In Vivo Imaging of the Tumor‐Associated Enzyme NCEH1 with a Covalent PET Probe

Herein, we report the development of an ¹⁸F‐labeled, activity‐based small‐molecule probe targeting the cancer‐associated serine hydrolase NCEH1. We undertook a focused medicinal chemistry campaign to simultaneously preserve potent and specific NCEH1 labeling in live cells and animals, while permitting facile ¹⁸F radionuclide incorporation required for PET imaging. The resulting molecule, [¹⁸F]JW199, labels active NCEH1 in live cells at nanomolar concentrations and greater than 1000‐fold selectivity relative to other serine hydrolases. [¹⁸F]JW199 displays rapid, NCEH1‐dependent accumulation in mouse tissues. Finally, we demonstrate that [¹⁸F]JW199 labels aggressive cancer tumor cells in vivo, which uncovered localized NCEH1 activity at the leading edge of triple‐negative breast cancer tumors, suggesting roles for NCEH1 in tumor aggressiveness and metastasis.     

(±) Gancochlearols A and B: cytotoxic and COX-2 inhibitory meroterpenoids from Ganoderma cochlear

Abstract

(+)- and (?)-gancochlearols A (1) and B (2), two pairs of dimeric mertoterpenoid enantiomers were isolated from the fruiting bodies of Ganoderma cochlear. Their structures were identified by spectroscopic methods. Biological assessments show that the enantiomers of 1 and 2 are cytotoxic against three human cancer cell lines (A549, K562, Huh-7) and could inhibit COX-2 expression with IC₅₀ values less than 10?μM.     

Autocatalytic polymerization of selenium/polypyrrole nanocomposites as functional theranostic agents for multi-spectral photoacoustic imaging and photothermal therapy of tumor

The synchronization of diagnosis and treatment is a new trend in cancer treatment. Photoacoustic imaging (PAI) and photothermal therapy (PTT) are recognized as one of the perfect combinations. The autocatalytic polymerization of selenium/polypyrrole (Se@PPy) nanocomposites with a wide-absorption band at near-infrared region (NIR, 800 nm) has been developed in this paper. The wide optical absorption characteristics enable Se@PPy nanocomposites to achieve multi-spectral PAI. Ex vivo experiments show desirable photoacoustic ability of the Se@PPy nanocomposites at wavelengths ranging from 700 nm to 900 nm, which is better than that of commercial indocyanine green (ICG). Se@PPy nanocomposites have high photothermal conversion efficiency up to 36.3% as well as excellent photo-thermal stability. In vitro cytotoxicity test demonstrates that the Se@PPy nanocomposites have good bio-safety. Furthermore, the feasibility of Se@PPy nanocomposites for enhancing multi-spectral PAI guided PTT was verified on 4T1 tumor-bearing nude mice. Our results indicate that Se@PPy nanocomposites could be used as an effective theranostic agent for near-infrared light-mediated PAI and PTT of tumor.     

利用自由基引发的1,2-炔基迁移实现非活性烯烃的炔膦酰化

研究了1,4-烯炔衍生物与二芳基膦氧化物在银介导下发生的炔酰化反应.该反应利用自由基引发的1,2-炔基迁移策略合成了一系列γ-酮膦氧化物,产率适中.该反应机理可能涉及膦中心自由基与乙烯基的加成、3-exo-dig环化和1,2-炔基迁移等连续的过程,一步形成了C-P、C-C键等化学键,实现了非活性烯烃的双官能化.     

可持续高分子-纤维素新材料研究进展

21世纪"绿色"化学已成为世界各国社会经济发展中的研究与开发战略方向.纤维素是自然界中储量最丰富的天然高分子,是重要的可再生资源以及未来的主要工业原料.然而由于纤维素存在着大量的分子内以及分子间氢键,其结构致密,难以溶解或熔融进一步加工.本文简要介绍了近几年来关于直接使用物理溶剂方法(非衍生化)对纤维素材料开发利用的新进展,主要包括以下4个方面:(1)纤维素在"绿色"溶剂-碱/尿素以及离子液体体系中的溶解和再生;(2)纳米纤维素的制备以及组装;(3)木材纳米技术的开发及利用;(4)细菌纤维素基材料等,旨在推进"绿色"技术实现纤维素资源的研究开发及利用.     

温度对乙醇电催化氧化的影响

升高温度可以提高反应速率和增加物质的输运,因此通过不同温度下反应机理的研究可以深入理解电催化过程,对催化剂的设计具有指导意义。本工作初步建立了变温原位红外测定方法。采用温控电极,用电势测温法进行温度的校准,实验得出控温仪器加热温度Th与电极表面温度TS的关系为T_S=0.57T_h+7.71 (30°C T_h≤50°C);T_S=0.62T_h+5.12 (50°C T_h≤80°C),误差分析最大温差为1°C。利用该方法我们研究了商业Pt/C催化剂在不同温度下乙醇的电氧化过程。从循环伏安图可以明显看到随着温度的升高整体氧化电流增大,起始电位、峰电位均负移,说明热活化使得氧化反应更容易进行;第一个峰电流与第二个峰电流的比值用于定性评估CO_2的选择性,对比25°C,商业Pt/C催化剂在65°C下第一峰提高30%,说明高温有利于C―C键的断裂。对比25°C的原位红外谱图,我们发现35°C及50°C下商业Pt/C催化剂上CO_2产物的起始电位负移200 m V,说明高温下,Pt/C催化剂能在更低的电位提供含氧物种;而CH_3CHO、CH_3COOH起始电位不随温度变化。用CO_2与CH_3COOH的积分面积比来评估CO_2选择性,发现高温低电位其选择性最高,说明高温低电位有利于乙醇完全氧化生成CO_2,而高温高电位下表面吸附含氧物种占据了活性位,阻碍C―C键断裂。     

Synthesis of two A-B-C type conjugated amphiphilic triblock fullerene derivatives and their application in organic solar cells

Two A-B-C type conjugated amphiphilic triblock fullerene derivatives C60-2 HMTPB and C60-2 EHTPB were obtained in multi steps synthesis with three different blocks,and the amphiphilic diblock molecular C60-4 TPB was also preferred as a reference.When as modifying layer on zinc oxide(ZnO),the three fullerene derivatives can all reduce the work function of ZnO via modulation of the interfacial dipoles and lead a better electrical coupling.As introducing treatment of toluene,the obvious self-assembly of fullerene derivatives were observed,which were supported by X-ray diffraction and contact angle of water measurement.Base on PTB7-Th:PC71 BM system,the inverted organic solar cells devices with structure of ITO/ZnO/fullerene derivatives/PTB7-Th:PC71BM/Mo03/Al got power conversion efficiencies of 8.62%,8.83%and 9.00%for C60-4 TPB,C60-2 HMTPB and C60-2 EHTPB,respectively,compared 8.13%of devices with bare ZnO.The result of conjugated amphiphilic triblock fullerene derivatives provides a straightforward approaching by simultaneously modulating the morphology and interfacial work function of ZnO,which can also lead high performance in optoelectronic devices.     

质子交换膜燃料电池电流密度分布特性和研究展望

质子交换膜燃料电池具有无污染、噪声低、能量密度高、燃料转换效率高、响应速度快的显著优点,得到了迅速发展,但寿命仍然是制约其大规模商业化的重要原因。局部电流密度作为质子交换膜燃料电池运行过程中的重要参数,既能作为电池运行过程中的故障诊断和定位工具,提升电池运行的稳定性和和耐久性;又能提供电池运行期间其内部现象的有关信息,为深入理解电池反应机理以及优化电池设计提供有力指导,因此研究局部电流密度具有非常重要的意义。本文介绍并分析了实时原位测量局部电流密度的方法,比较了前人实验所得结果与模拟所得结果,阐述了相关参数对局部电流密度分布的影响机制,回顾并评析了局部电流密度用于燃料电池分析中的实际工作。最后,立足于局部电流密度的研究现状,给出了局部电流密度下一步的研究方向。     

Visible photoluminescence of nanometer-sized SiGe/Si heterostructure fabricated by ion implantation

An innovative fabrication technique for the nanometer-sized SiGe/Si heterostructure was developed in this study. Ge was induced in Si substrate by two-step ion implantation. The spherical SiGe nanoclusters are self-assembled in the Si substrate by subsequent rapid thermal annealing at 1,100 °C. The diameter of the spherical SiGe nanoclusters is 5–7 nm. Visible photoluminescence from this nanometer-sized SiGe/Si heterostructure at room temperature was investigated. We found three peak energies of visible luminescence spectra at 1.97, 2.13, and 2.16 eV, respectively. The luminescence intensity depends on the number of the nanoclusters and will be decreased because of the micro-defects around the heterostructure, which is discussed in detail.     

Comparative Large Eddy Simulation study of a large-scale buoyant fire

A fully-coupled Large Eddy Simulation model which incorporates all essential combustion, radiation and soot chemistry considerations have been developed to simulate the temporal vortical structure of a large-scale buoyant fire. Numerical results are validated and compared against a full-scale fire measurements and predictions from other LES models. Quantitative comparisons against experimental data suggested that the present model successfully captured the vortical structures and the puffing behaviour of a buoyant fire.