Potential Protein Signatures for Recurrence Prediction of Ischemic Stroke.

BACKGROUND: Acute ischemic stroke is a major cause of mortality and disability worldwide, with approximately 7.4% to 7.7% recurrence within the first 3 months. This study aimed to identify potential biomarkers for predicting stroke recurrence. METHODS AND RESULTS: We conducted a nested case-control study using a hospital-based cohort from the Third China National Stroke Registry selecting 214 age- and sex-matched patients with ischemic stroke with hypertension and no history of diabetes or heart disease. Using data-independent acquisition for discovery and multiple reaction monitoring for quantitative validation, we identified 26 differentially expressed proteins in large-artery atherosclerosis (Causative Classification of Ischemic Stroke [CCS]1), 16 in small-artery occlusion (CCS3), and 25 in undetermined causes (CCS5) among patients with recurrent stroke. In the CCS1 and CCS3 subgroups, differentially expressed proteins were associated with platelet aggregation, neuronal death/cerebroprotection, and immune response, whereas differentially expressed proteins in the CCS5 subgroup were linked to altered metabolic functions. Validated recurrence predictors included proteins associated with neutrophil activity and vascular inflammation (TAGLN2 [transgelin 2], ITGAM [integrin subunit α M]/TAGLN2 ratio, ITGAM/MYL9 [myosin light chain 9] ratio, TAGLN2/RSU1 [Ras suppressor protein 1] ratio) in the CCS3 subgroup and proteins associated with endothelial plasticity and blood-brain barrier integrity (ITGAM/MYL9 ratio and COL1A2 [collagen type I α 2 chain]/MYL9 ratio) in the CCS3 and CCS5 subgroups, respectively. CONCLUSIONS: These findings provide a foundation for developing a blood-based biomarker panel, using causative classifications, which may be used in routine clinical practice to predict stroke recurrence.

Effects of fruits and vegetables on gut microbiota in a mouse model of metabolic syndrome induced by high-fat diet.

The aim of this study was to evaluate the effect of fruit and vegetable intake on gut microbiota using a mouse model of metabolic syndrome (MS) induced by a high-fat diet. Forty-eight male mice were randomly divided into four groups, control group (C), high-fat diet-fed model group (H), high fat plus low intake of fruits and vegetables diet-fed group (H.LFV), high fat plus high intake of fruits and vegetables diet-fed group (H.HFV), and each group were fed for 60 days. During the experiment, mouse body weights were recorded and fecal samples were collected. Cetyltrimethyl ammonium bromide (CTAB) method was used to extract fecal bacterial DNA, and the purity and concentration of the DNA were detected by electrophoresis. DNA samples underwent PCR amplification (primers in 16 S V4 (515F and 806R)). Raw sequencing data were processed, and sample complexity and multiple-sample comparisons were investigated. Mouse organ coefficient, serum lipid levels, fecal TC (total cholesterol) and TBA (total bile acid) levels, and hepatic glutathione and malondialdehyde levels were determined. Compared to the H group, the fecal TC and TBA levels decreased significantly in the H.HFV group (p < .05), and hepatic glutathione and malondialdehyde levels decreased significantly in both H.LFV and H.HFV groups (p < .05). Decreased abundance of Firmicutes, Burkholderiales, Syntrophomonas, and Pseudomonadales in gut microbiota was observed in H.LFV and H.HFV groups compared to the H group. The Anosim results showed significant differences in pairwise comparison between groups. The linear discriminant analysis effect size (LEfSe) results showed that k_bacteria not only exhibited statistically differences between H and C groups but also among H.LFV, H.LFV, and H groups, and hence, could be used as a biomarker between groups. To sum up, fruit and vegetable powder could increase the fecal excretion of TC and TBA, and the antioxidant capacity in C57BL/6N mice. Meanwhile, the mechanism that fruit and vegetable powder could prevent MS in C57BL/6N mice was related to the decreased abundance of gut microbiota, including Firmicutes, Syntrophomonadales, and Pseudomonadales. Hence, fruit and vegetable powder could be used as a recommended food to regulate gut microbiota and prevent the occurrence of MS-related diseases.

Supercritical CO2-assisted amorphization of WO2.72 and its high-efficiency photothermal conversion.

Amorphous materials with unique atomic arrangements have attracted great attention owing to their unique optical and electronic properties. In this work, amorphization of pristine WO2.72 was successfully achieved with the assistance of supercritical carbon dioxide (SC CO2). Experimental results indicate that the obtained amorphous sample has strong optical absorbance in the near-infrared (NIR) region. Furthermore, an excellent photothermal conversion efficiency (PCE) of 52.5% indicates that it enables the capture of solar energy and converts it into thermal energy efficiently.

Amorphous MoO3-x nanosheets prepared by the reduction of crystalline MoO3 by Mo metal for LSPR and photothermal conversion.

Amorphous MoO3-x with enhanced LSPR has been fabricated successfully by introducing Mo atoms into the interlayers of MoO3 nanosheets via a hydrothermal method. The inserted Mo atom could bond with inherent Mo atoms and further form a distorted atomic configuration structure. Thus, the amorphous MoO3-x possesses a relatively excellent photothermal conversion efficiency of 61.79%.

Fabrication of quasi-metallic NixMoO3 nanodots for enhanced plasmon resonance and photothermal conversion.

Quasi-metallic NixMoO3 nanodots with an enhanced localized surface plasmon resonance in the visible and NIR regions have been successfully fabricated. DFT calculations reveal the metallic nature of NixMoO3 nanodots. Thus, they exhibit an excellent photothermal conversion efficiency of 87.4%, and have a high water evaporation rate of 2.13 kg m-2 h-1.

The origin, type and hydrocarbon generation potential of organic matter in a marine-continental transitional facies shale succession (Qaidam Basin, China).

This organic-rich shale was analyzed to determine the type, origin, maturity and depositional environment of the organic matter and to evaluate the hydrocarbon generation potential of the shale. This study is based on geochemical (total carbon content, Rock-Eval pyrolysis and the molecular composition of hydrocarbons) and whole-rock petrographic (maceral composition) analyses. The petrographic analyses show that the shale penetrated by the Chaiye 2 well contains large amounts of vitrinite and sapropelinite and that the organic matter within these rocks is type III and highly mature. The geochemical analyses show that these rocks are characterized by high total organic carbon contents and that the organic matter is derived from a mix of terrestrial and marine sources and highly mature. These geochemical characteristics are consistent with the results of the petrographic analyses. The large amounts of organic matter in the Carboniferous shale succession penetrated by the Chaiye 2 well may be due to good preservation under hypersaline lacustrine and anoxic marine conditions. Consequently, the studied shale possesses very good hydrocarbon generation potential because of the presence of large amounts of highly mature type III organic matter.

Probing the Reactivity of the Ce═O Multiple Bond in a Cerium(IV) Oxo Complex.

The reactivity of the cerium(IV) oxo complex [(LOEt)2CeIV(═O)(H2O)]·MeC(O)NH2 (1; LOEt- = [CoCp{P(O)(OEt)2}3]-, where Cp = η5-C5H5) toward electrophiles and Brønsted acids has been investigated. The treatment of 1 with acetic anhydride afforded the diacetate complex [CeIV(LOEt)2(O2CMe)2] (2). The reaction of 1 with B(C6F5)3 yielded [CeIV(LOEt)2(Me2CONH2)2][B(C6F5)3(OH)]2 (3), in which the [B(C6F5)3(OH)]- anions are H-bonded to the O-bound acetamide ligands. The treatment of 1 with HCl and HNO3 afforded [CeIV(LOEt)2Cl2] and [CeIV(LOEt)2(NO3)2], respectively. Protonation of 1 with triflic acid (HOTf) gave the diaqua complex [CeIV(LOEt)2(H2O)2](OTf)2 (4), in which the triflate anions are H-bonded to the two aqua ligands. The treatment of 1 with phenol afforded the phenoxide complex [CeIV(LOEt)2(OPh)2] (5). The oxo-bridged bimetallic complex [(LOEt)2(Me2CONH2)CeIV(O)NaLOEt] (6) with the Ce-Ooxo and Na-Ooxo distances of 1.953(4) and 2.341(4) Å, respectively, was obtained from the reaction of 1 with [NaLOEt]. Density functional theory calculations showed that the model complex [(LOMe)2CeIV(Me2CONH2)(O)NaLOMe] (6A; LOMe- = [CoCp{P(O)(OMe)2}3]-) contains a polarized Ce═O multiple bond. The energy for dissociation of the {NaLOMe} fragment from 6A in acetonitrile was calculated to be +33.7 kcal/mol, which is higher than that for dissociation of the H-bonded acetamide from [(LOMe)2CeIV(═O)(H2O)]·MeC(O)NH2 (1A) (calculated to be +17.4 kcal/mol). In hexanes containing trace water, complex 1 decomposed readily to a mixture of a tetranuclear cerium(IV) oxo cluster, [CeIV4(LOEt)4(µ4-O)(µ2-O)4(µ2-OH)2] (7), and a cerium(III) complex, [CeIII(LOEt)2(H2O)2][LOEt] [8(LOEt)], whereas the cerium/sodium oxo complex 6 is stable under the same conditions. The crystal structures of 3, 4·H2O, 6, and 8(LOEt) have been determined.

Heterobimetallic cerium(iv) oxo clusters supported by a tripodal oxygen ligand.

Heterometallic Ce(IV)/M (M = Mo(VI), Re(VII), V(V)) oxo clusters supported by the Kläui tripodal oxygen ligand [(η(5)-C5H5)Co{P(O)(OEt)2}3](-) (LOEt(-)) have been synthesized and structurally characterized, and the catalytic activity of the Ce(IV)/V(V) oxo cluster in the oxidation of thioanisoles has been studied. Treatment of [Ce(LOEt)Cl3] (1) with [Ag2MoO4] afforded the reported Ce(IV)/Mo(VI) cluster [H4(CeLOEt)6Mo9O38] (2), whereas that with [AgReO4] yielded the Ce(IV)/Re(VII) cluster [{LOEtCe(ReO4)2(H2O)(µ-ReO4)}2] (3) that contains an 8-membered Ce2Re2O4 ring. Treatment of 1 with [Ag3VO4] afforded the Ce(IV)/V(V) cluster [H2(CeLOEt)4(V[double bond, length as m-dash]O)4(µ4-O)(µ3-O)12] (4) containing a {Ce4V4O13} oxo-metallic core. The solid-state structure of 4 consists of four {VO4}(3-) units bridged by four {LOEtCe(3+)} moieties and a µ4-oxo ligand. Each Ce atom in 4 is 9-coordinated, whereas the geometry around each V atom is pseudo square pyramidal with a terminal oxo at the apical position. Cluster 4 is an active catalyst for the oxidation of substituted thioanisoles with tert-butyl hydroperoxide. For example, the oxidation of thioanisole with tert-butyl hydroperoxide in the presence of 0.01 mol% of 4 gave a ca. 30 : 1 mixture of the sulfoxide and sulfone products in 96% yield.

Iodosylbenzene and iodylbenzene adducts of cerium(IV) complexes bearing chelating oxygen ligands.

Reactions of [Ce(IV)(LOEt)2Cl2] (LOEt(-) = [Co(η(5)-C5H5){P(O)(OEt)2}3](-)) and [Ce(µ-O){N(Pr(i)2PO)2}4Cl2] with PhIO afford the λ3-iodane complexes [Ce(IV)(LOEt)2{OI(Cl)Ph}2] and [Ce{N(Pr(i)2PO)2}3{OI(Cl)Ph}], respectively, whereas that between [Ce(IV)(LOEt)2Cl2] and PhIO2 or excess PhIO yields the λ5-iodane adduct [Ce(IV)(LOEt)2{OI(O)ClPh}2]. The crystal structures of the Ce(IV)λ3- and λ5-iodane complexes have been determined and their oxo transfer reactivities have been investigated.

Synthesis, Structure, and Reactivity of a Tetranuclear Cerium(IV) Oxo Cluster Supported by the Kläui Tripodal Ligand [Co(η(5) -C5 H5 ){P(O)(OEt)2 }3 ](.).

A tetranuclear Ce(IV) oxo cluster compound containing the Kläui tripodal ligand [Co(η(5) -C5 H5 ){P(O)(OEt)2 }3 ](-) (LOEt (-) ) has been synthesized and its reactions with H2 O2 , CO2 , NO, and Brønsted acids have been studied. The treatment of [Ce(LOEt )(NO3 )3 ] with Et4 NOH in acetonitrile afforded the tetranuclear Ce(IV) oxo cluster [Ce4 (LOEt )4 O7 H2 ] (1) containing an adamantane-like {Ce4 (µ2 -O)6 } core with a µ4 -oxo ligand at the center. The reaction of 1 with H2 O2 resulted in the formation of the peroxo cluster [Ce4 (LOEt )4 (µ4 -O)(µ2 -O2 )4 (µ2 -OH)2 ] (2). The treatment of 1 with CO2 and NO led to isolation of [Ce(LOEt )2 (CO3 )] and [Ce(LOEt )(NO3 )3 ], respectively. The protonation of 1 with HCl, ROH (R=2,4,6-trichlorophenyl), and Ph3 SiOH yielded [Ce(LOEt )Cl3 ] (3), [Ce(LOEt )(OR)3 ] (4), and [Ce(LOEt )(OSiPh3 )3 ] (5), respectively. The chloride ligands in 3 are labile and can be abstracted by silver(I) salts. The treatment of 3 with AgOTs (OTs(-) =tosylate) and Ag2 O afforded [Ce(LOEt )(OTs)3 ] (6) and 1, respectively. The electrochemistry of the Ce-LOEt complexes has been studied by using cyclic voltammetry. The crystal structures of complexes 1-5 have been determined.

A third-order mode high frequency biosensor with atomic resolution.

An atomic resolution ultra-high sensitivity surface acoustic wave (SAW) biosensor for DNA sequences and cells detection is proposed. Interdigitated transducers (IDTs) fabricated on LiNbO3 substrate achieve a high quality factor (Q) of over 4000 at a frequency of 6.4 GHz (third-order harmonic mode) using an optimized design and process. The biosensor shows excellent linear responses to target DNA in the range from 1 µg/ml to 1 ng/ml with a high sensitivity of 6.7 × 10(-16)g/cm(2)/Hz, hence the difference of a single hybridized DNA base can also be distinguished. With such a high mass resolution, the biosensor is capable of quantitative detection of living cancer cells. The frequency responses of single mouse mammary adenocarcinoma (EMT6) cell and mouse fibroblast (3T3) cell are studied. The interferences in the experiments show insignificant influence on the frequency shift, which verifies the high selectivity of the biosensor. The biosensor is also able to repeat the sensing ability after rough cleaning, therefore cost reduction is achieved from the recycling process in practical applications. The detection limit is defined from the noise analysis of the device, atomic resolution is realized according to the calculation, thereby initiating a potential tool for high-precision medical diagnoses and phenomena observation at the atomic-level.

A tetravalent cerium complex containing a Ce=O bond.

Whereas terminal oxo complexes of transition and actinide elements are well documented, analogous lanthanide complexes have not been reported to date. Herein, we report the synthesis and structure of a cerium(IV) oxo complex, [CeO(LOEt )2 (H2 O)]⋅MeC(O)NH2 (1; LOEt (-) =[Co(η(5) -C5 H5 ){P(O)(OEt)2 }3 ](-) ), featuring a short CeO bond (1.857(3) Å). DFT calculations indicate that the hydrogen bond to cocrystallized acetamide plays a key role in stabilizing the CeO moiety of 1 in the solid state. Complex 1 exhibits oxidizing and nucleophilic reactivity.

Clinical effect of vitrectomy with intravitreal ranibizumab for diabetic retinopathy / 国际眼科杂志(Guoji Yanke Zazhi)

AlM: To observe clinical effect of vitrectomy with intravitreal ranibizumab for the treatment of diabetic retinopathy ( DR) . METHODS:From February 2011 to February 2013, there were 90 cases in our hospital diabetic retinopathy patients withvitrectomy surgery. lt was randomly divided into observation group ( 45 cases ) and control group ( 45 cases ) . Two groups of patients were performed vitrectomy. Patients in observation group were injected intravitreal ranibizumab before surgery, then vitrectomy was underwent for diabetic retinopathy. Vitrectomy was only underwent in control group. RESULTS:The patients in observation group with good effect accounting for 71% (32/45) and good rate was 89%(40/45 ), which were significantly higher than that in control group 51% ( 23/45 ) , 71% ( 32/45 ) . Differences were statistically significant ( P CONCLUSlON: The vitrectomy with intravitreal ranibizumab treatment of diabetic retinopathy can not only reduce blood loss, but also reduce edema and improve effectiveness and safety. lt's worth recommending for clinical practice.

Heterometallic cerium(IV) perrhenate, permanganate, and molybdate complexes supported by the imidodiphosphinate ligand [N(i-Pr2PO)2]-.

Heterometallic cerium(IV) perrhenate, permanganate, and molybdate complexes containing the imidodiphosphinate ligand [N(i-Pr2PO)2](-) have been synthesized, and their reactivity was investigated. Treatment of Ce[N(i-Pr2PO)2]3Cl (1) with AgMO4 (M = Re, Mn) afforded Ce[N(i-Pr2PO)2]3(ReO4) (2) or Ce2[N(i-Pr2PO)2]6(MnO4)2 (3). In the solid state, 3 is composed of a [Ce2{N(i-Pr2PO)2}6(MnO4)](+) moiety featuring a weak Ce-OMn interaction [Ce-OMn distance = 2.528(8) Å] and a noncoordinating MnO4(-) counteranion. While 3 is stable in the solid state and acetonitrile solution, it decomposes readily in other organic solvents, such as CH2Cl2. 3 can oxidize ethylbenzene to acetophenone at room temperature. Treatment of 1 with AgBF4, followed by reaction with [n-Bu4N]2[MoO4], afforded [Ce{N(i-Pr2PO)2}3]2(µ-MoO4) (4). Reaction of trans-Ce[N(i-Pr2PO)2]2(NO3)2 (5), which was prepared from (NH4)2Ce(NO3)6 and K[N(i-Pr2PO)2], with 2 equiv of [n-Bu4N][Cp*MoO3] yielded trans-Ce[N(i-Pr2PO)2]2(Cp*MoO3)2 (6). 4 can catalyze the oxidation of methyl phenyl sulfide with tert-butyl hydroperoxide with high selectivity. The crystal structures of complexes 3-6 have been determined.

Tetravalent titanium, zirconium, and cerium oxo and peroxo complexes containing an imidodiphosphinate ligand.

Dinuclear Ti(IV), Zr(IV), and Ce(IV) oxo and peroxo complexes containing the imidodiphosphinate ligand [N(i-Pr(2)PO)(2)](-) have been synthesized and structurally characterized. Treatment of Ti(O-i-Pr)(2)Cl(2) with KN(i-Pr(2)PO)(2) afforded the Ti(IV) di-µ-oxo complex [Ti{N(i-Pr(2)PO)(2)}(2)](2)(µ-O)(2) (1) that reacted with 35% H(2)O(2) to give the peroxo complex Ti[N(i-Pr(2)PO)(2)](2)(η(2)-O(2)) (2). Treatment of HN(i-Pr(2)PO)(2) with Zr(O-t-Bu)(4) and Ce(2)(O-i-Pr)(8)(i-PrOH)(2) afforded the di-µ-peroxo-bridged dimers [M{N(i-Pr(2)PO)(2)}(2)](2)(µ-O(2))(2) [M = Zr (3), Ce (4)]. 4 was also obtained from the reaction of Ce[N(i-Pr(2)PO)(2)](3) with 35% H(2)O(2). Treatment of (Et(4)N)(2)[CeCl(6)] with 3 equiv of KN(i-Pr(2)PO)(2) afforded Ce[N(i-Pr(2)PO)(2)](3)Cl (5). Reaction of (Et(4)N)(2)[CeCl(6)] with 2 equiv of KN(i-Pr(2)PO)(2) in acetonitrile, followed by treatment with Ag(2)O, afforded the µ-oxo-bridged complex [Ce{N(i-Pr(2)PO)(2)}Cl](2)[µ-N(i-Pr(2)PO)(2)](2)(µ-O) (6). 6 undergoes ligand redistribution in CH(2)Cl(2) in air to give 5. The solid-state structures of [K(2){N(i-Pr(2)PO)(2)}(2)(H(2)O)(8)](n) and complexes 1-6 have been determined.

Synthesis and structure of a bismuth(III)/chromium(VI) oxo cluster containing a Bi4Cr4O12 core.

Bismuth(III) compounds containing the Kläui's oxygen tripodal ligand [CpCo{P(O)(OEt)(2)}(3)](-) (L(OEt)(-)) have been synthesized, and their interactions with dichromate in aqueous media were studied. The treatment of Bi(5)O(OH)(9)(NO(3))(4) with NaL(OEt) in water afforded [L(OEt)Bi(NO(3))(2)](2) (1), whereas that of BiCl(3) with NaL(OEt) in CH(2)Cl(2) yielded L(OEt)BiCl(2) (2). Chloride abstraction of 2 with AgX afforded [L(OEt)BiX(2)](2) [X(-) = triflate (OTf(-)) (3), tosylate (OTs(-)) (4)]. In aqueous solutions at pH > 4, 4 underwent ligand redistribution to give the bis(tripod) complex [(L(OEt))(2)Bi(H(2)O)][OTs] (5). The treatment of 4 with Na(2)Cr(2)O(7) in acetone/water afforded the Bi(III)/Cr(VI) oxo cluster [(L(OEt))(4)Bi(4)(µ(3)-CrO(4))(2)(µ(3)-Cr(2)O(7))(2)] (6) containing a unique Bi(4)Cr(4)O(12) oxometallic core. Compound 6 oxidized benzyl alcohol to give ca. 6 equiv of benzaldehyde. The reaction between 2 and CrO(3) yielded [L(OEt)Bi(OCrO(2)Cl)](2)(µ-Cl)(2) (7). The crystal structures of complexes 4-7 have been determined.

Up-regulation of glutathione metabolism and changes in redox status involved in adaptation of reed (Phragmites communis) ecotypes to drought-prone and saline habitats.

The glutathione (GSH) metabolic characteristics and redox balance in three ecotypes of reed (Phragmites communis), swamp reed (SR), dune reed (DR), and heavy salt meadow reed (HSMR), from different habitats in desert regions of northwest China were investigated. The DR possessed the highest rate of GSH biosynthesis and metabolism with the lowest levels of total and reduced GSH and its biosynthetic precursors, gamma-glutamylcysteine (gamma-EC) and cysteine (Cys), of the three reed ecotypes. This suggests that a higher rate of GSH biosynthesis and metabolism, but not GSH accumulation, might be involved in the adaptation of this terrestrial reed ecotype to its dry habitat. The HSMR shared this profile although it exhibited the highest reduced thiol levels of the three ecotypes. Two key enzymes in the Calvin-cycle possessing exposed sulfhydryl groups, NADP(+)-dependent glyceraldehydes-3-phosphate dehydrogenase (G3PD) and fructose-1,6-bisphosphatase (FBPase), and other two key enzymes in the pentose-phosphate pathway (PPP), glucose-6-phosphate dehydrogenase (G6PDH) and 6-phosphogluconate dehydrogenase (6-PGD), had very similar activities in the three reed ecotypes. Compared to the SR, the DR and HSMR had higher ratios of NADPH/NADP+ and NADH/NAD+, indicating that a more reduced redox status in the plant cells might be involved in the survival and adaptation of the two terrestrial reed ecotypes to long-term drought and salinity, respectively. These results suggest that changes of GSH metabolism and redox balance were important components of the adaptation of reed, a hydrophilic plant, to more extreme dune and saline habitats. The coordinated up-regulations of the rate of GSH biosynthesis and metabolism and reduction state of redox status of plant cells, conferred on the plant high resistance or tolerance to long-term drought and salinity.