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Background: Ovarian cancer (OC) progression is an unmet medical challenge. Since omental metastases were palpated harder than their primary counterparts during cytoreductive surgery of patients with epithelial ovarian cancer, we were inspired to investigate OC progression from the perspective of biomechanics. Methods: Atomic Force Microscope (AFM) was used to measure the young’s moduli of tissues. The collagen-coated polyacrylamide hydrogel (PA gel) system was prepared to mimic the soft and stiff substrates in vitro. The effect of TAGLN were evaluated both in vitro and in vivo using transwell, immunofluorescence, western blot analysis and immunohistochemistry. Findings: We quantitatively confirmed that omental metastases were stiffer and more abundant in desmoplasia compared with paired primary tumors, and further demonstrated that matrix stiffness could notably regulate OC progression. Remarkably, TAGLN, encoding an actin cross-linking/gelling protein, was identified as a potent mechanosensitive gene that could form a regulation loop with Src activation reacting to environmental stiffness, thus mediating stiffness-regulated OC progression through regulating RhoA/ROCK pathway. Interpretation: These data demonstrate that targeting extra-cellular matrix stiffness could probably hamper OC progression, and of note, targeting TAGLN might provide promising clinical therapeutic value for OC therapy. Funding: This work was supported by the “973” Program of China (No. 2015CB553903 to Ding Ma and Junbo Hu), Technical Innovation Special Project of Hubei Province (2018ACA138), the Fundamental Research Funds for the Central Universities (2019kfyXMBZ024), National Science and Technology Major Sub- Project (2018ZX10301402-002), and the National Science Foundation of China (81902661, 81772787, 82072889). Declaration of Interest: None to declare. Ethical Approval: Human ovarian cancer tissues were all obtained from patients undergoing surgery at the Department of Obstetrics and Gynecology, Tongji Hospital, Huazhong University of Science and Technology after obtaining written informed consent of the patients and the authorization of the Ethics Committee of Tongji Hospital (TJ-iRB20181103). Fresh tissues were prepared for the Atomic Force Microscope (AFM) measurement, frozen or formalin fixed.

Hyperglycemia contributes to the excessive proliferation and migration of vascular smooth muscle cells (VSMC), which are closely associated with atherosclerosis. MicroRNAs (miRNAs/miRs) constitute a novel class of gene regulators, which have important roles in various pathological conditions. The aim of the present study was to identify miRNAs involved in the high glucose (HG)‑induced VSMC phenotype switch, and to investigate the underlying mechanism. miRNA sequencing and reverse transcription‑quantitative PCR results indicated that inhibition of miR‑125a expression increased the migration and proliferation of VSMCs following HG exposure, whereas the overexpression of miR‑125a abrogated this effect. Furthermore, dual‑luciferase reporter assay results identified that 3‑hydroxy‑3-methyglutaryl‑coA reductase (HMGCR), one of the key enzymes in the mevalonate signaling pathway, is a target of miR‑125a. Moreover, HMGCR knockdown, similarly to miR‑125a overexpression, suppressed HG‑induced VSMC proliferation and migration. These results were consistent with those from the miRNA target prediction programs. Using a rat model of streptozotocin‑induced diabetes mellitus, it was demonstrated that miR‑125a expression was gradually downregulated, and that the expressions of key enzymes in the mevalonate signaling pathway in the aortic media were dysregulated after several weeks. In addition, it was found that HG‑induced excessive activation of the mevalonate signaling pathway in VSMCs was suppressed following transfection with a miR‑125a mimic. Therefore, the present results suggest that decreased miR‑125a expression contributed to HG‑induced VSMC proliferation and migration via the upregulation of HMGCR expression. Thus, miR‑125a‑mediated regulation of the mevalonate signaling pathway may be associated with atherosclerosis.

C29H24ClN2PPd, triclinic, P1̄ (no. 2), a = 9.9885(8) Å, b = 11.5836(8) Å, c = 11.6133(9) Å, α = 76.342(6)°, β = 89.821(6)°, γ = 71.435(7)°, V = 1233.96(16) Å3, Z = 2, R gt(F) = 0.0337, wR ref(F 2) = 0.0841, T = 291 K.

C30H26ClN2PPd, triclinic, P1̄ (no. 2), a = 9.1278(5) Å, b = 9.5892(7) Å, c = 15.5255(10) Å, α = 79.827(6)°, β = 89.131(5)°, γ = 78.358(5)°, V = 1309.74(14) Å3, Z = 2, R gt(F) = 0.0342, wR ref(F 2) = 0.0706, T = 291 K.

C21H21BrClNRu, triclinic, P1̄ (no. 2), a = 8.2185(4) Å, b = 10.1626(5) Å, c = 11.9356(6) Å, α = 100.399(4)°, β = 90.005(4)°, γ = 93.434(4)°, V = 978.68(9) Å3, Z = 2, R gt(F) = 0.0353, wR ref(F 2) = 0.0676, T = 291(2) K.

Excessive amount of higher alcohols in alcoholic beverages causes unwell and side-effect for consumers although adequate consumption offers joy and pleasure. Therefore, reducing higher alcohols in alcoholic beverages is necessary. We used nitrogen compensation to reduce higher alcohols with Chinese rice wine as an experimental model. Higher alcohols including isobutyl alcohols, isoamyl alcohols, and β-phenethyl alcohols were significantly decreased by 19.27, 23.03 and 19.43%, respectively, when 200 mg/L (NH(4))(2)HPO(4), 5% (w/v) yeast, and 11% wheat Koji were added to fermentation broth. Meanwhile, important quality parameters remained unchanged including free amino acids, organic acids, biogenic amines, and esters. The expression of glutamate dehydrogenase 1 gene (GDH1) and glutamine synthetase gene (GLN1) was significantly enhanced, 26.9- and 1.9-folds respectively. These results suggest that ammonium compensation could effectively decrease higher alcohols in Chinese rice wine by activating glutamate dehydrogenase (GDH) pathway in ammonium assimilation. ELECTRONIC SUPPLEMENTARY MATERIAL: The online version of this article (10.1007/s10068-019-00718-1) contains supplementary material, which is available to authorized users.

The Changjiang Estuary (CE), two transects along the Andong salt marsh (AD-A and AD-C) south-west of Hangzhou Bay, and three salt marshes on Zhoushan Island (ZS-A, ZS-B and ZS-C) were coastal zones receiving different flow regimes and human activities. In this study, sedimentary P species consisting of exchangeable P (Ex-P), iron P (Fe-P), authigenic P, detrital P (De-P) and organic P (OP) were determined in these sediments. The objectives of this study were to evaluate the degree of P pollution and the potential for these sediments to release P into the environment. Authigenic P was the largest fraction in AD-A, AD-C, CE, ZS-A and ZS-B (42–62%), followed by Ex-P (28–33%), Fe-P (4–19%), OP (2–8%) and De-P (1–2%); except in ZS-C where Ex-P was the most abundant (57.86%), followed by authigenic P (24.45%), Fe-P (12.34%), OP (2.85%) and De-P (2.49%). High portions of authigenic P indicate presence of apatite minerals; low levels of OP and De-P suggest low P pollution and low contribution from riverine input. The sedimentary total P (TP) in these locations (ranged from 91.30 to 324.74 mg/kg) indicates the risk of P pollution was very low. However, the bioavailable P (Ex-P, Fe-P and OP) constituted approximately 37–73% of TP. Thus, these locations are prone to release P from Ex-P fraction under oxic conditions and from Fe-P fraction under anoxic conditions.

Sedimentary phosphorus (P) forms are important representatives of P sources and their bioavailability as well as the potential of sediments to release P in water. In this study, surface sediments along a transect of the Changjiang Estuary and two transects along the Andong salt marsh in the southwest of Hangzhou Bay were subjected to the elucidation of sedimentary P species using the standards, measurements, and testing (SMT) and sequential extraction (SEDEX) methods. The results showed that the mean sedimentary P forms elucidated by the SMT method were as follows: organic P (OP; ∼11–14 mg/kg; ∼30–45% of total P; TP) > apatite P (∼5–15 mg/kg; ∼21–36% TP) > Fe/Al-P (∼8–14 mg/kg; ∼31–34% TP), with inorganic P (IP) composing 54–70% of TP. The mean sedimentary P forms elucidated by the SEDEX method were as follows: authigenic P (∼54–68 mg/kg; ∼41–46% TP) > extractable P (Ex-P; ∼36–53 mg/kg; ∼28–34%) > Fe-P (∼21–27 mg/kg; ∼13–19%) > OP (∼8.7–13 mg/kg; ∼5–8%) > detrital P (De-P; ∼2 mg/kg; ∼1–2% TP), with IP composed of ∼91–94% TP. These results showed that the SEDEX method elucidated higher concentrations of sedimentary P forms as well as the TP from these coastal sediments although the SMT method had the advantage of being more economic and faster. The results of both the SMT and SEDEX methods showed that the Andong salt marsh and Changjiang Estuary sediments had much bioavailable P. The mean percentages of bioavailable P from the SMT and SEDEX methods were ∼64–74% and 52–56% of TP, respectively, indicating that these sediments were prone to release P to the coastal areas.

A chromatographic purification free rapid oligosaccharide synthetic strategy was developed. The intermediates were conveniently purified by a new process based on a “capture–release” strategy on a resin that involved the Co2(CO)6-PPh2/alkyne complex and the oxidated de-complex reaction. This method avoids the redundant multi-step classical chromatographic purification protocol and has been proved to be efficient by the synthesis of linear and branched penta-mannosides.

C29H23Cl2N2PPd, monoclinic, P21/c (no. 14), a = 9.4028(16) Å, b = 30.928(5) Å, c = 9.3071(16) Å, β = 103.222(2)°, V = 2634.8(8) Å3, Z = 4, R gt(F) = 0.0423, wR ref(F 2) = 0.1047, T = 296(2) K.

C19H17ClN2OPd, monoclinic, P21/c (no. 14), a = 9.0720(8) Å, b = 10.9390(10) Å, c = 17.9604(7) Å, β = 97.054(6)°, V = 1768.9(2) Å3, Z = 4, R gt(F) = 0.0389, wR ref(F 2) = 0.0816, T = 293(2) K.

Lignin-derived phenols, C/N ratios and ratios of refractory to total organic matter were used to study the sources, distribution, and diagenesis of sedimentary organic matter along estuary, river bank, and salt marsh systems. The Changjiang Estuary showed a higher signal of terrestrial organic matter at the river mouth which decreased farther offshore. The locations along the Qiantang River were affected by their adjacent surroundings, and the Andong salt marsh showed higher terrestrial organic matter signal at the upper marsh compared to the lower marsh. All studied areas showed slight increases in organic matter decomposition farther downstream and towards the sea. Study of these three different systems will improve our understanding on their ecotoxicological impact. The Changjiang Estuary had higher pollutant levels near the river mouth, which decreased farther offshore due to dilution. The midstream Qiantang River was most likely affected by pollution from their adjacent surroundings. Pollutants were likely to be accumulated in the Andong salt marsh due to the presence of marsh plants and small-sized particles. Organic pollutants were likely to be decomposed during transport along the systems. The ability of the sediments to release inorganic pollutants was determined by whether these systems were oxic or anoxic.

Saline-alkaline (SA) stress is one of the major constraints to crop production worldwide. It is characterized by high salinity and high alkalinity (high pH), with the latter being the primary inhibiting factor to rice growth. We previously reported that pretreatment with abscisic acid (ABA) primed rice seedlings for enhanced tolerance to alkaline stress. In the present study, we conducted a 3-year field experiment to further assess the ABA-priming effect on the stress tolerance of rice plants in two paddy fields with different SA levels (field-A: non-reclaimed field, pH = 10.13 +/- 0.009, EC1:5 = 0.50 +/- 0.004; field-B: reclaimed field, pH = 9.74 +/- 1 0.005, EC1:5 = 0.48 +/- 0.001). Rice seedlings were treated with ABA at concentrations of 0 (control), 1, and 10 mu M by root-drenching for 24 h prior to transplanting to the two paddy fields with different SA levels. Compared to the control treatment, ABA application substantially reduced the occurrence of leaf withering by 22%-50% and seedling death by 11%-17%. Further, ABA application also significantly improved subsequent plant growth and the final grain yield by 8%-55%; a more profound effect was observed in the harder SA field. Expressions of the ABA-responsive genes SalT and OsWsi18 were highly induced by ABA treatment, and the induced levels were sustained until at least 8 d after transplanting. Collectively, these results suggest a potent priming effect of ABA on the SA stress tolerance of rice plants, providing an effective and practical approach to improving rice production in SA paddy fields. (C) 2016 Elsevier B.V. All rights reserved.

In this study, two sediment cores (C1 and C2) were collected from the Andong salt marsh southwest of Hangzhou Bay and analysed to determine their different sedimentary phosphorus (P) forms. The changes in the sedimentary P forms over the past 30 years and the implication of these changes on environmental risks were determined. The low mean total P (TP) contents along C1 (30.42 mg/kg) and C2 (68.60 mg/kg) indicate no P pollution in the Andong salt marsh. The sedimentary TP and all P forms decreased towards the present due to a reduction in particle size and an overall decrease in nutrient input. The sedimentary P contents were also affected by other factors, such as typhoons, bridge construction and aquaculture activities that facilitated erosion and increased P input, whereas drought caused a reduction in sedimentary P. Organic P (OP) represented more than half of the TP, and NaOH-P (P bound to Fe and Al oxides and hydroxides) represented more than half of the inorganic P (IP), indicating an overall high level of bioavailable P. Thus, the sediments in the Andong salt marsh could be releasing P during organic matter decomposition and under anoxic conditions.

C20H15N3, orthorhombic, Pbca (no. 61), a = 11.0487(4) Å, b = 13.5000(6) Å, c = 21.1032(10) Å, V = 3147.7(2) Å3, Z = 8, R gt(F) = 0.0448, wR ref(F 2) = 0.1136, T = 293(2) K.

A new silver coordination polymer [Ag4(BPTC)]n has been synthesized by solvothermal reaction of AgNO3 and H4BPTC. The X-ray crystal structural analysis indicates that 1 is a 2D coordinated framework, which contains argentophilic interactions and Ag–C interactions. The thermal stability and luminescent properties were also investigated. In addition, it was found to be efficient catalyst for the Sonogashira reaction.

In the combustion process of pulverized coal injection into blast furnace, the chlorine goes into the unburned pulverized coal is about 17%, the chlorine in the unburned coal keeps original state; The chlorine goes into the blast furnace gas is about 83%, and these chlorine stay as Hcl gas. Changes in air temperature and oxygen rate had no significant effect on the decomposition of chlorine in coal, resulting the rate of Cl into the blast furnace gas is difficult to increase significantly.

A new Co(II) compound, namely [Co(pam)(bpa)(H2O)2]n n(DMF) (1 H2pam = pamoic acid, bpa = 1,2-di(4-pyridyl)ethylene, DMF = N, N’-dimethylformamide), has been successfully synthesized and structurally characterized. Single-crystal X-ray analysis reveals that 1 is a 3-fold interpenetrated three-dimensional (3D) framework. Topological analysis shows that this compound can be simplified into a four-connected CdSO4 topological network. TG analysis reveals that compound 1 can be stable up to 316oC.

Alcohols are of great importance as cheap and readily available organic materials for the preparation of many pharmaceutical products and fine chemicals. In addition, alcohols as electrophiles instead of alkyl halides in C-C (N) bonds forming reactions are particularly attractive because the process produces only water as byproduct. In spite of the existence of many synthetic routes, there are limited reports involving biarylmethanols. The palladium-catalyzed Suzuki reaction is an extremely efficient method for the construction of biaryl compounds. Among various Pd catalysts, palladacycles are one of the most active catalysts for the coupling reactions. From the economical and environmental points of view, employing readily accessible aryl chlorides and the use of water as a solvent in this reaction offer many advantages. However, there have been a few reports which demonstrated that palladacycles catalyzed Suzuki reaction of limited aryl chlorides in water. To our knowledge, only two accounts has been reported concerning the Suzuki of 4-chlorophenylmethanol in organic solvent. Recently, we have developed a cationic cyclopalladated ferrocenylpyrimidine catalyzed Suzuki reaction of aryl halides and 4-(hydroxymethyl)phenylboronic acid for the synthesis of substituted biarylmethanols in water. However, substrates are limited to the aryl bromides and activated aryl chlorides. To date, there is no report that investigates the Suzuki reaction of chlorophenylmethanol in water. As a continuation of our interest in the synthesis of biarylmethanols, we have prepared a new phosphine adduct of palladacycle 2 from the reaction of cyclopalladated ferrocenyloxime dimer 1 with commercially available 2-dicyclohexylphosphanyl-2'-(N,Ndimethylamino) biphenyl (DCPAB) (Scheme 1) and developed a practical method for the synthesis of biarylmethanols by the Suzuki reaction of chlorophenylmethanol and arylboronic acids in water. Complex 2 is airand moisture-stable, both in solid state and in solution. It was fully characterized by elemental analysis, IR, NMR and ESI-MS. In comparison with the corresponding frequencies of the free ferrocenyloxime, the C=N absorptions of 2 has been shifted to low values (1599 cm), indicating that the N atom is coordinated to palladium. The H NMR spectrum of 2 exhibits more signals than expected, and the P NMR appears two singlets at δ 65.54 and 67.15 ppm, suggesting the existence of isomers in solution. A similar phenomenon was also found in the H NMR

A series of N-mustards, which was conjugated to mono- or bis-naphthalimides with a flexible amine link, were synthesized and evaluated for cytotoxicity against five cancer cell lines (HCT-116, PC-3, U87 MG, Hep G2 and SK-OV-3). Several compounds displayed better activities than the control compound amonafide. Further evaluations by fluorescence spectroscopy studies and DNA-interstrand cross-linking assays revealed that the derivatives showed both alkylating and intercalating properties. Among the derivatives, the bis-naphthalimide N-mustard derivative 11b was found to exhibit the highest cytotoxic activity and DNA cross-linking ability. Both 11b and 7b induce HCT-116 cell apoptosis by S phase arrest.

A new heterometallic coordination polymer, namely [Cd3Ca(L-tart)4]n (1 L-tart = L-tartaric acid), has been successfully synthesized and structurally characterized. Single-crystal X-ray analysis reveals that 1 is a complicated three-dimensional (3D) framework, which contains two distinct layers: one containing polyhedrons only based on Cd(II) and the other containing polyhedrons based on Cd(II) and Ca(II).

C15H10BrN, monoclinic, P21/c (no. 14), a = 14.6998(9) Å, b = 5.9337(4) Å, c = 14.6275(11) Å, β = 113.542(8)°, V = 1169.67(15) Å3, Z = 4, R gt(F) = 0.0396, wR ref(F 2) = 0.1103, T = 293(2) K.

Qe report a new compound, namely [Zn2(BTC)(NO3)(DMA)3]n, with 1,3,5-benzenetricarboxylic acid (H3BTC) and N,N′-dimethylacetamide (DMA) by the solvothermal method. The compound is characterized by elemental analysis, thermal analysis and X-ray diffraction (XRD). Single crystal XRD analysis reveals that the compound is an extended three-dimensional framework containing dinuclear [Zn2(COO)3] units as building blocks and can be simplified into a 3-connected srs topological network. There are two kinds of graceful helical chains with opposite chirality. The compound exhibits strong photoluminescent properties at room temperature.

Two new metal–organic entangled frameworks, namely [Cd(FA)0.5(bix)1.5(H2O)] n ·nNO3 (1) and [Cd(FA)(bib)(H2O)2] n (2) (FA = fumaric acid, bix = 4,4′-bis(imidazol-1-ylmethyl)benzene, bib = 1,4-bis(imidazolyl)butane), have been successfully hydrothermally synthesized through mixed ligands strategy. Single crystal X-ray diffraction analysis reveal that 1 is a 2D → 3D polycatenated framework, while 2 is a triply interpenetrated 4-connected dia topological net. Moreover, both compounds exhibit intense luminescence emission at room temperature.

Two air-stable N-heterocyclic carbene (NHC) adducts of cyclopalladated ferrocenylpyridine containing chloride or iodide anions 2–3 have been easily prepared from the bridge-splitting reaction of the palladacyclic dimer 1 and anion exchange reaction, respectively. They were characterized by elemental analysis, IR, 1H, and 13C NMR. Additionally, the structures of these complexes were determined by single-crystal X-ray analysis. These adducts have been successfully applied to the coupling of terminal alkynes with arylboronic acids under atmospheric conditions.

Ribonucleoprotein (RNP) complexes play essential roles in gene expression. Their assembly and disassembly control the fate of mRNA molecules. Here, we describe a method that examines the remodeling and disassembly of RNPs. One unique aspect of this method is that the RNA-binding proteins (RBPs) of interest are produced in HeLa cells with or without the desired modification and the RNP is assembled in cellular extracts with synthetic RNA oligonucleotides. We use this method to investigate how ubiquitination of an RBP affects its ability to bind its RNA target.

Mercury intrusion porosimetry injection is important in assessing microscopic pore structure of reservoirs. This paper introduces an estimated function for investigating the pore characteristic of western Sichuan tight gas reservoir based on VG model. Better correlations between the measured and estimated results have been obtained using VG model. Representative parameters were obtained by fitting the predictions of VG model to the experimental data, and then the estimated formulation was proposed for the studied reservoir. Correlation analysis of the parameters of VG model confirms that absolute permeability and irreducible water saturation are important in mercury injection porosimetry. The approach applied in this paper is helpful in investigating tight reservoirs, especially in the common cases when measurement is difficult to carry out, partly because of complicated variability in the field, and partly because measuring is time-consuming and expensive.

A new soften curing agent for toughening epoxy resins was synthesized by m-phenylene diamine modified with epoxypropyl butyl ether. Fourier transform infrared (FT-IR) analysis showed that the longer the reaction time was, the smaller the absorption peaks of epoxy group were. The results of the mechanical properties demonstrated that the impact property of the epoxy resin cured by modified m-phenylene diamine at the moderate temperature was better than that of cured by un-modified one because of the introduction of soft ether chain.

Three N-heterocyclic carbene (NHC) adducts of cyclopalladated ferrocenylchloropyrimidine, 2–4 [PdCl{[(η5-C5H5)]Fe[(η5-C5H3)-N2C4H2-Cl]}(NHCs)] have been prepared by reaction of the chloride-bridged palladacyclic dimer 1 [PdCl{[(η5-C5H5)]Fe[(η5-C5H3)-N2C4H2-Cl]}]2 with the corresponding imidazolium salts. These complexes were characterized by elemental analysis, IR, ESI–MS and NMR. The use of these complexes as catalysts for the Sonogashira reaction was examined. Complex 4 proved to be an efficient catalyst for the Sonogashira reaction of aryl bromides and some activated aryl chlorides under copper- and amine-free conditions. Typically, using 0.1–2 mol % of catalyst in the presence of 1.5 equivalents of CsOAc as base in dimethylacetamide at 120 °C provided coupling products in good yields.

C10H7ClN2, monoclinic, P21/n (no. 14), a = 7.582(5) Å, b = 11.059(8) Å, c = 10.734(8) Å, β = 99.661(8)°, V =887.3(11) Å3, Z = 4, R gt(F) = 0.0331, wR ref(F 2) = 0.0951, T = 296(2) K.

The existence forms of chlorine entered into blast furnace are chloride created by Cl- and metal cation or organic speciation absorbed in specular coal or structure macromolecule of coal. The chlorine entered into blast furnace merges with blast furnace gas in the form of HCl after conducted a series of chemical reactions. With the increasing of HCl content in blast furnace gas, the coke reactivity decreases and the coke post reaction strength increases, and the reduction process of iron ore is restrained and the low temperature reduction degradation property increases. However, the corrosion of gas pipeline and TRT blade is aggravated by the HCl in blast furnace gas, and then blast furnace gas conveying process and normal operation of TRT unit are affected.

The relation between chlorine and combustion process of pulverized coal in tuyere zone is affected by the existence form of chorine in coal. The combustion process of pulverized coal in tuyere zone is restrained by chorine of coal when the existence form of chorine is chloride created by Cl- and metal cation. The combustion process of pulverized coal in tuyere zone is improved by chorine of coal if chorine existents with the form of combination of HCl and nitrogen functional groups of coal macromolecules. Under the combustion conditions of tuyere zone in blast furnace, the distribution ratio of chlorine in unburned pulverized coal and blast furnace gas is approximately 60% and 40%, respectively.

Two new tri-p-tolylphosphine-cyclopalladated ferrocenylpyrimidine complexes 1 and 2 have been prepared in good yields by reaction of the corresponding chloride-bridged palladacyclic dimers 1a and 2a with tri-p-tolylphosphine. Complexes 1 and 2 were characterized by elemental analysis, IR, 1H NMR, and ESI–MS. Additionally, their crystal structures have been determined by X-ray diffraction, and intermolecular C–H···Cl hydrogen bonds were found in their crystals. Complex 1 was found to be a palladacycle cocrystallization adduct with {PdCl2[P(C6H4-p-Me)3]2}. These complexes were found to be efficient catalysts for the Suzuki reaction.

A novel one-component polyurethane was synthesized by 2,4,6-trichlorophenol (TCP) as blocking agent for polymethylene polyphenyl isocyanate (PAPI). FTIR spectrum indicates that the NCO groups of the isocyanate molecule are blocked with TCP and the added catalyst should make the reaction faster than that of un-added catalyst. The one-component was characterized by1H NMR and13C NMR.

A new Cd(II) coordination polymer, namely [Cd3(mbdc)(TZ)3(COO)(H2O)]n (1 H2mbdc = m-phthalic acid, TZ = 1, 2, 3-triazole), has been successfully synthesized under solvothermal conditions. Single-crystal X-ray analysis reveals that 1 features a two-dimensional (2D) layered structure based on 1,2,3-triazole controlled double helical chain subunits. Luminescent investigation shows that it emits strong fluorescence at room temperature in the solid state.

A new luminescent coordination polymer, namely [HN(CH3)2]n[In(mbdc)2]n·n(DMA) (1 H2mbdc = m-phthalic acid, DMA = N, N′-Dimethylacetamide), has been successfully synthesized and structurally characterized. Single-crystal X-ray analysis reveals that 1 is a two-dimensional layered structure, which is further stacked into a three-dimensional supramolecular framework through intermolecular CH···π interactions.

Density functional theory calculations were carried out for hydrogen atom binding on small AgnCum clusters (n + m ⩽ 5). It was found that hydrogen prefers to bind with Cu atoms when both Ag and Cu site co-exist in the cluster. In general the binding energies increase with the increasing Cu content for the given cluster size. The metal–H frequencies vary according to the way the metal atoms bound with hydrogen. The most favorable dissociation channels and the corresponding dissociation energies for the most stable bare clusters and cluster hydrides are determined.

A new ferrocene-based ligand, 4,6-dimethyl-2-pyrimidinylferrocene (1), was conveniently prepared via the coupling reaction of chloromercuriferrocene and 4,6-dimethyl-2-iodopyrimidine, and its monop...

The study demonstrates the effect of vernolepin on proliferation and apoptosis in ovarian cancer cell lines. The inhibition of cell growth was significant at 30 μM concentration after 48 hours in both OVCAR-3 and SK-OV3 cell lines. Phase-contrast microscopic examination revealed a decrease in number of vernolepin-treated cells. A number of membranous structures and vacuoles were visible in the cytoplasm after 24 hours. After 48 hours chromatin condensation and nuclear fragmentation indicating typical apoptotic changes were observed. Vernolepin treatment lead to 83.6% cell viability compared to control. However the cell viability was increased to 93.7% on after starvation followed by vernolepin treatment. On the other hand, 3-MA in combination with vernolepin decreased cell viability to 54.5%. Annexin V-FITC/PI staining and FACS demonstrated that in OVCAR-3 and SK-OV3 cells treatment with vernolepin (30 µΜ) for 48 hours caused apoptosis in 34.2% and 28.5% cells respectively. Thus, vernolepin-treatment in ovarian carcinoma cells leads to autophagy before the onset of apoptosis and protects cancer cells.

Alcohols are of great importance as cheap and readily available organic materials for the preparation of many pharmaceutical products and fine chemicals. In addition, alcohols as electrophiles instead of alkyl halides in C-C (N) bonds forming reactions are particularly attractive because the process produces only water as byproduct. In spite of the existence of many synthetic routes, there are limited reports involving biarylmethanols. The palladium-catalyzed Suzuki reaction is an extremely efficient method for the construction of biaryl compounds. Among various Pd catalysts, palladacycles are one of the most active catalysts for the coupling reactions. From the economical and environmental points of view, employing readily accessible aryl chlorides and the use of water as a solvent in this reaction offer many advantages. However, there have been a few reports which demonstrated that palladacycles catalyzed Suzuki reaction of limited aryl chlorides in water. To our knowledge, only two accounts has been reported concerning the Suzuki of 4-chlorophenylmethanol in organic solvent. Recently, we have developed a cationic cyclopalladated ferrocenylpyrimidine catalyzed Suzuki reaction of aryl halides and 4-(hydroxymethyl)phenylboronic acid for the synthesis of substituted biarylmethanols in water. However, substrates are limited to the aryl bromides and activated aryl chlorides. To date, there is no report that investigates the Suzuki reaction of chlorophenylmethanol in water. As a continuation of our interest in the synthesis of biarylmethanols, we have prepared a new phosphine adduct of palladacycle 2 from the reaction of cyclopalladated ferrocenyloxime dimer 1 with commercially available 2-dicyclohexylphosphanyl-2'-(N,Ndimethylamino) biphenyl (DCPAB) (Scheme 1) and developed a practical method for the synthesis of biarylmethanols by the Suzuki reaction of chlorophenylmethanol and arylboronic acids in water. Complex 2 is airand moisture-stable, both in solid state and in solution. It was fully characterized by elemental analysis, IR, NMR and ESI-MS. In comparison with the corresponding frequencies of the free ferrocenyloxime, the C=N absorptions of 2 has been shifted to low values (1599 cm), indicating that the N atom is coordinated to palladium. The H NMR spectrum of 2 exhibits more signals than expected, and the P NMR appears two singlets at δ 65.54 and 67.15 ppm, suggesting the existence of isomers in solution. A similar phenomenon was also found in the H NMR

BACKGROUND This study investigated the effects of monosialotetrahexosylganglioside (GM1) on the expression of N-methyl-D-aspartate receptor subunit 2B (NR2B) and phosphorylated (p)-cyclic AMP response element-binding protein (CREB) in the auditory cortex of rats with tinnitus. METHODS Tinnitus-like behavior in rats was tested with the gap prepulse inhibition of acoustic startle paradigm. We then investigated the NR2B mRNA and protein and p-CREB protein levels in the auditory cortex of tinnitus rats compared with normal rats. RESULTS Rats treated for 4 days with salicylate exhibited tinnitus. NR2B mRNA and protein and p-CREB protein levels were upregulated in these animals, with expression returning to normal levels 14 days after cessation of treatment; baseline levels of NR2B and p-CREB were also restored by GM1 administration. CONCLUSIONS These data suggest that chronic salicylate administration induces tinnitus via upregulation of p-CREB and NR2B expression, and that GM1 can potentially be used to treat tinnitus.

Two isomers of nitrochlorobenzene (o-, and p-NCB) were treated by a Pd/Fe catalyst in aqueous solutions through catalytic amination and dechlorination. Nitrochlorobenzenes are rapidly converted to form chloroanilines (CAN) first through an amination process, and then rapidly dechlorinated to become aniline (AN) and Cl(-), without the involvement of any other intermediate reaction products. The amination and dechlorination reaction are believed to take place predominantly on the surface site of the Pd/Fe catalysts. The dechlorination rate of the reductive degradation of the two isomers of nitrochlorobenzene (o-, and p-NCB) in the presence of Pd/Fe as a catalyst was measured experimentally. In all cases, the reaction rate constants were found to increase with the decrease in the Gibbs free energy (correlation with the activation energy) of NCBs formation; the activation energy of each dechlorination reaction was measured to be 95.83 and 77.05 kJ/mol, respectively for o- and p-NCB. The results demonstrated that p-NCBs were reduced more easily than o-NCBs.

An unusual reductive ring-opening reaction in the title compounds, of the phthalimide group with sodium hydride in anhydrous DMF is observed for the first time and the presumed mechanism is described in detail. An unexpected hydrogenation of the phthalimide group was also observed.

Department of Chemistry, Zhengzhou University, Zhengzhou, Henan 450052, ChinaReceived February 3, 2012, Accepted February 25, 2012Key Words : N-Heterocyclic carbene adduct, Palladacycle, Heck reaction, Crystal structurePalladium-catalyzed Heck reaction has become an ex-tremely powerful method in organic synthesis for the formationof carbon-carbon bond.

Since the first report on the use of palladacycles for the Suzuki and Heck reactions by Herrmann, Beller and coworkers in 1995, a wide variety of known and new palladacycles have been successfully used in the coupling reactions. Employing aryl chlorides for this reaction has been focused because aryl chlorides are cheaper and more available than their bromides and iodide counterparts. However, only a few palladacycles have proved to be efficient for the activation of notoriously unreactive aryl chlorides. In most cases the catalysts employed need to be used in relatively high loadings, and poor recovery, which negated the advantages associated with the use of aryl chlorides. PEGs [poly(ethylene glycol)] have clear advantages as a solvent in organic synthesis because they are cheap, steady, readily available, and nontoxic. Recently, liquid PEGs have been adopted as a new approach for catalyst recycling, in a broad range of catalytic organic reactions. We have also found biaryl phosphine adducts of cyclopalladated ferrocenylpyrimidine are very efficient for the amination of aryl chlorides in PEG-400. These adducts combine the stability induced by the presence of a palladacycle framework with the high activity commonly associated with phosphine ligands, and were far more active than the corresponding dimeric palladacycle. As a continuation of our interest in the synthesis and application of cyclopalladated complexes, we have prepared a new phosphine adduct of palladacycle 2 from the reaction of cyclopalladated ferrocenylpyrimidine dimer 1 with commercially available 2-dicyclohexylphosphanyl-2'-(N,N-dimethylamino)biphenyl (DCPAB) (Scheme 1) and examined its activity in the coupling reactions. Complex 2 is airand moisture-stable, both in solid state and in solution. It is very soluble in chloroform, dichloromethane and acetone, but insoluble in petroleum ether and n-hexane. The new complex was fully characterized by elemental analysis, IR, H NMR and ESI-MS. These spectra were well consistent with the title complex. Moreover, the molecular structure of 2 has been ascertained by means of X-ray studies. The molecule of 2 together with selected bond distances and angles is shown in Figure 1. The Pd atom is in a slightly distorted square-planar environment bonded to the phosphorus atom, the chlorine atom, the pyrimidinyl nitrogen atom and the carbon atom of the ferrocenyl moiety. The Pd–P bond length of 2 is similar to those of the related DCPAB-palladacycles, while the above bond length of 2 is longer than those of the related PPh3-palladacycles possibly due to the steric bulk of the DCPAB ligand. 16-18 In the crystal of 2 there exist two types of intermolecular C–H···Cl hydrogen bonds, which link the molecules into a 2D

A disulfated tetrasaccharide fragment with a spacer arm of human hepatocellular carcinoma carbohydrate antigen SB(1a), namely, 2-aminoethyl 3-O-sulfo-beta-D-galactopyranosyl-(1 --3)-2-acetamido-2-deoxy-beta-D-galactopyranosyl-(1 --4)-3-O-sulfo-beta-D-galactopyranosyl-(1 --4)-beta-D-glucopyranoside was synthesized via a [2 + 1 + 1] block building mode. In the last coupling step toward the trisaccharide acceptor 8, benzoyl protected galactosyl bromide donor 14 was found to be much more reactive than the acetyl-protected donors.

A new phenyldihydronaphthalene-type lignan, vitexdoin F (1), along with 22 known lignan derivatives (2-23) was isolated from the seeds of Vitex negundo var. cannabifolia. Their structures were established by comprehensive 1D and 2D NMR spectroscopic analyses. The antioxidant activities of these lignans were evaluated through 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical-scavenging assays, and 16 of these isolates exhibited obvious radical-scavenging effect on the stable-free radical, DPPH.

In contrast to the well-studied regulation of tissue- and developmental stage-specific alternative splicing, the regulated alternative splicing changes in cells responding to environmental cues is poorly understood. Here we report our discovery of a previously unknown calcium-mediated epigenetic program that regulates alternative splicing in mouse cardiomyocytes. We found that elevated calcium levels in cardiomyocytes induced by KCl-mediated depolarization or caffeine treatment led to a robust and reversible skipping of several alternative exons in a CaMKII- and PKD-dependent manner. We selected two genes that showed increased skipping, NF1 and KTN1, for mechanistic studies. We demonstrated that elevated calcium levels induce a translocation of class II HDACs from the cell nucleus to the cytoplasm leading to histone hyperacetylation throughout the gene body of these two genes. Transcriptional elongation rate analysis indicated a two-fold increase of elongation rate for these genes (3.2 to 6.8 kb/min for N...

C19H14BrFeN, monoclinic, P21/c (no. 14), a = 9.8612(3) Å, b = 13.8034(5) Å, c = 11.3372(5) Å, ( = 90.072(3)°, V = 1543.2 Å3, Z = 4, Rgt(F) = 0.0350, wRref(F2) = 0.0746, T = 291 K.