Doped-Sn Enhanced the Performance of BiOCl Nanosheet on Electrocatalytic Synthesis of Hydrogen Peroxide.

The hydrogen peroxide (H2O2) produced through electrochemical two-electron oxygen reduction reaction (2e- ORR) is a promising green synthesis method and served as potential strategy to replace the energy-intensive anthraquinone process. Nevertheless, the design of low-cost and efficient electrocatalysts for 2e- ORR remains a formidable challenge. In this study, Sn-BiOCl nanosheets electrocatalysts are prepared for expediting the 2e- ORR, achieving a high H2O2 selectivity of 92.9%, and the H2O2 yield of 10628 mg L-1 h-1 (0.1 mg cm-2) in a flow-cell device. The in situ ATR-SEIRAS results reveal that Sn-BiOCl enhances the adsorption and activation of *OOH compared to BiOCl, resulting in higher activity and selectivity for 2e- ORR. Furthermore, this study investigates the potential for on-site production and application of H2O2 using Sn-BiOCl, which displays a 95% degradation removal of dyes (RhB, MB, and MO) within 20 min. This work not only have an insight into the critical roles of Bi and Sn atoms in enhancing the catalytic performance but also provides a thought to design efficient catalysts for production H2O2 via electrochemical 2e- ORR.

Friction Properties of Crystalline Cellulose Sliding on Chromium under Water Lubrication Based on Molecular Dynamics Simulations.

This work studies the friction and wear behaviors of chromium (hard material) and crystalline cellulose (soft material) under water lubrication considering the loading and sliding velocity on friction force, temperature of contact interfaces, and worn atoms from the atomic view. The change of friction force with sliding velocity is greater than that with loading, and it is easier to obtain a stable friction at high velocity. The average friction force in the stabilization gradually increases with loading and velocity, and the growth rate decreases with loading, while it increases with velocity. The temperature of contact interfaces at the beginning of sliding changes rapidly and gradually becomes stable. The temperature at the stabilization increases distinctly with velocity, while it does not change much with loading. Both the loading and sliding velocity have an important influence on the wear of soft material; it is noticed that the amount of worn atoms increases close to exponentially with velocity and linearly with loading. However, the wear of hard material changes less with increasing loading and sliding velocity.

Research progress of clinical intervention and nursing for patients with post-stroke dysphagia.

Post-stroke dysphagia (PSD) is a common and costly complication of stroke and is associated with increased mortality, morbidity, and hospitalization. Although most patients can spontaneously resume swallowing, there are still many patients who do not recover and even die. Despite multiple advances in the acute treatment and secondary prevention of stroke, the effective treatment of PSD remains a neglected area. Studies have shown that repair mechanisms of neurostimulation techniques and increased cortical activity play an important role in the treatment of PSD. In addition, nutritional interventions are also crucial for the treatment of malnutrition in PSD patients. Therefore, this article reviews the effects of the current main clinical treatment methods and nutritional interventions on the treatment and rehabilitation of PSD patients. It also emphasized the necessity of developing an individualized care plan for PSD patients, which is of great significance to promote the clinical treatment, nutritional status, prognosis, and quality of life of PSD patients.

Sequence determinants of human junctophilin-2 protein nuclear localization and phase separation.

Junctophilin-2 (JPH2) was conventionally considered as a structural membrane binding protein. Recently, it was shown that proteolytically truncated mouse JPH2 variants are imported into nucleus to exert alternative functions. However, the intranuclear behaviors of human JPH2 (hJPH2) and underlying molecular determinants have not been explored. Here, we demonstrate that full-length hJPH2 is imported into nucleus in human cells by two nuclear localization signals (NLSs), including a newly discovered one at the C-terminus. Importantly, unlike the JPH2 N-terminal truncation which diffuses throughout the nucleus, full-length hJPH2 forms nuclear bodies behaving like liquid-liquid phase separated droplets that are separated from chromatin. The C-terminal transmembrane domain is required for the formation of hJPH2 droplets. Oxidation mimicking substitution of residues C678 and M679 augments the formation of hJPH2 nuclear droplets, suggesting nuclear hJPH2 liquid-liquid phase separation could be modulated by oxidative stress. Mutation A405D, which introduces a negatively charged residue into an intrinsic disordered region (IDR) of hJPH2, turns liquid-like droplets into amyloid-like aggregates. Depletion of an Alanine Rich Region in the IDR recapitulates the liquid-amyloid phase transition. The MORN repeat regions of hJPH2 encodes intrinsic tendency to form amyloid-like structure. Together, these data revealed the novel intrinsic properties of hJPH2 to form nuclear liquid droplets, and identified critical functional domains encoding these properties. We propose that hJPH2 droplets could function as membrane-less organelles participating in nuclear regulatory processes.

Chemical Isotope Labeling Exposome (CIL-EXPOSOME): One High-Throughput Platform for Human Urinary Global Exposome Characterization.

Human exposure to hundreds of chemicals, a primary component of the exposome, has been associated with many diseases. Urinary biomarkers of these chemicals are commonly monitored to quantify their exposure. However, because of low concentrations and the great variability in physicochemical properties of exposure biomarkers, exposome research has been limited by low-throughput and costly methods. Here, we developed a sensitive and high-throughput exposome analytical platform (CIL-EXPOSOME) by isotopically labeling urinary biomarkers with common functional groups (phenolic hydroxyl/carboxyl/primary amine). After a simple cleanup, we used mass spectrometry to perform a screening for both targeted and untargeted biomarkers, which was further processed by an automatic computational pipeline method for qualification and quantification. This platform has effectively introduced an isotope tag for the absolute quantification of biomarkers and has improved sensitivity of 2-1184 fold compared to existing methods. For putative identification, we built a database of 818 urinary biomarkers with MS/MS fragmentation information from either standards or in silico predictions. Using this platform, we have found 671 urinary exposure biomarker candidates from a 2 mL pooled urine sample. The exposome data acquisition and analysis time has also been greatly shortened. The results showed that CIL-EXPOSOME is a useful tool for global exposome analysis of complex samples.

Human Indoor Exposome of Chemicals in Dust and Risk Prioritization Using EPA's ToxCast Database.

Humans spend most of their time indoors and thus have long-term exposure to chemicals. Dust is a sink for most indoor chemicals, and its ingestion is an important pathway for chemical uptake. Therefore, the chemical atlas from dust is an ideal environmental sample to investigate the indoor exposome and associated risk. In this study, we aimed to establish an indoor exposome database through comprehensive data mining on the occurrence of identified compounds in dust, and we prioritize chemicals of health concern. Through an extensive literature review (2849 articles), 355 chemicals and their concentrations were documented and analyzed for human exposure. Together with 81 compounds without concentration and 75 volatile organic compounds, we have established an indoor exposome database with 511 chemicals. Sixteen toxicological end points were selected for toxicity prioritization. Toxic equivalency factor (TEF)-based toxicity, calculated from EPA's ToxCast database, revealed a comprehensive atlas of the chemicals that had a primary contribution. Many of the prioritized compounds are currently neglected or are not actively studied. Overall, this investigation provides one of the most comprehensive analyses on chemical occurrence in indoor dust and prioritizes their chemical toxicity. Our findings can be used as a database for future exposome studies of the indoor environment and provide guidance for indoor risk assessments.

[Identification of effective components from Naoxintong Capsules intestinal absorption liquid in inhibiting ADP-induced platelet aggregation].

Intestinal absorption liquid was prepared by using everted intestinal sac method; meanwhile, its recipes were decomposed or restructured. Platelet aggregation activity was examined by biochemical tests and a microplate reader. One or more kinds of Chinese medicines which displayed inhibiting activity in Naoxintong Capsules were screened through separation and combination of prescription. The results showed that Naoxintong Capsules could inhibit ADP-induced platelet aggregation. Recipe decomposition and restructuring results showed that Salviae Miltiorrhizae Radix et Rhizoma, Paeoniae Radix Rubra, Cinnamomi Ramulus and Hirudo were the main effective medicines in inhibiting platelet aggregation. Furthermore, Cinnamomi Ramulus played a vital role in inhibiting activity among those four kinds of Chinese medicines. Coumarin derived from intestinal absorption liquid of Cinnamomi Ramulus had inhibiting activity in the range of 50-200 µmol·L⁻¹, and other ingredients such as cinnamyl alcohol and cinnamaldehyde also had inhibiting activities. In conclusion, Salviae Miltiorrhizae Radix et Rhizoma, Paeoniae Radix Rubra, Cinnamomi Ramulus and Hirudo are the main components for inhibiting ADP-induced platelet aggregation, and Cinnamomi Ramulus has the most strongest inhibiting activity in Naoxintong Capsules.

New Probe of Departures from General Relativity Using Minkowski Functionals.

The morphological properties of the large scale structure of the Universe can be fully described by four Minkowski functionals (MFs), which provide important complementary information to other statistical observables such as the widely used 2-point statistics in configuration and Fourier spaces. In this work, for the first time, we present the differences in the morphology of the large scale structure caused by modifications to general relativity (to address the cosmic acceleration problem), by measuring the MFs from N-body simulations of modified gravity and general relativity. We find strong statistical power when using the MFs to constrain modified theories of gravity: with a galaxy survey that has survey volume ∼0.125(h^{-1} Gpc)^{3} and galaxy number density ∼1/(h^{-1} Mpc)^{3}, the two normal-branch Dvali-Gabadadze-Porrati models and the F5 f(R) model that we simulated can be discriminated from the ΛCDM model at a significance level ≳5σ with an individual MF measurement. Therefore, the MF of the large scale structure is potentially a powerful probe of gravity, and its application to real data deserves active exploration.

Nonperipheral Tetrakis(dibutylamino)phthalocyanines. New Types of 1,8,15,22-Tetrakis(substituted)phthalocyanine Isomers.

Cyclic tetramerization of 3-(dibutylamino)phthalonitrile in refluxing n-pentanol in the presence of magnesium pentanoate afforded the four regioisomer-containing nonperipheral 1,8-/11,15-/18,22-/25-tetrakis(dibutylamino)phthalocyaninato magnesium complexes with the 1,8,15,22-tetrakis(dibutylamino)phthalocyanine isomer Mg{Pc[α-N(C4H9)2]4-C4} (2). This, in combination with its much superior crystallinity over the remaining three isomers, renders the easy isolation of 2 only through two simple recrystallizations from THF and methanol. Treatment of 2 with trifluoroacetic acid induced the isolation of metal-free 1,8,15,22-tetrakis(dibutylamino)phthalocyanine, H2{Pc[α-N(C4H9)2]4-C4} (1), which further reacted with M(OAc)2·nH2O (M = Ni, Zn) in refluxing n-pentanol, giving the 1,8,15,22-tetrakis(dibutylamino)phthalocyaninato metal complexes M{Pc[α-N(C4H9)2]4-C4} (M = Ni (3), Zn (4)). The full series of four 1,8,15,22-tetrakis(dibutylamino)phthalocyanine isomeric compounds have been characterized by a series of spectroscopic methods and single-crystal X-ray diffraction analyses. Obviously, the present result provides a simple and effective pathway for the synthesis and isolation of novel 1,8,15,22-tetrakis(dibutylamino)phthalocyanine isomeric derivatives, providing one step forward toward completing bis(alkyl)amino-incorporated phthalocyanine species.

Phthalocyanine-cRGD conjugate: synthesis, photophysical properties and in vitro biological activity for targeting photodynamic therapy.

An unsymmetrical phthalocyanine conjugated with an RGDyK moiety (6) was synthesized and characterized. Its photophysical properties, including electronic absorption, fluorescence emission (ΦF = 0.20), singlet oxygen quantum yield (ΦΔ = 0.63) and two-photon absorption cross section (TPACS) at different wavelengths were studied. The in vitro cell study data demonstrate that this Pc conjugate possesses significantly high cellular uptake toward the ανß3 positive DU145 prostate cancer cells along with an efficient photocytotoxicity (IC50 = 0.04 µM), showing this compound is one of the most promising photosensitizers for targeting photodynamic therapy (PDT) of cancer.

Monomorphic epitheliotropic intestinal T-cell lymphoma with bone marrow involved: A case report.

BACKGROUND: Monomorphic epithelial intestinal T-cell lymphoma (MEITL) is a rare type of peripheral T-cell lymphoma. The clinical manifestations are diarrhea, abdominal pain, perforation and an abdominal mass. CASE SUMMARY: We present a 52-year-old female patient who was diagnosed with MEITL. Further disease progression was observed after multiline chemotherapy. Eventually, the patient died of a severe infection. CONCLUSION: MEITL is a rare intestinal primary T-cell lymphoma with aggressive behavior, a high risk of severe life-threatening complications, and a poor prognosis.

Investigation of the microscopic damage mechanisms in cotton fibers induced by mechanical friction.

For the problem of friction damage in cotton fiber processing, a multi-scale combination of investigation methods is proposed. The surface of damaged cotton fiber is detected by relevant test means with damage features such as dislocations, defects and cracks. The internal pyranose ring and glycosidic bond fail, the crystallinity decreases, and the number of hydrogen bonds decreases. Anisotropy exists in the frictional properties of the microscopic surface of the cotton fiber. The results of molecular dynamics simulation showed that the cellulose main chain failed mainly at the glycosidic bond, and the side chain failed mainly at the hydroxymethyl functional group. Its interchain hydrogen bond O3H…O5 was the least damaged. The cellulose crystal (200) surfaces had poor abrasion resistance, and the frictional properties of each crystal surface were anisotropic. The results of the study provide a theoretical basis for improving friction and wear problems in cotton fiber processing.

Trans-replicase helper activity of porcine circoviruses promotes the synergistic replication of torque teno virus.

While the primary pathogenic potential of torque teno viruses (TTVs) is yet to be defined, TTVs are often co-detected with other pathogens and are suspected of exacerbating clinical disease in coinfections. Swine TTVs (TTSuVs) enhance clinical signs of porcine circovirus type 2 (PCV2) in a gnotobiotic pig model. However, the mechanisms involved are unknown. In this study, we observed that co-culture of TTSuV1 and PCV1, and specifically supplementing TTSuV1 cultures with the PCV replicase protein in trans consistently resulted in higher levels of replication of TTSuV1 when compared to TTSuV1 cultured alone. Therefore, the hypothesis that the PCV replicase (rep) protein has trans-replicase helper activity for TTSuV1 was examined. Based on EMSA and reporter gene assays, it was determined that the PCV1 rep directly interacted with the TTSuV1 UTR. The TTSuV1 rep trans-complemented a PCV rep null mutant virus, indicating that the TTSuV1 and PCV1 replicase proteins supported the replication of both viruses. In mice, the administration of plasmids encoding the PCV1 rep and a TTSuV1 infectious clone resulted in the production of higher TTSuV1 genome copies in dually exposed mice when compared to singly exposed mice. Higher sero-conversion and lymphoid hyperplasia were also observed in the dually exposed experimental mice. Thus, this study provides evidence for trans-replicase activity of PCVs and TTVs as a novel mechanism of explaining enhanced viral replication in coinfections involving both viruses.

Maternal control of seed size by EOD3/CYP78A6 in Arabidopsis thaliana.

Seed size in higher plants is coordinately determined by the growth of the embryo, endosperm and maternal tissue, but relatively little is known about the genetic and molecular mechanisms that set final seed size. We have previously demonstrated that Arabidopsis DA1 acts maternally to control seed size, with the da1-1 mutant producing larger seeds than the wild type. Through an activation tagging screen for modifiers of da1-1, we have identified an enhancer of da1-1 (eod3-1D) in seed size. EOD3 encodes the Arabidopsis cytochrome P450/CYP78A6 and is expressed in most plant organs. Overexpression of EOD3 dramatically increases the seed size of wild-type plants, whereas eod3-ko loss-of-function mutants form small seeds. The disruption of CYP78A9, the most closely related family member, synergistically enhances the seed size phenotype of eod3-ko mutants, indicating that EOD3 functions redundantly with CYP78A9 to affect seed growth. Reciprocal cross experiments show that EOD3 acts maternally to promote seed growth. eod3-ko cyp78a9-ko double mutants have smaller cells in the maternal integuments of developing seeds, whereas eod3-1D forms more and larger cells in the integuments. Genetic analyses suggest that EOD3 functions independently of maternal factors DA1 and TTG2 to influence seed growth. Collectively, our findings identify EOD3 as a factor of seed size control, and give insight into how plants control their seed size.

Experimental and theoretical evidence of aromatic behavior in heterobenzene-like molecules with metal-metal multiple bonds.

Binding two quadruply bonded dimolybdenum units [Mo(2)(DAniF)(3)](+) (DAniF=N,N'-di-p-anisylformamidinate) with two chalcogen atoms generated two molecules with a central core composed of a cyclic six-membered [Mo(2)](2)(µ-EH)(2) species (E=S in 1 and O in 3, and [Mo(2)] is a quadruple-bonded [Mo(2)(formamidinate)(3)] unit). Aerobic oxidation of 1 and 3 followed by concomitant deprotonation gave rise to the corresponding [Mo(2)](2)(µ-E)(2) compounds 2 and 4. The latter show a striking coplanarity and near-bond equalization of the Mo/E cluster. The oxidized species 2 and 4 are diamagnetic in the measured temperature range of 5 to 300 K, which is somewhat unexpected for molecules that have dimetal units with a σ(2)π(4)δ(1) electronic configuration. This suggests there are strong interactions between the dimolybdenum units through the E atoms. The large electronic delocalization of the δ electrons over the entire Mo/E core is supported by the exceptionally large potential separation for the two successive one-electron reductions of the linked Mo(2)(5+) units from the oxidized species (ΔE(½)=1.7 V for the sulfur analogue). This large electronic delocalization has an important effect on the NMR spectroscopic signals for the two sets of methine (N-(CH)-N) protons from the DAniF ligands. Those essentially parallel to the core, H(∥), and those essentially perpendicular to the core, H(⊥), exhibit downfield and upfield chemical shifts, respectively, that are separated by δ=1.32 ppm. The structural, electronic, magnetic, and chemical behaviors for 2 and 4 are consistent with aromaticity, with the [Mo(2)E(2)Mo(2)] cores that resemble the prototypical benzene molecule. Theoretical studies, including DFT calculations, natural bond orbital (NBO) analyses, and gauge-independent atomic orbital (GIAO) NMR spectroscopic calculations, are also consistent with the aromaticity of the [Mo(2)](2)(µ-E)(2) units being promoted by d(δ)(Mo(2))-p(π)(E) π conjugation. The cyclic π conjugation of the central moiety in 2 and 4 involves a total of six electrons with 2e from δ(Mo(2)) and 4e from p(π)(E) orbitals, thereby conforming to Hückel's rule when electrons in the MOs with δ character are considered part of the delocalized system.

Regulation of Sirt1 on energy metabolism and immune response in rheumatoid arthritis.

Rheumatoid arthritis (RA) is a systemic autoimmune disease. Synovial hyperplasia and persistent inflammation serve as its typical pathological manifestations, which ultimately lead to joint destruction and function loss. Both clinical observations and metabolomics studies have revealed the prevalence of metabolic disorders in RA. In inflammatory immune microenvironments, energy metabolism is profoundly changed. Increasingly evidences suggest that this abnormality is involved in the occurrence and development of RA-related inflammation. Unsurprisingly, many energy metabolism sensors have been confirmed with immunoregulatory properties. As a representative, silent information regulator type 1 (Sirt1) controls many aspects of immune cells, such as cell lifespan, polarization, and secretion by functioning as a transcriptional regulator. Because of the profound clinical implication, researches on Sirt1 in the regulation of energy metabolism and immune functions under RA conditions have gradually gained momentum. This signaling balances glycolysis, lipid metabolism and insulin secretion orchestrating with other metabolism sensors, and consequently affects immune milieu through a so-called metabolism-immune feedback mechanism. This article reviews the involvement of Sirt1 in RA by discussing its impacts on energy metabolism and immune functions, and specially highlights the potential of Sirt1-targeting anti-rheumatic regimens. It also provides a theoretical basis for clarifying the mystery about the high incidence of metabolic complications in RA patients and identifying new anti-rheumatic reagents.

cis-Silicon phthalocyanine conformation endows J-aggregated nanosphere with unique near-infrared absorbance and fluorescence enhancement: a tumor sensitive phototheranostic agent with deep tissue penetrating ability.

Organic phototheranostic nanomedicines with an optimized near-infrared (NIR) biological transparent window (700-900 nm) are highly desirable for the diagnosis and treatment of deep-seated tumors in clinic. As excellent organic photosensitizers for photodynamic therapy (PDT) with outstanding photo- and thermo-stability, phthalocyanines (Pcs) have been used as the building blocks of single-component nanomedicines. However, to the best of our knowledge, all the Pc-based single-component self-assemblies reported to date are of an H-aggregate nature. This results in the simultaneous self-quenching of fluorescence emission and photodynamic activity as well as greatly reduced tissue penetration due to blue-shifted absorption. In the present work, intramolecular hydrogen bonding was formed between the two long and flexible axial NH2-terminated diethylene glycol ligands of the amphiphilic SiPc molecule (SiPc-NH2) in solution, leading to the employment of a cis-conformation of this molecule according to the 1H-NMR spectroscopy result, which as a building block then further self-assembled into monodisperse nanospheres (SiPcNano) with a J-aggregation nature on the basis of electronic absorption spectroscopic results. As a result, SiPcNano exhibited significantly enhanced red-shifted absorption in the NIR range of 750-850 nm and fluorescence emission. This in combination with the increased photodynamic effect for SiPcNano triggered by the protonation of amine groups due to the acidic nature of tumors endowed effective synergistic NIR photodynamic and photothermal effects in different cancer cells and thus effective inhibition of tumor growth in A549 tumor-bearing mice on the basis of a series of in vitro and in vivo evaluations. The present result provides a new approach for constructing novel single-component NIR organic nanomedicines for multifunctional cancer therapy.

Highly Efficient Zn-Cu-In-Se Quantum Dot-Sensitized Solar Cells through Surface Capping with Ascorbic Acid.

The balance between band structure, composition, and defect is essential for improving the optoelectronic properties of ternary and quaternary quantum dots and the corresponding photovoltaic performance. In this work, ascorbic acid (AA) as capping ligand is introduced into the reaction system to prepare green Zn-Cu-In-Se (ZCISe) quantum dots. Results show that the addition of AA can increase the Zn content while decrease the In content, resulting in enlarged band gap, high conduction band energy level, and suppressed charge recombination. When AA/Cu ratio is 1, the quantum dots possess the largest band gap of 1.49 eV and the assembled quantum dot-sensitized solar cells exhibit superior photovoltaic performance with ∼17% increment mainly contributed by the dramatically increased current density. The new record efficiencies of 10.44 and 13.85% are obtained from the ZCISe cells assembled with brass and titanium mesh-based counter electrodes, respectively.

Zn-Ag-In-S quantum dot sensitized solar cells with enhanced efficiency by tuning defects.

Being an important I-III-VI green quantum dot (QD), AgInS2 (AIS) has been used as sensitizers for QD sensitized solar cells (QDSCs) but with low power conversion efficiency (PCE). Herein, we have used oleylamine as surfactant to synthesize AIS and quaternary Zn-Ag-In-S (ZAIS) QDs via a facile and green method. The assembled AIS QDSCs show high PCE of 2.46%. After doping with Zn to form ZAIS QDs, the defect states have been modified, resulting in the enhanced photoluminescence. The assembled ZAIS QDSCs receive the greatly enhanced PCE of 4.50% with dramatically increased current density. Various characterizations verify that the high quality of QDs, large recombination resistance at QD/electrolyte interface, high photon to electron conversion efficiency and longer electron life are contributed by the tuned intrinsic defects which are strongly related with synthesis and composition, finally leading to the high performance of photovoltaic devices.

Enhancing Loading Amount and Performance of Quantum-Dot-Sensitized Solar Cells Based on Direct Adsorption of Quantum Dots from Bicomponent Solvents.

Intrinsically weak interaction between oil-soluble quantum dots (QDs) and TiO2 in a direct adsorption process limits QD loading and the performance of QD-sensitized solar cells (QDSCs). Herein, the underlying chemistry and mechanisms governing QD adsorption on TiO2 were studied to improve QD loading and cell performance. Experimental results indicate that solvent polarity plays the crucial role in determining QD loading. Compared with single-component solvents, substantially greater QD loading can be realized at the critical point (CP) of bicomponent solvents, where QDs become metastable and start to precipitate. Through this strategy, average efficiency of 12.24% was obtained for ZCISe QDSCs, which is comparable to those based on the capping ligand induced self-assembly route. This report demonstrates the great potential of bicomponent solvents at the CP for high QD loading and excellent cell performance and presents a platform for assembling functional composites with the use of different nanocrystals and substrates.