxide catalysts.8Ag oxide, the following experiments were carried out to compare the Ag‐Co oxides with a different Co/Ag ratio. First, we normalized the LSV curves based on the specific surface areas which were determined by N2 physisorption measurement. As shown in Figure S14, the Co8Ag oxide brought a significant higher current density at 1.7 VRHE, illustrating that it is intrinsically more efficient at uptaking electrons from OH− to generate oxygen. Second, we investigated the correlation between the catalytic performance and the charge transfer ability that is a crucial factor in electrocatalysis. For this, the electrochemical impedance spectroscopy (EIS) measurement was conducted to unveil the reaction kinetics on these oxides. Figure S15 depicts the Nyquist plots measured at 1.6 VRHE, from which we can derive the corresponding resistances according to Randle model . As expected, introducing Ag significantly decreased the charge transfer resistance (based on the diameter of the semicircle in the low‐frequency region). Among the Ag‐containing oxides, similar values of charge transfer resistance (16–19 ohm) are shown except for CoAg oxide which possesses relatively higher value (28 ohm). The high resistance of CoAg oxide could be resulted from the numerous points of contact interconnected between particle domains in a collapsed ordered structure.8Ag oxide possesses the lowest charge transfer resistance, in other words the highest intrinsic property. This contributes to the superior OER activity on Co8Ag oxide over other Co–Ag oxides in the absence of Fe uptake. Furthermore, we measured the double‐layer capacitance (Cdl) to estimate the electrochemical surface area (ECSA) of nanocast Co–Ag oxides upon activation. As shown in Figure S17 and S18, the electrochemical surface area (ECSA) of all samples were similar except Co2Ag and CoAg oxides with much lower BET surface areas . The slightly higher value of Cdl for Co4Ag, Co8Ag, and Co16Ag oxides relative to Co3O4 could be due to the compensation of their lower BET surface area by the electron storing behavior of silver.To elucidate the origin of superior OER activity on Co− reactant to electrode, thus expediting the OER reaction. In addition, it was found that the catalytic behavior of Co8Ag oxide is affected by the concentration of Fe impurity in KOH electrolyte. As shown in Figure S19, Co8Ag electrocatalyst was activated in all Fe‐containing KOH electrolytes. Depending on the Fe content, varying OER activities were shown after Fe‐activation. Figure m KOH electrolyte that contains 10 ppm Fe impurity, further supports that Fe uptake induced activity enhancement on Co‐Ag oxides.In addition to the improved OER kinetics, it has been recently demonstrated that Fe uptake leads to the formation of oxidized Fe species, which plays a crucial role in lowering the activation energy barrier for the OER.2 and CoOOH were able to uptake Fe impurities from the electrolyte and thus got activated.3O4 electrocatalysts indicates that the spinel structure is not favorable to uptake Fe impurities from KOH electrolyte.3O4 in both unpurified and Fe‐free KOH electrolyte  Fe‐modified Co sites,3O4 matrix that can act as a good electron conductor, (ii) ultrasmall Ag2O clusters homogeneously dispersed on the surface of Co3O4 particles that provide the sites for uptaking Fe from KOH electrolyte as schematically illustrated in Figure 2O cluster on the OER activity of Co8Ag oxide, we prepared the sample by physically mixing with pure Ag and the OM Co3O4 (Co:Ag 8:1). As seen in Figure 8Ag oxide. Constructing a hetero‐interface with Ag has been well reported as an effective strategy to increase the electron transfer ability on transition metal based electrocatalysts.I–V curves (under bias sweeping from 9 to 1 V) is displayed in Figure S20. The resistance of Co3O4 is 12.37 MΩ and the value is curtailed and then risen with increasing the atomic ratio of silver to cobalt, the lowest resistance is observed in Co8Ag oxide (0.27 MΩ). This trend matches well with the OER activity results  was found to be presented in normal 1 m KOH solution, likely in the form of [Fe(OH)4]−.4]− species in KOH electrolyte. Although, both Co3O4 and Ag2O are typical p‐type semiconductor,3O4 is not able to accommodate [Fe(OH)4]−.2O nanoclusters are preferred sites for [Fe(OH)4]− adsorption and the corresponding iron uptake under the mild condition.On the basis of the detailed characterizations, it is confirmed that two Ag species are formed with the introduction of Ag, which are: (i) metallic Ag particles coupled with OM Co8Ag oxide, we continuously applied the potential fixed at 10 mA cm−2 using a chronopotentiometry (CP) in unpurified 1 m KOH for 10 h . The electrocatalytic performance of Co8Ag oxide was checked by LSV scan after CP measurement  and pristine Co3O4 (392 mV). A lower Tafel slope was calculated on the activated Co8Ag oxide (48 mV/dec) compared to that of pristine Co3O4 . This suggests the formation of new surface active species that are kinetically more favorable for OER.4+ species which can serve as dynamically active sites at the catalyst/electrolyte interface with balanced binding energies of oxygen intermediates.3+ stimulating the oxidation of M2+ (M: Co and Ni) to M3+/4+ instead of its further oxidation to Fe4+.2O itself showed a very poor OER activity even in the presence of an excess amount of iron impurity. Therefore, it does make sense to postulate either (i) the interaction between Ag2O adsorbed by iron impurities and Co3O4 or (ii) the formation of new active species consisting of cobalt‐silver‐iron synergistically facilitated the OER kinetics. Resultantly, much higher current density at 1.7 VRHE was achieved on the activated Co8Ag oxide (211 mA cm−2), more than twice of that of Co3O4 (102 mA cm−2). Even compared with the recent‐reported benchmarked cobalt electrocatalysts, Co8Ag oxide displayed competitive catalytic performance, as listed in Table S2.To evaluate the stability performance of nanocast Coh Figure  a. The a8Ag electrocatalyst. First, we studied the change in the surface oxidation state of Ag by XPS. For that, the electrode was fabricated by depositing Co8Ag oxide on the carbon fiber paper. The survey XPS spectra suggest a similar chemical composition on the electrode before and after electrochemical activation . Both Ag metal and Ag+ cations are detected on the surface of the catalyst after OER measurement in KOH electrolyte. However, the peak intensity ratio of Ag+/Ag increased significantly, indicating that during the electrochemical measurement metallic silver was converted to silver oxide. It should be noted that the peak at binding energy of 377.0 eV can be ascribed to the remaining K+ originating from the electrochemical measurement.8Ag oxide . Electrochemical leaching of transition metals like Ni and Co has been monitored using inductively coupled plasma optical emission spectroscopy in our previous work.2O clusters remained on Co3O4 matrix with a similar concentration comparing to as‐prepared sample . Notably, the adsorbed Fe species were also detected on the identical location with a concentration of 1.7 at. %. This observation suggests that equivalent amount of Fe species was adsorbed on Ag2O clusters and involved in the OER as catalytically active sites.In addition, post characterizations were conducted to examine the structural durability of the Coe Figure  d, the ws Figure  e, which3O4. Following the nanocasting route, two different silver species, namely metallic Ag and ultrasmall Ag2O clusters, were formed on/in the mesostructured Co3O4 matrix. The introduction of metallic Ag increases the conductivity of the electrocatalyst and leads to a faster electron transfer while Ag2O species cause the Fe‐induced activation of electrocatalyst. The detailed structural analysis confirmed that metallic Ag particles were grown within the mesostructure of cobalt while Ag2O nanoclusters were homogeneously dispersed on the surface of Co3O4 matrix. Our control experiments and post‐characterization have proven the Fe uptake from the KOH electrolyte through small silver oxide clusters. The adsorbed Fe species improved the OER performance of Co8Ag oxide significantly by delivering a current density of 211 mA cm−2 at 1.7 VRHE and an overpotential of 344 mV at 10 mA cm−2. Increasing Fe content in 1 m KOH electrolyte resulted in a faster activation kinetic where a maximum activation was achieved in the electrolyte containing 10 ppm Fe impurity. This study not only puts forward a direct way to construct active cobalt oxide based electrocatalysts with silver coupling, but also provides experimental evidences on the active role of Fe species originated from KOH electrolyte.We have fabricated a series of ordered mesoporous silver cobalt oxides and demonstrated that addition of silver has a dual effect on electrocatalytic OER activity of CoThe authors declare no conflict of interest.As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re‐organized for online delivery, but are not copy‐edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.SupplementaryClick here for additional data file.


To report PCR results and vaccination status of rabbits with rabbit haemorrhagic disease following an investigation into sudden or unexpected death.per mg liver, categorised as negative, inconclusive or positive. The vaccination status of rabbits with both histopathological features of rabbit haemorrhagic disease and positive PCR test results were collated.PCR testing for RHDV2 and RHDV1 was performed on rabbit liver samples at two laboratories. Laboratory A reported results as positive or negative; Laboratory B reported results quantitatively as RNA copies PCR results matched histopathological findings in 188 of 195 (96%) cases. Seven individuals showed equivocal results, all of which had histopathological features of RHD but three tested PCR‐negative and four results conflicted between laboratories. RHDV2 was the serotype detected in all PCR‐positive cases. Histological features of rabbit haemorrhagic disease and PCR test results were positive in 125 rabbits; 51 unvaccinated, 56 in‐date with Nobivac Myxo‐RHD and 13 vaccinated against RHDV2 – although nine of these were vaccinated within 10 days of death.PCR testing complements histopathology in cases of sudden death in rabbits by confirming the diagnosis and identifying virus serotype, but there can be false negatives. Although RHDV2 is currently prevalent in UK pet rabbits, vaccination against both RHDV1 and RHDV2 is recommended. Failures of RHDV2 vaccine are infrequent. Lagovirus  is caused by a non‐enveloped single‐stranded positive‐sense RNA virus (RHDV) that belongs to the genus postmortem examination and histopathology (Part 1). PCR testing recognises viral RNA and identifies the RHDV serotype (RHDV1 or RHDV2). Here we present results of PCR testing and vaccination status of rabbits that died from RHD.A diagnosis of RHD can be made from the clinical history, gross postmortem examination by veterinary practitioners . From April 2017, PCR testing was conducted at a pharmaceutical laboratory (Laboratory B) and frozen liver samples were requested for PCR testing from all the rabbits that died unexpectedly, instead of just those with histopathological signs of RHD. Samples destined for Laboratory B were sent to us, where they were stored in a domestic freezer and dispatched in batches of 35‐55 samples to Laboratory B. From August 2017 until the end of the investigation, veterinarians were requested to submit two pieces of frozen liver instead of a single piece, so a reserve sample was available for cases with equivocal PCR results.et al. et al.  according to manufacturer instructions. Real‐time PCR for the detection of RHDV/RHDV1  and 107 RNA copies/mg were positive with medium‐low load of RHDV2 RNA, but not high enough to cause certain death from RHD. Additional information from clinical finding, gross postmortem examination and histopathology was necessary to make a diagnosis.“Negative”: Samples with test results below the quantification limit of 1.9 × 103 RNA copies/mg liver were negative or inconclusive for RHDV2 RNA. The quantification limit is the lowest amount that can be reliably quantified with an acceptable level of precision and trueness  cases. The remaining seven (4%) samples showed equivocal results because there was conflict between histopathology and PCR testing or between PCR results from Laboratory A and B Table .At Laboratory A, RHDV2 positive results matched histopathological findings consistent with, or suspicious of, RHD in all 16 cases that were submitted Fig. .At Laboratory B, there were histopathological changes consistent with RHD in all 112 cases categorised as PCR‐positive for RHDV2 Fig.  and in tTwenty duplicate liver samples were sent to both Laboratory A and B. Of these, 14 of 16 samples with inconclusive PCR test results from Laboratory B tested negative for RHDV2 at Laboratory A and the remaining two tested positive (Cases 1 and 2, Table In the seven cases with conflicting results, histopathological review agreed with the original report in six cases and disagreed in one (Case 2, Table i.e. the vaccine was given between 7 days and a year of death. Six of these rabbits were also vaccinated against RHDV2.The vaccination status of 125 rabbits with both histopathological diagnosis of RHD and positive RHDV2 PCR result is shown in Table RHD was diagnosed in a further seven rabbits that were vaccinated against RHDV2 alone. Vaccination against RHDV2 was often in response to the death of another rabbit in the household and nine of 13 deaths in rabbits vaccinated against RHDV2 occurred within 7 days of their demise. The vaccination certificate was missing in another case; only verbal assurance of vaccination against RHDV2 was given by the vendor at the time of purchase.et al. It has been suggested that residues of RHDV2 vaccine virus could interfere with interpretation of PCR results (Carvalho 7 RNA copies/mg liver for a positive quantitative result was supported by the results.In this investigation, all RHDV2 PCR‐positive results matched histopathological findings that were consistent with, or suspicious for, RHD Figs.  and 2, iet al. (et al. et al. The inconclusive results from Laboratory B were difficult to interpret and histopathology yielded additional information. This in agreement with Carvalho et al.  who indiet al.  showed het al. . There a. et al. . Medium‐via phagocytes or the association of inactivated viral particles with erythrocytes (Eschbaumer et al. et al. et al. Low amounts of vaccine virus are another explanation for medium‐low viral RNA, and three of 22 rabbits with inconclusive quantitative PCR results had been vaccinated against RHDV2 within 10 days of death. There are several hypotheses to explain the detection of vaccine virus in tissues. These include unintentional intravascular administration, increased permeability of the blood vessels near the inoculation site, the systemic distribution of viral RNA Negative RHDV2 PCR results from Laboratory A and Laboratory B agreed with the histopathological findings in 44 of 48 cases but disagreed in four in which there were histopathological features of RHD. Overall, there were seven cases with histopathological features of RHD but with a negative or inconclusive PCR test result from one of the laboratories Table . Histopaet al. et al. et al. et al. In this study, all 147 of 195 rabbits with a positive or inconclusive PCR test result showed viral RNA of RHDV2 serotype. All 37 rabbits that were tested for RHDV1 showed a negative result, suggesting that RHDV2 is replacing RHDV1 as the cause of RHD in the UK. This is the conclusion of several other authors (Westcott & Choudhury In this study, 13 rabbits that were vaccinated against RHDV2 died from the disease Table  but therWe conclude that RHDV2 is a common cause of sudden death in the UK pet rabbit population, especially in unvaccinated rabbits or those that are only vaccinated against RHDV1. PCR testing complements histopathology in the diagnosis of RHDV2 although false‐negative PCR test results are possible. False‐positives are unlikely. Failure of vaccination against RHDV2 appears rare in rabbits that have received inactivated RHDV2 vaccines, especially if more than 10 days has elapsed since inoculation. Vaccination against both RHDV1 and RHDV2 is still recommended for all pet rabbits.


To explore the biological function and molecular mechanism of Sp2 in hepatocellular carcinoma (HCC).Tissue microarray immunohistochemistry and western blot were used to study the expression of Sp2 in hepatocellular tissue and adjacent non‐neoplastic tissues (ANT). In HCC cell lines, the role of Sp2 was determined by in vitro experiments such as CCK8, clone formation test, Transwell assay, wound‐healing assay, and flow cytometry apoptotic analysis, and its possible mechanism was analyzed.Compared with ANT, Sp2 expression in HCC tissues was significantly up‐regulated, which was strongly associated with stage of tumor and poor prognosis of patients. TCGA database were further confirmed these results. Besides, functional studies had shown that Sp2 knockdown not only leads to a decrease in cell proliferation and an increase in cell apoptosis but also inhibits the cells' abilities of migration and invasion. Sp2 silencing could inhibit the expression of TRIB3 protein and down‐regulate the endoplasmic reticulum stress (ERS) level of HCC.Sp2 may play a part in promoting cancer by regulating TRIB3 protein, which may be a factor of prognostic and a potential new therapeutic target for HCC. We found that Sp2 expression was significantly up‐regulated in HCC tissues, which was closely related to tumor staging and poor prognosis of patients. Functional studies had shown that Sp2 knockdown not only leads to a decrease in cell proliferation and an increase in cell apoptosis, but also inhibits migration and invasion of hepatoma cells. Sp2 may play a role in promoting cancer by regulating TRIB3 protein, which may be a prognostic factor and a potential new therapeutic target for HCC. Its incidence rate ranks sixth among all malignant tumors and its mortality rate ranks second.Transcription factor Sp2 is a member of the SP protein family, which is involved in the regulation of cell proliferation, differentiation, apoptosis and other functions.22.1The clinical samples of 95 pairs of patients with HCC and corresponding ANT from the First Affiliated Hospital of Anhui Medical University from 2004 to 2010 were collected. The specific data of the studied patients including the age, gender, size of tumor, histological grade, Lymphatic metastasis, and clinical stage were recorded for further study. Tumor clinical stage was classified on the basis of TNM stage of the International Union Against Cancer (UICC). In addition, we also obtained matched four pairs HCC/ ANT liver tissue samples from surgical patients to carry out the western blot. Our scientific research program follows the relevant moral standards officially issued in the Declaration of Helsinki, and is reviewed and finally approved by the ethical standards committee of our hospital. All patients involved in the study have signed the informed consent in written form.2.2Ninety‐five pairs of tissue microarrays of HCC/ANT samples were constructed. Rabbit polyclonal anti‐human Sp2 antibody , TRIB3 antibody , GRP78 antibody  was immunohistochemically detected by two‐step method. Positive signal intensity scores were as follows: 1 point is negative (not stained); 2 point is weak (light yellow); 3 point is medium (yellow brown); 4 point is strong (brown). The positive degree was scored according to the actual proportion of positive cells: 0 point corresponds to <5%; 1 point corresponds to 5%‐25%; 2 points correspond to 26%‐50%; 3 points correspond to 51%‐75%; 4 points correspond to more than 75%. The staining index (SI) was taken as the total score obtain a range of 0‐16. In addition, the median SI was equal to 8 as the cutoff value. For the samples with SI <8 and SI ≥8, they correspond to the samples of low and high expression group, respectively.2.3The human HepG2, Huh7, and Hep3B cell line used in this study were all from the Chinese Academy of Sciences and were identified by Wuhan Procell Co., Ltd. The HepG2 cells and Hep3B cells were cultured in DMEM medium (Gibco) containing streptomycin , penicillin , and 10% fetal bovine serum . The Hub7 cells were cultured in RPMI‐1640 medium (Hyclone) containing the same substances as mentioned above. Cells were cultured in 37℃ incubator containing 5% carbon dioxide.2.4HCC cells were plated and grown in six‐well plates before transfection at approximately 50% confluence. The transfection process completely in accordance with the instructions of the manufacturer. Lipofectamine TM 2000 (Invitrogen) was used to finish this process. Small interfering RNA for the Sp2 (si‐Sp2) were obtained from the GenePharma Co.,Ltd. Small hairpin RNA plasmids for the TRIB3 gene (shTRIB3) were obtained from the Genechem Co.,Ltd. The target sequences for SP2 were 5′‐ GGAGCAUCAUCAGCCUGAATT −3′ (sense) and 5′‐ UUCAGGCUGAUGAUGCUCCTT −3′ (antisense). The primer sequences for TRIB3 were 5′‐ TGGATGACAACTTAGATACCG −3′ (sense) and 5′‐ CGGTATCTAAGTTGTCATCCA −3′ (antisense). A non‐silencing siRNA （si‐NC） sequence (target sequence 5′‐ UUCUCCGAACGUGUCACGUTT −3′(sense) and 5′‐ ACGUGACACGUUCGGAGAATT −3′ (antisense)) and a non‐silencing shRNA (shCtrl) sequence (target sequence 5′‐ TTCTCCGAACGTGTCACGT −3′) sequence were used as the negative control.2.52 concentration was 5%. After 12 hours, 24 hours, 48 hours, and 72 hours of culture. Add CCK‐8 detection reagent (BestBio) (10 μL/well), and measure the absorbance at 450 nm.Cells were seeded into 96‐well plates with a seeding volume of 100 μL (density 3 × 104 cells/mL) per well, incubation temperature was 37℃, and the CO2.6Forty‐eight hours after transfection, use the Annexin V‐FITC/PI staining method to accurately analyze apoptosis in each group. Cells were collected in the reaction tube and prepared into single cell suspension. PBS which has been precooled in advance was used to wash the above samples. After adding 5 μL of annexin V‐FITC and PI (eBiosciences) and avoided light for 15 minutes, apoptosis was detected using the Beckman CytoFLEX LX flow cytometry system (Beckman Coulter).2.7A 24‐well Transwell chamber (Corning) with gelatin‐coated polycarbonate membrane filter and Matrigel were used. Cells were collected and suspended in the medium without serum to a cell density of 5 × 104/mL. Volume of 100 μL was added to the upper cavity of the transfer well. The lower rooms added 600 μL of medium contained 20% serum . Twenty‐four hours later, the cells were dyed with crystal violet (0.1%) for 15 minutes, and then washed with PBS twice. The cells were observed and counted using ImageJ. Cells were observed by light microscope, and then randomly selected different areas (5 for each) to count.2.8The cells were collected efficiently and then inoculated into a six‐well plate(5 × 105/well). Cells were incubated and cultured to the level of 90%. The HCC cells were scraped using 200 μL tips and incubated in the serum‐free medium. The typical images have been collected under microscope at 0 hour, 12 hours, and 24 hours after scratch creation.2.9Total protein was extracted and then quantified. SDS‐PAGE was used to separate protein and transfer them to PVDF membranes (Millipore). Incubate in skim milk (5%) at room temperature for 2 hours. And then, primary antibody was incubated at 4°C, including anti‐Sp2 , anti‐TRIB3 , anti‐GRP78 , anti‐ATF6 , anti‐PERK . Incubate with the corresponding secondary antibody (with dilution of 1:10 000) for a total of 120 minutes at 37°C. Finally, the protein band signal was observed with an enhanced chemiluminescence reagent (ThermoFisher).2.10t test. Images were plotted using Graph Prism 8.0 software. SPSS software (version 20.0) was selected for statistical analysis of data. P < .05 means statistically significant.In this study, the mean ± standard deviation is used to represent the experimental data effectively. Statistical tests for data analysis included Log‐rank test, Fisher's exact test, chi‐squared test, Kaplan‐Meier analysis and paired/unpaired 33.1P = .041), lymph node metastasis (P = .032), clinical stage (P = .011), but did not relate to the histological grade, gender and age of patients , so as to evaluate its biological function in vitro. Finally, HepG2 cell lines with high expression level were selected for subsequent studies Figure ,B. The S3.3Our clinical results showed Sp2 overexpression was positively correlated not only with tumor stage but also with lymph node metastasis. Accordingly, it can be considered that SP2 should have a certain impact on tumor migration and invasion. Wound‐Healing test indicated that the healing rate of HepG2 and Huh7 cells after Sp2 knockout was significantly slowed down after scratch creation Figure A,B. At t3.4Previous studies had investigated the changes of super‐enhancers in HCC cell lines before and after ERS by Chromatin immunoprecipitation and high‐throughput sequencing (ChIP‐seq). The target genes of specific super‐enhancers were analyzed in combination with the sequencing results of HCC cells transcriptome. The results showed that some genes were differentially expressed under ERS and might be regulated by super‐enhancers. Transcription factor Sp2 might play a regulation role by combining with these ERS specific super‐enhancers. In order to further clarify the function of Sp2 in HCC and its relationship with ERS, IHC was used to detect the expression of ERS marker protein GRP78 in 95 cases of primary HCC and ANT liver tissues Figure , while W3.5TRIB3 gene is differentially expressed under ERS and non‐stress conditions. For purpose of further explore the molecular mechanism of Sp2 action, we used IHC to detect the expression of TRIB3 in 95 cases of HCC and ANT tissues Figure ,B. The a4This study confirmed the role of Sp2 in the carcinogenesis and development of HCC and explored its possible mechanism. The results of WB and IHC study confirmed that SP2 expression was conspicuously up‐regulated in tumor tissues of HCC, which was strongly linked with the progression and poor prognosis of HCC patients. In vitro studies show that Sp2 knockout can significantly inhibit the proliferation and colony formation of HCC cells, induce apoptosis, inhibit migration and invasion. Further experiments show that Sp2 silencing can down‐regulate the expression of TRIB3 and the level of ERS. These findings emphasize that Sp2, as a transcription factor, may combine with enhancers to act on TRIB3 protein, further regulate endoplasmic reticulum stress of HCC, and promote the occurrence and progression of HCC.Sp2 is one of the transcription factors of the SP family. Previous results show that SP may play a key role in the emergence, evolution, and metastasis of tumors.Previous studies have found that differentially expressed genes under endoplasmic reticulum stress may be regulated, and TRIB3 protein is among them. TRIB3 belongs to a member of the mammalian pseudokinase tribbles family, which plays a crucial part in unfolded protein response (UPR).Many kinds of research indicate that TRIB3 promotes the emergence and gradual growth of various types of cancers, such as gastric cancer,In conclusion, this study provides the first evidence that Sp2 plays a vital part in the emergence and evolution of HCC. The function may be related to the regulation of TRIB3 protein and ERS. Although the specific mechanism is not yet clear, and also need to further follow‐up experiments to clarify. However, the current study may offer new insights into HCC's pathogenesis and therapeutic targets. As mentioned above, the role of TRIB3 in malignant tumors is still controversial, and further work is needed to understand its role in ERS response pathway fully. More studies are required to elucidate the effects of Sp2 and TRIB3 expression on the occurrence, development and prognosis of HCC.The authors declare no conflict of interest.Guoping Sun initiated and designed the study, Yue Zhu and Jie Cui carried out relevant experiments, Wei Hua collected samples and provided clinical information, Jiatao Liu helped perform the analysis with constructive discussions, Yue Zhu wrote the manuscript. Wei Wei supervised the study. All authors have read and approve the final manuscript.


In the original article, there were errors in Results section, sub-section Pfs230, Seroprevalence, Paragraph 1.Furthermore, owing to the omission of the study site from Amoah et al.'s study, the figures quoted in the text on the overall number of study sites and the total number of study sites reporting seroprevalence to Pfs230 and Pfs48/45 were incorrect. The total number of study sites for Pfs230 was given as “14” instead of “15” and for Pfs48/45 given as “14” instead of “13”. Also, we inadvertently provided the total number of individual study locations (“23”) instead of the study sites—based on administrative region—(“17”) when providing a summary of the 12 studies that we included in the analysis. In addition, the citation for “Amoah et al.” was was incorrectly cited as “Acquah et al.” in the These errors have been corrected and amendments made to the relevant result sections, given below.Results section, sub-section Study Selection and Characteristics, Paragraph 1:“The 12 studies were carried out across 17 study sites, majority of which were in West Africa  with only one study site in East Africa (Tanzania) and two study sites in Southern Africa (Zimbabwe) . Ten artResults section, sub-section Pfs230, Seroprevalence, Paragraph 1:Figure 2). Significant heterogeneity was observed between the studies  therefore, a pooled prevalence estimate was not calculated.”“Ten studies from across 15 study sites in Africa analyzed immune responses to Pfs230. The range of seroprevalence estimates was quite wide, ranging from 6% reported by Stone et al. in Soumousso and Dande villages, Burkina Faso (20) to 72% reported by Amoah et al.  , and hence no pooled estimate was calculated .”“A total of 9 studies carried out over 13 study sites measured immune responses to Pfs48/45. The range of seroprevalence estimates reported was 0% from Stone et al.'s study sites in Burkina Faso (20) to 64% reported by Paul et al. from their study in the Makoni district in Zimbabwe (43). As with Pfs230, there was significant heterogeneity between the studies, No. of Studies (No. of Sites) under the variable Antigen. For Gametocyte extract read “7 (12)” instead of “3 (3)” and under the variable Recombinant protein read “3 (3)” instead of “7 (12).” For Recombinant protein read “5 (10)” instead of “6 (10).” The corrected Additionally, there were errors in The authors apologize for these errors and state that this does not change the scientific conclusions of the article in any way. The original article has been updated.


This work presents the technological development of a hydrothermal refluxing method first applied for GaPO4 single crystal growth. Crystals of 10–20 g were grown in mixtures of aqueous solutions of low- and high-vapor-pressure acids (H3PO4/HCl) at 180–240 °C (10–20 bars). The principal feature of the refluxing method is a spatial separation of crystal growth and nutrient dissolution zones. This leads to a constant mass transportation of the dissolved nutrient, even for materials with retrograde solubility. Mass transport is carried out by dissolution of GaPO4 nutrient in a dropping flow of condensed low-vapor-pressure solvent. This method allows an exact saturation at temperature of equilibrium and avoids spontaneous crystallization as well loss of seeds. Grown crystals have a moderate OH− content and reasonable structural uniformity. Moreover, the hydrothermal refluxing method allows a fine defining of GaPO4 concentration in aqueous solutions of H3PO4, H2SO4, HCl and their mixtures at set T–P parameters . The proposed method is relatively simple to use, highly reproducible for crystal growth of GaPO4 and probably could applied to other compounds with retrograde solubility.Bulk GaPO The development of modern radio communication devices and different kinds of electronic measurement technologies puts increasing demands on the requirements of piezoelectric inventory materials. Generally, this means the values of the electromechanical constants and its temperature dependencies. The most widely used quartz crystals have an α–β phase transformation at 573 °C . Thus, a2. This compound is stable in the α-quartz structural phase in a temperature range of 1033 to 1080 °C. It has a metastable α-quartz structure state at temperatures up to 180 °C for crystals grown by hydrothermal method [The best piezoelectric coefficients of α-quartz-like structure materials have been found for α-GeOl method ,5 and mul method . Currentl method .4. The temperature of α-quartz structural stability is nearly 930 °C [2, but the quality and volume of crystals crystallized by the proposed refluxing hydrothermal method look both more suitable and reproducible than GaPO4 single crystals [Another known high-temperature α-quartz-like structure material is GaPOy 930 °C ,9. Its pcrystals ,11.4 crystal growth [4 solubility in aqueous solutions, accordingly. A possibility of GaPO4 crystallization under high-temperature conditions in molybdates fluxes has also been confirmed [4 crystals, but with a series of restrictions. The crystals grown at temperatures up to 250 °C in aqueous H3PO4 or H3PO4/H2SO4 solutions have a considerable OH− content. Crystals grown in aqueous H2SO4 solution have a low OH− content, but growth rates of {0001} faces equal to zero that leads to formation of plate-like crystals. Additionally, the use of hydrothermal methods up to 250 °C is associated with a number of technique-engineering complexities such as a preliminary saturation of crystal growth solutions and inconstant temperature of equilibrium. Crystal growth by the direct temperature gradient hydrothermal method at 320 °C or higher needs very complex equipment (Pt lined high-pressure autoclaves with an inert gas-injection system) [4 crystals grown from fluxes are very small (millimeters size) and contains impurities coming from the flux [The existing methods of GaPOl growth ,19,20,21onfirmed . All the system) ,13,17. Tthe flux ,27,28.4 solubility [4 solubility in aqueous acid solutions  in the temperature range from 200 to 260 °C . The papers [− content in GaPO4 crystals was fixed with the following parameters: temperature higher than 220 °C, solvent of aqueous H3PO4, H2SO4 or a mixture of these solutions. Unfortunately, growing bulk GaPO4 crystals by known methods at such temperatures is difficult or impossible. The principal problem facing GaPO4 crystal growth at temperatures up to 230 °C is the low convection of the solution, which obstructs mass transportation. The practically constant solubility of GaPO4 in acids at temperatures of 200–260 °C  in the refluxing method allowed us to use a technique of autoclave reversing to stop the dissolution at a set temperature. This enabled us to keep the nutrient into the initial solution during the run and to stop dissolution cycle at a set temperature by reversing the autoclave. Two values of GaPO4 concentration were found in the mixing 9 M H3PO4/6 M HCl (vol. proportion 95/5%) at temperatures 160–240 °C: with and without crystallization at the same T–P conditions  showed a large difference between the values without and with crystallization  were determined. The main results of the runs are presented in More than 20 runs with durations up to 35 days of GaPOThe face of basal pinacoid c{0001} is flat at temperature gradients up to 15 °C, it is represented by layer a. At graz{011¯1} a. GrowthThe internal structure of basal pinacoid growth sectors was more homogenous in the first case under conditions of low temperature gradients b. At groCrystal growth on trigonal prism faces was characterized by high velocities, more than 1 mm/day. However, the crystals grown on x{sm faces a,b.4 crystals.Crystal growth of all trigonal rhombohedron and trigonal dipyramid faces was presented by layer or dislocation mechanism. Stairs a and low4 crystals by the refluxing method in aqueous solution of H3PO4–HCl at temperatures of 200–240 °C and pressures up to 30 bar showed a strong influence of temperature gradient to the crystal habit. However, the growth rates sequence of different faces of the crystals was constant. The following sequence of growth rates took place for GaPO4 crystals obtained by the refluxing method:Growing of GaPOx{4 crystals grown from aqueous solutions of H2SO4 by the temperature gradient method at temperatures of 170–240 °C and pressures of 10–30 bar.This growth rate sequence was in a good correlation with similar ones of GaPO− content on electromechanical properties of piezoelectric crystals is well known [−). This could be in different forms: independent OH− bonds—in unstructural impurities and OH− bonds in substitution to cations—as interstitial defects. Regardless, the resulting OH− bond is highly polar and as a consequence this dipole absorbs the infrared radiation.The influence of OHll known ,33. It i−1 of such absorption are the vibrations of OH− bonds of GaPO4 crystals [−1.It was found that the wave numbers near to 3400, 3290 and 3167 cmcrystals ,36. For crystals ,36 we us− content is a high structural homogeneity of crystals, absence of cracks and gas–liquid inclusions (mother solution impurity-free). As grown by the refluxing method, GaPO4 crystals satisfied this condition. The refluxing method applied to the growth of GaPO4 crystals showed that the solvents and T–P conditions similar to hydrothermal slow temperature gradient method allowed obtaining GaPO4 single crystals characterized by relatively low OH− content (α) value ; seeds and a nutrient material are placed in two principally different zones of the autoclave; seeds are found in a solution (in the bottom of the autoclave), but a nutrient is above the solution. Mass transport is carried out by evaporation of the solvent, condensation in the “cold” upper part of the autoclave (refrigerator) followed by diffusion into the nutrient basket, dissolution of the nutrient material and then, dropping down into the solution in the bottom part of the autoclave. As a result of the multiple recirculation (refluxing) of the solvent, the initial solution is gradually saturated and maintains this supersaturation for the full crystal growth cycle.2 crystal growth and the base of previous studies on GaPO4 crystal growth have driven us to experimentally test the refluxing method to grow GaPO4 crystals.The practical application of the refluxing method for α-GeO4 by the refluxing method. A wide range of temperatures and solvents considered for the experiments led us to use platinum (Pt), tantalum (Ta) and polytetrafluoroethylene (PTFE) liners for the high pressure and temperature steel autoclaves. Precise temperature control was realized with the help of an internally inserted temperature control probe (thermocouple Type K). All autoclaves included a PTFE nutrient basket  were designed and approved for growing of GaPOt basket . Using t4 crystallization, in order to obtain the lowest OH− content in the crystals, the most suitable solvents are aqueous H3PO4, H2SO4 and HCl solutions or their mixtures and temperatures exceeding 200 °C. These temperatures correspond to retrograde or constant solubility of GaPO4  solution must be already saturated with GaPO4 at the precise concentration of GaPO4 corresponding to the equilibrium temperature to avoid spontaneous crystallization or dissolution of the seed.This is why we cannot use a unsaturated solution for starting crystal growth of GaPO2 crystal growth concerning conditions of GaPO4 crystal growth has allowed carrying out the saturation of initial solution and further growth of GaPO4 crystals in the same run cycle. This does not interrupt the course of the run, and as a consequence, neither spontaneous crystals nor losing of seed were observed. Technically, the following steps are in the first part of run: the autoclave is charged by solvent, nutrient and seeds are installed with the seeds on the top and nutrient below. The temperature is 10–30 °C higher in the top of autoclave  acids at temperatures of 170–260 °C and pressures up to 50 bar. We used the same solutions as mineralizers in our experiments. However, the vapor pressure of such acids that excludes a formation of condensate in sufficient quantities at temperatures up to 250 °C is low  to the initial solution allowed increasing nutrient dissolution under vapor/condensate recirculation conditions.As reported by ,18,29,31C is low a,b. Cons4 from the nutrient to the mother solution  acids as the mineralizer and a low-vapor-pressure acid as the conveyor of dissolved GaPOtion see .4 crystals grown by slow temperature rise method in aqueous solution of 9 M H3PO4 at temperatures of 150–165 °C and pressure up to 5 bar were used as seeds. Different crystallographic orientations c{0001}, s{Plates (with sizes up to 45 × 15 × 1 mm) cut from GaPO4 crystals were studied on the surface and in polished cuts by optical microscopyMBS-9 (Russia), ADF STD16 (China), Nikon Eclipse LV100Pol (Japan). The IR spectroscopy of the crystals or polished plates was performed on PerkinElmer 820 spectrometer (USA). The OH− content in crystals were estimate by α value, which was calculated using the formula α = (1/l)*(Log(T3800/T3400))-0,078, where: l—thickness of sample in cm, T3800 and T3400—intensity of absorption at wave numbers of 3800 and 3400 cm−1, 0.078—absorption of the intrinsic lattice vibrations of GaPO4 at 3400 cm−1 [The morphology and internal structure of the obtained GaPOogT3800/T00)-0,078400 cm−1 . The pre4 crystals grown by the hydrothermal refluxing method at temperatures close to 240 °C and pressures up to 10–20 bar in aqueous solutions of the H3PO4–HCl mixtures have a relatively low OH− content and considerably high structural uniformity in comparison to crystals grown by other low temperature (< 250 °C) hydrothermal methods.The GaPO4 crystals growth has shown a very high reproducibility of the results.Hydrothermal refluxing method of GaPO4 crystal growth gave a new technique of measurement of GaPO4 concentration in solution at set parameters. The presented technique allows increasing the accuracy of GaPO4 concentration definition in aqueous solutions of H3PO4, H2SO4, HCl and their mixtures at least up to 250 °C and pressures of 10–30 bar.Improvement of the hydrothermal refluxing method concerning application to GaPO


Successive transitions toward unconventional charge density wave states are shown by resistivity measurements and thermal X-ray diffraction. m = 8 member of the low-dimensional monophosphate tungsten bronzes (PO2)4(WO3)m2 family were grown by chemical vapour transport technique and the high crystalline quality obtained allowed a reinvestigation of the physical and structural properties. Resistivity measurements revealed three anomalies at TC1 = 258 K, TC2 = 245 K and TC3 = 140 K, never observed until now. Parallel X-ray diffraction investigations showed a specific signature associated with three structural transitions, i.e. the appearance of different sets of satellite reflections below TC1, TC2 and TC3. Several harmonics of intense satellite reflections were observed, reflecting the non-sinusoidal nature of the structural modulations and a strong electron–phonon coupling in the material. These transitions could be associated with the formation of three successive unconventional charge density wave states.Single crystals of the  The PO4 slices provide electrons to the WO3 slabs; these slabs support the conductive character of the MPTBp.Monophosphate tungsten bronzes with pentagonal tunnels (MPTBp) were discovered several decades ago during the quest for low-dimensionality conductors  exhibits a 1D structural character with the formation of WO3 chains, the intermediate terms are quasi-2D, the largest terms (m ≥ 10) are 2D and for m = ∞ (WO3) the system becomes 3D. Moreover, although the number of 5d electrons per unit cell is constant and equal to 4 for the members of the MPTBp, the average conduction electron density per W atoms decreases with m and therefore with the dimensionality. One strong interest of MPTBs arises from this possibility to investigate, within one system, the impact of dimensionality on electronic instabilities such as superconductivity, spin-density waves and charge density waves (CDWs), essentially associated with 1D and 2D conductors , 0, 0], q1 =  and q2 = . The observation of the three sets of broad satellite reflections is in agreement with the setup of short-range-order structural modulations. Additionally, at all temperatures, diffuse lines perpendicular to the a ± b directions are reported; the authors claim these diffuse lines are a signature of quasi-1D CDW instabilities already observed in the lower m members. The analysis of the resistivity versus T, from 3 to 600 K, for m = 8, reported by Dumas et al.  CDW  plane, were obtained by chemical vapour transport technique described by Roussel et al. , crystals exhibiting diffuse scattering (DS) located in the  planes and crystals without any additional diffraction features (NO); SR crystals are considered to present long-range-order states while DS crystals exhibit only short-range-order states and NO crystals show no additional order. Samples from each of these different categories   using sputtering. Then one gold wire (25 µm in diameter) was glued onto each pad with epoxy silver paste (Dupont 6828). For technical reasons, we used a four probe-like geometry, where current non-uniformity can occur along the thickness in an anisotropic conductor and the measured resistivity can not be directly associated to ρab. Note however that because of the reduced thickness of the sample compared with the square root of the surface area (a factor of 3), the difference between the effective thickness probed by the current and the real thickness of the sample should be reduced. None of the measured resistivity versus temperature [R(T)] curves show signs of insulating/semiconducting components which would indicate c-axis resistivity components, so we can assume that the reported resistivity behaviour is related to the ab conducting plane.Samples with large dimensions were chosen for the resistivity measurements. However, the preliminary XRD experiments were performed at room temperature; only single crystals exhibiting sharp Bragg peaks, ab) crystallographic plane. Three different behaviours can be identified for the three categories of samples; they are reported in Fig. 2m = 8. Future studies will be conducted on samples of this category.Resistivity measurements were performed using a physical property measurement system (PPMS) Quantum Design. Resistance data were obtained during cooling of the sample in the 300–2 K temperature range using an alternating 5 mA current at 7 Hz injected along the  a Synergy-S Rigaku 4-circles diffractometer equipped with a Hypix 6000 hybrid photon-counting detector and Mo PhotonJet-S microfocus X-ray sources. An Oxford cryostream 700 system was used to cool down the crystal with a ramp of 5 K min−1. A thermalization time of 5 min was applied before each measurement. The collection strategy was performed with APEX2  an automatic 4-circles Bruker–Nonius diffractometer equipped with an 3.3.1.4W16O56 sample of category SR (approximate size of 550 × 250 × 150 µm) are shown in Fig. 3et al. . The extensive study of the first discontinuity shows an 8 K thermal hysteresis and an intermediate step at 255 K (258 K), when the crystal is cooled (heated). The low-temperature anomaly is characterized by a large (35 K) and asymmetric hysteresis. These observations are then in favour of the final occurrence in the temperature dependence of the electrical resistivity of three different anomalies: the first one is observed at 255 K, the second one at 252 K  220 K ≤ T ≤ 350 K to follow the first anomaly of Fig. 3T ≤ 145 K for the second anomaly. The same region of the reciprocal space has been measured for these two temperature intervals; (hkl)* planes were reconstructed using CrysAlisPro software  Å, b = 6.5534 (4) Å, c = 29.700 (4) Å, α = β = γ = 90° and is in perfect agreement with the structure already published in the work by Labbé et al.  for 247 K ≤ TC1 ≤ 258 K, state (2) for 142 K ≤ TC2 ≤ 245 K and state (3) for TC3 ≤ 140 KThe previous screening then identifies four different structural states: state (0) for 260 K ≤ TA with the double resistivity steps while state (3) corresponds to the anomaly at TB.These different states can be attributed to the anomalies shown in the resistivity curves Fig. 3. States m members, successive transitions were already observed but each new structural state was characterized by the occurrence on the reciprocal space of an additional set of satellite reflections. Surprisingly, for the m = 8 member, after each transition the satellite reflections related to the previous state abruptly vanished in favour of the installation of a new set of satellite reflections. This specific behaviour could be attributed to a competition regime between different modulated states. Such phenomena were never observed in the MPTB family.For the low-3.2.2.4W16O56.The analysis of the different states shown above is important to obtain clues on the nature of the transitions. Now, let us determine the main characteristics of the different states observed for Pa = 5.2821 (2) Å, b = 6.5341 (3) Å, c = 29.630 (2) Å. A structural refinement using the space group P212121 confirms that the crystal is in its fundamental orthorhombic state as already described by Labbé et al. (1986In state (0), which is the fundamental state, all the reflections are indexed using the orthorhombic cell given by  al. 1986.q1 = 0.446 (5) a*; the deviation from the rational value (4/9) of the component along a* is not significant and then the wavevector is considered to be in agreement with the setup of a commensurate modulated structure. The clear absence of a component along c* for the modulation vector of state (1) is in agreement with a distinct structural phase and not the coexistence of state (0) and state (2) .In state (1)  Å, b = 6.5591 (8) Å, c = 29.74 (4) Å and α = 90°, β = 90.221 (13)°, γ = 90° is compatible with a monoclinic symmetry with b as the binary axis. The indexing of the satellite reflections is more complex. They require the introduction of two wavevectors q2 and q2′ drawn in Fig. 6c and can be considered as characteristic of two twin domains of a non-merohedral twinning. This assumption of twinning can be confirmed by the observation in Fig. 6a, b, c) and  related by the twofold axis parallel to c are characterized by q2 = 4/9a* − 4/9c* and q2′ = 4/9a′* − 4/9c′* respectively; they have only rational components and are characteristic of a commensurate modulated structure. Each of these wavevectors is in agreement with the monoclinic symmetry (planar case).In state (2)  → state (2) is accompanied by a symmetry breaking from orthorhombic to monoclinic symmetry.a = 5.3010 (2) Å, b = 6.5656 (2) Å, c = 29.761 (1) Å with α = β = 90° and γ = 90.25 (1)°. The metric is compatible with a monoclinic symmetry with c as the binary axis. An accurate observation of the diffracted intensities in the (h0l)* plane  and (b) sets in the scheme of Fig. 7a) with positions defined by the vector 1/2a* − 1/2c* are intense and sharp. Reflections of set (b) are relatively weak and split along the c* direction; they can be indexed using two vectors related by a twofold axis parallel to a (1/6a* − 1/6c* and 1/6a* + 1/6c*); first- and second-order satellite reflections are identified. The observation of the weak but significant deviation of the angle γ from 90° induces a lowering of symmetry from Laue class of state (0) (mmm) to Laue class of state (3) (112/m) associated with the loss of twofold axes parallel to a and b. Following this observation and considering the splitting observed for reflections of the (b) set, i.e. the existence of both vectors 1/6a* − 1/6c* and 1/6a* + 1/6c*, it seems natural to consider the existence of two twin domains of a non-merohedral twinning related by a twofold axis parallel to a.In state (3)  set. (I) The reflections of the (a) set define a supercell  and can be considered as a set of main reflections. The reflections of the (b) set are then satellites of all the reflections of the supercell and are indexed with the wavevectors qs3 = 1/3s*a − 1/3s*c and qs′3 = 1/3s*a + 1/3s*c. This idea is supported by the observation of the equivalent distribution of the intensities of the reflections of the (b) set around the main reflections of the  cell and of the reflections of the (a) set [see for instance, areas (i) and (ii) in Fig. 7a) set are third-order satellites of the satellite reflections defined by the wavevectors q3 = 1/6a* − 1/6c* and q′3 = 1/6a* + 1/6c* already used to define reflections of the (b) set. As shown in Fig. 7b) set, split over two positions, exhibit a one half-intensity in comparison with the intensity expected for a single domain crystal. On the contrary, the reflections of the (a) set corresponding to the summation of the intensity of {ha*, kb*, lc*, 3 × q′3}, {ha*, kb*, (l + 1)c*, 3 × q3}, {(h + 1)a*, kb*, lc*,−3 × q3} and {(h + 1)a*, kb*, (l + 1)c*,−3 × q′3} perfectly overlap.Two hypotheses can be proposed to index the diffraction pattern observed in state (3), they are related to the interpretation given for the reflections of the  shows a distortion with a metric compatible with a monoclinic symmetry with c as the unique axis. But the observation of the modulation vector (q3 or qs3) is fully in disagreement with the monoclinic symmetry for a (3 + 1)d modulated structure and this then implies a lowering of symmetry toward triclinic symmetry. In the assumption of a (3 + 1)d modulated structure the transition state (2) → state (3) would be accompanied by a symmetry breaking from monoclinic to triclinic symmetry; two additional twin domains are then expected. However, the possibility of a (3 + 2)d modulated structure with monoclinic symmetry cannot be fully rejected. In that case, q3 and q′3 (or qs3 and qs′3) would be related to the existence to a twofold axis parallel to c and not to the presence of twinning expected in the case of a first-order phase transition associated with such weak monoclinic distortion.Whatever the interpretation chosen, state (3) is characterized by a commensurate modulated structure. These two hypotheses will have to be tested during a structural resolution but the report of a wavevector 1/2uget 1996 for m = et al., 2009We can focus on the fact that the cell volume decreases linearly with the temperature when the symmetry of the system is conserved, and then a negative compressibility is observed at lower temperature with a variation of +1.09% when the system passes from state (1) to state (2) and a variation of +0.19% passing from state (2) to state (3). This can be explained by a rearrangement/rotation of the polyhedra constituting the crystal, increasing the symmetry of the structure when the temperature is increased , characterized by a 35 K large asymmetric thermal hysteresis  modulated states with incommensurate wavevectors were observed, marking this material in the pretransitional regime of CDW condensation. There were no clear resistive anomalies, but a prominent weak localization component was reported. These puzzling results were tentatively attributed to the proximity in transition temperature of two different CDWs in competition and hence lacking correlation at long range. Here, we showed using thermal diffraction that the m = 8 MTBP can display LRO modulated states, and no evidence of weak localization phenomena is observed in the resistivity. It gives an experimental support for the proposed role of uncorrelated Peierls-like lattice distortions as an original source of disorder for weak localization  can be viewed as due to the locking at 1/2 of the 4/9 components of the q2 wavevector shown for state (2). This locking to 1/2a* − 1/2c*, whose wavevector is also observed for m = 14 and 12, should be stabilized by the local establishment of the anti-ferroelectric (AFE) order of WO3 corresponding to the limit m infinite (Ottolenghi & Pouget, 1996m = 10 member at room temperature (Roussel et al., 2000m = 8 member would outline the specific position of this MPTBp at the border in between the low- and high-m members.The three LRO states have commensurate modulations and can be associated to three sharp and hysteretic resistivity changes. Then, Pm = 8 crystals with apparent similar crystalline quality could present no modulation, SRO modulation or LRO modulation, with direct and major consequences to the electronic properties. We do not have a clear understanding of the genuine reason behind this contrasting behaviour that would deserve more detailed investigation such as microstructural probes, but we hope that it will help gain strong insights into the understanding of CDW stabilization.Finally, it is worth noting that