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The Chinese mitten crab, Eriocheir sinensis, is an important economic aquatic product in China. Oxygen is essential for the crab, hypoxia is a natural phenomenon common in the process of aquaculture and will bring a harmful impact on the growth, development and disease outbreak of crab. To understand the effect of hypoxia on the crab, the proteome changes of E. sinensis hemocytes in the hypoxia (1.5 ± 0.5 mg/L of DO) and the normoxia groups (6.0 ± 0.5 mg/L of DO) were obtained using iTraq labeling and affinity enrichment followed by high-resolution LC-MS/MS analysis. In total, 664 differentially expressed proteins were reliably quantified (567 up-regulated and 97 down-regulated) using 1.2-fold change in expression as a physiologically significant benchmark. GO annotation, KEGG annotation, etc. were used to analysis these significantly different expression proteins. Many pathways or biological process were identified in the process of E. sinensis hemocytes response hypoxia, such as tricarboxylic acid (TCA) cycle, cell apoptosis, VEGFR/MAPK pathway, prophenoloxidase system (proPO system), phagocytosis, and so on. Ten selected genes from these different expression proteins were verified by qRT-PCR analysis. Finally, the activity of several major antioxidant enzymes (phenoloxidase (PO), superoxide dismutase (SOD), catalase (CAT) and malondialdehyde (MDA)) were analysis, the results showed that hypoxia stress significantly increased these enzymes activity. These study could serve as a basis to understand the relationship between E. sinensis hemocytes and hypoxia stress, and also provide reference to study hypoxia stress in other crustaceans.

Nuclear magnetic resonance (NMR) is an effective method used for measuring and predicting the properties of methane hydrate (MH)-bearing sediments. In this work we present the results of MH-related interface evolution during the MH dissociation process obtained by X-ray computed tomography (CT) imaging technique. Some implications of interface evolution for the NMR-based property predictions are analysed based on the experimental measurements. The results show that the areas of MH surface and MH-brine interface decrease slowly in the early stage of dissociation, but turns to decrease rapidly in the later stage. A conceptual model for determining the NMR transverse surface relaxivity (ρ2) in the hydrate-bearing sediment is proposed by considering these changes of MH-related interface. Predictions based on this model show that the NMR transverse surface relaxivity and effective permeability are both influenced by the influencing weight and surface area proportions of the MH-brine surface and sand-brine surface.

Ginsenosides have been studied extensively in recent years due to their therapeutic effects in cardiovascular diseases. While most studies examined the different ginsenosides individually, few studies compare the therapeutic effects among the different types. This study examined how effective protopanaxadiol, protopanaxatriol ginsenosides Rh2, Rg3, Rh1, and Rg2 of the ginsenoside family are in protecting H9c2 cardiomyocytes from damage caused by hypoxia/reoxygenation. In the current study, a model of myocardial ischemia and reperfusion was induced in H9c2 cardiomyocytes by oxygen deprivation via a hypoxia chamber followed by reoxygenation. Our data show that structures similar to that of protopanaxadiol, which lacked the hydroxide group at C6, were more effective in lowering apoptosis than structures similar to protopanaxatriol with a hydroxide group at C6. As the compounds increased in size and complexity, the cardioprotective effects diminished. In addition, the S enantiomer proved to be more effective in cardioprotection than the R enantiomer. Furthermore, the immunoblotting analysis demonstrated that ginsenosides activate AMPK but suppress JNK signaling pathways during hypoxia/reoxygenation. Thus, ginsenosides treatment attenuated hypoxia/reoxygenation-induced apoptosis via modulating cardioprotective AMPK and inflammation-related JNK signaling pathways.

Using two trans-dicyanidechromium(III) precursors K[Cr(bpdmb)(CN)2] (bpdmb2− = 1,2-bis(pyridine-2-carboxamido)-4,5-dimethyl-benzenate), K[Cr(bpClb)-(CN)2] (bpClb2− = 1,2-bis(pyridine-2-carboxamido)-4-chloro-benzenate) and one Cu(II) complex of a 14-membered macrocycle as ancillary organic ligand as assembling segments, two one-dimensional cyanide-bridged CrIII–CuII complexes {{[Cu(cyclam)][Cr(bpdmb)(CN)2]}ClO4} n ·nCH3OH·nH2O (1) and {{[Cu(cyclam)][Cr(bpClb)(CN)2]}ClO4} n ·nCH3OH (2) (cyclam = 1,4,8,11-tetraazacyclotetradecane) have been synthesized and characterized by elemental analysis, IR spectroscopy and X-ray structure determination. Single X-ray diffraction analysis shows that their similar one-dimensional cationic single-chain structures consist of alternating units of [Cu(cyclam)]2+ and [Cr(bpdmb)(CN)2]−/[Cr(bpClb)(CN)2]− with free ClO4 − as balancing anions. Investigations of the temperature dependences of magnetic susceptibility and the field-dependent magnetization reveal that both complexes have overall ferromagnetic coupling between the neighboring Cr(III) and Cu(II) centers through the bridging cyanide groups.

Spiroplasma eriocheiris is a novel pathogen similar to the Spiroplasma mirum and also had an ability to infect the newborn mice and caused cataract. Our study was designed to study how S. eriocheiris infects mouse 3T6-Swiss albino cells and to elucidate the cellular molecular pathogenesis of Spiroplasma. FCM analysis and MTT analysis clearly shown that S. eriocheiris could induce 3T6 cell apoptosis and cause cell viability decreased seriously. Immunofluorescence experiments and TEM analysis shown that S. eriocheiris can invade 3T6 cells and form typical inclusion bodies and exhibit vacuolization in vitro. S. eriocheiris-oxytetracycline protection assay show that the infective bacteria already were detected at 1h post infection, and sharply increased at 12h after the bacteria infection. To further study the infection mechanism of S. eriocheiris, global mRNA and microRNA (miRNA) expression profiling were analyzed after the cells infected with the bacteria. A total of 619 non-redundant annotated transcripts (183 up-regulated and 436 down-regulated) and 22 miRNAs (8 up-regulated and 14 down-regulated) were differential expression after 6h S. eriocheiris infection compared to control group. Integrated analysis shown that homologous genes from differential expression miRNA targets and the differential expression genes of the mRNA microarray were major focused on two important pathways focal adhesion and MAPK signaling pathway. To validate the results of microarray, eight focal adhesion (β-Catenin, Parvin, Grb2 and ERK) and MAPK signaling pathway (FGFR, Grb2, ERK, MKK3, p38 and JNK) genes and the housekeeping gene GAPDH were assayed by qPCR and Western blot to confirm the results. Eight miRNAs (miR-143-3p, miR-214-5p, miR-322-3p, miR-328-5p, miR-351-5p, miR-466h-5p, miR-503-5p and miR-30c-1-3p) and the housekeeping gene U6 miRNA were assayed by qPCR to confirm the results of microarray. All the results help us better understand the infection mechanism of S. eriocheiris.

Spiroplasma eriocheiris, which causes tremor disease in Chinese mitten crab Eriocheir sinensis, has led to huge economic losses in aquaculture. Immunoproteomics, a new scientific technique combining proteomics and immunological analytical methods, provided the direction of our research on S. eriocheiris. The aim of our study was to identify the proteome, antigen proteins and antigen membrane proteins of S. eriocheiris. A total of 780 S. eriocheiris proteins were identified by the LC-MS/MS technique. Based on immunoproteomics, 51 proteins and 7 proteins in S. eriocheiris were identified by anti-S. eriocheiris serum and negative serum respectively (six proteins in common). Thus, 45 antigenic proteins in S. eriocheiris were identified; among them, molecular chaperone DnaK, glyceraldehyde-3-phosphate dehydrogenase (GAPDH), ATP synthase subunit beta and enolase can be considered as immunogenic proteins. Similarly, 32 membrane proteins and 6 membrane proteins were identified by anti-S. eriocheiris serum and negative serum respectively (two proteins in common). Thus, 30 antigenic membrane proteins in S. eriocheiris were identified; three of them have been reported as surface proteins including pyruvate kinase, enolase and GAPDH. All of these proteins may play key roles in the pathogeny and can be used in the future for diagnoses and prevention. Significance and Impact of the Study Spiroplasma eriocheiris is a novel pathogen causing the tremor disease in Chinese mitten crab Eriocheir sinensis. This is the first time LC-MS/MS was used to identify the proteome, antigen protein and antigen membrane protein of S. eriocheiris. The results can certainly provide valuable information towards the identification of virulent proteins or diagnosis of pathogenic mechanisms.

The Chinese mitten crab Eriocheir sinensis is an important economic crustacean that has been exposed to various diseases. Spiroplasma eriocheiris , isolated from tremor-diseased E. sinensis , was first identified as a lethal pathogen of freshwater crustaceans. To understand the pathogenesis of S. eriocheiris to E. sinensis , the transcriptomic profiles of haemocytes in the experimental and control groups at 1 d and 7 d post-injection were obtained using Illumina HiSeq 2500. These results showed that 40,358,724, 44,462,112, 45,516,576 and 37,713,728 paired-end clean reads were obtained from the cDNA libraries of DZ1 (the control group at 1 d), DZ7 (the control group at 7 d), SY1 (the experimental group at 1 d) and SY7 (the experimental group at 7 d), respectively. In total, 106,641 unique transcript fragments (unigenes) were assembled, with an average length of 710 bp. On the first day of stimulation, 33,084 up-regulated transcripts and 19,208 down-regulated transcripts were found in the experimental group compared with those in the control group. On the seventh day of stimulation, 40,198 up-regulated transcripts and 12,032 down-regulated transcripts were found in the experimental group compared with those in the control group. Some canonical immune-related pathways were identified via KEGG pathway analysis, including complement and coagulation cascades, the VEGF signalling pathway, the Wnt signalling pathway, natural killer cell-mediated cytotoxicity, the MAPK signalling pathway, neuroactive ligand-receptor interactions, and the Lysosome pathway. We found important immune-related genes (GNPTAB, MASP2, F7, F5, NFATC, TRAF6, MAP3K5, and TRa) in the KEGG pathway, and those genes were confirmed by qRT-PCR analysis. In addition, the significantly enriched neuroactive ligand-receptor interaction pathway was associated with intense paroxysmal tremors of infected crabs. Our results provide valuable information for the further analysis of the mechanisms of E. sinensis defence against S. eriocheiris invasion.

The characteristics of the hydrate-bearing layer are important parameters for gas hydrate exploration and exploitation, which can be provided by laboratory analysis. We have carried out a systematic analysis of modern instruments, including the laser grain size analyzer, X-ray computed tomography, scanning electron microscopy, X-ray diffraction (XRD), Raman spectroscopy, gas chromatography, and isotope mass spectrometry, on the hydrate-bearing sediment samples recovered from the Shenhu area in the South China Sea in 2016. We focused on the structure, hydration number, and gas composition of the gas hydrate samples. We also evaluated the effects of sediments on the occurrence and distribution of gas hydrate. Our results showed that the sediments are much finer than those recovered from the Shenhu area in 2007. Some samples are found to contain calcareous microfossils and foraminifera, which are beneficial for dispersed gas hydrate formation. Whereas the only visible hydrate sample (FC4) has not found any bioclast in the sediments. Based on the Raman data and the XRD analysis, the gas hydrates demonstrate typical structure I (sI) hydrates, with cage occupancies of methane molecules higher than 99.3% in large cages and 81.5%–91.4% in small cages, respectively. The crystal lattice parameter is 11.89 Å with the hydration number being approximately 6.0. Methane is obviously the dominant component, ranging from 97.6% to 99.95% in these samples. Comprehensive study of carbon and hydrogen isotopes suggests that the hydrate-bound gases are from biogenic and thermogenic gases in the study area.

Carbon Nitride is considered as a promising photocatalyst material because of its unique properties such as environment-friendly, suitable band gap and high stability. However, the photocatalytic activity of pristine g-C3N4 was greatly hindered by the recombination of photo-generated electron-hole pairs. In this work, we provide an alternative method to address this problem by the construction of g-C3N4 isotype heterojunction (CNH−T/CNH−U) structure, which was successfully synthesized by a facile protonation assisted hydrothermal method. Under the irradiation of visible light (λ > 420 nm), the CNH−T/CNH−U isotype heterojunction photocatalyst displays much higher photodegradation activity of organic dyes degradation and H2-production activity than the pure CNH−T or CNH−U sample. This remarkably improved photocatalytic performance is attributed to the successful construction of CNH−T/CNH−U isotype heterojunction associated by protonation, which results in larger surface area and the more efficient separation of photo-generated electron-hole pairs, further investigated by electron paramagnetic resonance, photoluminescence, photocurrent measurement, and a series of active species trapping experiments.

Ocotillol-type saponins are one kind of tetracyclic triterpenoids, sharing a tetrahydrofuran ring. Natural ocotillol-type saponins have been discovered in Panax quinquefolius L., Panax japonicus, Hana mina, and Vietnamese ginseng. In recent years, the semisynthesis of 20(S/R)-ocotillol-type saponins has been reported. The biological activities of ocotillol-type saponins include neuroprotective effect, antimyocardial ischemia, antiinflammatory, antibacterial, and antitumor activities. Owing to their chemical structure, pharmacological actions, and the stereoselective activity on antimyocardial ischemia, ocotillol-type saponins are subjected to extensive consideration. In this review, we sum up the discovery, semisynthesis, biological activities, and metabolism of ocotillol-type saponins.

In the current study, a mediator-free solid-state BiVO4/pyridine-doped g-C3N4 nano-Z-scheme photocatalytic system (BDCN) with superior visible-light absorption and optimized photocatalytic activity was constructed via an in situ hydrothermal method for the first time. The pyridine-doped g-C3N4 (DCN) nanosheets show strong absorbance in the visible-light region by pyridine doping, and the BiVO4 (∼10 nm) nanoparticles are successfully in situ grown on the surface of DCN nanosheets by the controlled hydrothermal method. Under the irradiation of visible light (λ > 420 nm), the BiVO4/DCN nanocomposite photocatalysts efficiently degrade phenol and methyl orange (MO) and display much higher photocatalytic activity than the individual DCN, bulk BiVO4, or the simple physical mixture of DCN and BiVO4. The greatly improved photocatalytic ability is attributed to the construction of the direct Z-scheme system in the BiVO4/DCN nanocomposite free from any mediator, which leads to enhanced separation of photogenerated electron–hole pairs, as confirmed by the photocurrent analysis. The possible Z-scheme mechanism of the BiVO4/DCN nanocomposite photocatalyst was investigated by transient time-resolved luminescence decay spectrum, active species trapping experiments, electron paramagnetic resonance (EPR) technology, and hydrogen evolution test.

Four ocotillol-type (20R)-protopanaxadiol metabolites, (20R,24S)-20,24-epoxy-12β,25-dihydroxdammaran-3-one (M3), and (20R,24R)-20,24-epoxy-12β,25-dihydroxydammarane-3-one (M4), (20R,24S)-20,24-epoxy-3β,25-dihydroxydammaran-12-one (M9) and (20R,24R)-20,24-epoxy-3β,25-dihydroxydammaran-12-one (M10) are synthesised from (20R)-protopanaxadiol. Their structures are confirmed by HRMS, 1H NMR and 13C NMR. Moreover, the absolute configurations of M3 and M4 are confirmed by the X-ray single crystal diffraction.

A large Ho 3+ :Li 3 Ba 2 La 3 (MoO 4 ) 8 crystal with high optical quality and well-developed appearance was grown by the flux method. The main spectral properties of the crystal, including the absorption spectra, fluorescence spectra and fluorescence decay curves were recorded at room temperature. The Judd-Ofelt (J-O) theory was applied to calculate the oscillator strength parameters Ω t ( t =2, 4, 6), spontaneous emission probabilities, fluorescence branching ratios, and radiative lifetimes of Ho 3+ ions undergoing transitions from ground state 5 I 8 to the excited states. The stimulated emission cross-section for the 5 I 7 → 5 I 8 transition was estimated to be 1.32×10 −20 cm 2 at 2045 nm by Fuchtbauer-Ladenburg (F-L) equation and the quantum efficiency of the 5 I 7 level was calculated to be 89%.

In this work, we have prepared a series of efficient visible-light-driven WO3/Fe(III) nanofiber photocatalysts by electrospinning and impregnation method. The physical and optical properties of the prepared photocatalysts were characterized by field emission scanning electron microscope (FESEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and the nitrogen adsorption analysis. Under the irradiation of visible light, all the prepared WO3/Fe(III) nanofiber photocatalysts exhibit much higher activity for degrading methyl orange (MO) solution than the pristine WO3 nanofibers, and reaches 94.6% under visible light irradiation for 3 h when the relative grafting amount of Fe(III) ions was 0.003 by mass percentage. Grafting of Fe(III) ions on the surface of WO3 nanofiber could enhance its visible-light absorption and reduce the photo-generated electron-hole pairs recombination due to the interfacial charge transfer (IFCT) effect, and thus improve its photocatalytic activity, which were further verified by the ultraviolet–visible diffuse reflectance spectroscopy (UV–Vis DRS), photoluminescence (PL) and the ns-level time-resolved fluorescence decay spectrum measurements.

A photoelectrochemical (PEC) cell made of metal-free carbon nitride (g-C3N4) @siliconnanowire(Si NW) arrays (denoted as Si NWs/g-C3N4) is presented in this work. The as-prepared photoelectrodes with different mass contents of g-C3N4 have been synthesized via a metal-catalyzed electroless etching (MCEE), liquid atomic layer deposition (LALD) and annealing methods. The amount of g-C3N4 on the Si NW arrays can be controlled by tuning the concentration of the cyanamide solution used in the LALD procedure. The dense and vertically aligned Si NWs/g-C3N4 core/shell nanostructures were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray diffraction (XRD). In comparison with FTO/g-C3N4 and Si NW samples, the Si NWs/g-C3N4 samples showed significantly enhanced photocurrents over the entire potential sweep range. Electrochemical impedance spectroscopy (EIS) was conducted to investigate the properties of the charge transfer process, and the results indicated that the enhanced PEC performance may be due to the increased photo-generated interfacial charge transfer between the Si NWs and g-C3N4. The photocurrent density reached 45 μA/cm2 under 100 mW/cm2 (AM 1.5 G) illumination at 0 V (vs. Pt) in neutral Na2SO4 solution (pH ∼ 7.62). Finally, a systematical PEC mechanism of the Si NWs/g-C3N4 was proposed.

Graphene nanoplatelets with excellent electrical conductivity in polymer matrices are highly promising for the industrial application of electrical conductive materials, however, poor dispersion results in high contents of graphene nanoplatelets being required for electrical property enhancement. In this study, graphene nanoplatelets (GNP)@polyaniline (PANI) nanocomposites were synthesized by in situ polymerization whereas the compatibility between GNP@PANI nanocomposites and the polymer matrix improved significantly due to graphene nanoplatelet encapsulation with polyaniline. GNP@PANI nanocomposites were utilized to prepare a permanent antistatic high-density polyethylene (HDPE) composite through solution blending and press forming in order for GNP@PANI nanocomposites to be dispersed homogeneously in the HDPE. The dispersion and compatibility of GNP@PANI nanocomposites in the HDPE were verified by morphology characterization, resulting in significant improvement of the electrical properties of the GNP@PANI/HDPE composites. It was observed that surface resistivity (ρs) and volume resistivity (ρv) decreased sharply with a 10 wt% GNP@PANI addition of nanocomposites. The results displayed that in situ polymerization and solution blending were effective methods for a conductive network establishment by addition of only 2 wt% of GNP and 8 wt% of PANI.

C25H23Br2ClN3NaNiO9, monoclinic, P21/n (no. 14), a = 15.595(4) Å, b = 10.993(3) Å, c = 18.660(5) Å, β = 114.536(4), V = 2910.2(14) Å3, Z = 4, R gt(F) = 0.0390, wR ref(F 2) = 0.0998, T = 293 K.

Spiroplasma eriocheiris causes great economic losses in the crustacean aquaculture industry. However, the mechanism of S. eriocheiris infecting host cells has been poorly studied. We established a Spiroplasma-infected Drosophila Schneider 2 (S2) cell model and investigated its pathogenic mechanism. First, S. eriocheiris induced S2 cell apoptosis and necrosis, seriously decreased cell viability, and increased the production of intracellular reactive oxygen species. Further research showed that S. eriocheiris can invade S2 cells, and the number of copies of intracellular spiroplasmas is sharply increased by 12 h postinfection. In addition, S. eriocheiris can cause S2 cells to form typical inclusion bodies and exhibit large vacuoles. Second, S. eriocheiris is internalized into S2 cells and strongly inhibited through blocking clathrin-mediated endocytosis using chlorpromazine and dynasore. Inhibitors of macropinocytosis, protein kinase C and myosin II, cause a significant reduction in S. eriocheiris in S2 cells. In contrast, disruption of cellular cholesterol by methyl-β-cyclodextrin and nystatin has no effect on S. eriocheiris infection. These results suggest that the entry of S. eriocheiris into S2 cells relies on clathrin-dependent endocytosis and macropinocytosis, but not via the caveola-mediated endocytic pathway. In addition, the intracellular numbers of S. eriocheiris are dramatically reduced after S2 cells are treated with cytoskeleton-depolymerizing agents, including nocodazole and cytochalasin B. Thus, cellular infection by S. eriocheiris is related to microtubules and actin filaments. This research successfully shows for the first time that S. eriocheiris can invade Drosophila S2 cells and provides a process for S. eriocheiris infection.

Use of echocardiography to evaluate the characteristics of right heart and pulmonary artery of Tibetans with hepatic hydatidosis living in a high plateau area. We recruited 222 Tibetan adults diagnosed with hydatidosis from June 2016 to June 2017 in Shiqu and Seda areas of Tibet; 40 healthy control from the same area, denoted as the high plateau group. We also include 755 Healthy adults of Han nationality living in the plain from the EMINCA study as the low altitude group. Compared to high plateau group, hydatidosis individuals showed decreased RVADed, RVTDed, increased E(T)/A(T) and reduced RVFAC and TAPSE (p < 0.05). The 2 groups did not differ in the incidence rate of tricuspid regurgitation (TR) and pulmonary regurgitation (PR) (63.9% vs. 55.0%, p = 0.281 and 15.3% vs. 5.0%, p = 0.135, respectively) or incidence of pulmonary hypertension (PH) (13.9% vs. 20.5%, p = 0.167). PH risk did not differ between hydatidosis individuals and high plateau controls (OR 0.559, 95% CI 0.243-1.287). The RVADed and TAPSE were higher and E(T)/A(T) was lower for high plateau group than low altitude group (p < 0.05). The decreased right ventricular size and reduced diastolic and systolic function were found in Tibetans with hydatidosis. Hepatic hydatidosis had no significant effect on the incidence of pulmonary hypertension in Tibetans. Healthy Tibetans showed increased right ventricular size, decreased diastolic function, and increased systolic function compared to the Han counterparts.

We describe a female patient who received hybrid catheter intervention and occlusion of the patent ductus arteriosus (PDA) and left atrial appendage (LAA). Four hours after the procedure, pericardial tamponade suddenly occurred. Surgical exploration of the heart found that a fixation hook of the WATCHMAN device, had protruded through the LAA wall and tore the dilated pulmonary artery (PA). This is the first case report to describe PA perforation caused by barbs of the WATCHMAN device, and more attention should be paid to the relationship between the LAA and its adjacent structures before LAA closure.

Two luminescent 3D supramolecular structures [Cd

Spiroplasma eriocheiris, a novel pathogen of Chinese mitten crab Eriocheir sinensis tremor disease, has led into catastrophic economic losses in aquaculture. S. eriocheiris invaded the hemocytes in the early stage, then invaded nerve tissue and caused typically paroxysmal tremors of pereiopod in the late stage of infection. The purpose of this study was to detect the infection mechanism of hemocytes in the early stage and thoracic ganglion in the late stage of S. eriocheiris infection at the protein level. Hemocytes and thoracic ganglion were collected at 24 h and 10 d after injection (the crabs with typical paroxysmal tremors of the pereiopod), respectively. TMT was performed with isobaric markers, followed by liquid chromatography tandem mass spectrometry (LC-MS/MS). In hemocytes, 127 proteins were up-regulated and 85 proteins were down-regulated in 2747 quantified proteins. Many proteins and process including proPO system proteins, hemolymph coagulation system proteins and lectins were differently expressed in hemocytes and involved in the early immune process of E. sinensis against S. eriocheiris infection. Meanwhile, 545 significantly different expression proteins (292 down-regulated and 253 up-regulated protein including a number of immune-associated, nervous system development and signal transmission related proteins) were identified in thoracic ganglion in the late stage of S. eriocheiris infection. The qRT-PCR analysis results shown that the selected significantly changed proteins in hemocytes and thoracic ganglion were consistent with the TMT proteomics. This paper reported for the first time to study the responses of crab hemocyte and thoracic ganglion against the S. eriocheiris infection at different stages. These findings help us understand the infection mechanism of S. eriocheiris at different stage with the different tissue.

Cystosepiment-like cobalt nanoparticles@N-doped carbon composite named Co-NPs@NC with highly efficient electrocatalytic performance for oxygen evolution reaction was prepared from carbonization of N-doped Co-MOFs. The optimized Co-NPs@NC-600 shows overpotentials of 315 mV to afford a current density of 10 mA&middot, cm&minus, 2. Meanwhile, the electrocatalys presents excellent long-term durability. The outstanding electrocatalytic performance can be attributed to the unique cystosepiment-like architecture with high specific surface area (214 m2/g), high conductivity of N-doped carbon and well-distributed active sites.

To explore the photocatalytic performances and optoelectronic properties of pure and doped bismuth oxyhalides D-doped BiOX (D = Ag, Pd, X = F, Cl, Br, I) compounds, their atomic properties, electronic structures, and optical properties were systematically investigated using first-principles calculations. In previous experiments, the BiOX (X = Cl, Br) based system has been observed with enhanced visible light photocatalytic activity driven by the Ag dopant. Our calculations also show that the potential photocatalytic performance of Ag-doped BiOCl or BiOBr systems is enhanced greatly under visible light, compared with other Pd-doped BiOX (X = Cl, Br) compounds. Furthermore, it is intriguing to find that the Pd-doped BiOF compound has strong absorption over the infrared and visible light spectrum, which may offer an effective strategy for a promising full spectrum catalyst. Indicated by various Mulliken charge distributions and different impurity states in the gap when Ag or Pd was doped in the BiOX compounds, we notice that all D-doped BiOXs exhibit a p-type semiconductor, and all impurity levels originated from the D-4d state. The charge transfer, optoelectronic properties, and absorption coefficients for photocatalytic activities among D-doped BiOX photocatalysts caused by the electronegativity difference of halide elements and metal atoms will finally affect the photocatalytic activity of doped BiOX systems. Therefore, it is significant to understand the inside physical mechanism of the enhanced Ag/Pd-doped BiOX photocatalysts through density functional theory.

Modification of a photocatalyst with single-atom noble metals can improve its activity while a remaining challenge is the stabilization of single atoms. As a proof of concept, g-C3N4 with desired amount of carbon defects was fabricated to manipulate the distribution of single-atom Pd by taking advantage of its affinity with carbon vacancy-resulted nitrogen atoms. The single-atom Pd was produced by photo-reduction, preferentially located on the carbon vacancy sites as supported by HAADF-STEM and XAFS analyses. As obtained photocatalyst showed high and stable photocatalytic activity in NO conversion; its activity is about 4.4 times higher than that of the pristine g-C3N4. The improved photoactivity was attributed to the preferential separation and transportation of the photo-generated charge carriers due to the introduction of single-atom Pd as evidenced by UV–vis, static and time-resolved photoluminescence spectroscopic analyses. The present work underlines the impetus of surface defect chemistry in the fabrication of single-atom catalysts.

As one of the most devastating diseases in Eriocheir sinensis, tremor disease (TD) is caused by Spiroplasma eriocheiris and dramatically increases the economic losses of crab aquaculture. With the development of biotechnology, metabolomics plays an important role in the screening of metabolites related to physiological and pathological changes. In this study, the different metabolites induced by S. eriocheiris were investigated in hemocytes of crab E. sinensis using metabolomics based on GC/MS among diverse phenotypes groups (tremor group, no-symptom group, and control group). Compared with the tremor group, 42 differential metabolites (26 up-regulated and 16 down-regulated) were significantly different in the no-symptom group. The KEGG pathway enrichment analysis showed that the differential metabolites were enriched in “ABC transporters”, “Vitamin B6 metabolism”, “Ascorbate and aldarate metabolism” and “Starch and sucrose metabolism”. The cellobiose and α-ketoglutarate (AKG) were chosen to verify the function of these two metabolites. The crabs were fed with dietary cellobiose (1, 5, and 10 mg/g diet weight) or AKG (1, 5, and 10 mg/g diet weight) before S. eriocheiris injection. The results show that all three concentrations of cellobiose and AKG could reduce the mortality of crabs and decrease the copies of S. eriocheiris in the hemocytes. The histopathological sections of the hindgut of E. sinensis show that cellobiose and AKG affect the connective tissue of the outer layer of muscle. Overall, these results provide insight into TD control and the sustainable development of aquaculture.

Hydrate saturation estimation in the field is mainly controlled by proper interpretations of downhole electrical logging data based on Archie's law. However, saturation exponent value in Archie's law is site dependent, and its proper selection for hydrate-bearing sediments is still a challenge. In this study, a fractal model of saturation exponent is derived to show physical connections between saturation exponent and pore structure parameters. Hydrate saturation dependent pore-area and tortuosity fractal dimensions of effective pores to electrical conductivity are extracted from X-ray computed tomography (CT) images of xenon-hydrate-bearing alumina ball packings, and these values of pore structure parameters are applied to validate the model. Effects of hydrate saturation, intrinsic/primary pore structure parameters, and salt-removing effect due to hydrate formation on values of saturation exponent in Archie's law are discussed. Results and discussions show that model predicted and experimental values of formation factor in hydrate-free porous media are consistent; Pore-area fractal dimension of effective pores to electrical conductivity decreases while tortuosity fractal dimension increases with increasing hydrate saturation; The discrepancy in saturation exponent values is largely due to the different enhancement degrees of tortuosity due to hydrate formation; A larger intrinsic volume porosity, lower pore-area and tortuosity fractal dimensions, and the salt-removing effect due to hydrate formation all lead to a lower saturation exponent in Archie's law. This study has a great potential to facilitate interpretations of downhole electrical logging data in gas hydrate sites.

Photofragmentation mechanisms of gas-phase lanthanide tris(isopropylcyclopentadienyl) complexes, Ln(iCp)3, were studied through experimental photoionization time-of-flight mass spectrometry (PI-TOF-MS). A DFT-based time-dependent excited-state molecular dynamics (TDESMD) algorithm, under standard approximations, was used to simulate the photofragmentation process. Two competing reaction pathways, intact ligand stripping and ligand cracking within the metal–ligand complex, were hypothesized based on experimental data. It was evident that intramolecular hydrogen, methyl, and isopropyl abstraction play an important role in the ligand-cracking reaction pathway, leading to metal carbide and metal hydrocarbide products. The TDESMD simulations also produced branching reaction pathways for ligand ejection and ligand cracking and further suggested that both pathways are initiated by ligand-to-metal charge transfer. Although the simulations reproduced several of the proposed reactions and several of the products of...

MIL-53(Al) was synthesized in a mixture of aluminum nitrate, 1,4-benzenedicarboxylic acid, and water using the hydrothermal and reflux methods. A metal–organic-framework-supported Au-based heterogeneous catalyst (Au/MIL-53(Al)) was prepared using the impregnation method under mild conditions with HAuCl4·4H2O as the Au precursors. The physicochemical properties of the samples were characterized by X-ray diffraction (XRD), infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TG), transmission electron microscopy (TEM), and inductively coupled plasma atomic emission spectroscopy (ICP–AES). MIL-53(Al) indicates excellent chemical stability without structure degradation during the loading and catalysis process. The XPS spectra indicate that the catalyst Au/MIL-53(Al) contains coexisting Au0 and Au3+ ions. The catalytic performance of the catalyst was examined in one-pot synthesis of structurally divergent propargylamines via three component coupling of aldehyde, alkyne, and amine (A3) in 1,4-dioxane. The results showed that the catalyst Au/MIL-53(Al) displayed high activity without any additives or an inert atmosphere (the yield reached 97.9 % for 5 h at 120 °C). Au/MIL-53(Al) has proven to be applicable to a wide range of substrates. Various aromatic/aliphatic aldehydes, aromatic alkynes, and piperidine were able to undergo A3 coupling on the catalyst Au/MIL-53(Al). In addition, the catalyst could be recovered easily by centrifugation and reused three times.

Two C24 epimeric 3-acetylated ocotillol-type sapogenins, 20 R,24 S-epoxy-dammarane-3β,12β,25-triol acetate and 20 R,24 R-epoxy-dammarane-3β,12β,25-triol acetate have been achieved from 20( R)-protopanaxadiol. Their structures were confirmed by HRMS, 1H NMR, 13C NMR and single crystal X-ray diffraction which showed that their configurations were (20 R, 24 S) and (20 R, 24 R), respectively. In the crystal structure of the 24 ( S)-epimer, there were two intramolecular hydrogen bonds and a left-handed helical chain whilst in the 24 ( R)-epimer there was one intramolecular hydrogen bond and a right-handed helical chain.

C-type lectins (CTLs) play important roles in invertebrate innate immunity by recognizing and eliminating pathogens. In the present study, a low-density lipoprotein receptor class A (LDLa) domain-containing CTL was identified from the oriental river prawn Macrobrachium nipponense, designated as MnCTLDcp1. The full-length cDNA of MnCTLDcp1 was composed of 1462 bp, with a 999-bp ORF encoding a 332-aa protein. An LDLa and a single C-type lectin-like domain (CTLD) were found. The mRNA transcripts of MnCTLDcp1 was expressed the highest in heart. After the prawns were challenged by Aeromonas hydrophila and Staphylococcus aureus, the expression level of MnCTLDcp1 in heart and hemocytes were all significantly up-regulated. Sugar binding assay revealed that the MnCTLDcp1 could bind to the glycoconjugates of bacteria surface, such as LPS, PGN and they can compete with bacterial as competitors. The recombinant MnCTLDcp1 agglutinates Gram-positive (S. aureus and Bacillus subtilis) and Gram-negative bacteria (A. hydrophila, Vibrio parahaemolyticus, Escherichia coli and Pseudomonas aeruginosa) in the presence of calcium and also could bind to these bacteria. These results clearly suggested that MnCTLDcp1 functions as a pattern-recognition receptor involved in the innate immunity of M. nipponense.

Spiroplasma eriocheiris, as a novel aquaculture pathogen, has led into catastrophic economic losses in aquaculture. The Macrobrachium rosenbergii hemocytes were major target cells in S. eriocheiris infection. Our study was designed to examine the hemocytes' immune response at the protein levels. The differential proteomes of the prawn hemocytes were analyzed immediately prior to injection with the pathogen, and at 192 h post-injection by isobaric tags for relative and absolute quantization (iTRAQ) labeling, followed by liquid chromatogramphytandem mass spectrometry (LC–MS/MS). A total of 69 differentially expressed proteins were identified. Forty-nine proteins were up-regulated and 20 proteins were down-regulated resulting from a S. eriocheiris infection. Up-regulated proteins included vertebrate gliacolin-like protein, vitellogenin, Gram-negative binding protein 1, alpha2 macroglobulin isoform 2 (a2M), etc. Down-regulated proteins, involved with beta-1,3-glucan-binding protein (BGBP), immunoglobulin like, Rab7, lipopolysaccharide and β-1,3-glucan (LGBP), actin-related protein, etc. Selected bioactive factors (tachylectin, α2M and vitellogenin, BGBP, C-type lectin, LGBP and Rab7) were verified by their immune roles in the S. eriocheiris infection using real-time PCR. The present work could serve as a basis for future studies on the proteins implicated in the susceptibility/resistance of M. rosenbergii to S. eriocheiris, as well as contribute to our understanding of disease processes in prawns. Biological significance This is the first time using an iTRAQ approach to analyze proteomes of M. rosenbergii mobilized against S. eriocheiris infection and substantiated the hemocytes' proteomic changes in M. rosenbergii using an infection model. The results reported here can provide a significant step forward toward a more complete elucidation of the immune relationship between M. rosenbergii and the pathogen S. eriocheiris.

A novel dinuclear Cu(II) coordination polymer, [Cu(BCPPO)H2O]n (1) [H2BCPPO = bis -4-carboxyphenyl phenyl phosphine oxide], has been synthesized and structurally characterized by single crystal X-ray diffraction, powder X-ray diffraction, thermogravimetric analysis, elemental analysis and infrared spectroscopy. As revealed by the single crystal X-ray diffraction, in complex 1, two paddle-wheel-type Cu2 units were connected by two BCPPO ligands to form one-dimensional infinite chain. The A3 coupling reaction of phenylacetylene, aldehyde and amine (piperidine) in the presence of the dinuclear Cu(II) coordination polymer as an efficient heterogeneous catalyst has also been studied. Complex 1 displayed high activity and afforded the corresponding propargylamines with moderate yields.

To investigate use of posterior groove of palatovaginal (PV) canal as an anatomic landmark in determining the location of PV canal in axial computed tomography (CT) images of pterygopalatine fossa (PPF). A total of 20 skull specimens were examined in this analysis. Each skull was scanned by CT with and without a probe inserted through PV canal to measure the anatomic structures. CT images of 70 patients were used for comparing the rate of correct location of PV canal between the conventional method (using the vidian canal as a landmark) and the method of using the posterior groove as a landmark. Two skulls were dissected using endoscopy to further reveal the advantage of the posterior groove as a landmark. In all 20 skull specimens, the groove showed the morphology of a narrow groove and elliptical fossa in 24 and 16 sides, respectively. In CT images, the angle from PV canal and the posterior groove to the hard palate was 53.14° ± 5.48° and 20.93° ± 6.28°, respectively, which was significantly different (P ≤ 0.05). The rate of correct location of PV canal was statistically significantly higher with the method of posterior groove as a landmark than the conventional method (70.7 vs 49.3 %, P

The structures of coordination polymers are strongly influenced by the organic ligands and metal ions used for their construction, so it is important to choose suitable ligands and metal ions and appropriate synthetic processes. Two noveld10coordination polymers, namely poly[[diaquabis(2,2′-bipyridine)[μ4-4,4′-(1,4-phenylenedioxy)bis(benzene-1,2-dicarboxylato)]dizinc(II)] dihydrate], {[Zn2(C22H10O10)(C10H8N2)2(H2O)2]·2H2O}n, (1), and poly[[diaquabis(1,10-phenanthroline)[μ4-4,4′-(1,4-phenylenedioxy)bis(benzene-1,2-dicarboxylato)]dicadmium(II)] dimethylformamide disolvate], {[Cd2(C22H10O10)(C12H8N2)2(H2O)2]·2C3H7NO}n, (2), have been synthesized from 4,4′-(1,4-phenylenedioxy)bis(benzene-1,2-dicarboxylic acid) (H4L) and two different N-containing auxiliary ligands through a mixed-ligand synthetic strategy under a solvothermal environment. The structures were characterized by single-crystal X-ray diffraction, powder X-ray diffraction, elemental analysis and IR spectroscopy. Compounds (1) and (2) both present one-dimensional chain structures and two-dimensional supramolecular layer structures constructed by weak hydrogen bonds. It is interesting to note that the carboxylate ligands reveal stabletransconfigurations in both compounds. The fluorescence properties of (1) and (2) in the solid state were also investigated.

Addition polymerization usually results in polymers with long carbon-carbon main chains. Cyanoacrylate (CA) is arguably an important example of such polymerization and has gained widespread acceptance as an all-purpose adhesive. However, CA-based medical adhesives have never been approved by the U.S. Federal Drug Administration for use below the skin, mainly due to the low biodegradability and biocompatibility of their solid glue after polymerization. In this research, a cross-linking strategy involving the combination of alkyl-CA and the cross-linking agent poly(ethylene glycol)-di(cyanoacrylate) (CA-PEG-CA) to form a copolymeric network was used to synthesize a new generation of biodegradable CA medical adhesives. The degradability could be modulated by adjusting the ratio of CA-PEG-CA to alkyl-CA and the length of PEG. An optimal composite adhesive, LKJ11, was shown to have excellent biodegradability, adhesive capability, and biocompatibility. Importantly, the molecular weight of polycyanoacrylate chains in the polymerized LKJ11 was greatly reduced compared to those polymerized from pure butyl-CA. Thus, the degradation product could be readily extracted. The results showed that LKJ11 represents a new generation of CA-based biodegradable medical adhesives. This advance also provides a general strategy to facilitate the conversion of other polymers with long carbon-carbon main chains to a biodegradable form, thereby expanding the novel applications available for traditional polymeric materials.

Deltamethrin is used widely in Eriocheir sinensis aquaculture to remove wild fish and parasites. The residual deltamethrin greatly affects the growth and quality of E. sinensis. In this study, the LC50 of deltamethrin against E. sinensis at 24, 48 and 96 h was determined to be 6.5, 5.0 and 2.8 μg/L, respectively. The enzyme activity and gene transcription of SOD, CAT, and PO in the hepatopancreas of E. sinensis after deltamethrin stimulation showed an increasing tendency, and these enzymes reached their maximum activities at 6–10 d. The MDA content accumulated with increased time of deltamethrin stress. After 15 d of deltamethrin stress, the hepatopancreas of E. sinensis was found to be damaged based on HE staining. These results showed that deltamethrin is highly toxic to E. sinensis. But the half-life of deltamethrin is long and mainly relies on biodegradation. To resolve the pollution of residual deltamethrin, a strain of deltamethrin-degrading bacteria, P-2, was isolated from the sediment of an E. sinensis culture pond. Through morphological observation, physiological and biochemical identification and 16S rDNA sequence analysis, we found that this strain belonged to Paracoccus sp. When the pH was 7, the substrate concentration was low, the inoculation amount was high, and the deltamethrin degradation effect of Paracoccus sp. P-2 was good. The deltamethrin residue in the hepatopancreas and muscle of E. sinensis decreased significantly when Paracoccus sp. P-2 was added at 6.0 × 108 CFU/L. The degradation efficiency of Paracoccus sp. P-2 in the hepatopancreas and muscle was more than 70%. These results showed that Paracoccus sp. P-2, the first deltamethrin-degrading bacterium in aquaculture, could be used to remove residual deltamethrin and improve the food safety of E. sinensis.

Spiroplasma eriocheiris, has been identified as a novel lethal pathogen of Eriocheir sinensis tremor disease (TD, typically paroxysmal tremors of the pereiopod). The thoracic ganglion of E. sinensis infected by S. eriocheiris was the direct reason of the TD. This study was designed to understand of TD processes in crab and the immune response of thoracic ganglion at the transcriptomic levels. The transcriptomic profiles of thoracic ganglion in the experimental group (S. eriocheiris inject, termed SI) and the control group (R2 medium inject, termed RI) were obtained using Illumina HiSeq 2500. In total, there were 60,159,089 and 47,613,445 high-quality clean reads assembled from SI and RI, respectively. In addition, 39,636 unigenes were obtained with an N50 length of 575 bp. Moreover, by RPKM analysis, a total of 8049 differentially expressed genes (SI vs RI) were detected, including 927 up-regulated and 7122 down-regulated genes. The transcription levels of gene in prophenoloxidase-activating system (proPO), Wnt signaling pathway, phagocytosis, Toll-like system, Ca2+ regulation related process, etc. of SI were significantly changed compare with RI. Finally, 12 selected differentially expressed genes (Serpin, TLR, FZ4, SPI2, Tax1, TLSP, AI, CTLR, Rab11A, LAMP-1, Trx1 and PI3K) were verified using qRT-PCR showed similar tendency with the RNA-seq. The results shown that the proPO, Wnt signaling pathway, phagocytosis, Toll-like system, Ca2+ regulation related process, glutamate signal related process, etc. were involved in the process of the S. eriocheiris infection.

Hydrate occupancy, morphology and spatial distribution in sediment pore can significantly affect the physical properties of hydrate-bearing sediment, but their evolutions with hydrate dissociation under various brine saturations are not well understood. X-ray micro-CT is employed to image the pore-scale dynamic process of methane hydrate dissociation in both sediments with different brine saturations. On the basis of processing and statistical analysis of X-ray CT images, several topological parameters, including volume, shape factor, fractal dimension and Euler characteristic of individual hydrate cluster, are selected to quantify hydrate occupancy, morphology and microstructure evolution with hydrate dissociation in the host sediments. Results show that the degree of brine saturation within the sediments can exert a significant impact on hydrate pore occupancy, morphology and microstructure connectedness during hydrate dissociation. In contrary to those of fully brine-saturated sediment, the topological parameters of individual hydrate cluster usually experience more dramatic changes with hydrate dissociation in partially brine-saturated sediment. It is inferred that in partially brine-saturated sediment the isolated hydrate clusters occupying in pore bodies are dissociated earlier in the initial experimental stage, and the dissociation of interpore hydrate frameworks interconnected through pore throats get dominated when hydrate saturation declines below a critical threshold value. On the other hand, in fully brine-saturated sediment the kinetics of pore-scale hydrate dissociation exhibit a completely opposite trend.

As a novel lethal pathogen of Eriocheir sinensis tremor disease, Spiroplasma eriocheiris, has led into catastrophic economic losses in aquaculture. The hemocytes of E. sinensis is the first target cells of S. eriocheiris. Our study is the first time designed to understanding of the N-glycoproteome dynamics of E. sinensis hemocytes under S. eriocheiris infected at the early phage. In the current study, the N-glycoproteome changes of E. sinensis hemocytes after S. eriocheiris infection were obtained using tandem mass tags (TMT) labeling and affinity enrichment followed by high-resolution Liquid chromatography coupled tandem mass spectrometry (LC-MS/MS) analysis. Using a 1.2-fold change in expression as a physiologically significant benchmark, 167 differentially expressed N-glycosylated proteins were reliably quantified, including 79 up-regulated glycosylated proteins and 88 down-regulated glycosylated proteins subsequented to S. eriocheiris infection. Gene ontology (GO) annotation, protein domain annotation, Kyoto Encyclopedia of Genes and Genomes (KEGG) annotation, subcellular localization annotation and protein-protein interaction network were used to analyze those significantly differently expression proteins shown that many biological process and pathway are participate in S. eriocheiris infected host cell, such as phagocytosis, ECM-receptor interaction, lysosome, prophenoloxidase system, and so on. Six selected different expressed glycosylated proteins were studied the transcription at RNA level by qRT-PCR. Our study could serve as a basis to understand the relationship between E. sinensis and the pathogen S. eriocheiris, and also provide reference to study protein N-glycosylation in other crustaceans.

Evaluating deformation characteristics and predicting strength parameters of hydrate-bearing sediments (HBS) are indispensable for natural gas hydrate exploration and development. A series of triaxial shearing tests were conducted in this paper to analyze the mechanical behaviors and failure mechanisms of hydrate-bearing sediments. The failure strength is discussed comprehensively based on the Mohr-Coulomb criterion, the Drucker-Prager criterion, and the Lade-Duncan criterion. Failure mechanisms of the specimens during shearing are discussed at the micro-level. The results indicate that specimens with relatively high hydrate saturation exhibit strain-softening brittle failure mode, whereas those with relatively low hydrate saturation exhibit obvious strain-hardening ductile failure mode. The cohesion of HBS is enhanced from 0.42 MPa to 1.0 2 MPa, and the friction angle increases from 26.4° to 34.2° with hydrate saturation rising. Additionally, the modified criteria based on the Drucker-Prager criterion can predict the strength with the highest accuracy. The results provide a theoretical and experimental reference for developing the natural gas hydrate reservoirs efficiently.

Enterocytozoon hepatopenaei (EHP) causes hepatopancreatic microsporidiosis (HPM) in shrimp. HPM is not normally associated with shrimp mortality, but is associated with significant growth retardation. In this study, the responses induced by EHP were investigated in hepatopancreas of shrimp Litopenaeus vannamei using proteomics and metabolomics. Among differential proteins identified, several (e.g., peritrophin-44-like protein, alpha2 macroglobulin isoform 2, prophenoloxidase-activating enzymes, ferritin, Rab11A and cathepsin C) were related to pathogen infection and host immunity. Other proteomic biomarkers (i.e., farnesoic acid o-methyltransferase, juvenile hormone esterase-like carboxylesterase 1 and ecdysteroid-regulated protein) resulted in a growth hormone disorder that prevented the shrimp from molting. Both proteomic KEGG pathway (e.g., "Glycolysis/gluconeogenesis" and "Glyoxylate and dicarboxylate metabolism") and metabolomic KEGG pathway (e.g., "Galactose metabolism" and "Biosynthesis of unsaturated fatty acids") data indicated that energy metabolism pathway was down-regulated in the hepatopancreas when infected by EHP. More importantly, the changes of hormone regulation and energy metabolism could provide much-needed insight into the underlying mechanisms of stunted growth in shrimp after EHP infection. Altogether, this study demonstrated that proteomics and metabolomics could provide an insightful view into the effects of microsporidial infection in the shrimp L. vannamei.

Atomically modified graphitic carbon nitride quantum dots (QDs), characterized by strongly increased reactivity and stability, are developed. These are deposited on arrays of TiO2 nanopillars used as a photoanode for the photoelectrochemical water splitting. This photoanode shows excellent stability, with 111 h of continuous work without any performance loss, which outperforms the best‐reported results by a factor of 10. Remarkably, our photoanode produces hydrogen even at zero bias. The excellent performance is attributed to the enhancement of photoabsorption, as well as to the promotion of charge separation between TiO2 nanopillars and the QDs.