Stereospecific solid-state NaBH4-promoted reduction of 1-methylpentacyclo[5.4.0.02,6.03,10.05,9]undecane-8,11-dione

NaBH₄ reduction of a cage dione proceeds in a stereospecific fashion to give theendo,endo-diol. This reactivity is related to the crystal structure.     

Selective effect of guest molecule length and hydrogen bonding on the supramolecular host structure

A host supramolecular structure consisting of bis-(2,2':6',2' '-terpyridine)-4'-oxyhexadecane (BT-O-C16) is shown to respond to guest molecules in dramatic ways, as observed by using scanning tunneling microscopy (STM) on a highly oriented pyrolytic graphite surface under ambient conditions. It is observed that small linear molecules can be encapsulated within the host supramolecular lattice. The characteristics of the host structure were nearly unaffected by the encapsulated guest molecules of terphthalic acid (TPA) dimers, whereas appreciable changes in cavity dimension can be observed with azobenzene-4,4'-dicarboxylic acid. The STM study and density functional theory (DFT) analysis reveal that intermolecular hydrogen bonding interaction plays an essential role in forming the assembling structures. The difference in guest molecule length is considered the important cause for the different guest-host complexes.     

Theory on the molecular characteristic contour (II)--Molecular intrinsic characteristic contours of several typical organic molecules

The molecular intrinsic characteristic contour (MICC) is defined based on the classical turning point of electron movement in a molecule. Three typical organic molecules, I.e. Methane, methanol and formic acid, were employed as examples for detailed introduction of our method. Investigations on the cross-sections of MICC provide important information about atomic size changing in the process of forming molecules. The electron density distributions on the MICCs of these molecules were calculated and shown for the first time. Results showed that the electron density distribution on the MICC correlates closely with molecular chemical properties, and it provides a new insight into molecular boundary.     

Molecular Hydrogels with Esterase-like Activity

The development of molecular hydrogels that can be applied for mimicking bioactive molecules attracts extensive interests of researchers in fields of self‐assembly. In this study, we reported on several molecular hydrogels based on naphthylacetic acid‐peptides containing L‐histidine formed by the heating‐cooling process. All hydrogels exhibited higher activity to hydrolyze 4‐nitrophenyl acetate (4‐NPA) than the free L‐histidine probably due the high density of L‐histidine residue at the surface of self‐assembled nanofibers. To calculate the 4‐NPA hydrolysis rates, the Michaelis‐Menten enzyme kinetics model was made. Among these gels, the gel of Nap‐GFFYGHY possesses the highest enzyme activity of making the ester bond cleavage, which is approximately 25 times higher than that of the control (free L‐histidine and Nap‐GFFYGYY). These results indicate that molecular hydrogels with self‐assembled nanofibers have great potential for the generation of self‐assembled multivalent materials.     

Syngas production from methane over CeO2-Fe2O3 mixed oxides using a chemical-looping method

A series of mixed oxides Ce_{1 ? x} Fe _x O₂ was prepared by a hydrothermal method. XRD and Raman spectra were measured to study the structure of the prepared materials. The temperature-programmed reduction was undertaken to estimate reducibility of the oxides. Syngas generation from methane using these materials as oxygen carriers/catalysts via a chemical-looping procedure was investigated in detail. This procedure includes catalytic oxidation and decomposition of methane to produce H₂-rich gas at the first step followed by the production of the CO-rich gas by oxidizing the carbon deposited on deactivated catalysts. The results showed that all iron ions were incorporated into the ceria lattice with the formation of oxygen vacancies in the Ce_0.9Fe_0.1O₂ sample, while isolated Fe₂O₃ particles were distributed on the surface of the Ce_0.8Fe_0.2O₂ sample. TPR measurements and the analysis of the two-step chemical-looping reactions indicated a strong interaction between the Ce and Fe species which accounts for an increased activity of the mixed oxides in the syngas generation compared to that of individual oxides. Among the several samples, the Ce_0.8Fe_0.2O₂ catalyst showed the highest activity for methane partial oxidation due to the synergetic effects caused by the interaction of surface iron entities and Ce-Fe solid solution. In addition, selective oxidation of carbon by oxygen to CO can also be found over this material since gaseous products are formed at the carbon oxidation step with the selectivity to CO reaching 91.2%. Evidence is presented that syngas can be feasibly produced from methane with high selectivity via the chemical-looping procedure over the CeO₂-Fe₂O₃ mixed oxides.     

FDU-15-Pt composites with different Pt loading and their electrocatalytic reduction to ultratrace nitroaromatic compounds

FDU-15 is a hexagonal mesoporous material with nanometer-sized, highly ordered arrays and large special surface area. In this work, FDU-15-Pt with 2.0%, 5.0% and 8.0% Pt loading were synthesised and used for electrochemical detection of trace nitroaromatic compounds (NACs). The FDU-15-Pt samples were characterised by CO Chemisorption, transmission electron microscopy (TEM) and X-ray diffraction (XRD). It has been demonstrated that FDU-15-Pt with 2.0% Pt loading has the smallest Pt particle size of 2.9?nm, highest Pt metal dispersion of 37.7% and largest Pt metal surface area of 21.36?m^2?g^?1. The FDU-15-Pt/PDDA modified electrode were assembled by electrostatic adsorption of Poly (diallyldimethylammonium chloride) (PDDA) and FDU-15-Pt. The 2.0% FDU-15-Pt modified sensor showed higher selectivity for NACs than those of 5.0% and 8.0% FDU-15-Pt, which were verified by electrochemical experiments. A linear response over TNT concentration ranging from 8.8?×?10^?9?M to 1.2?×?10^?5 M was exhibited with a low detection limit of 2.9?×?10^?9?M (S/N?=?3). Moreover, the proposed 2.0% FDU-15-Pt/PDDA modified sensor has been applied to the detection of NACs in spiked environmental water samples and shows promise for fast and accurate determination of trace NACs in real samples.     

多层CT与DSA对急性冠状动脉综合征患者冠状动脉支架置入术后通畅性及狭窄程度的影响

研究多层CT与DSA对急性冠状动脉综合征患者冠状动脉支架置入术后通畅性及狭窄程度的影响。以我院2017年8月-2018年11月在我院诊断治疗的急性冠脉综合征患者80例作为研究对象,对所有患者进行经皮冠状动脉介入治疗(percutaneous coronary intervention,PCI)手术后,分别进行DSA检查以及64排螺旋CT检查。分析不同检查的冠状动脉狭窄、通畅性之间的差异以及不同检查的一致性。通过对CT检查结果以及DSA检查结果的配对卡方检验,两组患者的检查结果之间的差异不存在统计学意义,两种检查对患者的冠状动脉的狭窄情况诊断一致性较好;两种检查方法对患者的管壁厚度以及管径直径诊断之间的差异不存在统计学意义,两种检验方法对患者的管壁厚度以及管径直径诊断一致性较好。总之,多层CT与DSA对急性冠状动脉综合征患者冠状动脉支架置入术后通畅性及狭窄程度的诊断具有较高的一致性,建议临床推广。     

无液接裸露式Ag/AgCl参比电极的研制及应用

提出了一种无液接裸露式Ag/AgC l参比电极制备方法,测试了该参比电极的稳定性、重现性、可逆性、响应时间、温度影响等因素。实验结果表明,该电极电位稳定在49 mV,响应时间在30 s以内时,具有重现性、可逆性好,使用寿命长,温度影响小等特点,可替代饱和甘汞和Ag/AgC l参比电极。     

Rational design of iridium–porphyrin conjugates for novel synergistic photodynamic and photothermal therapy anticancer agents

Near-infrared (NIR) emitters are important probes for biomedical applications. Nanoparticles (NPs) incorporating mono- and tetranuclear iridium(iii) complexes attached to a porphyrin core have been synthesized. They possess deep-red absorbance, long-wavelength excitation (635 nm) and NIR emission (720 nm). TD-DFT calculations demonstrate that the iridium–porphyrin conjugates herein combine the respective advantages of small organic molecules and transition metal complexes as photosensitizers (PSs): (i) the conjugates retain the long-wavelength excitation and NIR emission of porphyrin itself; (ii) the conjugates possess highly effective intersystem crossing (ISC) to obtain a considerably more long-lived triplet photoexcited state. These photoexcited states do not have the usual radiative behavior of phosphorescent Ir(iii) complexes, and they play a very important role in promoting the singlet oxygen (¹O₂) and heat generation required for photodynamic therapy (PDT) and photothermal therapy (PTT). The tetranuclear 4-Ir NPs exhibit high ¹O₂ generation ability, outstanding photothermal conversion efficiency (49.5%), good biocompatibility, low half-maximal inhibitory concentration (IC₅₀) (0.057 μM), excellent photothermal imaging and synergistic PDT and PTT under 635 nm laser irradiation. To our knowledge this is the first example of iridium–porphyrin conjugates as PSs for photothermal imaging-guided synergistic PDT and PTT treatment in vivo.

Iridium–porphyrin conjugates assembled in nanoparticles are photosensitizers that exhibit excellent photothermal imaging and synergistic PDT and PTT in vivo.     

利用ABEEMσπ模型研究哺乳类催产素及其衍生物

哺乳类催产素及其衍生物是一系列包含S—S键的多肽分子. 应用原子-键电负性均衡σπ(ABEEMσπ)模型, 我们研究了该系列多肽分子的分子内氢键和整体软度与生物活性关系. 首先利用点电荷模型计算了该系列多肽分子的分子内氢键能, 并与实验值对比, 得到了基本一致的结果. 再根据整体软度与生物活性的关系: 即整体软度越大, 分子生物活性越大, 我们成功解释了催产素及其衍生物的分子生物活性的变化关系. 将ABEEMσπ模型初步应用于研究含 S—S键多肽的相关性质方面, 并取得了和实验以及其它理论计算较为一致的结果. 因此, 以上研究为该模型进一步探讨其它多肽的相关性质提供了一定的理论基础.