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Dynamic binary analysis is a prevalent and indispensable technique in program analysis. While several dynamic binary analysis tools and frameworks have been proposed, all suffer from one or more of: prohibitive performance degradation, a semantic gap between the analysis code and the program being analyzed, architecture/OS specificity, being user-mode only, and lacking APIs. We present DECAF, a virtual machine based, multi-target, whole-system dynamic binary analysis framework built on top of QEMU. DECAF provides Just-In-Time Virtual Machine Introspection and a plugin architecture with a simple-to-use event-driven programming interface. DECAF implements a new instruction-level taint tracking engine at bit granularity, which exercises fine control over the QEMU Tiny Code Generator (TCG) intermediate representation to accomplish on-the-fly optimizations while ensuring that the taint propagation is sound and highly precise. We perform a formal analysis of DECAF's taint propagation rules to verify that most instructions introduce neither false positives nor false negatives. We also present three platform-neutral plugins - Instruction Tracer, Keylogger Detector, and API Tracer, to demonstrate the ease of use and effectiveness of DECAF in writing cross-platform and system-wide analysis tools. Implementation of DECAF consists of 9,550 lines of C++ code and 10,270 lines of C code and we evaluate DECAF using CPU2006 SPEC benchmarks and show average overhead of 605 percent for system wide tainting and 12 percent for VMI.

Polyoxometalates (POMs), anionic nanosized oxoclusters that can be considered as fragments of metal oxides, have been extensively studied for their diverse composition and structure, showing promise in various fields such as catalysis and electronics. Proton conduction, relevant to catalysis and electronics, has attracted interest in materials chemistry, and POM anions are advantageous in terms of their proton carrier density and mobility. Recently, polar POMs have attracted attention for their unique ferroelectric behaviors, yet they have been little studied with regard to proton conduction, as their polarity has generally been believed to have a negative impact. Here, we propose that polar POMs can be used to align polar proton carriers, such as H 2 O and polymers, to construct efficient proton-conducting pathways. In this study, we present ionic crystals composed of polar Preyssler-type POMs ([X n + (H 2 O)P 5 W 30 O 110 ] (15- n )- , X n + = Ca 2+ , Eu 3+ ) and K + exhibiting ultrahigh proton conductivity surpassing 10 -2 S cm -1 , which is required for practical applications. In contrast, ionic crystals with nonpolar Preyssler-type POMs show an order of magnitude lower proton conductivity. Structural and spectroscopic studies combined with theoretical calculations reveal that proton carriers align with the aid of staggered arrays of polar POMs, forming a hydrogen-bonding network favorable for proton conduction. This study integrates molecular chemistry by the design of POMs and solid-state chemistry by exploring long-range proton conduction mechanisms, offering novel insights for future materials design.

To explore the action mechanism of berberine in improving adipocytic insulin resistance(IR) by mediating brain and muscle arnt-like 1(BMAL1): circadian locomotor output cycles kaput(CLOCK) complex and regulating glucose and lipid metabolism. After the IR-3T3-L1 adipocyte model was established by dexamethasone induction for 96 h, 0.5, 1, 5, 10, and 20 μmol·L~(-1) berberine was administered for 24 h. The glucose oxidase method and cell counting kit-8(CCK-8) were used to detect extracellular glucose content and cell viability, respectively. The triglyceride(TG) and glycerol contents were detected by enzyme colorimetry. Oil red O staining was used to detect lipid droplets, and fluorescence staining was used to detect Ca~(2+), mitochondrial structure, and reactive oxygen species(ROS). Adiponectin(ADPN), BMAL1, CLOCK, hormone-sensitive triglyceride lipase(HSL), carbohydrate-response element-binding protein(ChREBP), sterol regulatory element-binding protein 1C(SREBP-1C), peroxisome proliferator-activated receptor γ coactivator 1α(PGC1α), carnitine palmitoyl transferase 1α(CPT1α), and peroxisome proliferator-activated receptor α(PPARα) were detected by Western blot(WB). Moreover, the nuclear localization of BMAL1 was detected by immunofluorescence. In addition, 20 μmol·L~(-1) CLK8 inhibitor was added to detect glucose consumption and BMAL1/ChREBP/PPARα protein. The results showed that berberine increased glucose consumption in IR-3T3-L1 adipocytes without affecting cell viability and reduced TG content. In addition, 5 μmol·L~(-1) berberine increased glycerol content and reduced lipid droplet accumulation due to enhanced lipolysis, while 10 μmol·L~(-1) berberine did not affect glycerol content, and fewer lipid droplets were observed due to enhanced lipolysis and glycerol utilization. Berberine improved mitochondrial function by reducing intracellular Ca~(2+) and ROS in IR-3T3-L1 adipocytes and upregulated PGC1α to improve the mitochondrial structure. The results also showed that berberine elevated ADPN to increase the insulin sensitivity of IR-3T3-L1 adipocytes, upregulated peripheral rhythm-related proteins BMAL1 and CLOCK, and strengthened the nuclear localization of BMAL1. In addition, berberine increased key lipolysis protein and lipid oxidation rate-limiting enzyme CPT1α and downregulated the key protein of TG synthesis, SREBP-1C. Moreover, ChREBP and PPARα in IR-3T3-L1 adipocytes were upregula-ted. All the above results suggested that berberine may transform glucose into lipids to enhance the hypoglycemic effect. By considering that CLK8 specifically inhibited the CLOCK acylation to modify BMAL1 and form complex, the results showed that the addition of CLK8 to the berberine group reduced glucose consumption, which suggested that berberine upregulated the formation of BMAL1:CLOCK complex to improve glucose metabolism. The addition of CLK8 to the berberine group upregulated BMAL1 but downregulated ChREBP and PPARα, which suggested that berberine mediated BMAL1:CLOCK complex for the regulation of glucose and lipid metabo-lism to improve adipocytic IR.

Carbon dioxide (CO 2 ) coupled with epoxide to generate cyclic carbonate stands out in carbon neutrality due to its 100% atom utilization. In this work, the mechanism of CO 2 cycloaddition with propylene oxide (PO) cocatalyzed by windmill-shaped polyoxovanadate, [(C 2 N 2 H 8 ) 4 (CH 3 O) 4 V IV 4 V V 4 O 16 ]·4CH 3 OH (V 8 -1), and n -Bu 4 NX (X = Br, I) was thoroughly investigated using density functional theory (DFT) calculations. The ring-opening, CO 2 -insertion, and ring-closing steps of the process were extensively studied. Our work emphasizes the synergistic effect between V 8 -1 and n -Bu 4 NX (X = Br, I). Through the analysis of an independent gradient model based on Hirshfeld partition (IGMH), it was found that the attack of n -Bu 4 NX (X = Br, I) on C β of PO triggers a distinct attractive interaction between the active fragment and the surrounding framework, serving as the primary driving force for the ring opening of PO. Furthermore, the effect of different cocatalysts was explored, with n -Bu 4 NI being more favorable than n -Bu 4 NBr. Moreover, the role of V 8 -1 in the CO 2 cycloaddition reaction was clarified as not only acting as Lewis acid active sites but also serving as "electron sponges". This work is expected to advance the development of novel catalysts for organic carbonate formation.

Catalytic hydrogenation of nitrobenzene (Ph-NO 2 ) to aniline (Ph-NH 2 ) is a model reaction in the field of catalysis, in which the development of efficient catalysts remains a great challenge due to the lack of strategies to solve activity and selectivity problems. In this work, the mechanism of Ph-NO 2 hydrogenation over Pt 1 supported on phosphomolybdic acid (α-PMA) was proposed by density functional theory (DFT) calculations. The results show that the dissociation of the first and second N-O bonds is triggered by single H-induced and double H-induced mechanisms, respectively. The limiting potential of the reaction process is -0.19 V, which is the smallest potential in the field of Ph-NO 2 reduction reaction to date. In the whole reaction process, the catalytic active site is the Pt atom, and polyoxometalate plays the role of an electronic sponge in the reaction. Additionally, based on experimentally confirmed Pt 1 /Na 3 PMA, the reduction capacity of Pd 1 /Na 3 PMA toward Ph-NO 2 was predicted by DFT calculation. The distinctive adsorption patterns of Ph-NO 2 on Pt 1 /Na 3 PMA and Pd 1 /Na 3 PMA were elucidated using the DOS diagram and fragment molecular orbital analysis. We anticipate that our theoretical calculations can provide novel perspectives for experimental researchers.

Anchoring transition metal (TM) atoms on suitable substrates to form single-atom catalysts (SACs) is a novel approach to constructing electrocatalysts. Graphdiyne with sp-sp 2 hybridized carbon atoms and uniformly distributed pores have been considered as a potential carbon material for supporting metal atoms in a variety of catalytic processes. Herein, density functional theory (DFT) calculations were performed to study the single TM atom anchoring on graphdiyne (TM 1 -GDY, TM=Sc, Ti, V, Cr, Mn, Co and Cu) as the catalysts for CO 2 reduction. After anchoring metal atoms on GDY, the catalytic activity of TM 1 -GDY (TM=Mn, Co and Cu) for CO 2 reduction reaction (CO 2 RR) are significantly improved comparing with the pristine GDY. Among the studied TM 1 -GDY, Cu 1 -GDY shows excellent electrocatalytic activity for CO 2 reduction for which the product is HCOOH and the limiting potential (U L ) is -0.16 V. Mn 1 -GDY and Co 1 -GDY exhibit superior catalytic selectivity for CO 2 reduction to CH 4 with U L of -0.62 and -0.34 V, respectively. The hydrogen evolution reaction (HER) by TM 1 -GDY (TM=Mn, Co and Cu) occurs on carbon atoms, while the active sites of CO 2 RR are the transition metal atoms . The present work is expected to provide a solid theoretical basis for CO 2 conversion into valuable hydrocarbons., (© 2023 Wiley-VCH GmbH.)

This study investigated the mechanism of Gegen Qinlian Decoction(GQD) in improving glucose metabolism in vitro and in vivo by alleviating endoplasmic reticulum stress(ERS). Molecular docking was used to predict the binding affinity between the main effective plasma components of GQD and ERS-related targets. Liver tissue samples were obtained from normal rats, high-fat-induced diabetic rats, rats treated with metformin, and rats treated with GQD. RNA and protein were extracted. qPCR was used to measure the mRNA expression of ERS marker glucose-regulated protein 78(GRP78), and unfolded protein response(UPR) genes inositol requiring enzyme 1(Ire1), activating transcription factor 6(Atf6), Atf4, C/EBP-homologous protein(Chop), and caspase-12. Western blot was used to detect the protein expression of GRP78, IRE1, protein kinase R-like ER kinase(PERK), ATF6, X-box binding protein 1(XBP1), ATF4, CHOP, caspase-12, caspase-9, and caspase-3. The calcium ion content in liver tissues was determined by the colorimetric assay. The ERS-HepG2 cell model was established in vitro by inducing with tunicamycin for 6 hours, and 2.5%, 5%, and 10% GQD-containing serum were administered for 9 hours. The glucose oxidase method was used to measure extracellular glucose levels, flow cytometry to detect cell apoptosis, glycogen staining to measure cellular glycogen content, and immunofluorescence to detect the expression of GRP78. The intracellular calcium ion content was measured by the colorimetric assay. Whereas Western blot was used to detect GRP78 and ERS-induced IRE1, PERK, ATF6, and eukaryotic translation initiation factor 2α(eIF2α) phosphorylation. Additionally, the phosphorylation levels of insulin receptor substrate 1(IRS1), phosphatidylinositol 3-kinase regulatory subunit p85(PI3Kp85), and protein kinase B(Akt), which were involved in the insulin signaling pathway, were also measured. In addition, the phosphorylation levels of c-Jun N-terminal kinases(JNKs), which were involved in both the ERS and insulin signaling pathways, were measured by Western blot. Molecular docking results showed that GRP78, IRE1, PERK, ATF4, and various compounds such as baicalein, berberine, daidzein, jateorhizine, liquiritin, palmatine, puerarin and wogonoside had strong binding affinities, indicating that GQD might interfere with ERS-induced UPR. In vivo results showed that GQD down-regulated the mRNA transcription of Ire1, Atf6, Atf4, Grp78, caspase-12, and Chop in diabetic rats, and down-regulated GRP78, IRE1, PERK, as well as ERS-induced apoptotic factors ATF4 and CHOP, caspase-12, caspase-9, and caspase-3, while up-regulating XBP1 to enhance adaptive UPR. In addition, GQD increased the calcium ion content in liver tissues, which facilitated correct protein folding. In vitro results showed that GQD increased glucose consumption in ERS-induced HepG2 cells without significantly affecting cell viability, increased liver glycogen synthesis, down-regulated ATF6 and p-eIF2α(Ser51), and down-regulated IRE1, PERK, and GRP78, as well as p-IRS1(Ser312) and p-JNKs(Thr183/Tyr185), while up-regulating p-PI3Kp85(Tyr607) and p-Akt(Ser473). These findings suggested that GQD alleviates excessive ERS in the liver, reduces insulin resistance, and improves hepatic glucose metabolism in vivo and in vitro.

We previously introduced a three-stage design and associated end-of-stage analyses for allergen immunotherapy (AIT) trials. End-of-stage differences alone may not provide a fuller picture of Stages 2 and 3 effects because they may depend upon stage-specific durations. Therefore, we introduce an additional trend analysis to evaluate the difference in progression curves of two groups over the entire stage. Results from such analysis are used to inform persistence of end-of-stage benefit and thus provide evidence for stagewise effects beyond the study periods. We jointly apply end-of-stage and trend analyses to support the enhanced three-stage design to determine treatment response over time and sustained response to AIT. A simulation study was performed to illustrate the statistical properties (bias and power) of trend analyses under varying statistical missing mechanisms and effect sizes. The extent of bias depended on the missing mechanism and magnitude. Powers were largely driven by effect and sample sizes as well as pre-specified success margins, particularly of relative trend. As an illustration, assuming relative treatment differences of 25-30%, stagewise dropout rate of 15%, and parallel outcome progressions, a sample size of 200 per group may achieve 97% power to demonstrate a treatment effect and 53% power to demonstrate a sustained effect post-treatment. Trend analysis supplements the end-of-stage analysis to enhance the statistical claims of stagewise effects. Inferential statistics support our proposed trend analysis for evaluating benefits of AIT over time and inform clinical understanding and decisions., Competing Interests: The authors have declared that no competing interests exist., (Copyright: This is an open access article, free of all copyright, and may be freely reproduced, distributed, transmitted, modified, built upon, or otherwise used by anyone for any lawful purpose. The work is made available under the Creative Commons CC0 public domain dedication.)

Electrocatalytic nitrogen reduction reaction (NRR) under ambient conditions provides an intriguing pathway to convert N 2 into NH 3 . However, significant kinetic barriers of the NRR at low temperatures in desirable aqueous electrolytes remain a grand challenge due to the inert N≡N bond of the N 2 molecule. Herein, we propose a unique strategy for in situ oxygen vacancy construction to address the significant trade-off between N 2 adsorption and NH 3 desorption by building a hollow shell structured Fe 3 C/Fe 3 O 4 heterojunction coated with carbon frameworks (Fe 3 C/Fe 3 O 4 @C). In the heterostructure, the Fe 3 C triggers the oxygen vacancies of the Fe 3 O 4 component, which are likely active sites for the NRR. The design could optimize the adsorption strength of the N 2 and N x H y intermediates, thus boosting the catalytic activity for the NRR. This work highlights the significance of the interaction between defect and interface engineering for regulating electrocatalytic properties of heterostructured catalysts for the challenging NRR. It could motivate an in-depth exploration to advance N 2 reduction to ammonia., (© 2023 Wiley-VCH Verlag GmbH.)

Background: The architecture of retrorectal fasciae is complex, as determined by different anatomical concepts. The aim of this study was to examine the anatomical characteristics of the inferomedial extension of the urogenital fascia (UGF) involving the pelvis to explore its relationship with the adjacent fasciae. Furthermore, we have expounded on the clinical application of UGF., Method: For our study, we examined 20 adult male pelvic specimens fixed in formalin, including 2 entire pelvic specimens and 18 semipelvic specimens. Our department has performed 466 laparoscopic rectal cancer procedures since January 2020. We reviewed the surgical videos involving UGF preservation and analyzed the anatomy of the UGF., Results: The bilateral hypogastric nerves ran between the visceral and parietal layers of the UGF. The visceral fascia migrated ventrally at the fourth sacral vertebra, which formed the rectosacral fascia together with the fascia propria of the rectum; the parietal layer continually extended to the pelvic diaphragm, terminating at the levator ani muscle. At the third to fourth sacral vertebra level, the two layers constituted the lateral ligaments., Conclusion: The double layers of the UGF are vital structures for comprehending the posterior fascia relationship of the rectum. The upper segment between the fascia propria of the rectum and the visceral layer has no evident nerves or blood vessels and is regarded as the " holy plane" for the operation., (© 2023. The Author(s).)

Background: Controversies regarding the anatomical structure of Denonvilliers' fascia and its relationship with surrounding fasciae have sparked a heated discussion, especially concerning whether Denonvilliers' fascia is multilayered. This study aimed to expound on the anatomical structure of Denonvilliers' fascia and its correlation with the peritoneum from the sagittal view and clarify the complex fascial relationship., Methods: Our study was performed on 20 adult male pelvic specimens fixed in formalin, including 2 entire pelvic specimens and 18 semipelvic specimens. The local adjacent organs and fasciae were dissected, and Denonvilliers' fascia was observed and removed for histological examination., Results: Denonvilliers' fascia was typically single-layered and tough. On the sagittal plane, the peritoneum constituting the peritoneal reflection and Denonvilliers' fascia formed a "Y" shape. Denonvilliers' fascia originated from the peritoneal reflection, extended along the ventral side of the seminal vesicles and prostate, continuing caudally; its bilateral sides closely connected to the urogenital fascia (UGF) of the pelvic wall. In addition, histology preliminarily indicated that the basal cell layers of the peritoneum and Denonvilliers' fascia were continuous and formed a "Y" shape. Furthermore, the basal cells of the two peritonea extended to Denonvilliers' fascia, creating a fused double-layered structure. Some tiny blood vessels or a network of such vessels extended from the peritoneum to Denonvilliers' fascia., Conclusion: Denonvilliers' fascia, the extension of the peritoneum in the pelvic floor, appears as a single-layered "Y"-shape on the sagittal plane. Our study provides new support for the peritoneal fusion theory. Understanding the anatomical characteristics of Denonvilliers' fascia and its relationship with the UGF is of guiding significance for inexperienced colorectal surgeons to conduct rectal cancer surgery., (© 2023. The Author(s).)

Background: Clinical trials of allergen immunotherapy (AIT) may require up to 5 years to complete. These lengthy trials may be complicated by high and potentially differential dropouts, especially among participants who perceive that they are receiving placebo. We propose a three-stage design in which the placebo group in Stage 1 crosses over to receive active treatment in Stage 2. In Stage 3, AIT is discontinued to determine whether benefit is maintained post-treatment. We apply inferential statistics to support the three-stage design for clinical trials to determine clinical efficacy, treatment response over time, and sustained response to AIT., Methods: The proposed framework constitutes a series of hypothesis tests for comparing treatment responses at the end of each stage. A simulation study was performed to illustrate the statistical properties under varying statistical missing mechanisms and effect sizes., Results: The statistical properties in terms of bias and statistical power were consistent with what are expected from conventional analyses. Specifically, the extent of bias depended on the missing mechanism and magnitude. The statistical powers were largely driven by effect and sample sizes as well as prespecified success margins. As an illustration, assuming relative treatment differences of 25% and stagewise dropout rate of 15%, a sample size of 200 per group may achieve 93% power to demonstrate a treatment effect and 60% power to demonstrate a maintained response post-treatment., Conclusions: Inferential statistics support our proposed study design for evaluating benefits of AIT over time and inform clinical understanding and decisions., (© 2021 European Academy of Allergy and Clinical Immunology and John Wiley & Sons Ltd.)

Conditional power (CP) is widely used in clinical trial monitoring to quantify the evidence for futility stopping or sample size adaptation during the trial. When planning an interim analysis in vaccine trials for seasonal infectious diseases, CPs calculated under the hypothesized or currently estimated effect sizes may not truly reflect future data due to seasonal variations in disease incidence and/or vaccine efficacy (VE). Relying on these estimates alone could lead to erroneous decisions. Therefore, we carried out simulation studies to investigate the use of seven different choices for the drift parameter in computing CP or predictive power (PP) in end-of-season interim analysis. Our simulations showed that, when used to inform futility stopping, CP under the hypothesized effect and a weighted PP under a normal prior distribution appear to outperform others in terms of the overall type II error rate. All CPs and PPs considered in this study resulted in comparable powers and expected sample sizes when used to inform sample size adaptation. The performance of either CP or PP largely depends on the extent to which the chosen drift parameter or the prior distribution of the drift parameter matches the remainder of the trial. Weighted CP/PP tends to be less sensitive to settings where observed data and emerging data in future seasons differ substantially as they incorporate both current estimate and future variations. Therefore, weighted strategies deserve further exploration and perhaps increased usage in guiding trial operations because they are more robust to inaccuracies in prediction. In summary, for vaccine trials with seasonal variations, a decision on trial operations should be guided by a careful consideration of plausible CPs and PPs calculated under reasonable assumptions leveraging the data, prior hypotheses, and new evidence on clinical relevance.

The remarkably reversible thermochromic luminescence behavior and the rare nonlinear optical (NLO) properties of the [Ag 55 (MoO 4 ) 6 (C[triple bond, length as m-dash]C t Bu) 24 (CH 3 COO) 18 (CH 3 COO)]·2H 2 O ({Ag 55 Mo 6 } for short) nanocluster reported were investigated experimentally. The important contributions of Ag + , C[triple bond, length as m-dash]C - ions and MoO 4 2- groups to the NLO properties were proved by further density functional theory (DFT) calculations., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

We demonstrate a facile synthesis method of a porous ionic crystal (PIC) composed of the little-known δ-Keggin-type cationic polyoxoaluminum cluster ([δ-Al 13 O 4 (OH) 24 (H 2 O) 12 ] 7+ , δ-Al 13 ) with an oppositely-charged polyoxometalate, which enabled us to investigate the activity as a solid acid. The δ-Al 13 based PIC exhibited much higher activity in pinacol rearrangement, a typical acid-catalyzed reaction, than the PIC based on the well-known and thermodynamically stable rotational isomer (ε-Al 13 ). This work is a rare example of rotational isomers of polyoxoaluminum clusters exhibiting remarkably different catalytic activities.

Fenton reaction, a typical inorganic reaction, is broadly utilized in the field of wastewater treatment. Recently In case of its ability to inhibit the growth of cancer cells, it has been frequently reported in cancer treatment. Using the unique tumor microenvironment in cancer cells, many iron-based nanoparticles have been developed to release iron ions in cancer cells to induce Fenton reaction. In this mini review, we outline several different types of iron-based nanoparticles and several main means to enhance Fenton reaction in cancer cells. Finally, we discussed the advantages and disadvantages of iron-based nanoparticles for cancer therapy, prospected the future development of iron-based nanoparticles. It is believed that iron-based nanoparticles can make certain contribution to the cause of human cancer in the future.

Photocatalytic carbon dioxide reduction (CO 2 RR) is considered to be a promising sustainable and clean approach to solve environmental issues. Polyoxometalates (POMs), with advantages in fast, reversible, and stepwise multiple-electron transfer without changing their structures, have been promising catalysts in various redox reactions. However, their performance is often restricted by poor thermal or chemical stability. In this work, two transition-metal-modified vanadoborate clusters, [Co(en) 2 ] 6 [V 12 B 18 O 54 (OH) 6 ]·17H 2 O (V 12 B 18 -Co) and [Ni(en) 2 ] 6 [V 12 B 18 O 54 (OH) 6 ]·17H 2 O (V 12 B 18 -Ni), are reported for photocatalytic CO 2 reduction. V 12 B 18 -Co and V 12 B 18 -Ni can preserve their structures to 200 and 250 °C, respectively, and remain stable in polar organic solvents and a wide range of pH solutions. Under visible-light irradiation, CO 2 can be converted into syngas and HCOO - with V 12 B 18 -Co or V 12 B 18 -Ni as catalysts. The total amount of gaseous products and liquid products for V 12 B 18 -Co is up to 9.5 and 0.168 mmol g -1 h -1 . Comparing with V 12 B 18 -Co, the yield of CO for V 12 B 18 -Ni declines by 1.8-fold, while that of HCOO - increases by 35%. The AQY of V 12 B 18 -Co and V 12 B 18 -Ni is 1.1% and 0.93%, respectively. These values are higher than most of the reported POM materials under similar conditions. The density functional theory (DFT) calculations illuminate the active site of CO 2 RR and the reduction mechanism. This work provides new insights into the design of stable, high-performance, and low-cost photocatalysts for CO 2 reduction.

The development of inexpensive and efficient bifunctional electrocatalysts is significant for widespread practical applications of overall water splitting technology. Herein, a one-pot solvothermal method is used to prepare hollow porous MnFe 2 O 4 spheres, which are grown on natural-abundant elm-money-derived biochar material to construct MnFe 2 O 4 /BC composite. When the overpotential is 156 mV for both the oxygen evolution reaction and the hydrogen evolution reaction, the current density reaches up to 10 mA cm -2 , and its duration is 10 h. At 1.51 V, the overall water decomposition current density of 10 mA cm -2 can be obtained in 1 m KOH. This work proves that elm-money-derived biochar is a valid substrate for growing hollow porous spheres. MnFe 2 O 4 /BC give a promising general strategy for preparing the effective and stable bifunctional catalysis that can be expand to multiple transition metal oxide., (© 2020 Wiley-VCH GmbH.)

The electronic properties of dyes can be readily tuned by modifying the structure. Herein, the polyoxometalate (POM)-based dyes derived from dye XW11 with new patterns, donor-acceptor-π linker-acceptor (D-A-π-A) structure (dye 1), and D-π-A-π-A structure (dye 2) were designed by inserting a POM moiety besides the extensively exploited D-π-A structure (dye 3). Based on density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations, the configuration effect on the designed dyes was investigated. The results indicate that dye 3 possesses the largest short-circuit photocurrent density JSC due to the red-shifted absorption spectra, superior intramolecular charge transfer (ICT) parameters and the largest electron injection efficiency. At the same time, dye 1 with a D-A-π-A structure not only benefits the conduction band energy shift, but also retards the charge recombination and dye aggregation effect, which is beneficial for open-circuit photovoltage VOC. Moreover, the dynamics analysis of interfacial electron transfer shows that the electrons in dye 1 are almost completely injected after 14 fs, while it takes a long time for dyes 2 and 3. The present work is expected to establish a structure-property relationship for future dye design.

Photocatalytic CO 2 reduction into energy carriers is of utmost importance due to the rising concentrations of CO 2 and the depleting energy resource. However, the highly selective generation of desirable hydrocarbon fuel, such as methane (CH 4 ), from CO 2 remains extremely challenging. Herein, we present two stable polyoxometalate-grafted metalloporphyrin coordination frameworks (POMCFs), which are constructed with reductive Zn-ϵ-Keggin clusters and photosensitive tetrakis(4-carboxylphenyl)porphyrin (H 2 TCPP) linkers, exhibiting high selectivity (>96%) for CH 4 formation in a photocatalytic CO 2 -reduction system. To our knowledge, the high CH 4 selectivity of POMCFs has surpassed all of the reported coordination-framework-based heterogeneous photocatalysts for CO 2 -to-CH 4 conversion. Significantly, the introduction of a Zn-ϵ-keggin cluster with strong reducing ability is the important origin for POMCFs to obtain high photocatalytic selectivity for CH 4 formation, considering that eight Mo V atoms can theoretically donate eight electrons to fulfill the multielectron reduction process of CO 2 -to-CH 4 transformation., (© The Author(s) 2019. Published by Oxford University Press on behalf of China Science Publishing & Media Ltd.)

The design and synthesis of polynuclear metal cluster-based coordination cages is of considerable interest due to their appealing structural characteristics and potential applications. Herein, we report a calix[4]resorcinarene-based [Co 12 ] coordination cage, [Co 12 (TPC4R-I) 2 (1,3-BDC) 10 (μ 3 -OH) 4 (H 2 O) 10 (DMF) 2 ]·7DMF·23H 2 O ( 1 ), assembled with 2 bowl-shaped calix[4]resorcinarenes (TPC4R-I), 10 angular 1,3-benzenedicarboxylates (1,3-BDC), and 12 Co(II) cations. Remarkably, it is shown to be a highly efficient recyclable heterogeneous catalyst for CO 2 conversion due to its exposed Co(II) Lewis acid sites.

The performance of Mn II/III -monosubstituted heteropolytungstates [Mn III (H 2 O)GeW 11 O 39 ] 5- ([GT-Mn III -OH 2 ] 5- , where GT = GeW 11 O 39 ) and [Mn II (H 2 O)GeW 11 O 39 ] 6- ([GT-Mn II -OH 2 ] 6- ) as water oxidation catalysts at pH 9 was explored using density functional theory calculations. The counterion effect was fully considered, in which five and six Na + ions were included in the calculations for water oxidation catalyzed by [GT-Mn III -OH 2 ] 5- and [GT-Mn II -OH 2 ] 6- , respectively. The process of water oxidation catalysis was divided into three elemental stages: (i) oxidative activation, (ii) O-O bond formation, and (iii) O 2 evolution. In the oxidative activation stage, two electrons and two protons are removed from [Na 5 -GT-Mn III -OH 2 ] and three electrons and two protons are removed from [Na 6 -GT-Mn II -OH 2 ]. Therefore, the Mn IV -O • species [Na 5 -GT-Mn IV -O • ] is obtained. Two mechanisms, (i) water nucleophilic attack and (ii) oxo-oxo coupling, were demonstrated to be competitive in O-O bond formation triggered from [Na 5 -GT-Mn IV -O • ]. In the last stage, the O 2 molecule could be readily evolved from the peroxo or dinuclear species and the catalyst returns to the ground state after the coordination of a water molecule(s).

The system of hepatocyte growth factor (HGF) and its receptor c-Met plays a critical role in tumor invasive growth and metastasis. The mortality rate of colorectal cancer (CRC), one of the most commonly diagnosed malignancies, is increased by it gradual development into metastasis, most frequently in the liver. Overexpression of c-Met, the protein tyrosine kinase receptor for the HCF/scatter factor, has been implicated in the progression and metastasis of human colorectal carcinoma. In this study, we aimed to investigate the role of c-Met in CRC liver metastasis and illustrate the clinical impact of regulating HGF/c-Met signaling in patients with CRC liver metastasis. We found that (I) higher levels of c-Met expression (mRNA and Protein) in CRC liver metastasis than primary CRC by assessing the patient tissue samples; (II) a positive correlation of c-Met expression with tumor stages of CRC liver metastasis, as well as c-Met expression in CRC, live metastasis concurred with regional lymph node metastasis; (III) the clinical impact of downregulation of HGF/c-Met signaling on the reduction of proliferation and invasion in CRC liver metastasis. Therefore, we demonstrate that the regulation of HGF/c-Met pathways may be a promising strategy in the treatment of patients with CRC liver metastasis., (© 2019 The Authors. Journal of Biochemical and Molecular Toxicology Published by Wiley Periodicals, Inc.)

Dual catalysis has become a desirable alternative because of the synergetic effect of two distinct catalysts, but little is known about the mechanism of dual catalysis and its effect on the high reactivity and selectivity. Here, a novel Ullmann C-C cross-coupling of bromobenzene and 4-methoxyphenyltriflate via nickel/palladium dual catalysis has been investigated using density functional theory. The orthogonal reactivity of NiI/Pd0 combination is the precondition and foundation of achieving such a Ullmann cross-coupling reaction. In the present dual catalysis, the NiI complex acts as the primary catalyst, while the Pd0 catalyst plays a decisive role in the cross-selectivity.

A novel oxidation state modulation mechanism, merging oxidative quenching (IrIII-*IrIII-IrIV-IrIII) and nickel catalytic (NiII-NiI-NiIII-NiI-NiII) cycles, has been illuminated unambiguously for photoredox-mediated iridium(iii)/nickel(ii) dual catalyzed C-O cross-coupling of aryl bromide and alcohol. Quinuclidine participates in a crucial proton-coupled electron transfer process to accelerate the reaction and regulate C-O coupling selectivity.

Density functional theory calculations combined with the energy and building-block decomposition analyses have been carried out to investigate the structures, stability orders, redox potentials and proton binding of the six Baker-Figgis isomers (α, β, γ, α*, β* and γ*) of [(SbO 6 )W 18 O 54 (OH) 2 ] 9- {H 2 SbW 18 } and [(NaF 6 )W 18 O 54 (OH) 2 ] 7- {H 2 NaW 18 } anions at the level of PBEsol-D3/TZP. Both bonding energy and Gibbs free energy analyses exhibit that the two non-classical Wells-Dawson (WD) species behave quite differently from each other. The pyroanimonate {H 2 SbW 18 }, with a stability order of γ* > β* > α > α* > β > γ, is a non-classical WD species, while the hexafluoride {H 2 NaW 18 } (α > β > γ > γ* > β* > α*) is a transition intermediate between classical and non-classical WD types, possessing both non-classical ([XW 18 O 60 (OH) 2 ] n- , X = I, Te and W) and classical [Si 2 W 18 O 62 ] 8- properties. Energy decomposition analyses (EDA) reveal that spatial arrangement (E host ), host-guest fragment interaction energy (FIE), and structural distortion energy (DE) are three key factors governing the relative stability of isomers; among these, DE is always dominant, while FIE and E host are subordinated but are still important. Building-block decomposition analyses (BDA) disclose that the octahedral {MO 6 } units of the equatorial belt, particularly the staggered belt, are always more distorted than those of the two polar caps inside each structure. The theoretical redox potentials demonstrate that the oxidizing power increases with a trend of α < β < γ and α* < β* < γ* for both species, and the first redox potential is closely related to the energy level of the LUMO of each anion. Evaluation of the proton inclusion energies suggests that {H 2 NaW 18 } can only embed two protons, while {H 2 SbW 18 } may encapsulate four; the number of embedded protons is controlled by both the charge of the heteroatom X and the volume of the tetrahedral {O 4 }/{OF 3 } cavity.

Unlabelled: ᅟ: Starch requires six enzymes for digestion to free glucose: two amylases (salivary and pancreatic) and four mucosal maltase activities; sucrase-isomaltase and maltase-glucoamylase. All are deficient in suckling rodents., Objective: The objective of this study is to test (13)C-starch digestion before weaning by measuring enrichment of blood (13)C-glucose in maltase-glucoamylase-null and wild-type mice., Methods: Maltase-glucoamylase gene was ablated at the N-terminal. Dams were fed low (13)C-diet and litters kept on low (13)C-diet. Pups were weaned at 21 days. Digestion was tested at 13 and 25 days by intragastric feeding of amylase predigested (13)C-α-limit dextrins. Blood (13)C-glucose enrichment was measured by gas chromatography combustion isotope ratio mass spectrometry (GCRMS) using penta-acetate derivatives., Results: Four hours after feeding, blood (13)C-glucose was enriched by 26 × 10(3) in null and 18 × 10(3) in wild-type mice at 13 days and 0.3 × 10(3) and 0.2 × 103 at 25 days (vs. fasting p = 0.045 and p = 0.045). By jejunal enzyme assay, immunohistochemistry, or Western blots, there was no maltase activity or brush border staining with maltase-glucoamylase antibodies at 13 days, but these were fully developed in the wild-type mice by 25 days. In 13-day null mice, luminal contents were stained by maltase-glucoamylase antibodies. Lactating the mammary gland revealed maltase-glucoamylase antibody staining of alveolar cells. Reverse transcription/polymerase chain reaction (RT/PCR) of lactating glands revealed a secreted form of maltase-glucoamylase., Conclusions: (1) (13)C-α-limit dextrins were rapidly digested to (13)C-glucose in 13-day mice independent of maltase-glucoamylase genotype or mucosal maltase activity. (2) This experiment demonstrates that a soluble maltase activity is secreted in mouse mother's milk which enables suckling pup starch digestion well before brush border enzyme development. (3) This experiment with (13)C-α-limit dextrins needs to be repeated in human breast fed infants.

The cleavage of inert C-C bonds is a central challenge in modern chemistry. Multinuclear transition metal complexes would be a desirable alternative because of the synergetic effect of multiple metal centers. In this work, carbon-carbon bond cleavage and rearrangement of benzene by a trinuclear titanium hydride were investigated using density functional theory. The reaction occurs via a novel "two-state reactivity" mechanism. The important elementary steps consist of hydride transfer, benzene coordination, dehydrogenation, oxidative addition, hydride-proton exchange, and reductive elimination. Most importantly, the ground-state potential energy surface switches from nearly degenerate triplet and antiferromagnetic singlet states to a closed-shell singlet state in the dearomatization of benzene, which effectively decreases the activation barrier. Furthermore, the roles of the transition metal centers and hydrides were clarified.

DNA binding protein A (dbpA) belongs to the Y-box binding protein family and has been reported to play an important role in carcinogenesis. Our previous study demonstrated that the knockdown of dbpA in gastric cancer cells inhibited cell proliferation by modulating the cell cycle. However, the role of dbpA in human colorectal cancer (CRC) remains unclear. In this study, immunohistochemical (IHC) staining and clinicopathological parameter analysis were employed to detect dbpA expression in 44 paired CRC samples and 7 CRC cell lines. Lentivirus-mediated short hairpin RNA (shRNA) was used to silence dbpA, and the effects of dbpA knockdown on cell proliferation were determined by MTT assay, colony formation assay and flow cytometry. Furthermore, a xenograft model was established to observe tumor growth in vivo. Functional analysis indicated that dbpA was overexpressed in the CRC tissues and cell lines, and a high dbpA expression was associated with the depth of invasion (p<0.001), the degree of differentiation (p<0.001), lymphatic metastasis (p<0.001) and vessel invasion (p<0.001). The suppression of dbpA expression resulted in decreased cell proliferation in vitro and tumor growth in vivo, and it induced cell cycle arrest and promoted the apoptosis of the CRC cells. As a whole, our findings illustrate the crucial role of dbpA in colorectal tumorigenesis. Thus, dbpA may be used as a novel and potent therapeutic target in CRC.

A thorough theoretical analysis was carried out on the sulfoxidation with H2O2 catalyzed by a tetranuclear peroxotungstate [SiO4{WO(O2)2}4](4-). The active species is the [SiO4{WO(O2)2}4(H2O2)](4-) (SiW4(H2O2)) complex rather than [SiO4{WO(O2)2}4](4-) (SiW4). The catalytic cycle consists of three elementary processes: oxygen transfer, sulfoxide dissociation, and catalyst regeneration. The oxygen transfer occurs from the peroxo oxygen atom O1 of SiW4(H2O2) to the sulfur center of dimethyl sulfide with a moderate Gibbs activation energy (ΔG°(‡)) of 17.1 kcal mol(-1). By comparing potential energy surfaces and condensed Fukui functions (ƒ(+)), the electrophilicity of the outer peroxo atoms in SiW4(H2O2) determines which oxygen transfers to the dimethyl sulfide. Then, the sulfoxide dissociation proceeds with a small ΔG°(‡) value of 2.3 kcal mol(-1) by elongation of the peroxo O1-O4 distance and elimination of the product dimethylsulfoxide. Finally, the catalyst regeneration is found to occur via two successive proton transfers from H2O2 to the oxygen atoms of peroxotungstates with the ΔG°(‡) values of 15.9 and 15.3 kcal mol(-1), which has been firstly examined in the present study. All of these steps occur easily with moderate ΔG°(‡) values, but the oxygen transfer is the rate-determining step of this catalytic reaction. In addition, the catalytic activity of peroxotungstates can be effectively tuned by changing the heteroatom X of [XO4{WO(O2)2}4(H2O2)](n-) in the order: Se(VI) ≈ S(VI) > As(V) ≈ P(V) > Si(IV).

An ultrastable [Ag55(MoO4)6](43+) ({Ag55Mo6} for short) nanocluster with a Ag-centered multishell structure in compound [Ag55(MoO4)6(C≡C(t)Bu)24(CH3COO)18](OAc)·2H2O (1) has been obtained. The ultrastability of 1 was demonstrated by Mulliken population analysis. In addition, the potential wide gap semiconductor property and electrochemical properties of 1 were investigated.

Density functional theory (DFT) calculations and natural bond orbital (NBO) analysis were carried out to investigate the electronic structures and bonding features between the ruthenium(ii) atom and the SO2 molecule in two ruthenium-sulfur dioxide (SO2) adducts, trans-Ru(NH3)4(SO2)Cl(+) and [{SiW11O39}Ru(II)(SO2)](6-). In addition, the bonding interactions between SO2 and the metal-ruthenium fragment were determined by binding energy (ΔEabs) calculation and electronic structures. The results indicate that the η(1)-S-planar model in both trans-Ru(NH3)4(SO2)Cl(+) and [{SiW11O39}Ru(II)(SO2)](6-) are more favorable. NBO analysis of the bonding interaction between ruthenium and sulfur centers in the [{SiW11O39}Ru(II)(SO2)](6-) complex shows that it possesses a σ and a π bond. It predicts that the polyoxometalate [SiW11O39Ru](6-) can serve as a potential adsorbent for the SO2 molecule because of the strong Ru-S bond relative to Ru(NH3)4Cl(+).

We report a rare all-thiol-stabilized [Ag28(S(t)Bu)23](5+) ({Ag28S23} for short) nanocluster with a "crab-like" shape in compound [Ag28(S(t)Bu)23](CF3COO)5·8CH3OH (1), which has been synthesized by the self-assembly of AgS(t)Bu with CF3COOH, Et3N and KBr/KI in methanol. The diffuse reflection spectrum and luminescence spectra of 1 were investigated.

A new organic-inorganic hybrid titaniobate compound, [Cu(en)2][Cu(en)2(H2O)2]3[Ti2Nb8O28]·8H2O (1) (en = ethylenediamine), was successfully synthesized, characterized by single-crystal X-ray diffraction, IR spectroscopy, thermogravimetric analysis (TGA) and UV-Vis diffuse reflectance spectroscopy and its photoluminescence studied.

The rotary motion based on metallacarboranes around a molecular axis can be controlled by simple electron transfer processes, which provides a basis for the structure-property relationship for the nonlinear optical (NLO) switching. However, this phenomenon has not been previously reported in the development of NLO properties of metallacarboranes. In this work, the metallacarboranes [Ni(III/IV)(C2B9H11)2](-/0) and their C-,B-functionalized derivatives are studied by the density functional theory (DFT) method. By calculating relative energies, we obtained the stable states before and after rotation controlled by simple electron transfer. Then, the static and frequency-dependent second-order NLO properties were calculated by several DFT functionals. According to the TDDFT results, the large NLO responses of the studied compounds are mainly caused by substituent group-to-carborane cage charge transfer (L'LCT) and substituent group-to-metal charge transfer (L'MCT) processes. The order of first hyperpolarizabilities (β values) illustrates that the NLO response can be enhanced by introducing a strong electron-donating group. Significantly, the geometric interconversions resulting from the redox reaction of 1C/1T-6C/6T allow the NLO responses to be switched "ON" or "OFF". The B(9,9')-methoxyphenyl-functionalized derivative of nickelacarborane, having low energetic cost and large different NLO responses between two states (from 0 to 20 998 a.u.), can be an excellent switchable NLO material.

Objectives: Six enzyme activities are needed to digest starch to absorbable free glucose; 2 luminal α-amylases (AMY) and 4 mucosal maltase-glucoamylase (MGAM) and sucrase-isomaltase (SI) subunit activities are involved in the digestion. The AMY activities break down starch to soluble oligomeric dextrins; mucosal MGAM and SI can either directly digest starch to glucose or convert the post-α-amylolytic dextrins to glucose. We hypothesized that MGAM, with higher maltase than SI, drives digestion on ad limitum intakes and SI, with lower activity but more abundant amount, constrains ad libitum starch digestion., Methods: Mgam null and wild-type (WT) mice were fed with starch diets ad libitum and ad limitum. Fractional glucogenesis (fGG) derived from starch was measured and fractional gluconeogenesis and glycogenolysis were calculated. Carbohydrates in small intestine were determined., Results: After ad libitum meals, null and WT had similar increases of blood glucose concentration. At low intakes, null mice had less (f)GG (P = 0.02) than WT mice, demonstrating the role of Mgam activity in ad limitum feeding; null mice did not reduce fGG responses to ad libitum intakes demonstrating the dominant role of SI activity during full feeding. Although fGG was rising after feeding, fractional gluconeogenesis fell, especially for null mice., Conclusions: The fGNG (endogenous glucogenesis) in null mice complemented the fGG (exogenous glucogenesis) to conserve prandial blood glucose concentrations. The hypotheses that Mgam contributes a high-efficiency activity on ad limitum intakes and SI dominates on ad libitum starch digestion were confirmed.

The switchable second-order nonlinear optical (NLO) properties on two-dimensional (2D) molecules based on Lindqvist-type [Mo6O19](2-) and dithienylperfluorocyclopentene (DTE) have been investigated at density functional theory (DFT) level. The CAM-B3LYP and M06-2X functionals were employed to study the switching behavior on NLO properties by photoisomerization reaction. The βtot value of system 2c (closed-ring form) is 15920.5 au, which is 150.1 times larger than that of the corresponding open-ring form (system 2o). The time-dependent DFT calculations predict that the charge transfer from DTE to polyoxometalate, and DTE intramolecular charge transfer in closed-ring systems effectively improve the static first hyperpolarizability. Furthermore, the Λ-shaped systems possess a larger u value than those of W-shaped systems owing to different orientation for substituent groups.

Water oxidation is a key half reaction in the energy conversion scheme. The reaction mechanism for the oxidation of H2O to O2 catalyzed by single-Ru-substituted polyoxometalates, [Ru(III)(H2O)XW11O39](n-) (X = Si(IV), Ge(IV)), was investigated by means of density functional calculations. The electronic structure of the pre-activation intermediates indicates that the aqua ligand is prone to accommodate the proton coupled electron transfer (PCET) process to achieve the active group [Ru(V)=Oa], and the high valent oxo-ruthenium(V) species are responsible for the O-O forming event. Three possible proton acceptors were designed for the rate-determining step (Ob, Oa, and H2O), the calculated results support that the bridge Ob atom of the polytungstate ligand will act as the most favorable proton acceptor in the O-O bond formation, with an energy barrier of 28.43 kcal mol(-1). A detailed information of the peroxidic intermediates in the oxidation process was also characterized, both the peroxo-species [Ru(IV)(OO)SiW11O39](6-) and [Ru(V)(OO)SiW11O39](5-) show the six-coordinate isomer with an open terminal geometry is more favorable than the close seven-coordinate ones. In addition, the replacement of the heteroatom in XO4(n-) can effectively tune the catalytic activity of polyoxometalates, in the order of Ge(IV) > Si(IV).

The ultraviolet-visible and electronic circular dichroism (UV-vis/ECD) spectra of diphosphonate-functionalized asymmetric cantilever-type chiral polyoxomolybdate (POM) enantiomer R-{Mo2O5[(Mo2O6)NH3CH2CH2CH2C(O)(PO3)2]2}(6-) (R) were systematically investigated using time-dependent density functional theory (TDDFT) method. From the view of molecular structure and relative energy, we inferred that there is likely a structural conversion from enantiomers R to S-{Mo2O5[(Mo2O6)NH3CH2CH2CH2C(O)(PO3)2]2}(6-) (S) via the intermediate configuration (IN). The ECD spectra of the enantiomer R were produced over the range of 3.0-6.3eV. The UV-vis and ECD spectra of enantiomer R in the gas phase and different solvents were calculated. The results reveal that the UV-vis and ECD spectra of the chiral POM in gas phase, polar solvent, or non-polar solvent are different. The calculated electron density difference maps (EDDMs) display that the POM cluster is a chiroptical chromophore in studied compound., (Copyright © 2013 Elsevier Inc. All rights reserved.)

The electronic circular dichroism (ECD) and UV-visible absorption (UV-vis) spectra of Strandberg-type polyoxometalates (POMs) (R, R)-[(R*PO3)2M5O15](2-) (R* = CH3CH(NH3), (M = Mo, W)) have been explored using the time-dependent density functional theory (TDDFT) method. It demonstrates that the absolute configurations of chiral systems can be determined by chiroptical spectroscopic methods combined with DFT calculations. The calculated ECD spectra of the Strandberg-type molybdate were produced over the range of 3.3-6.5 eV, which are generally in agreement with the experimental spectra. In addition, the ECD spectra of (R, R)-[(R*PO3)2W5O15](2-) (R* = CH3CH(NH3)) were produced over the range of 4.5-8.5 eV. The Becke's half-and-half hybrid exchange-correlation functional (BHandHLYP) with the HF exchange fraction to 55% hybrid functional was found to well predict the excitation energies of studied systems. The origins of the ECD bands of two systems are mainly ascribed to charge-transfer (CT) transitions from oxygen atoms to metal atoms in polyanion. The results suggest that the polyanion are chiroptical chromophores. The polyanion plays a role as an optically active chromophore and contribute to the absorptions of ECD spectra. The difference of the UV-vis/ECD spectra between two systems shows that the transition metal atom significantly influences on the chiroptical properties of the studied Strandberg-type POMs.

The switchable second-order nonlinear optical (NLO) responses of the photoisomerized chromophore dithienylperfluorocyclopentene (DTE) derivatives, organic-inorganic systems of Lindqvist-type [Mo₆O₁₉]²⁻, have been investigated by tuning open-ring and the closed-ring form. In the present paper, we performed density functional theory (DFT) combined with finite field (FF) methods to calculate the second-order NLO coefficients for these organic-inorganic compounds. The calculations with three functionals (B3LYP/CAM-B3LYP/LC-BLYP) confirm the switching behavior on NLO properties by the photoisomerization reaction. The β(tot) value of system 2c (closed-ring form) is 10 times larger than that of its open-ring form (system 2o). And the other two pairs of systems also show good tuning properties. The ampliative ratio on second-order NLO coefficients between systems 2o and 2c (β(2c)/β(2o)) is 13 times as large as that of DTE (β(DTEc)/β(DTEo)). It suggests that introduction of [Mo₆O₁₉]²⁻ and organic groups to the DTE monomer effectively improve the conversion ratio of second-order NLO coefficients between the open-ring and closed-ring forms., (Copyright © 2013 Elsevier Inc. All rights reserved.)

Two S-containing MOFs, interpenetrating and non-interpenetrating , were synthesized by altering solvent size. The nanoporous reveals high selective adsorption for Cu(2+) ions and has been applied as a chromatographic column for separating transition metal ions for the first time.

A novel 3D hexadecanuclear heteropolyoxozincate organic framework, IFMC-200, has been successfully synthesized based on a late transition metal-oxygen cluster. IFMC-200 not only represents the first example of (3,4,24)-connected framework but also contains the first 24-connected single metal cluster in a crystal structure. It exhibits superior thermal stability, good water-stability, and even insensitivity to the existence of acid and base within a certain range of pH values. Furthermore, it performs as a heterogeneous crystalline Lewis acid catalyst with good activity for the conversion of long-chain fatty acids rather than short-chain ones, and high recycling efficiency for esterification reaction of fatty acids with alcohols to produce biodiesel.

The formation mechanism is always a fundamental and confused issue for polyoxometalate chemistry. Two formation mechanisms (M1 and M2) of the Lindqvist anion [W(6)O(19)](2-) have been adopted to investigate it's self-assembly reaction pathways at a density functional theory (DFT) level. The potential energy surfaces reveal that both the mechanisms are thermodynamically favorable and overall barrierless at room temperature, but M2 is slightly dominant to M1. The formation of the pentanuclear species [W(5)O(16)](2-) and [W(5)O(15)(OH)](-) are recognized as the rate-determining steps in the whole assembly polymerization processes. These two steps involve the highest energy barriers with 30.48 kcal mol(-1) and 28.90 kcal mol(-1), respectively, for M1 and M2. [W(4)O(13)](2-) and [W(4)O(12)(OH)](-) are proved to be the most stable building blocks. In addition, DFT results reveal that the formation of [W(3)O(10)](2-) experiences a lower barrier along the chain channel.

We theoretically investigate a novel switching phenomenon based on the divacant Keggin-type polyoxotungstate bearing chiral organophosphonate [{NH(2)CH(CH(3))PO}(2)(γ-SiW(10)O(36))](4-), that is the synchronous chiroptical and nonlinear optical (NLO) switch triggered by redox. The ECD calculations on the Boltzmann weighted conformations of the three oxidation states of this chiral polyoxometalate (POM) clearly present a chiroptical switching process. The electronic transition and the bond-length alternation studies show that the chirality transfer from chiral carbon atom to POM cage increases as the polyanion is reduced. Simultaneously, the static first hyperpolarizability of studied chiral POM quadrupled from the oxidized state to the 1e-reduced state, and is further doubled to the 2e-reduced state, which is mainly due to the increasing electronic-dipole-allowed d-d charge transfer transitions in the POM cage. This work firstly reproduces the ECD spectrum of chiral POM with high accuracy and proves the possibility for confirming the molecular conformations of flexible chiral POMs in solution by the aid of ECD calculations. Most importantly, a sensitive diplex switch based on a chiral POM is predicted in theory, which may aid the design of novel POM-based switches.

Bridging between silver clusters and polyoxoanion clusters, the first 1D assembly, [Ag(34)(S(t)Bu)(26)(W(6)O(21))(CF(3)COO)](CF(3)COO)·Et(3)N·20CH(3)OH (1), based on POM-templated silver-thiolate nanoclusters featuring a [Ag(34)(S(t)Bu)(26)(CF(3)COO)](7+) shell and a [W(6)O(21)](6-) core is reported. This novel core-shell nanocluster possesses nanoscopic morphology, displays intense deep-blue emission in solution under ambient conditions and also shows special electrochemical properties.

The chiroptical properties of bisarylimidos bearing o-alkoxy chain-substituted polyoxomolybdates [Mo(6)O(17)(2,2'-NC(6)H(4)OC(n)H(2n)OC(6)H(4)N)](2-) [n=4(2), 6(3±), 8(4)] were investigated using the time-dependent density functional method. The results showed that the studied chiral polyoxometalates (POMs) manifested similar absorption sites but displayed different shapes and magnitudes in their electronic circular dichroism (ECD) spectra. The ECD spectra of the studied chiral POMs originated from charge-transfer (CT) transitions from arylimido fragments to the POM cages and from oxygen atoms to the molybdenum atoms in the POM cages. The o-alkoxy chain served as a scaffold for generating chirality rather than contributing to the ECD spectrum of the studied POMs. The induced chiralities of the POM cages were defined by the CT transitions, which were completely localized on the POM cages. Furthermore, the long-range corrected CAM-B3LYP hybrid functional and a basis set that is larger than Lanl2DZ should be used for ECD calculations of chiral POMs. Our work establishes the use of computational studies to investigate the chiroptical properties of chiral POMs and provides theoretical interpretations., (Copyright © 2012 Elsevier Inc. All rights reserved.)

The UV/CD spectra of tin-bearing acetonyl-substituted Wells-Dawson polyoxotungstates α(1)- and α(2)-[P(2)W(17)O(61){SnCH(2)CH(2)C(═O)}](6-) were systematically investigated using the time-dependent density functional theory (TDDFT) method. The electronic circular dichroism (ECD) spectra were produced over the range of 3.3-5.8 eV. The calculated ECD spectra of the α(1)-R isomer were generally in agreement with the experimental spectra. The CAM-B3LYP hybrid functional was found to predict the excitation energies of tin-containing polyoxotungstates well. The fact that the UV/ECD spectra of α(1)-isomers are different from those of α(2)-isomers demonstrates the effect of the tin substitution site on the chiroptical properties of the studied isomers. The origins of the ECD bands are mainly ascribed to charge-transfer (CT) transitions from oxygen atoms to W atoms, from organic fragments to W atoms, or from the combination of two CT transitions. The results suggest that the organic fragment and polyoxometalate (POM) cage are chiroptical chromophores.

The vertical excitation energies of tetrathiafulvalene (TTF)-annulated zinc porphyrazine (ZnPzTTF) were investigated using time-dependent density functional theory (TDDFT) calculations and compared to the experimental UV-vis spectra. To examine the effects of the aza substitutions and TTF groups on the molecular properties, zinc complexes of porphyrin (ZnP), porphyrazine (ZnPz) and tetraTTF-annulated porphyrin (ZnPTTF) were also selected for comparison. It was shown that numerous electronic transitions with TTF-to-porphyrin or porphyrazine charge transfer character exist and the Q band of ZnPzTTF is dominated by TTF-to-porphyrazine charge transfer transition mixed with porphyrazine core unit itself except for classic porphyrazine π→π* transitions. The Q band of ZnPzTTF mixes with other configurations, which breaks down the Gouterman's classic four-orbital model for the spectral interpretation. The data suggest that TDDFT/SAOP performs best for Q and B bands of ZnPzTTF with the maximum error in excitation energy being 0.17 eV. The CAM-B3LYP, ωB97XD and M06-2X calculations qualitatively predict that the low-lying electronic transitions of ZnPzTTF with TTF-to-porphyrazine charge transfer character located below the Q band. The broad and intense red-shifted Q band suggests that ZnPzTTF can be a candidate for dye-sensitized solar cells., (Copyright © 2011 Elsevier Inc. All rights reserved.)

In this paper, density functional theory is used to investigate the linear optical and nonlinear optical (NLO) properties of a series of Λ-type chiral compounds composed of two Lindqvist-type polyoxometalates (POMs) linked by 1,1'-binaphthyl derivatives through arylimido. It shows that compound 1 which has two POMs on 6-6'-sites of 1,1'-binaphthyl possesses large static first hyperpolarizability and the strongest two-dimensional NLO response among studied compounds. The organic substituents on 2-2'-sites of 1,1'-binaphthyl twofold control the NLO responses of studied compounds. They act as electron acceptors or donors therefore suppress or enhance the NLO responses of studied compounds, and they restrain the torsion angles between two naphthyl rings at certain degrees which are inversely proportional to the NLO responses. Compound 6 with remarkable NLO response is obtained as ferrocene substitutes on 2-2'-sites of 1,1'-binaphthyl. Additionally, the electronic circular dichroism (ECD) spectra of studied compounds are simulated with CAM-B3LYP and B3LYP hybrid functionals. The results agree well with the experimental ECD spectra. The charge-transfer transitions from organic fragment to POM are responsible for the ECD differences between molecular hybrids and their precursors. It is confirmed that these Λ-type chiral compounds are potentially high-dimensional NLO materials and the structure-property relationship of these compounds is presented., (Copyright © 2011 Elsevier Inc. All rights reserved.)