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To obtain a pure product without the isomer byproducts is a goal that many chemists are pursuing. As one kind of very important synthesis method, the photochemical reaction is simple and straightforward yet low-selective. In this work, a coordination interaction-based oriented synthesis strategy has been proposed to realize the precise stereochemical control of the isomeric cyclic compounds in the photocycloaddition reaction. Through fixing the reactants via coordination interactions, the arrangements and configurations of the reactants can be adjusted, thereby successfully producing all of the related photocycloaddition products without isomer byproducts for the first time. This work not only provides a new route to synthesize the pure cyclic compounds but also expands the application of the photocycloaddition reaction.

Aims Vascular adventitial fibroblasts (AFs) in the vascular remodeling during atherosclerosis are increasing arousing attention. Acid sphingomyelinase (ASM) is a soluble glycoprotein which is involved in the development and progression of atherosclerosis. However, it remains unknown if ASM is expressed in vascular AFs and regulates vascular adventitial remodeling and underlying mechanisms. Main methods and key findings ASM downregulation with gene silencing was used in the rat AFs treated with angiotensin (Ang) II, which is universally demonstrated to induce vascular adventitia remodeling. It was showed that ASM was indeed expressed in vascular AFs and ASM downregulation resulted in a significant decrease in the protein level of PCNA and collagen I and cell migration under Ang II stimulation. Such improvement of adventitial remodeling was not further augmented by Ang-(1–7), which is deemed as an endogenous Ang II blocker. We further found that ASM downregulation blocked the Nox2-dependent superoxide (O2− ) generation, which regulated vascular remodeling in AFs under Ang II. ASM siRNA decreased the aggregation of membrane rafts (MRs) and the consequent recruiting of ceramide and Nox2 in MRs. Significance In conclusion, these results suggested that ASM downregulation could improve vascular adventitial remodeling which was attributed to inhibiting MRs/Nox2 redox signaling pathway in AFs. Thus, these data supported the idea that ASM is a potential therapeutic target for diabetic vascular complication.

Tetraphosphine ligand dpppda reacts with AgNO3 to generate two 1D coordination polymers containing cubic and chair-like [Ag4(NO3)4] clusters. ESR spectroscopy supported by DFT calculations indicated the presence of dpppda˙+, a Wurster's blue - like radical cation formed by intramolecular ligand-to-metal charge transfer (LMCT). This LMCT results in higher AgI → Ag0 potentials and good photocurrent responses.

Summary Ortho-selective aromatic C-H functionalization is frequently used in organic synthesis and chemical/pharmaceutical industries. However, this reaction relies heavily on the use of directing groups suffering from limited substrate scope and extra steps to put on and remove the directing/protecting groups. Herein we present the previously neglected concept that enables good to nearly complete selective ortho position. Proton transfer was utilized to tune the electron density on the aryl ring and determine the positional selectivity of electrophilic substitution. Consistently with deuteration experiments and DFT studies, this work demonstrates that acid-promoted proton transfer directs accelerated ortho-selective halogenation of NH/OH contained aromatic amines/phenols with excellent selectivity (>40 examples; up to 98:2 ortho/para selectivity). The application potential of this Fe-catalyzed method is demonstrated by the convenient synthesis of three alkaloids and tizanidine. This report raises the possibility that proton transfer could serve as the basis of developing new selective C-H functionalization reactions., Graphical Abstract, Highlights • Highly ortho-selective halogenations of anilines and carbazoles • Lewis acids being able to accelerate EAS reactions • Proton shift found to be crucial for the regioselectivity • Practical iron sulfonate catalysis being scaled up to 100 g, Catalysis; Organic Chemistry; Organic Synthesis

Background The active components of Dracocephalum moldavica L. (TFDM) can inhibit myocardial ischemia by inhibiting oxidative stress. However, the effects of TFDM on astrocytes have not been investigated in vitro. The current study aimed to explore whether TFDM protects astrocytes against H2O2-induced apoptosis through a mitochondria-dependent pathway. Methods The human glioma cell line U87 was used to investigate the ability of TFDM to protect astrocytes against H2O2-induced apoptosis. The cell counting kit-8 assay and flow cytometry were used to detect cell viability, apoptosis, MMP, Ca2+ influx and reactive oxygen species (ROS). Lactate dehydrogenase (LDH) and malonic dialdehyde (MDA) levels were measured by ELISA. In addition, protein and mRNA expression changes were detected by Western blotting and qRT-PCR. Results TFDM (0.78~200 μg/ml) had limited cytotoxic effects on the viability of U87 cells. Compared with the model group (treated with H2O2 only), cells treated with medium- and high-dose TFDM exhibited reduced MDA concentrations (P P P P ). The percentage of annexin V-FITC-stained cells was markedly suppressed by TFDM, confirming its anti-apoptotic properties. WB results showed that protein expression of Bcl-2-associated X protein (BAX), Caspase-3, Caspase-9, Caspase-12, and B-cell leukemia/lymphoma 2 (Bcl2) was reduced in the TFDM group compared with that in the model group (P Conclusions The current study revealed the protective effects of TFDM on U87 cells under oxidative stress conditions through the inhibition of a mitochondria-dependent pathway that is associated with the CaMKII/P38MAPK/ERK1/2 and PI3K/AKT/mTOR pathways.

BACKGROUND This study aimed to explore the effects of plumbagin (PLB) on epithelial-to-mesenchymal transition in retinal pigment epithelial (RPE) cells and in proliferative vitreoretinopathy (PVR) rabbit models. MATERIAL AND METHODS Rabbit RPE cells were exposed to various concentrations (0, 5, 15, and 25 µM) of PLB. Motility, migration, and invasion of PLB-treated cells were determined in vitro using Transwell chamber assays and scratch wound assays. The contractile ability was evaluated by cell contraction assay. Expression of matrix metalloproteinases (MMPs) and epithelial-mesenchymal transition (EMT) markers were assessed by western blotting. Furthermore, PLB was injected in rabbit eyes along with RPE cells after gas compression of the vitreous. The presence of PVR was determined by indirect ophthalmoscopy on days 1, 7, 14, and 21 after injection. Also, optical coherence tomography (OCT), ultrasound images, electroretinograms (ERG), and histopathology were used to assess efficacy and toxicity. RESULTS PLB significantly inhibited the migration and invasion of RPE cells. The agent also markedly reduced cell contractive ability. Furthermore, PLB treatment resulted in the decreased expression of MMP-1, MMP2, α-SMA, and the protection of ZO-1. In addition, the PLB-treated eyes showed lower PVR grades than the untreated eyes in rabbit models. PLB exhibited a wide safety margin, indicating no evidence of causing retinal toxicity. CONCLUSIONS PLB effectively inhibited the EMT of rabbit RPE cells in vitro and in the experimental PVR models. The results open new avenues for the use of PLB in prevention and treatment of PVR.

Retinal pigment epithelial (RPE) cells, the major cell type in the fibrotic membrane of proliferative vitreoretinopathy, display enhanced proliferative and migratory capacities and epithelial-mesenchymal transition (EMT). In this study, we investigated the potential impact of crocetin on the proliferation, migration and EMT of cultured ARPE-19 cells. The cells were treated with crocetin alone or in combination with transforming growth factor-β2 (TGF-β2). Cell proliferation was examined using the CCK-8 assay. Cell cycle distribution was analyzed by flow cytometry after propidium iodide staining. The expression levels of proliferating cell nuclear antigen (PCNA), p21 and p53 were examined by Western blot analysis. Cell migration was assessed by in vitro scratch and Transwell assays. Real-time PCR, Western blotting and immunofluorescence were used to assess EMT features. Treatment of ARPE-19 cells with crocetin (50-200μM) significantly inhibited their proliferation and migration in a concentration- and time-dependent manner. Crocetin induced G1 arrest, reduced PCNA protein expression and increased the p21 and p53 accumulation in ARPE-19 cells. Crocetin inhibited TGF-β2-induced EMT in ARPE-19 cells by maintaining the expression of E-cadherin and ZO-1 and by reducing the expression of vimentin and α-SMA through the suppression of phosphorylation of p38. These results indicate that crocetin is an effective inhibitor of the proliferation, migration and TGF-β2-mediated EMT of ARPE-19 cells.

1,7-Dihydroxy-3,4-dimethoxyxanthone (XAN) is a bioactive compound isolated from Securidaca inappendiculata Hassk. and exerts the inhibitory effects on fibroblast-like synoviocytes by targeting NF-κB and p38. This study was designed to elucidate mechanisms underlying the divergent regulation on the two pathways in HFLS-RA cells by XAN. Expressions of hallmark proteins and transcription of GADD45α mRNA were determined by Western-blot and RT-qPCR methods, respectively. Fluorescence staining was employed to evaluate intracellular oxidative stress. Effects of XAN and N-acetyl-l-cysteine (NAC) on the proliferation of cells were investigated by MTT assay, and pro-apoptotic effects of XAN were assessed by Annexin V-FITC/PI method. It was found XAN blocked NF-κB signaling in HFLS-RA cells shortly after treatment. Moreover, it up-regulated both transcription and expression of GADD45α, and subsequently activated p38 pathway. As time went on, XAN significantly promoted the generation of reactive oxygen species (ROS), which accompanied with sustained up-regulation of p-p38 and increased apoptosis. 48H later, dual-effects of XAN on NF-κB and p38 were reversed. As activation of p38 and increased apoptosis induced by XAN were antagonized by NAC, they were deemed as ROS mediated effects. Furthermore, the accumulated ROS should also account for the activation of NF-κB in the late stage of treatments via interfering in p38/MSK1/NF-κB feedback. Altogether, these findings suggested XAN-induced ROS contributed great importance to the proliferation inhibition of HFLS-RA cells by mediating NF-κB/p38 feedback loop and apoptosis, which provided us a panoramic view of potential target in the therapy of RA by XAN.

Treatment of N,N-bis(diphenylphosphanylmethyl)-3-aminopyridine (3-bdppmapy) with AgX (X = Br, I, CN, SCN, dicyanamide (dca)) under different reaction conditions afforded seven mononuclear, dinuclear, and polymeric coordination complexes including [Ag4I4(3-bdppmapy)2]n (1), [Ag2I2(3-bdppmapy)3]·CH3OH (2·CH3OH), [Ag2Br(3-bdppmapy)3]Br·4CH3OH (3·4CH3OH), [Ag4(CN)4(3-bdppmapy)3]·2CH3OH (4·2CH3OH), [Ag(3-bdppmapy)2]SCN (5), [Ag(3-bdppmapy)2](dca) (6), and {[Ag4(dca)4(3-bdppmapy)2]·4DMF}n (7). Compound 1 contains a unique two-dimensional (2D) network in which chairlike [Ag4I4] units are interconnected by μ3-3-bdppmapy bridges. Compounds 2 and 4 hold a similar centrosymmetric framework in which two [(3-bdppmapy)AgI] (2) or [(3-bdppmapy)Ag2(CN)2] (4) units are linked by a μ-3-bdppmapy. Compound 3 has a batlike cationic structure in which two Ag/3-bdppmapy units are joined by a pair of μ-Br and μ-3-bdppmapy bridges. Compounds 5 and 6 have a similar cationic mononuclear structure in which the Ag(I) center is chelat...

Rhenium is one of the most valuable elements found in nature, and its capture and recycle are highly desirable for resource recovery. However, the effective and efficient collection of this material from industrial waste remains quite challenging. Herein, a tetraphenylmethane-based cationic polymeric network (CPN-tpm) nanotrap is designed, synthesized, and evaluated for ReO4 - recovery. 3D building units are used to construct imidazolium salt-based polymers with positive charges, which yields a record maximum uptake capacity of 1133 mg g-1 for ReO4 - collection as well as fast kinetics ReO4 - uptake. The sorption equilibrium is reached within 20 min and a kd value of 8.5 × 105 mL g-1 is obtained. The sorption capacity of CPN-tpm remains stable over a wide range of pH values and the removal efficiency exceeds 60% for pH levels below 2. Moreover, CPN-tpm exhibits good recyclability for at least five cycles of the sorption-desorption process. This work provides a new route for constructing a kind of new high-performance polymeric material for rhenium recovery and rhenium-contained industrial wastewater treatment.

The study was designed to determine the safety and pharmacokinetics of intraocular crocetin and examine whether crocetin inhibits the development of proliferative vitreoretinopathy (PVR) in a rabbit model. In the toxicity study, the right eyes of rabbits were injected with 0.2 μmol or 0.4 μmol crocetin. The left eyes were injected with 0.1 ml phosphate buffered saline (PBS) containing the same concentration of DMSO. Fundus photography, optical coherence tomography (OCT), and electroretinogram (ERG) were obtained at baseline and 14 days. Afterward, the eyes were enucleated for histopathological analysis and terminal deoxynucleotidyl transferasemediated dUTP nick end labeling (TUNEL) assay. In the pharmacokinetic study, the eyes received an intravitreous injection of 0.4 μmol crocetin to detect vitreous drug levels with HPLC at specific time points. In the efficacy study, PVR was induced with an intravitreal injection of ARPE-19 cells in rabbits. Then ten eyes were injected with 0.4 μmol crocetin, and the other 10 eyes received 0.1 ml PBS. Fundus photography, OCT and ERG were performed at days 3 and 7 and weekly for a total of 4 weeks after injection. Afterward, the eyes were enucleated and subjected to histological analysis and TUNEL staining. The results demonstrated no signs of retinal toxicity. Intravitreal injection of 0.4 μmol crocetin had a half-life of 4.231 h. Treatment with crocetin significantly inhibited the progression of PVR in parallel with a reduced expression of α-SMA, collagen fibers and Ki67. These results indicate that crocetin is an effective and safe inhibitor of PVR in rabbit models.

Post-traumatic stress disorder (PTSD) is characterized by cognitive deficits including impaired explicit memory. Nitric oxide (NO), which is generated by nitric oxide synthase (NOS), has been considered to modulate learning and memory. In current study, we evaluated the role of NOS in the mouse model of PTSD. We established the immobilization (IMO) mouse model of PTSD and analyzed mice behavior, NOS expression and hippocampal excitatory synaptic transmission after immobilization. We inhibited iNOS by applying of iNOS inhibitor 1400 W and monitored the effect of iNOS inhibition by 1400 W in IMO mice. IMO induced iNOS expression and resulted in abnormal behavior and deficits in synaptic plasticity and memory in mice. Inhibition of iNOS rescued abnormal hippocampal long-term potentiation and abnormal behavior in IMO mice. Inhibition of iNOS ameliorates traumatic stress-induced deficits in synaptic plasticity and memory.

Unsaturated alcohols and saturated carbonyls are important chemical, pharmaceutical, and biochemical intermediates. We herein report an efficient transfer hydrogenation protocol in which conversion of unsaturated carbonyl compounds to either unsaturated alcohols or saturated carbonyls was catalyzed by Cu(I) N-donor thiolate clusters along with changing hydrogen source (isopropanol or butanol) and base (NaOH or K2CO3). Mechanistic studies supported by DFT transition state modeling indicate that such a chemoselectivity can be explained by the relative concentrations of Cu(I) monohydride and protonated Cu(I) hydride complexes in each catalytic system.

Room temperature ionic liquids (RTILs) played an important role in the electrochemistry because of the advantageous properties. Due to the different electrochemical behavior from the dilute solution, it was still remained a significant challenge to obtain the insight into the interfacial structure. Although the spectroelectrochemistry offered the rich spectroscopic information for obtaining the interfacial structure at molecular level, the lack of the spatial information of those techniques at nano/subnanometer scale led the difficulties in the determination of the spatial structure of double layer. Here, the surface enhanced Raman spectroscopy (SERS) Stark tuning rates of CN stretching frequency were employed to determine the electric double layer structure on Au electrode, and probes with different lengths, involving cyanide ion (CN − ), thiocyanate (SCN − ), 3-aminopropanenitrile (3-APN) and 6-aminohexanenitrile (6-AHN), were used as rulers to measure the spatial structure of double layer. In this approach, SERS combined with electrochemical control was performed to distinguish the orientation of surface species and detect the vibrational frequency of the nitrile stretching mode. For shorter probes (such as CN − and SCN − ), the nitrile group were located in the electric double layer region, resulting in measureable Stark tuning rates (d ν CN /d E ), while for longer probe molecules (such as 3-APN and 6-AHN), the interfacial potential completely decayed before reaching the nitrile group location, resulting in the negligible Stark tuning rates. The vibrational Stark tuning rates suggested that the potential drop occurred over a range of 5–6 A from the metal surface into the bulk phase of ionic liquids. The results demonstrated that the overall potential mostly dropped across the first layer and only a small fraction across the second layer. The preliminary results allowed us to obtain an insight into the physical picture of the interfacial structure of RTILs/metal system.

Casein-dextran nanoparticles (CDNs) were prepared from casein-dextran conjugates by heating in a dry/wet state and then adjusting the pH to the isoelectric point of the protein (pH 4.6) to investigate their physicochemical characteristics. The effects of the dry and wet heating methods on the properties of the CDNs were also evaluated. The CDNs were spherically shaped and uniformly dispersed, as confirmed by atomic force microscopy. Compared with CDNs prepared by wet heating (CDN-W), those prepared by dry heating (CDN-D) were much smaller (P

Background This study aimed to explore the effects of plumbagin (PLB) on ARPE-19 cells and underlying mechanism. Methods Cultured ARPE-19 cells were treated with various concentrations (0, 5, 15, and 25 μM) of PLB for 24 h or with 15 μM PLB for 12, 24 and 48 h. Then cell viability was evaluated by MTT assay and DAPI staining, while apoptosis and cell cycle progression of ARPE cells were assessed by flow cytometric analysis. Furthermore, the level of main regulatory proteins was examinated by Western boltting and the expression of relative mRNA was tested by Real-Time PCR. Results PLB exhibited potent inducing effects on cell cycle arrest at G2/M phase and apoptosis of ARPE cells via the modulation of Bcl-2 family regulators in a concentration- and time-dependent manner. PLB induced inhibition of phosphatidylinositol 3-kinase (PI3K) and p38 mitogen-activated protein kinase (p38 MAPK) signaling pathways contributing to the anti-proliferative activities in ARPE cells. Conclusions This is the first report to show that PLB could inhibit the proliferation of RPE cells through down-regulation of modulatory signaling pathways. The results open new avenues for the use of PLB in prevention and treatment of proliferative vitreoretinopathy.

We investigated the mechanism of heparin-derived oligosaccharide on the proliferation of vascular smooth muscle cell (VSMC) induced by vascular endothelial growth factor (VEGF). Expression levels of VEGFR 1 and VEGFR 2 were examined by RT-PCR, and the corresponding protein expression levels were detected by Western blotting and immunocytochemistry. Western blotting was taken to identify the expression levels of mechanism proteins. The binding of VEGF and VEGFR 2 was measured by co-IP. Besides, HS competition assay was to detect the ability of HDO to compete with Heparin for VEGF165. HDO showed an inhibitory effect on the expression of VEGFR1/2 proteins and PKC, MAPK, PI3K/Akt pathways. In addition, HDO affected the binding of VEGF-VEGFR, which may be one of the most important mechanisms of HDO suppress the cell proliferation induced by growth factors. Thus HDO showed the ability as a VEGF antagonist.

Acidosis has been known to cause “Ca2+ transients”, however, the mechanism is still uncertain. Here, we demonstrated that multiple H+ sensors, such as ASICs, TRPV1 and proton-sensing G protein coupled receptors (GPCRs) are involved in extracellular acidification-induced intracellular calcium ([Ca2+]i) elevation. By using calcium imaging measures, we observed that both ASIC and TRPV1 channels inhibitors suppressed the [Ca2+]i elevation induced by extracellular acidosis in cultured rat cardiac myocytes. Then, both channels mRNA and proteins were identified by RT-PCR, western blotting and immunofluorescence. ASIC-like and TRPV1-like currents were induced by extracellular acidification, suggesting that functional ASIC and TRPV1 channels jointly mediated extracellular calcium entry. Furthermore, either pre-exhaustion of sarcoplasmic reticulum (SR) Ca2+ with thapsigargin or IP3 receptor blocker 2-APB or PLC inhibitor U73122 significantly attenuated the elevation of [Ca2+]i, indicating that the intracellular Ca2+ stores and the PLC-IP3 signaling also contributed to the acidosis-induced elevation of [Ca2+]i. By using genetic and pharmacological approaches, we identified that ovarian cancer G protein-coupled receptor 1 (OGR1) might be another main component in acidosis-induced release of [Ca2+]i. These results suggest that multiple H+-sensitive receptors are involved in “Ca2+ transients” induced by acidosis in the heart.

Treatment of [Et4N][Tp*WS3] (1) (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) with [Cu(MeCN)4]PF6 and NH4PF6 (molar ratio = 1:2:1) in excess pyridine (py) produced one discrete trinuclear cluster [Et4N][Tp*WS3Cu2(py)3](PF6)2 (2). Reactions of 1 with [Cu(MeCN)4]PF6, NH4PF6, and 4,4′-bipyridine (4,4′-bipy) (or 1,2-bis(4-pyridyl)ethane (bpea)) (molar ratio = 1:2:1:2) afforded a two-dimensional (2D) [Tp*WS3Cu2]-based cationic polymer {[Tp*WS3Cu2(4,4′-bipy)1.5](PF6)·2MeCN}n (3·2MeCN) and a one-dimensional (1D) [Tp*WS3Cu2]-based cationic polymer {[(Tp*WS3Cu2)2(bpea)3](PF6)2·2DMF}n (4·2DMF), respectively. Analogous reactions of 1 with CuCN, NH4PF6, and 4,4′-bipy (or 1,2-bis(4-pyridyl)ethylene (bpee)) (molar ratio = 1:2:1:2) gave rise to a 2D [Tp*WS3Cu2]-based polymer {[Tp*WS3Cu2(μ-CN)(4,4′-bipy)0.5]·MeCN}n (5·MeCN) and a three-dimensional (3D) [Tp*WS3Cu2]-based anionic polymer {[Et4N][(Tp*WS3Cu2)2{Cu(μ-CN)2.5}2(bpee)]·3MeCN}n (6·3MeCN), respectively. Compounds 2–6 were characterized by elemental analysis, ...

Reactions of N,N-bis(diphenylphosphanylmethyl)-2-aminopyridine (bdppmapy) with [Ag(MeCN)4]ClO4 or AgX (X = Cl, Br, I, SCN, CN) afforded a family of oligomeric and polymeric complexes: [Ag2(MeOH)(bdppmapy)2](ClO4)2 (1), [AgCl(bdppmapy)] (2), [AgBr(bdppmapy)] (3), [AgI(bdppmapy)] (4), [AgSCN(bdppmapy)] (5), [{(η2-bdppmapy)Ag(μ-CN)AgCN}2(μ-bdppmapy)] (6), [Ag4(μ-CN)4(μ-bdppmapy)] (7), and [Ag2(μ-CN)(μ-bdppmapy)2][Ag5(μ-CN)6] (8). Compounds 1–8 were characterized by elemental analyses, IR spectra, 1H and 31P{1H} NMR, electrospray ionization (ESI) mass spectra, powder X-ray diffraction (XRD), and single-crystal X-ray diffraction. Compounds 1–3 and 5 hold a one-dimensional (1D) chain in which [Ag(MeOH)]+ or [AgX] motifs are linked by bdppmapy bridges. Compound 6 has a tetrameric framework in which two linear [(η2-bdppmapy)Ag(μ-CN)AgCN] fragments are connected by a μ-bdppmapy ligand. Compound 7 contains a 1D staircase chain in which two zigzag [Ag(μ-CN)]n chains are linked by pairs of μ-bdppmapy bridges. Compoun...

The aims of the present study were to determine the effects of heparin-derived oligosaccharides (HDOs) on vascular intimal hyperplasia (IH) in balloon-injured carotid artery and to elucidate the underlying mechanisms of action. An animal model was established by rubbing the endothelia within the common carotid artery (CCA) in male rabbits. The rabbits were fed a high-cholesterol diet. Arterial IH was determined by histopathological changes to the CCA. Serum lipids were detected using an automated biochemical analysis. Expressions of mRNAs for vascular endothelial growth factor (VEGF), basic fibroblast growth factor (bFGF), vascular cell adhesion molecule-1 (VCAM-1), monocyte chemoattractant protein-1 (MCP-1), scavenger receptor class B type I (SR-BI), and ATP-binding cassette transporter A1 (ABCA-1) were analyzed using reverse transcription polymerase chain reaction assays. Expressions of VEGF, VCAM-1, MCP-1, SR-BI and ABCA-1 proteins were analyzed by Western blotting. Enzyme-linked immunosorbent assays were used to quantify expression levels of VEGF and bFGF. Our results showed that administration of HDO significantly inhibited CCA histopathology and restenosis induced by balloon injury. The treatment with HDOs significantly decreased the mRNA and protein expression levels of VEGF, bFGF, VCAM-1, MCP-1, and SR-BI in the arterial wall; however, ABCA-1 expression level was elevated. HDO treatment led to a reduction in serum lipids (total cholesterol, triglycerides, high-density and low-density lipoproteins). Our results from the rabbit model indicated that HDOs could ameliorate IH and underlying mechanism might involve VEGF, bFGF, VCAM-1, MCP-1, SR-BI, and ABCA-1.

A 3D coordination polymer {[Cd(L(1))(L(2))]2}n (1) spontaneously resolves into enantiomorphic crystals of 1P and 1M without any chiral source. Bulk quantities of 1P and 1M can be predictably and reliably obtained by using chiral cyclohexane-1,2-diamine. 1 can be transformed into {[Cd(L(1))(L(3))0.5]2}n (2) by highly selective [2+2] photodimerization of L(2) ligands. The reverse process can be achieved by microwave irradiation. The cycloreversion/cycloaddition cycles result in chiroptical switching behavior.

Reactions of PdCl 2 ·2H 2 O with 2 equiv. of 4-(trimethylammonio)benzenethiolate (Tab) (prepared in situ from a mixture of TabHPF 6 and Et 3 N in MeOH) and seven phosphine ligands: PPh 3 , 1,1-bis(diphenylphosphino)methane (dppm), 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp), 1,4-bis(diphenylphosphino)butane (dppb), N , N , N ′, N ′-tetra(diphenylphosphanylmethyl)ethylene diamine (dppeda), and 1,4- N , N , N ′, N ′-tetra(diphenylphosphanylmethyl)benzene diamine (dpppda), afforded a family of mononuclear and dinuclear Pd(II)/Tab/phosphine complexes, [Pd 2 (PPh 3 ) 2 (Tab) 2 ( μ -Tab) 2 ](PF 6 ) 4 ( 1 ), [Pd 2 (dppm) 2 (Tab) 2 ( μ -Tab)](PF 6 ) 4 ( 2 ), [Pd 2 (dppb)(Tab) 2 ( μ -Tab) 2 ]Cl 4 ( 3 ), [PdL(Tab) 2 ](PF 6 ) 2 ( 4 : L = dppe; 5 : L = dppp) and {[PdL(Tab) 2 ] 2 }Cl 4 ( 6 : L = dppeda; 7 : L = dpppda). These compounds were characterized by elemental analysis, IR spectra, UV–Vis spectra, 1 H and 31 P{ 1 H} NMR, electrospray ionization (ESI) mass spectra and single-crystal X-ray diffraction. In the structure of 1 – 7 , each Pd(II) adopt an approximate square planar coordination geometry. The results provide an interesting insight into the chemistry of palladium(II)/thiolate/phosphine complexes.

Reactions of Cd(NO(3))(2)·4H(2)O with TabHPF(6) (TabH = 4-(trimethylammonio)benzenethiol) and Et(3)N in the presence of NH(4)SCN and five other N-donor ligands such as 2,2'-bipyridine (2,2'-bipy), phenanthroline (phen), 2,9-dimethyl-1,10-phenanthroline (2,9-dmphen), 2,6-bis(pyrazd-3-yl)pyridine (bppy) and 2,6-bis(3,5-dimethyl-1H-pyrazol-1-yl)pyridine (bdmppy) gave rise to a family of Cd(II)/thiolate complexes of N-donor ligands, {[Cd(2)(μ-Tab)(4)(NCS)(2)](NO(3))(2)·MeOH}(n) (1), [Cd(2)(μ-Tab)(2)(L)(4)](PF(6))(4) (2: L = 2,2'-bipy; 3: L = phen), [Cd(Tab)(2)(L)](PF(6))(2) (4: L = 2,9-dmphen; 5: L = bppy), and [Cd(2)(μ-Tab)(2)(Tab)(2)(bdmppy)](2)(PF(6))(8)·H(2)O (6·H(2)O). These compounds were characterized by elemental analysis, IR spectra, UV-Vis spectra, (1)H NMR, electrospray ionization (ESI) mass spectra and single-crystal X-ray diffraction. For 1, each [Cd(NCS)](+) fragment is connected to its equivalents via a pair of Tab bridges to a one-dimensional chain. For 2 and 3, two [Cd(2,2'-bipy)(2)](2+) or [Cd(phen)(2)](2+) units are linked by a pair of Tab bridges to form a cationic dimeric structure. The Cd atom in [Cd(Tab)(2)(L)](2+) dication of 4 or 5 is coordinated by two Tab ligands and chelated by two N atoms from 2,9-dmphen (4) or three N atoms from bppy (5), forming a distorted tetrahedral (4) or trigonal bipyramidal (5) coordination geometry. For 6, each of two [Cd(Tab)(bdmppy)] fragments is linked to one [(Tab)Cd(μ-Tab)(2)Cd(Tab)] fragment via two Tab bridges to generate a unique cationic zigzag tetrameric structure where the Cd centers take a tetrahedral or a trigonal bipyramidal coordination geometry. The results may provide an interesting insight into mimicking the coordination spheres of the Cd(II) sites of metallothioneins and their interactions with various N-donor ligands encountered in nature.

Solvothermal reactions of CuI with 4-cyanopyridine (4-cypy) or 4,4′-bipyridine (4,4′-bipy) and alcohols (methanol, ethanol, propanol, isopropanol) in the presence of I2 and a trace amount of water in acetonitrile gave rise to a family of multi-dimensional iodocuprate complexes of 4-cyanopyridinium and N,N′-dialkyl-4,4′-bipyridinium including {[MC]2[Cu4(μ3-I)4(μ-I)2]}n (MC+ = N-methyl-4-cyanopyridium) (1), {[PC][(Cu2I4)1/4(Cu2I4)1/4]}n (PC+ = N-propyl-4-cyanopyridinium) (2), {[iPC][(Cu2I4)1/4((Cu1/2)4I4)1/4]}n (iPC+ = N-isopropyl-4-cyanopyridium) (3), {[EV]1/4[((Cu1/2)4I4)1/4]}n (EV2+ = N,N′-diethyl-4,4′-bipyridinium) (4) and {[PV]1/2[(Cu2I4)1/4((Cu1/2)4I4)1/4]}n (PV2+ = N,N′-dipropyl-4,4′-bipyridinium) (5). The resulting 4-cyanopyridinium and viologen cations were generated in situ via the cleavage of the C–O bond of alcohols followed by alkylation of 4-cypy or 4,4′-bipy. X-ray analysis revealed that compound 1 consists of a unique three-dimensional anionic [Cu4I6]n2n− framework while compounds 2–5 contain one-dimensional anionic [Cu2I4]n2n− chains that are enclosed into different cationic channels formed by either 4-cyanopyridinium or N,N′-dialkyl-4,4′-bipyridinium. The dielectric properties of 1–5 were investigated.

Reaction of silver nitrate with N,N,N′,N′-tetra(diphenylphosphanylmethyl)ethylenediamine (dppeda) in the presence of aminothiocarbamide in CH2Cl2/MeOH afforded an unexpected and low-yield binuclear complex [Ag2(dppatc)2](NO3)2·2MeOH (dppatc = N,N-bis(diphenylphosphanylmethyl)aminothiocarbamide) (1). An X-ray analysis revealed that the [Ag2(dppatc)2]2+ dication of 1 contains a centrosymmetric double half-open cage structure in which two Ag centers are bridged by a pair of the heteroscopionate dppatc ligands via four Ag-μ-S and four Ag P bonds. The in situ-formed dppatc ligand in 1 could be readily generated by one-pot and high-yield reaction of diphenylphosphine with formaldehyde and aminothiocarbamide. Further reaction of AgNO3 with dppatc could produce 1 in a relatively high yield. The results provided an efficient route to the synthesis of dppatc and also an interesting insight into its coordination chemistry.

Solvothermal reactions of Cu2(OH)2CO3 with 1,2-bis(4-pyridyl)ethane (bpe) and iodobenzene or 4-iodotoluene in acetonitrile and aqueous ammonia afforded two arylamine-solvated [Cu2I2]-based coordination polymers {[Cu2I2(bpe)2]∙Am}n (1: Am = aniline; 2: Am = p-toluidine). Compounds 1 and 2 were characterized by elemental analysis, IR spectra, and powder X-ray diffraction (PXRD). Compounds 1 and 2 have a two-dimensional (4,4) topological network in which every rhombic [Cu2I2] dimer acts as a planar four-connected node to link other four equivalent ones by four bpe bridges. Each layer is further stacked via π–π interactions to form a 3D structure with 1D rhombic channels occupied by the guest aniline or p-toluidine molecules. These guest molecules were in situ generated through Ullmann coupling reactions of iodobenzene or 4-iodotoluene with ammonia. The thermal and photoluminescent properties of 1 and 2 were also investigated.

An experimental research was performed on the compressive strength and splitting tensile strength for HSC with various polypropylene（PP） fibers after exposure to temperatures 300°C, 500°C, 700°C, 900°C. Cubes of 150mm×150mm were designed and fabricated with C60, blended with silica fume and slag, mixed with PP fibers, respectively. These specimens were naturally cooled to room temperature after being heated in an electric furnace. No explosive spalling was observed during the fire test on all HSC with PP fibers. From the results of nine types of concretes, both the compressive strength and splitting tensile strength of HSC with PP fibers decreased with the increase of temperature. Through a series of measurement, the relationships between the mechanical properties and the various PP fibers in HSC were analyzed, including the dosage and length of PP fiber. Based on the comparison in the experimental results, the proposed optimum of PP fiber in HSC was 1.5kg/m3 under the test condition. In addition, PP fiber with the length of 8mm could be more applicable to use.

Flammable liquid storage tanks usually plant a potential dangerous zone. The damage gets worse and worse. In order to avoid the tank fire, the tanks extended to the nearby storage tanks-facilities and buildings. In consideration of safety conditions, flammable liquid storage tanks for the safety and security distance is necessary. Through the FDS (Fire Dynamics Simulator) computer simulation of fire, flammable liquid storage tanks for spot the fires numerical simulation to detect a fire to happen. In order to establish an optimized model, the flammable liquid storage tanks save the temperature distribution by obtaining flammable safety distance of the liquid storage tank, by talking about the current laws and regulations, by looking forward to meeting the economic and security considerations.

In situ electrochemical surface-enhanced infrared absorption spectroscopy (EC-SEIRAS) together with a periodic density functional theory (DFT) calculation has been initially applied to investigate the mechanism of formic acid electro-oxidation on Sb-modified Pt (Sb/Pt) electrode. EC-SEIRAS measurement reveals that the main formic acid oxidation current on Sb/Pt electrode is ca. 10-fold enhanced as compared to that on clean Pt electrode, mirrored by nearly synchronous decrease of the CO and formate surface species, suggesting a “non-formate” oxidation as the main pathway on the Sb/Pt electrode. On the basis of the calculations from periodic DFT, the catalytic role of Sb adatoms can be rationalized as a promoter for the adsorption of the CH-down configuration but an inhibitor for the adsorption of the O-down configuration of formic acid, kinetically facilitating the complete oxidation of HCOOH into CO2. In addition, Sb modification lowers the CO adsorption energy on Pt, helps to mitigate the CO poisoning ef...

As an important class of catalytic reactions, the reaction at solid/liquid interfaces is less understood at the atomic level. From a theoretical point of view, the difficulty lies at the simultaneous consideration of the extended solid surface and the dynamic liquid environment. In taking the oxidation of formic acid (HCOOH → CO2 + H2) at the Pt(111)/H2O interface as the model system that has great potentials in direct fuel cells applications, this work combines density functional theory (DFT) slab calculations with a continuum solvation model to simulate the reactions at the metal/H2O interface for the first time. The solvation effect is treated by including (i) a few explicit water molecules as the core solvation shell and (ii) an implicit continuum solvation model to take into account the long-range electrostatic interaction from water solution. We show that formic acid can be directly oxidized to CO2 only in the presence of preadsorbed formate. Although the formate itself can not be oxidized to CO2 at...

Self-consistent periodic slab calculations based on gradient-corrected density functional theory (DFT-GGA) were conducted to investigate the potential energy diagram for ethanol oxidation over Pt(111). Ethanol oxidation on Pt is found to be dominated by an one-step concerted dehydrogenation pathway to produce acetaldehyde, which is about 600 times faster than the traditionally regarded stepwise pathways. The same mechanism is transferable to methanol oxidation but with a minor contribution. The results can help to clarify the long-standing puzzles on the selectivity of direct alcohol fuel cell over Pt.

The DMol3 calculations, based on the density functional theory (DFT), have been used to study the structure–activity relationship of trans-resveratrol in the reaction of scavenging free radicals. The geometries of trans-resveratrol and its three phenoxy radicals were obtained at the Generalized Gradient Approximation (GGA) level, with the spin unrestricted approach and BLYP/DND method. Three possible reactions of scavenging hydroperoxyl radicals, in terms of H-atom-transfer mechanism, were designed. The transition state for each reaction was determined, and the intrinsic reaction coordinate was analyzed. The activation energy and thermodynamic state functions were calculated. The differences of the BDE and structure properties of stationary points show that 4′-radical is stabler and 4′-hydroxyl is more reactive. And the results also show that the reaction of 4′-hydroxyl scavenging hydroperoxyl radicals is more competitive in view of thermodynamics and kinetics. Thus, the dissimilarity of antioxidant activity among O–H groups of trans-resveratrol, which had been reported by many experimental studies, is explained.

Enzymatic browning and bacterial putrefaction are mainly responsible for quality losses of Chinese Olive ( Canarium album ) postharvest and lead to very short shelf life on average. Screening anti-browning and anti-bacterial agents is important for preservation of Chinese Olive. Caffeic acid N -nonyl ester (C-9) and caffeic acid N - Heptyl ester (C-7) was synthesized as inhibitors of tyrosinase, which is a key enzyme in browning process. The compound of C-9 could inhibit the activity of tyrosinase strongly and its IC 50 value was determined to be 37.5 μM, while the compound of C-7 had no inhibitory ability. Kinetic analyses showed that compound of C-9 has been a reversible inhibitory mechanism below 50 μM and been irreversible mechanisms above 50 μM. For the reversible inhibitory mechanism, the values of inhibitory constants ( K I and K IS ) were determined to be 24.6 and 37.4 μM, respectively. The results of Chinese Olive fruit postharvest showed that the compound of C-9 could effectively anti-browning and anti-bacterial putrefaction. In addition, this compound had strong antibacterial activities against Staphylococcus aureus , Escherichia coli , Bacillus subtilis and Salmonella . Therefore, C-9 could be a potential anti-browning and anti-bacterial reagent.

In the present study, new Schiff’s base derivatives: (Z)-4-amino-5-(2-(3- fluorobenzylidene)hydrazinyl)-4H-1,2,4-triazole-3-thiol (Y1), (Z)-3-((2-(4-amino-5- mercapto-4H-1,2,4-triazol-3-yl)hydrazono)methyl)phenol (Y2), (Z)-2-((2-(4-amino-5- mercapto-4H-1,2,4-triazol-3-yl)hydrazono)methyl)phenol (Y3) and 3-((Z)-(2-(4- (((E)-3-hydroxybenzylidene)amino)-5-mercapto-4H-1,2,4-triazol-3-yl)hydrazono)methyl)phenol (Y4) were synthesized and their structures were characterized by LC-MS, IR and 1H NMR. The inhibitory effects of these compounds on tyrosinase activites were evaluated. Compounds Y1, Y2 and Y3 showed potent inhibitory effects with respective IC50 value of 12.5, 7.0 and 1.5 μM on the diphenolase activities. Moreover, the inhibition mechanisms were determined to be reversible and mixed types. Interactions of the compounds with tyrosinase were further analyzed by fluorescence quenching, copper interaction, and molecular simulation assays. The results together with the anti-tyrosinase activities data indicated that substitution on the second position of benzene ring showed superior ant-ityrosinase activities than that on third position, and that hydroxyl substitutes were better than fluorine substitutes. In addition, two benzene rings connecting to the triazole ring would produce larger steric hindrance, and affect the bonding between tyrosinase and inhibitors to decrease the inhibitory effects. The anti-tyrosinase effects of these compounds were in contrast to their antioxidant activities. In summary, this research will contribute to the development and design of antityrosinase agents.

Freeze injury, one of the most destructive agricultural disasters caused by climate, has a significant impact on the growth and production of winter wheat. Chlorophyll content is an important indicator of a plant's growth status. In this study, we analyzed the hyperspectral reflectance of normal and freeze-stressed leaves of winter wheat using a spectro-radiometer in a laboratory. The response of the chlorophyll spectra of plants under freeze stress was analyzed to predict the severity of freeze injury. A continuous wavelet transform (CWT) was conducted in conjunction with a correlation analysis, which generated a correlation scalogram that summarized the correlation between the chlorophyll content (SPAD value) and wavelet power at different wavelengths and decomposition scales. A linear regression model was established to relate the SPAD values and wavelet power coefficients. The results indicated that the most sensitive wavelet feature (region E: 553 nm, scale 5, R(2) = 0.8332) was located near the strong pigment absorption bands, and the model based on this feature could estimate the SPAD value with a high coefficient of determination (R(2) = 0.7444, RMSE = 7.359). The data revealed that the chlorophyll content of leaves under different low temperatures treatments could be accurately estimated using CWT. Also, this emerging spectral analytical approach can be applied to other complex datasets, including a broad range of species, and may be adapted to estimate basic leaf biochemical elements, such as nitrogen, cellulose, and lignin.

Pyrimethanil myristic salt was synthesized and its heat capacities were measured with an automated adiabatic calorimeter over the temperature range from T=(79 to 360) K.The melting point, molar enthalpy, ΔfusHm and entropy, ΔfusSm, of fusion of this compound were determined to be (321.84 ± 0.05) K, (56.53 ± 0.03) kJ · mol−1 and (175.64 ± 0.05) J · mol−1 · K−1, respectively. The purity of the compound was calculated to be 98.99 mol% by using the fractional melting technique. The thermodynamic functions relative to the reference temperature, T=298.15 K, were calculated based on the heat capacity measurements in the temperature ranges from T=(80 to 360) K. The TG-DTG results demonstrate that the mass loss of the sample takes place in one step with the maximum rate at T=500 K, which was caused by evaporation of the sample.

Reaction of PdCl2 with N,N-bis-(diphenylphosphanylmethyl)-2-aminopyridine (bdppmapy) afforded a mononuclear complex [(bdppmapy)PdCl2] (1). Compound 1 was characterized by elemental analysis, IR, 1H, 13C and 31P NMR, electrospray ion mass spectra (ESI-MS) and X-ray single crystal crystallography. The Pd(II) center in 1 is chelated by bdppmapy, showing a cis-square planar geometry. With the assistance of additive Cu2O, complex 1 exhibited good catalytic activity toward the decarboxylative cross-coupling reactions between 4-picolinic acid and aryl bromides. In the presence of only 2 mol% catalyst, a family of 4-aryl-pyridines could be isolated in up to 83% yield.

Liver steatosis is characterized by lipid dysregulation and fat accumulation in the liver and can lead to oxidative stress in liver. Since proanthocyanidins are present in plant-based foods and have powerful antioxidant properties, we investigated whether proanthocyanidins can prevent oxidative stress and subsequent liver injury. Carbon tetrachloride (CCl4) treatment can cause steatosis in rats that models both alcoholic and non-alcoholic fatty liver disease in humans. We pre-treated rats by oral administration of proanthocyanidins extracted from grape seeds 7 days prior to intragastrically administering CCl4. Proanthocyanidin treatment continued for an additional 2 weeks, after which time liver and serum were harvested, and mediators of liver injury, oxidative stress, and histological features were evaluated. CCl4-treated rats exhibited significant increases in the following parameters as compared to non-treated rats: fat droplets in the liver, liver injury (ALT, AST), and DNA damage (8-OHdG). Additionally, CCl4 treatment decreased antioxidant enzymes SOD, GSH, GPX, and CAT in the liver due to their rapid depletion after battling against oxidative stress. Compared to CCl4-treated rats, treatment with proanthocyanidins effectively suppressed lipid accumulation, liver injury, DNA damage, as well as restored antioxidant enzyme levels. Further investigation revealed that proanthocyanidins treatment also inhibited expression of CYP2E1 in liver, which prevented the initial step of generating free radicals from CCl4. The data presented here show that treatment with orally administered proanthocyanidins prevented liver injury in the CCl4-induced steatosis model, likely through exerting antioxidant actions to suppress oxidative stress and inhibiting the free radical–generating CYP2E1 enzyme.

In this study, the interactions of different groups substituted isoeuxanthone derivatives with calf thymus DNA (ct DNA) were investigated by spectrophotometric methods and viscosity measurements. Results indicated that the xanthone derivatives could intercalate into the DNA base pairs by the plane of xanthone ring and the various substituents may influence the binding affinity with DNA according to the calculated quenching constant values. Furthermore, two tumor cell lines including the human cervical cancer cell line (HeLa) and human hepatocellular liver carcinoma cell line (HepG2) were used to evaluate the cytotoxic activities of xanthone derivatives by acid phosphatase assay. Analyses showed that the oxiranylmethoxy substituted xanthone exhibited more effective cytotoxic activity against the cancer cells than the other substituted xanthones. The effects on the inhibition of tumor cells in vitro agreed with the studies of DNA-binding.

Treatment of [CuCl(2)(bppyH(2))] (1, bppyH(2) = 2,6-di(1H-pyrazol-3-yl)pyridine) with 2 equiv. of AgNO(3) in DMF gave rise to a binuclear Cu(II) complex [Cu(2)(bppyH)(2)(NO(3))(2)] (bppyH = 2-(pyrazol-3-yl)-6-(pyrazolate)pyridine) (2). Complex 2 was characterized by elemental analysis, IR and single crystal X-ray diffraction. Complex 2 has a dimeric structure in which the two Cu(ii) centers are bridged by a couple of the in situ-generated bppyH(-) anions. Each Cu(II) center is further coordinated by one O atom of a NO(3)(-) anion and three N atoms of one bppyH(-) anion. Complex 2 exhibited a higher catalytic activity in the polymerization of methyl methacrylate (MMA) than the precursor complex 1. Even though the ratio of catalyst to MMA was raised up to 1 : 1500, the PDI for 2 (reaction time was fixed at 4 h) is 1.63 and the conversion is up to 72%. The effects of solvent, reaction temperature and the ratio of MMA to catalyst were also investigated.

Reaction of MeHgI with Ag(2)O in H(2)O followed by addition of equimolar TabHPF(6) in MeCN gave rise to a methylmercury zwitterionic thiolate complex [MeHg(Tab)]PF(6) (1) (TabH = 4-(trimethylammonio)benzenethiol) in a high yield. Treatment of 1 with KI and KSCN afforded an anion exchange product [MeHg(Tab)]I·0.25H(2)O (2·0.25H(2)O) and [MeHg(Tab)]SCN (3), respectively, while that of 1 with equimolar Tab resulted in the formation of another MeHg/Tab compound [MeHg(Tab)(2)]PF(6) (4). The cation of 2 or 3 shows an approximately linear structure in which the central Hg(II) is coordinated by one C atom of one CH(3) group and one S atom of a Tab ligand. The Hg(ii) center of the cation of 4 is trigonally coordinated by one C atom of the CH(3) group and two S atoms of two Tab ligands. The analogous reaction of 1 with NH(4)SCN led to the cleavage of the Hg-C bond of 1 and the formation of a known four-coordinated Hg(II)/Tab complex [Hg(Tab)(2)(SCN)(2)] (5). When 4 was treated with 4,6-Me(2)pymSH or EtSH, another four-coordinated Hg(II)/Tab complex [Hg(Tab)(4)](3)(PF(6))(6) (6) was generated in a high yield. The Hg(II) center of each cation of 6 is tetrahedrally coordinated by four S atoms of four Tab ligands. The results suggested that cleavage of the Hg-C bond in the methylmercury complex 1 could be completed by increasing the coordination number of its Hg(II) center by S-donor ligands and protonating the methyl group by weak acids.

Reactions of [H(4)L][PF(6)](4) with 4 equiv. of Mn(OAc)(2)·4H(2)O in the presence of air gave rise to a mononuclear Mn(III)-superoxo complex [Mn(III)L(O(2))(H(2)O)](PF(6))(2), which contains a bowl-shaped cationic structure with a D(4d) symmetry. It has an unprecedented linear end-on Mn(III)-O(2) unit and exhibited good efficiency and selectivity in the catalytic oxidation of alkenes with O(2) plus isobutyraldehyde under mild conditions.

Treatment of [Et(4)N][Tp*WS(3)] (1) (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) with 2 equiv of AgSCN in MeCN afforded a novel neutral compound [(Tp*WS(2))(2)(μ-S(2))] (2). Reactions of 2 with excess CuX (X = Cl, Br, I) in MeCN and CH(2)Cl(2) or CHCl(3) formed three neutral W/Cu/S clusters [{Tp*W(μ(3)-S)(3)Cu(3)(μ-Cl)}(2)Cu(μ-Cl)(2)(μ(7)-Cl)(MeCN)](2) (3), [{Tp*W(μ(3)-S)(3)Cu(3)}(2)Br(μ-Br)(2)(μ(4)-Br)(MeCN)] (4), and [{Tp*W(μ(3)-S)(3)Cu(3)}(2){Cu(2)(μ-I)(4)(μ(3)-I)(2)}] (5), respectively. On the other hand, treatment of 2 with CuX (X = Cl, Br) in the presence of Et(4)NX (X = Cl, Br) produced two anionic W/Cu/S clusters [Et(4)N][{Tp*W(μ(3)-S)(3)Cu(3)X}(2)(μ-X)(2)(μ(4)-X)] (6: X = Cl; 7 X = Br). Compounds 2-7 were characterized by elemental analysis, IR, UV-vis, (1)H NMR, electrospray ionization (ESI) mass spectra, and single-crystal X-ray crystallography. The dimeric structure of 2 can be viewed as two [Tp*WS(2)] fragments in which two W atoms are connected by one S(2)(2-) dianion. Compounds 3-7 all possess unique halide-bridged double cubanelike frameworks. For 3, two [Tp*W(μ(3)-S)(3)Cu(3)](2+) dications are linked via a μ(7)-Cl(-) bridge, two μ-Cl(-) bridges, and a [Cu(MeCN)(μ-Cl)(2)](+) bridge. For 4, one [Tp*W(μ(3)-S)(3)Cu(3)(MeCN)](2+) dication and one [Tp*W(μ(3)-S)(3)Cu(3)Br](+) cation are linked via a μ(4)-Br(-) and two μ-Br(-) bridges. For 5, the two [Tp*W(μ(3)-S)(3)Cu(3)](2+) dications are bridged by a linear [(μ-I)(2)Cu(μ(3)-I)(2)Cu(μ-I)(2)](4+) species. For 6 and 7, two [Tp*W(μ(3)-S)(3)Cu(3)X](+) cations are linked by a μ(4)-X(-) and two μ-X(-) bridges (X = Cl, Br). In addition, the third-order nonlinear optical (NLO) properties of 2-7 in MeCN/CH(2)Cl(2) were investigated by using femtosecond degenerate four-wave mixing (DFWM) technique.

A 2D network [Zn4(OH)2(5-NO2-1,3-BDC)2(5-NO2-1,3-HBDC)2(ppene)2]n underwent a highly selective [2+2] photodimerization reaction upon UV irradiation. The coordination polymer retains its single crystallinity after photoreaction.

Through the precoating of TiO2 on Ni foam and the subsequent hydrothermal reaction of the coated species with NaOH and tetrabutyl titanate, we successfully demonstrated the engineered growth of TiO2 nanofibers on the NiO–Ni foam. The adsorption and photodecomposition of Rhodamine B in water showed that the resulting foam is very convenient for the purification of contaminated water. Selective permeability of Au nanoparticles of different sizes revealed that the modified foam possesses size-dependent separation functionality.

Reactions of Zn(NO3)2 with tetrakis(4-pyridyl)cyclobutane (tpcb) and 1,4-benzenedicarboxylic acid (1,4-H2BDC), 4,4′-biphenyldicarboxylic acid (4,4′-H2BPDB), 5-methyl-1,3-benzenedicarboxylic acid (5-CH3-1,3-H2BDC), 1,3,5-benzenetricarboxylic acid (1,3,5-H3BTC), 5-amino-1,3-benzenedicarboxylic acid (5-NH2-1,3-H2BDC), 4,4′-benzophenonedicarboxylic acid (4,4′-H2BPNDB) under solvothermal conditions led to the formation of six polydimensional coordination polymers {[Zn5(1,4-BDC)5(tpcb)2.5]·5H2O}n (1), {[Zn2(4,4′-BPDB)2(tpcb)]·0.5MeCN}n (2), [Zn2(OH2)2(5-CH3-1,3-BDC)2(tpcb)]n (3), {[Zn2(1,3,5-HBTC)2(tpcb)]·H2O}n (4), {[Zn2(5-NH2-1,3-BDC)2(tpcb)·H2O]}n (5), and [Zn2(4,4′-BPNDB)2(tpcb)]n (6). Compounds 1–6 were characterized by elemental analysis, IR, powder X-ray diffraction, and single crystal X-ray diffraction. Compounds 1 and 6 have different 3D (4,4) connected structures. Compounds 2–4 have different two-fold interpenetrating 3D (4,4)-connected structures. Compound 5 holds a 2D (3,4)-connected structure. The solid state luminescent properties of compounds 1–6 at ambient temperature were also investigated. The results provided some interesting insights into ligand effects on the structures and luminescent properties of zinc(II) coordination polymers.

Reactions of the preformed cluster [(η(5)-C(5)Me(5))(2)Mo(2)(μ(3)-S)(4)Cu(2)(MeCN)(2)](ClO(4))(2) (1) with two tetraphosphine ligands, 1,4-N,N,N',N'-tetra(diphenylphosphanylmethyl)benzene diamine (dpppda) and N,N,N',N'-tetra(diphenylphosphanylmethyl)ethylene diamine (dppeda), produced two bicyclic clusters {[(η(5)-C(5)Me(5))(2)Mo(2)(μ(3)-S)(4)Cu(2)](2)(L)}(ClO(4))(4) (3: L = dpppda; 4: L = dppeda). Analogous reactions of 1 or [(η(5)-C(5)Me(5))(2)Mo(2)(μ(3)-S)(4)Cu(2)(MeCN)(2)](PF(6))(2) (2) with two N,P mixed ligands, N,N-bi(diphenylphosphanylmethyl)-2-aminopyridine (bdppmapy) and N-diphenylphosphanylmethyl-4-aminopyridine (dppmapy), afforded two monocyclic clusters {[(η(5)-C(5)Me(5))(2)Mo(2)(μ(3)-S)(4)Cu(2)](2)(L)(2)}X(4) (5: L = bdppmapy, X = ClO(4); 6: L = dppmapy, X = PF(6)). Compounds 3-6 were fully characterized by elemental analysis, IR spectra, UV-vis spectra, (1)H and (31)P{(1)H} NMR spectra, ESI-MS and single-crystal X-ray crystallography. In the tetracations of 3-6, two cubane-like [Mo(2)(μ(3)-S)(4)Cu(2)] cores are linked either by one dpppda or dppeda bridge to form a bicyclic structure or by a pair of bdppmapy or dppmapy bridges to afford a monocyclic structure. The third-order nonlinear optical (NLO) properties of 1 and 3-6 in MeCN were also investigated by femtosecond degenerate four-wave mixing (DFWM) technique with a 50 fs pulse width at 800 nm. Compounds 3-6 exhibited enhanced third-order NLO performances relative to that of 1.

Background Nonalcoholic steatohepatitis (NASH) is characterized by fat accumulation in the hepatocyte, inflammation, liver cell injury, and varying degrees of fibrosis, and can lead to oxidative stress in liver. Here, we investigated whether Salidroside, a natural phenolic antioxidant product, can protect rat from liver injury during NASH. Methods NASH model was established by feeding the male SD rats with high-fat and high-cholesterol diet for 14 weeks. Four groups of male SD rats including, normal diet control group, NASH model group, and Salidroside treatment group with150mg/kg and 300 mg/kg respectively, were studied. Salidroside was given by oral administration to NASH in rats from 9 weeks to 14 weeks. At the end of 14 weeks, liver and serum were harvested, and the liver injury, oxidative stress and histological features were evaluated. Results NASH rats exhibited significant increases in the following parameters as compared to normal diet control rats: fat droplets with foci of inflammatory cell infiltration in the liver. ALT, AST in serum and TG, TC in hepatocyte elevated. Oxidative responsive genes including CYP2E1 and Nox2 increased. Additionally, NASH model decreased antioxidant enzymes SOD, GSH, GPX, and CAT in the liver due to their rapid depletion after battling against oxidative stress. Compared to NASH model group, treatment rats with Salidroside effectively reduced lipid accumulation, inhibited liver injury in a does-dependent manner. Salidroside treatment restored antioxidant enzyme levels, inhibited expression of CYP2E1 and Nox2 mRNA in liver, which prevented the initial step of generating free radicals from NASH. Conclusion The data presented here show that oral administration of Salidroside prevented liver injury in the NASH model, likely through exerting antioxidant actions to suppress oxidative stress and the free radical–generating CYP2E1 enzyme, Nox2 in liver.