Synthesis and Study of Photothermal Properties of a Mixed-Valence Nanocluster CuI/CuII with Strong near-Infrared Optical Absorption Supported by 4-tert-Butylcalix[4]arene Ligand.

The first mixed-valence nanocluster CuI/CuII with the highest percentage of CuII ions was synthesized by using 4-tert-butylcalix[4]arene (Calix4), with the formula DMF2⊂[(CO3)2-@CuII6CuI3(Calix4)3Cl2(DMF)5(H3O)]•DMF (1), as a photothermal nanocluster. Its structure was characterized using single-crystal X-ray diffraction, Fourier-transform infrared spectroscopy, and powder X-ray diffraction. In addition, the charge state and chemical composition of the nanocluster were determined using electrospray ionization spectrometry and X-ray photoelectron spectroscopy (XPS) spectrum. The results of the XPS and X-ray crystallography revealed that there are two independent CuII and CuI centers in nanocluster 1 with the relative abundances of 66.6 and 33.3% for CuII and CuI, respectively. The nanocluster contains three four-coordinated CuI ions with a square-planar geometry and six five-coordinated CuII ions with a square pyramid geometry. The nanocluster shows strong near-infrared optical absorption in the solid state and excellent photothermal conversion ability (the equilibrium temperature ∼78.2 °C) with the light absorption centers in 286-917 nm over previous reported pentanucleus CuI4CuII clusters and CuII compounds.

Netrin-1 promotes the vasculogenic capacity of human adipose-derived stem cells.

Adipose derived stem cells (ADSCs) have been increasingly explored for use in cell-based therapy against ischemic diseases. However, unsatisfactory angiogenesis limits the therapeutic efficacy. Netrin-1, a known axon guidance molecule, improves neovascularization in the ischemic region. Thus, our study was performed to evaluate the potential effect of Netrin-1 on the angiogenic behaviors of human ADSCs (hADSCs). hADSCs acquired from human abdominal adipose tissue were modified by liposome transfection of Netrin-1 plasmid, and the proliferation of hADSCs was determined by Cell Counting Kit-8 (CCK-8) assay. The transcript levels of pro-invasive proteins such as matrix metalloproteinase 2 (MMP2) and matrix metalloproteinase 9 (MMP-9), were measured to test migratory and invasive capabilities, and the levels of vascular endothelial growth factors were assayed to monitor angiogenic activity. Our results showed that Netrin-1 overexpression enhanced the proliferation of hADSCs, and promoted the migration and invasion of hADSCs, as indicated by increased levels of MMP-2 and MMP-9. Furthermore, Netrin-1 overexpression increased the expression of vascular endothelial growth factor and placental growth factor in hADSCs. Our results highlighted the possibility that genetic modification of hADSCs by Netrin-1 overexpression might be beneficial for cell transplantation therapy against ischemic diseases.

[Microfluidic Chip and Flow Cytometry for Examination of the Antiplatelet Effect of Ticagrelor].

Objective To examine the antiplatelet effect of ticagrelor by microfluidic chip and flow cytometry under shear stress in vitro. Methods Microfluidic chip was used to examine the effect of ticagrelor on platelet aggregation at the shear rates of 300/s and 1500/s.We adopted the surface coverage of platelet aggregation to calculate the half inhibition rate of ticagrelor.The inhibitory effect of ticagrelor on ADP-induced platelet aggregation was verified by optical turbidimetry.Microfluidic chip was used to construct an in vitro vascular stenosis model,with which the platelet reactivity under high shear rate was determined.Furthermore,the effect of ticagrelor on the expression of fibrinogen receptor (PAC-1) and P-selectin (CD62P) on platelet membrane activated by high shear rate was analyzed by flow cytometry. Results At the shear rates of 300/s and 1500/s,ticagrelor inhibited platelet aggregation in a concentration-dependent manner,and the inhibition at 300/s was stronger than that at 1500/s (both P<0.001).Ticagrelor at a concentration ≥4 µmol/L almost completely inhibited platelet aggregation.The inhibition of ADP-induced platelet aggregation by ticagrelor was similar to the results under flow conditions and also in a concentration-dependent manner.Ticagrelor inhibited the expression of PAC-1 and CD62P. Conclusion We employed microfluidic chip to analyze platelet aggregation and flow cytometry to detect platelet activation,which can reveal the responses of different patients to ticagrelor.

New 3D Porous Silver Nanopolycluster as a Highly Effective Supercapacitor Electrode: Synthesis and Study of the Optical and Electrochemical Properties.

A high-nucleus silver nanopolycluster as a new type of silver-based polymer supercapacitor (SSc) by a simple and single-step synthesis process was designed and synthesized. The structural, optical, and electrochemical properties of SSc-2 were determined. This highly stable conductive 3D nanopolycluster shows great cycling stability, large capacity, and high energy density without any modification or doping process and so acts as an excellent SSc (412 F g-1 at 1.5 A g-1). In addition, there was a stable cycling performance (94% capacitance) following 7000 cycles at 3 A g-1 current density. The presence of fluorinated groups, 3D expansion of high-nucleus metallic clusters, and porosity are the advantages of SSc-2 that lead to stability, conductivity, and high capacity, respectively. These results lead to the development of a novel kind of SSc by overcoming the low conductivity and limited capacity challenges without any modification.

[Chemical constituents of Cassia occidentalis].

Compounds(1-6) were isolated and identified from 90% ethanol extract of the stems and leaves of Cassia occidentalis through column chromatography with silica gel, ODS, and Sephadex LH-20. These compounds were identified as 7-hydroxy-5-(3-hydroxy-2-oxopropyl)-2-methyl-4H-chromen-4-one(1), saccharonol A(2), S-6-hydroxymullein(3), 2-methyl-5-acetonyl-7-hydroxy-chromone(4), 2-(2'-hydroxypropyl)-5-methyl-7-hydroxychromone(5) and 7,4'-dihydroxyflavone(6) based on their physicochemical and spectroscopic data. Among them, compound 1 was a new compound, and all the compounds were isolated from this plant for the first time. DPPH method was employed to determine the antioxidant activities of these compounds in vitro. Six compounds exhibited weak antioxidant activities.

All-Carboxylate-Protected Superatomic Silver Nanocluster with an Unprecedented Rhombohedral Ag8 Core.

We report the synthesis and structure of the first all-carboxylate-protected superatomic silver nanocluster. It was prepared by heating a dimethylformamide solution of perfluoroglutaric acid and AgNO3 under alkaline conditions, yielding a single crystal of [(CH3)2NH2]6[Ag8(pfga)6]. The [Ag8(pfga)6]6- cluster has a rhombohedral Ag86+ core, with each of its faces protected by one dianionic perfluoroglutarate (pfga) ligand. Electronic-structure analysis from density functional theory confirms the stability of this two-electron cluster due to the shell closing of the superatomic orbital in the (1S)2 configuration and explains the optical absorption of the cluster in the visible region as the transition from 1S to 1P orbital. The [Ag8(pfga)6]6- cluster emits bright green-yellow light in THF solution and bright orange light in the solid state. This work opens the door to using the widely available carboxylic acids to synthesize atomically precise Ag clusters of attractive properties.

Comparative Study of the Supercapacitive Performance of Three Ferrocene-Based Structures: Targeted Design of a Conductive Ferrocene-Functionalized Coordination Polymer as a Supercapacitor Electrode.

As redox-active based supercapacitors are known as highly desirable next-generation supercapacitor electrodes, the targeted design of two ferrocene-functionalized (Fc(COOH)2 ) clusters based on coinage metals, [(PPh3 )2 AgO2 CFcCO2 Ag(PPh3 )2 ]2 ⋅7 CH3 OH (SC1 : super capacitor) and [(PPh3 )3 CuO2 CFcCO2 Cu(PPh3 )3 ]⋅3 CH3 OH (SC2 ), is reported. Both structures are fully characterized by various techniques. The structures are utilized as energy storage electrode materials, giving 130 F g-1 and 210 F g-1 specific capacitance at 1.5 A g-1 in Na2 SO4 electrolyte, respectively. The obtained results show that the presence of CuI instead of AgI improves the supercapacitive performance of the cluster. Further, to improve the conductivity, the PSC2 ([(PPh3 )2 CuO2 CFcCO2 ]∞ ), a polymeric structure of SC2 , was synthesized and used as an energy storage electrode. PSC2 displays high conductivity and gives 455 F g-1 capacitance at 3 A g-1 . The PSC2 as a supercapacitor electrode presents a high power density (2416 W kg-1 ), high energy density (161 Wh kg-1 ), and long cycle life over 4000 cycles (93 %). These results could lead to the amplification of high-performance supercapacitors in new areas to develop real applications and stimulate the use of the targeted design of coordination polymers without hybridization or compositions with additive materials.

Investigation of the Effect of a Mixed-Ligand on the Accommodation of a Templating Molecule into the Structure of High-Nucleus Silver Clusters.

Advancement of the synthesis and control of the self-assembly process of new high-nucleus silver clusters with desired structures is important for both the material sciences and the many applications. Herein, three new silver clusters, 20-, 22-, and 8-nucleus, based on alkynyl ligands were constructed and their structures were confirmed by single-crystal X-ray diffraction, powder X-ray diffraction, elemental analyses, and Fourier-transform infrared spectroscopy (FT-IR). For the first time, the trivalent tetrahedron anion of AsO43-, as a template, and the surface ligand of Ph2PO2H, with new coordination modes, were employed in preparation of the silver clusters. The role of surface ligands and template anions in the size and structure of the clusters was investigated. The presence of the template in the structure of the clusters led to the formation of the high-nucleus clusters. Also, in this report, it was shown that the participation of the template in the assembly of a cluster can be controlled by the surface ligands. UV-vis absorption and luminescent properties of the clusters and the thermal stability of the 8-nucleus cluster were also studied.

Long-term outcomes of individualized treatment strategy in treatment of type I Budd-Chiari syndrome in 456 patients.

AIM: To evaluate individualized treatment strategy (ITS) and long-term outcomes of endovascular treatment of Budd-Chiari syndrome (BCS) with obstructed inferior vena cava (IVC) based on different degrees of hepatic vein (HV) involvement. METHODS: From January 2006 to June 2017, 456 consecutive patients with BCS with obstructed IVC underwent endovascular treatment with ITS. All patients received IVC recanalization. Then, 426 patients with at least one patent HV received no additional treatment. Twenty-fivepatients with membranous or segmental occlusion of HVs underwent HV recanalization and for the remaining five patients with diffuse HVs occlusion, a transjugular intrahepatic portosystemic shunt (TIPS) was performed. RESULTS: The endovascular treatment was technically successful in 455 of the 456 patients (99.8%). The complication rate was 5.0% (23/456), with major complications in 13 patients (2.8%) and minor complications in 10 patients (2.2%). Median follow-up time was 60.5 months (range, 4-120 months). The cumulative 1-, 2-, 5- and 10-year primary vessel patency rates were 93.6%, 89.9%, 80.5% and 74.3% respectively and the cumulative 1-, 2-, 5-, 10- year secondary patency rates were 99.8%, 99.8%, 98.2% and 97.2% respectively. The cumulative 1-, 2-, 5- and 10-year survival rates were 98.4%, 95.8%, 91.2% and 76.5% respectively. Illness duration and decreased serum albumin were independent predictors of survival. CONCLUSION: The ITS for Asian BCS with obstructed IVC and varying degrees of HV involvement appears to be effective and with good long-term outcomes.

Trivalent Tetrahedral Anion Template: A 26-Nucleus Silver Alkynyl Cluster Encapsulating Vanadate.

In order to study the charge effect on the formation of an anion-templated silver cluster, a trivalent tetrahedral anion was incorporated into the silver assembly. A 26-nuclear silver cluster was prepared, and its structure was confirmed by single-crystal X-ray diffraction. Also, the resulting structure was characterized by powder X-ray diffraction data. Its light absorption and photoluminescent properties were studied by solid-state UV diffuse-reflectance and fluorescence spectroscopy. Compared with the other reported silver clusters with tetrahedral anion templates, the more negative VO43- anion led to the formation of a bigger silver cluster. Also, the supramolecular motif O-H(CH3OH)···O(trifluoroacetate) was confirmed on the cluster surface for the first time.

[Chemical constituents of Cassia siamea].

A total of ten compounds were isolated from the 90% Et OH extract of Cassia siamea by using various chormatographic techniques,and their structures were established as( 2' S)-2-( propan-2'-ol)-5,7-dihydroxy-benzopyran-4-one( 1),chrobisiamone( 2), 2-( 2'-hydroxypropyl)-5-methyl-7-hydroxychromone( 3), 2,5-dimethyl-7-hydroxychromone( 4), 2-methyl-5-acetonyl-7-hydroxychromone( 5),3-O-methylquercetin( 6),3,5,7,3',4'-pentahydroxyflavonone( 7),luteolin-5,3'-dimethylether( 8),4-( trans)-acetul-3,6,8-trihydroxy-3-methyl-dihydronapht halenone( 9) and 6-hydroxymellein( 10) based on the spectroscopic data.Compound 1 was a new compound,and 3,4,6,8 were isolated from this plant for the first time.

Three new biphenyls from the twigs of Garcinia tetralata and their anti-tobacco mosaic virus activity.

Phytochemical investigations on the ethanol extract of the twigs of Garcinia tetralata resulted in the isolation of three new biphenyls, tetralatabiphenyls A-C (1-3), along with three known biphenyl derivatives (4-6). Structural elucidations of 1-3 were performed by spectroscopic methods such as 1D and 2D NMR spectra, in addition to high-resolution mass spectra. Compounds 1-6 were also evaluated for their anti-tobacco mosaic virus (anti-TMV) activity. The results showed that compound 3 showed high anti-TMV activity with inhibition rate of 31.1%. Compounds 1, 2, and 4-6 also showed modest anti-TMV activities with inhibition rates in the range of 18.9-24.5%, respectively.

[Histological changes in the circum-maxillary sutures during alternate maxillary expansions and constrictions in a rat model].

OBJECTIVE: To investigate changes in the circum-maxillary sutures during alternate maxillary expansions and constrictions in a rat model. METHODS: Twenty-two male Sprague-Dawley rats (6 weeks old) were used and divided into three groups. In maxillary expansion (ME) group (n=9), an expander was activated for 5 d, and then sacrificed. In alternate maxillary expansions and constrictions (Alt-MEC) group (9 animals), an alternate expansion and constriction protocol (5 d expansion and 5 d constriction for one cycle) was conducted for 2.5 cycles (25 d total), and then sacrificed. The control group comprised 4 animals with no appliances used, each of two sacrificed on day 5 and day 25, respectively. Circum-maxillary sutures (mid-palatal, maxillopalatine, premaxillary, zygomaticotemporal, and frontonasal suture) in each group were characterized histologically. RESULTS: Histological findings of circum-maxillary sutures: in control group, the normal sutures were divided into 5 zones, the center was polygon mesenchyme zone, the lateral was mature chondrocyte zone, the next lateral was bone tissue. In ME group, the mid-palatal suture was expanded after ME, the fibre and connective tissue were extracted and invaded into cartilage zone. Osteoblast hyperplasia and new bone formation occurred. The orientation of the new bone trabecula was consistent with force. The osteoclast appeared in some area. Findings of other sutures were similar with those of control group, osteogenesis was active in some area without obvious reconstruction in Alt-MEC group, mid-palatal suture and other sutures in some area were widened after Alt-MEC with much more osteoblast hyperplasia and new bone formation. Fibre and connective tissue were extracted, distorted or even broken. Sutures in some areas were narrowed with osteoblast cytopenia and osteoclast hyperplasia. Fibre and connective tissue compressed because of the different force and orientation. Osteoclast count results showed that compared with the control group, the number of the osteoclast was increased only in the palatal suture in ME group (P<0.05). Other sutures did not show obvious changes (P>0.05). In Alt-MEC group, the numbers of the osteoclast in circum-maxillary sutures were the most, and had statistical significances (P<0.05). CONCLUSION: These RESULTS suggested that circum -maxillary sutures were actively reconstructed after Alt-MEC. while only midpalatal suture had active reaction after ME.

[A new cytotoxic isocoumarin from endophytic fungus Aspergillus versicolor].

A new isocoumarin, along with five known ones,were isolated from the fermentation products of an endophytic fungus Aspergillus versicolorby using various chromatographic techniques.Their structures were elucidated on the basis of extensivespectroscopic analysis, including 1D-and 2D-NMR techniques. Compound 1 was evaluated for cytotoxicity against five human tumor cell lines. The results showed that 1 exhibited weak cytotoxicityagainst NB4, SHSY5Y and MCF7 cells with IC50 values of 6.8, 4.3,8.8 µmol•L⁻¹, respectively.

Antiviral butyrolactones from the endophytic fungus Aspergillus versicolor.

Versicolactones A-D (1-4), four new butyrolactones, along with four known butyrolactones (5-8) were isolated from the fermentation products of the endophytic fungus Aspergillus versicolor. The structures of compounds 1-4, including absolute configuration, were elucidated by interpretation of the NMR and CD data. Compound 2 was further confirmed by single-crystal X-ray diffraction analysis. In particular, compound 1 is the first naturally occurring butyrolactone possessing an unusual 2-oxopropyl group. More importantly, compounds 1 and 8 displayed significant antitobacco mosaic virus activities with inhibition rates of 46.4 % and 35.4 %, even more potent than the positive control ningnanmycin (30.8 %). Compound 1 also showed moderate cytotoxicity against A549 and MCF7 cells with IC50 values of 3.2 and 2.5 µM, respectively.

7,8-Secolignans from the fruits of Schisandra neglecta.

Two new 7,8-secolignans, neglectahenols E and F (1 and 2), together with four known 7,8-secolignans (3-6), were isolated from the fruits of Schisandra neglecta. The structures were elucidated by spectroscopic methods, including extensive 1D and 2D NMR techniques. Compounds 1-6 were tested for their anti-tobacco mosaic virus (anti-TMV) activities at the concentration of 20 µM. Compounds 1 and 6 showed high anti-TMV activities with inhibition rates of 38.2% and 32.7%, respectively. These rates are higher than that of a positive control. Compounds 2-5 also showed modest anti-TMV activities with inhibition rates in the range of 22.8-28.7%. These rates are close to that of a positive control.

Dihydroxanthenones from the fermentation product of an endophytic fungus Gliomastix murorum.

Three new dihydroxanthones, muroxanthenones A-C (1-3), together with three known dihydroxanthones (4-6) were isolated from the fermentation products of an endophytic fungus Gliomastix murorum. Their structures were elucidated by spectroscopic methods, including extensive 1D and 2D NMR techniques. Compound 3 showed high cytotoxicities against NB4 and PC3 cell with IC(50) values of 2.2 and 2.8 µM. The other compounds also showed moderate cytotoxicities for some tested cell lines with IC(50) values between 4.1 and 9.5 µM.

Flavones from Cassia siamea and their anti-tobacco mosaic virus activity.

Two new flavones, siameflavones A and B (1 and 2), together with five known flavones (3-7) were isolated from the stem of Cassia siamea. Their structures were elucidated by spectroscopic methods including extensive 1D and 2D NMR techniques. Compounds 1-5 were evaluated for their anti-tobacco mosaic virus (Anti-TMV) activity. The results showed that compounds 1-5 showed weak anti-TMV activity with inhibition rates in the range of 11.6-18.5%.

[Resting pressure of the tongue body on the tongue anchorage pad].

OBJECTIVE: To measure the resting pressure of the tongue body on the sagittal and vertical dimensions of the tongue anchorage pad (TAP), and to investigate the proper position of TAP as an anchorage. METHODS: Nineteen volunteers with individual normal occlusion (4 males and 15 females, age 23-33 years) were recruited in the study. Individualized TAP was designed and made for each subject. On the sagittal dimension, the pressure along the midline at the level of the distal of the second premolar (PM2), the first molar (M1) and the second molar (M2) were measured. On the vertical dimension, pressures on TAPs with height of -3 mm, 0 mm, and 3 mm were measured, with 0 mm standing for the reference point recorded by the tongue position record. The tongue resting pressure of the volunteers in the upright position was measured by miniature sensors (FSS1500NS, Honeywell, USA) embedded in TAP. Nonparametric analysis was applied with the significant level of 0.05. RESULTS: On the vertical dimension, the pressure obtained at the height of -3 mm, 0 mm, and 3 mm were 105.83 Pa, 167.75 Pa, and 254.25 Pa, respectively (P<0.001). On the sagittal dimension, the pressure detected at the level of PM2, M1, and M2 were 177.64 Pa, 126.72 Pa, and 109.37 Pa, respectively (P<0.001). CONCLUSION: Tongue pressure rises significantly with the increase of TAP height. On the sagittal dimension, pressure decreases along the palatal midline in an anteroposterior direction. But in the clinical practice, we should also put comfort into consideration.

[Gynecologic cancers in a hospital: a retrospective analysis of admission data over ten years].

OBJECTIVE: To investigate admission patterns of patients with gynecologic cancers over a ten year period, which will provide a basis for further epidemiological studies. METHODS: We reviewed medical records of patients with gynecologic cancers who were admitt d to the West China Second University Hospital of Sichuan University from 2003 to 2012. Their clinicopathological data were extracted and analysed. RESULTS: The number of admitted patients increased over the years, with cervical, uterine and ovary cancers as the top three gynaecological cancers. They accounted for 92.13% of total gynaecological cancers. The peak age of gynaecological cancers was 40-49 years, which accounted for 34.02% (3132/9207) of all patients, followed by 50-59 years (26.64%, 2453/9207). Most (72.46%, 3062/4226) cervical cancer patients aged 30-49 years, compared with 40-59 years for uterine cancers (69.77%, 1768/2534) and 40-59 years for ovarian cancers (58.30%, 1004/1722). Patients in their 20th account for 4.43% (408/9 207) of total cancers, with in which cervical and ovarian cancers as the most common pathological type. Patients under 20 years of age accounted for only 0.98% (90/9207) of total cancers, with ovarian cancers as the most common pathological type. Patients over 60 years accounted for 12.90% (1188/9207) of total cancers, with uterine and ovarian cancers as the most common pathological type. Most patients were at an early stage of cancers when they were admitted to the hospital. CONCLUSION: Hospitalized patients with gynecologic cancers increase over years. Cervical, uterine and ovary cancers remain to be a focus of treatment. Peak age of those cancers varies.