Improved Catalytic Performance toward Selective Oxidation of Benzyl Alcohols Originated from New Open-Framework Copper Molybdovanadate with a Unique V/Mo Ratio.

A new organic-inorganic hybrid open-framework molybdovanadate with mixed-valences of vanadium (V4+ /V5+ =4/3) and molybdenum (Mo5+ /Mo6+ =8/2) cations has been synthesized. The complex possesses the unique V/Mo ratio (7/10), fascinating 8-C topological network and 1D 4-MR channels (7.793 Å×6.699 Å). Importantly, its catalytic activities for the selective oxidation of benzyl alcohol to benzaldehyde (oxidant: H2 O2 , 30 wt %) have been well evaluated. The results indicated that it exhibited improved catalytic activities (conv.: 96.8 %) compared with the catalyst (Cpyr)5 PV2 Mo5 W5 O40 [conv.: 88.51 %, Cpyr=(C16 H32 C5 H4 N)+ )], high recyclability and structural stability. Moreover, the conversions and selectivities (conv.: 82.4-92.5 %; sele.: 91.5-95.7 %) of the substrates containing electron donating groups (-OH, -CH3 , -OCH3 and -Cl) were significantly higher than those of the substrate containing electron withdrawing group (-NO2 ) (conv. 67.4 %; sele.: 80.8 %). This is due to the fact that the -NO2 with a large Hammett substituent constant is not conducive to the generation of transition state products. The studies revealed the complex could act as a highly efficient heterogeneous catalyst in selective oxidation of benzyl alcohols.

A highly efficient heterogeneous catalyst for selective oxidation of sulfides derived from an open-framework copper borovanadate containing a unique crown-shaped anion.

A novel 3D open-framework copper borovanadate with a unique crown-shaped anion [(VIVO)8(VVO)4B32O64(OH)8]12- and the largest ratio of Cu2+/borovanadate anions (6/1) has been successfully synthesized and systematically studied. The compound not only possesses high stability in a wide pH range of 3.2-10.8 (DMF solution), but also exhibits excellent catalytic activities for selective oxidation of sulfides.

Glucocorticoid-induced dose-related and site-specific bone remodelling, microstructure, and mechanical changes in cancellous and cortical bones.

The study investigated the effects of long-term glucocorticoid (GC) administration on bone remodelling, microstructure, and biomechanical strength in cortical and cancellous (trabecular) bones. Thirty-one female Sprague-Dawley rats were randomly divided into three dexamethasone (Dex) dosage groups, 1.0, 2.5, and 5.0 mg/kg twice a week for 8 weeks, and one control group treated with saline. At the end of the experiment, the tibia of one side and the fourth lumbar vertebrae were processed into sections for a histomorphometric analysis, while the femur of the same side and the fifth vertebrae were isolated for a biomechanical test. A dose-dependent decline in bone formation was observed in both trabecular and cortical (periosteal and endosteal) bones. In contrast, bone resorption was inhibited only in cancellous bone in the two higher dose groups and not dose-related. The ratio of Node/Termini increased, while marrow star volume (MSV) decreased in all Dex groups in metaphyseal trabecular bones, both of which were dose-dependent. Subendosteal cortex porosity increased in parallel with non-uniform trabecular distribution, but cortical thickness remained unchanged. Interestingly, there were no significant changes in microstructure or mechanical strength in lumbar trabecular bone. The cortical elastic load was dose-independently reduced in all three Dex groups when compared with the control group. In summary, bone remodelling was dose-dependently inhibited in cancellous bones but enhanced in intracortical bones. The non-uniform distribution of trabecular bone and increased porosity in the inner edge of cortical bone were both in parallel with GC dosage, and the porosity increase was more likely to occur, leading to reduced cortical mechanical strength.

Predicting and Exploring the Mechanisms of Erzhi Pill in Prevention and Treatment of Osteoporosis Based on Network Pharmacology and Zebrafish Experiments.

BACKGROUND: Erzhi Pill (EZP), a traditional Chinese medicine (TCM) prescription, has been widely applied to improve bone metabolism and treat osteoporosis (OP) in China. However, its effective constituents and mechanisms remain unclear. METHODS: By combining network pharmacology and zebrafish experiments, an integrative method was employed to address this problem. Firstly, the disease targets of OP were collected from two public gene databases. Secondly, the active compounds and drug targets of EZP were obtained from the traditional Chinese medicine systems pharmacology database and analysis platform (TCMSP). Thirdly, a drug-target-disease interaction network was constructed, and the key active components were identified by analyzing the topological characteristics of the network. Finally, these predicted results were tested by zebrafish experiments and compared with those from the literature. Specifically, quercetin as an important representative active component of EZP was applied to wild type and transgenic zebrafish larvae to assess its effects on skull mineralization and osteoplastic differentiation. RESULTS: Our study identified 72 active compounds, 220 targets and 166 signaling pathways probably involved in the prevention and treatment of OP by EZP, wherein quercetin, apigenin, daidzein, luteolin, ursolic acid and kaempferol could be the key compounds, while PI3K-Akt signaling pathway, TNF signaling pathway and IL-17 signaling pathway could be the key signaling pathways. The experiments indicated that quercetin attenuated both the decrease of skull mineralization and the inhibition of skull osteoplastic differentiation in zebrafish larvae trigged by dexamethasone. CONCLUSION: Our study not only investigated potentially effective constituents and mechanisms of EZP in the prevention and treatment of OP, but also provided a reference for the in-depth research, development and application of TCM.

CsBP2O6(OH)2: a second-order NLO material with a unique borophosphate anionic partial structure and strong SHG effect.

A noncentrosymmetric (NCS) alkali-metal borophosphate CsBP2O6(OH)2 (CBPO) containing a unique borophosphate anionic partial structure has been obtained through a mixed-solvent thermal method. Its structure could be regarded as a 1-D chain that is built by Cs+ cations and a unique anionic chain [BP2O6(OH)2]∞n- composed of BO4 and PO3(OH) groups. CBPO possesses a wide UV-vis transparent range and shows a strong SHG response. Moreover, we have well explored and established the origin of the SHG effect by dipole moment and PDOS calculations. This work will help inspire and stimulate scientists to discover more such excellent NLO materials.

A Novel Open-Framework Copper Borovanadate with Enhanced Catalytic Performance for Oxidation of Benzylic C-H Bond.

A novel open-framework copper borovanadate, with a 6-connected topological net and 1D 8-membered ring channels, has been obtained for the first time. The compound not only exhibits a unique -B3 O7 (OH)-Cu-B(OH)3 linkage and features the largest ratio between TM2+ (Cu2+ ) and the borovanadate anion, but also possesses enhanced catalytic performance, high recyclability, and stability during the oxidation of benzylic C-H bonds.

Cd3(MoO4)(TeO3)2: A Polar 3D Compound Containing d10-d0 SCALP-Effect Cations.

The new polar 3D cadmium molybdotellurite Cd3(MoO4)(TeO3)2 was obtained by means of a high-temperature solid-state method. Cd3(MoO4)(TeO3)2 is a monoclinic crystal system, and it exhibits the polar space group P21 (No. 4). The structure of Cd3(MoO4)(TeO3)2 can be viewed as a complicated 3D architecture that is composed of distorted CdOn (n = 6, 7) polyhedra, TeO3 trigonal pyramids, and MoO4 polyhedra. The compound features the first 3D NCS cadmium molybdotellurite with 1D 4- and 6-MR channels and a polar structure originating from the TeO3 groups, MoO4 groups, and displacements of d10 Cd2+ cations. The results were further confirmed by calculations of the net polarization. The UV-vis spectrum and thermal properties indicate that Cd3(MoO4)(TeO3)2 exhibits a broad transparent region and excellent thermal stability. SHG tests of Cd3(MoO4)(TeO3)2 revealed that its response is approximately the same as that of KH2PO4 at the same grain size between 105 and 150 µm and that it is phase-matchable.

Salvianolic acid B stimulates osteogenesis in dexamethasone-treated zebrafish larvae.

AIM: Our previous studies show that salvianolic acid B (Sal B) promotes osteoblast differentiation and matrix mineralization. In this study, we evaluated the protective effects of Sal B on the osteogenesis in dexamethasone (Dex)-treated larval zebrafish, and elucidated the underlying mechanisms. METHODS: At 3 d post fertilization, wild-type AB zebrafish larvae or bone transgenic tg (sp7:egfp) zebrafish larvae were exposed to Sal B, Dex, or a mixture of Dex+Sal B for 6 d. Bone mineralization in AB strain larval zebrafish was assessed with alizarin red staining, and osteoblast differentiation in tg (sp7:egfp) larval zebrafish was examined with fluorescence scanning. The expression of osteoblast-specific genes in the larvae was detected using qRT-PCR assay. The levels of oxidative stress markers (ROS and MDA) in the larvae were also measured. RESULTS: Exposure to Dex (5-20 µmol/L) dose-dependently decreased the bone mineralization area and integral optical density (IOD) in wild-type AB zebrafish larvae and the osteoblast fluorescence area and IOD in tg (sp7:egfp) zebrafish larvae. Exposure to Dex (10 µmol/L) significantly reduced the expression of osteoblast-specific genes, including runx2a, osteocalcin (OC), alkaline phosphatase (ALP) and osterix (sp7), and increased the accumulation of ROS and MDA in the larvae. Co-exposure to Sal B (0.2-2 µmol/L) dose-dependently increased the bone mineralization area and IOD in AB zebafish larvae and osteoblast fluorescence in tg (sp7:egfp) zebrafish larvae. Co-exposure to Sal B (2 µmol/L) significantly attenuated deleterious alterations in bony tissue and oxidative stress in both Dex-treated AB zebafish larvae and tg (sp7:egfp) zebrafish larvae. CONCLUSION: Sal B stimulates bone formation and rescues GC-caused inhibition on osteogenesis in larval zebrafish by counteracting oxidative stress and increasing the expression of osteoblast-specific genes. Thus, Sal B may have protective effects on bone loss trigged by GC.

Tanshinol stimulates bone formation and attenuates dexamethasone-induced inhibition of osteogenesis in larval zebrafish.

BACKGROUND/OBJECTIVE: Tanshinol is the main active component of Salvia miltiorrhiza Bunge, a significant Traditional Chinese Medicine used to treat cardiovascular disease. We have shown that tanshinol exerts an antiosteoporostic effect via the enhancement of bone formation in vivo and in vitro. However, the mechanism remains unclear. Based on the polyphenol group in the structure of tanshinol, we speculate the protective action on skeletal tissue is related to antioxidative capacity. Our in vitro evidence indicated that tanshinol stimulated osteoblastic differentiation by its antioxidaive capacity. In this study, we aim to further confirm the effect of tanshinol on bone formation and the underlying mechanism in zebrafish in vivo. METHODS: We used a Danio rerio (zebrafish) model, which has a bone formation process similar to humans, and evaluated the relationship between the dose and the effect of tanshinol on bone formation determined using alizarin red S staining or fluorescence intensity analysis in normal and glucocorticoid (GC)-induced inhibition of an osteogenesis model using wild-type zebrafish and cortical bone transgenic zebrafish tg(sp7:egfp). The expression of osteoblast-specific genes and reactive oxygen species (ROS) were tested. RESULTS: Our data showed that dexamethasone exerts a series of consequences, including the inhibition of bone formation, decrease of bone mass, downregulation of expression of osteoblast-specific genes (runx2a, ALP, osteocalcin, and sp7), as well as the accumulation of ROS generation and decreased capacity of antioxidants. Tanshinol showed a protective effect on promoting bone formation and bone mass both in wild-type larval zebrafish and transgenic zebrafish. Furthermore, tanshinol attenuated the inhibition of osteogenesis elicited by oxidative stress in the zebrafish exposed to dexamethasone. CONCLUSION: The present findings suggest that tanshinol prevented decreased osteogenesis in GC-treated larval zebrafish via scavenging ROS and stimulated the expression of osteoblast-specific genes. Tanshinol treatment may be developed as a novel therapeutic approach under recent recognised conditions of GC-induced osteoporosis.

Employing a new 12-connected topological open-framework copper borovanadate as an effective heterogeneous catalyst for oxidation of benzyl-alkanes.

A new 12-connected topological open-framework copper borovanadate with a unique B/V ratio (20/12) and a -B3O7(OH)-Na(µ-OH)[B(OH)2]-B3O7(OH)- connection mode has been hydrothermally obtained and characterized. It not only features the first 3-D copper(II) borovanadate which possesses the largest ratio of TM(2+) and borovanadate anion, but also displays highly catalytic activities for the oxidation of benzyl-alkanes.

[Study on effect of total flavonoids of Oldenlendia difflusa on ulcerative colitis and its immunological mechanism].

OBJECTIVE: To observe the effect of total flavonoids of Oldenlendia difflusa (FOD) on NF-kappaB and IL-8, TNF-alpha, IL-10 expressions of ulcerative colitis (UC) model rats, and explore its immunological mechanism of anti-UC. METHOD: Sixty Kunming male mice with the average weight of (20 +/- 2) g were randomly divided into six groups. The control group (cont) was orally administered with distilled water. Whereas the remaining five groups were fed with 4% dextran sulphate sodium (DSS) solution for seven days to induce acute UC, and orally administered with the following drugs: distilled water (for the DSS group), SASP at dose of 500 mg x kg(-1) x d(-1) for the DSS + SASP group, FOD at dose of 60 mg x kg(-1) x d(-1) for the DSS + FOD-H group, FOD at dose of 40 mg x kg(-1) x d(-1) for the DSS + FOD-M group, and FOD at dose of 26.7 mg x kg(-1) x d(-1) for the DSS + FOD-L group. During the modeling and drug administration, the mice were scored for DAI. Seven days later, the mice were put to death, and their colonic tissue samples were collected to evaluate colonic mucosal lesions. The NF-kappaB p65, IL-8, TNF-alpha, IL-10 expressions were tested by immunohistochemical staining and ELISA. RESULT: Seven-day feeding with 4% DSS solution could successfully induce acute UC in mice. Compared with the cont group, the DSS group showed significantly higher DAI and colonic mucosal lesions, remarkable increase in NF-kappaB p65, IL-8, TNF-alpha expression in colonic tissues, and notable decrease in IL-10 expression (P < 0.05). FOD could prevent acute UC in mice included by DSS. Seven-day administration of 60 mg x kg(-1) x d(-1) or 40 mg x kg(-1) x d(-1) FOD could completely or partially resist the above mentioned changes caused by DSS. Compared with the DSS group, the DSS + FOD-H group and the DSS + FOD-M group showed reduction in colonic mucosal lesions, down-regulation in IL-8, TNF-alpha and NF-kappaB p65 expressions and up-regulation in IL-10 expression (P < 0.05). CONCLUSION: FOD could significantly resist UC in mice. Its mechanism may be related to the inhibition of NF-kappaB p65 activation, the reduction of IL-8 and TNF-alpha expressions and the increase in the anti-inflammatory factor IL-10.

catena-Poly[bis(µ-2,2'-bipyridin-6-olato)-κ³N,N':O;O:N,N'-dicopper(I,II) [[tetrafluoridoniobium(V)]-µ-oxido]].

A novel copper-niobium oxyfluoride, {[Cu2(C10H7N2O)2][NbOF4]}n, has been synthesized by a hydrothermal method and characterized by elemental analysis, EDS, IR, XPS and single-crystal X-ray diffraction. The structural unit consists of one C2-symmetric [NbOF4]⁻ anion and one centrosymmetric coordinated [Cu2(obpy)2]⁺ cation (obpy is 2,2'-bipyridin-6-olate). In the [NbOF4]⁻ anion, each NbV metal centre is five-coordinated by four F atoms and one O atom in the first coordination shell, forming a square-pyramidal coordination geometry. These square pyramids are then further connected to each other via trans O atoms [Nb-O = 2.187 (3) Å], forming an infinite linear {[NbOF4]⁻}n polyanion. In the coordinated [Cu2(obpy)2]⁺ cation, the oxidation state of each Cu site is disordered, which is confirmed by the XPS results. The disordered Cu sites are coordinated by two N atoms and one O atom from two different obpy ligands. The [NbOF4]⁻ and [Cu2(obpy)2]⁺ units are assembled via weak C-H∙∙∙F hydrogen bonds, resulting in the formation of a three-dimensional supramolecular structure. π-π stacking interactions between the pyridine rings [centroid-centroid distance = 3.610 (2) Å] may further stabilize the crystal structure.

Tetra-aqua-(nitrato-κO,O')bis-(pyridinium-4-carboxyl-ate-κO)europium(III) dinitrate.

The asymmetric unit of the title compound, [Eu(NO(3))(C(6)H(5)NO(2))(2)(H(2)O)(4)](NO(3))(2), consists of one-half of the C(2) symmetric coordination cation and one nitrate anion. The eight-coordinated Eu(III) atom is in a distorted dodeca-hedral coordination environment. The coordination cations and nitrate anions are connected via O-H⋯O and N-H⋯O hydrogen bonds into a three-dimensional network.

The preparation and antioxidant activity of 2-[phenylhydrazine (or hydrazine)-thiosemicarbazone]-chitosan.

Chitosan (CS) with two different molecular weight were modified by reacting with methyl hydrazine-dithiocarboxylate and methyl phenylhydrazine-dithiocarboxylate to give 2-(hydrazine-thiosemicarbazone)-chitosan (2-HTCHCS, 2-HTCLCS) and 2-(phenylhydrazine-thiosemicarbazone)-chitosan (2-PHTCHCS, 2-PHTCLCS). The structure of the derivatives was characterized by FT-IR spectroscopy and elemental analysis. The antioxidant activities of the derivatives were investigated employing various established systems, such as hydroxyl radical (OH)/superoxide anion (O(2)(.-)) scavenging/reducing power and chelating activity. All of the derivatives showed strong scavenging activity on hydroxyl radical than chitosan and ascorbic acid (Vc), and IC(50) of 2-HTCHCS, 2-HTCLCS, 2-PHTCHCS and 2-PHTCLCS was 0.362, 0.263, 0.531 and 0.336mg/mL respectively. The inhibitory activities of the derivatives toward superoxide radical by the PMS-NADH system were strong. The results showed that the superoxide radical scavenging effect of 2-[phenylhydrazine (or hydrazine)-thiosemicarbazone]-chitosan were higher than that of chitosan. The derivatives had obviously reducing power and chelating activity. The data obtained from vitro models clearly establish the antioxidant potency of 2-[phenylhydrazine (or hydrazine)-thiosemicarbazone]-chitosan.

[Effect of acupuncture combined with massage of sole on sleeping quality of the patient with insomnia].

OBJECTIVE: To assess effect of acupuncture combined with massage of sole on sleeping quality of the patient with insomnia. METHODS: Fifty-eight cases of insomnia were randomly divided into an observation group (n = 32) and a control group (n = 26). The observation group were treated with oral administration of Alprazolam, massage of sole, and acupuncture at Zhongwan (CV 12), Guanyuan (CV 4), Qihai (CV 6), etc. on the abdomen as main points; the control group were treated with Alprazolam. Clinical therapeutic effects, and scores for Pittsburgh Sleep Quality Index (PSQI), Self-rating Anxiety Scale (SAS) and Self-rating Depression Scale (SDS) were assessed before and after treatment in the two groups. RESULTS: The effective rate was 93.75 in the observation group and 88.46% in the control group with no significant difference between the two groups; after treatment, there were significant or very significant differences in scores for various factors in the PSQI, SAS and SDS (P < 0.01, P < 0.05). CONCLUSION: Abdominal acupuncture as main combined with massage of sole can obviously improve sleeping quality of the patient with insomnia.