高效液相色谱-四极杆-飞行时间质谱快速筛查鉴别食品中非法添加的62种中药材北大核心CSCD

建立了高效液相色谱-四极杆-飞行时间质谱快速筛查鉴别食品中非法添加的62种中药材的方法。依据卫生部关于进一步规范保健食品原料管理的通知(卫法监发[2002]51号)中可用于保健食品的物品名单,确定食品中可能非法添加的62种中药材原料清单,再从62种中药材中筛选其特征组分,获得不同中药材对应的特征组分清单。62种对照药材经甲醇超声提取后,于Thermo Accucore aQ色谱柱(150 mm×2.1 mm,2.6μm)上分离,在电喷雾正负离子扫描模式下,分别以0.1%(v/v)甲酸水溶液-乙腈和水-乙腈为流动相梯度洗脱,进行一级质谱和二级质谱全扫描检测,采用Library View软件建立不同中药材对应的特征组分的一级精确质量数据库和二级碎片质谱库。样品同法处理后上样分析,采用Peak View软件将样品高分辨数据与自建数据库中的质谱图、精确分子离子质量数、碎片离子质量数、保留时间等相关参数进行快速筛查鉴别分析。该工作通过建立“中药材-特征组分”对应清单,构建了食品中易非法添加的62种中药材中共388种特征组分的高分辨质谱库,每种中药材包括5~10种特征组分,通过对实际食品样品配制酒、代用茶及饮料进行筛查分析,1批次配制酒样品与淫羊藿中药材的7种特征组分匹配一致,推断该配制酒样品中加入了淫羊藿中药材。该法可实现无标准品情况下中药材的定性筛查,具有高通量、准确、简便、快捷的特点,解决了食品中非法添加中药材难以识别和确证的难题,可以实现食品中非法添加中药材的快速筛查鉴别分析。     

Ba0.6Sr0.4TiO3/聚偏氟乙烯-聚甲基丙烯酸甲酯复合材料的制备及其介电性能

采用流延热压工艺制备Ba_0.6Sr_0.4TiO₃(BST)/聚偏氟乙烯(PVDF)?聚甲基丙烯酸甲酯(PMMA)复合薄膜,研究了PMMA含量对复合材料微观组织结构和介电性能的影响规律。结果表明,BST相能够均匀分散在聚合物基体中,归因于PMMA与PVDF良好的相容性,2种聚合物之间的界面不分明;随着PMMA含量的增加,复合材料的介电常数先降低后升高,耐击穿强度和介电可调性先增加后减少。PMMA含量(体积分数)为15%的BST/PVDF?PMMA₁₅复合材料的综合性能最佳:介电常数为23.2,介电损耗为0.07,耐击穿强度为1412 kV·cm^-1,在550 kV·cm^-1偏压场下,介电可调性为26.2%。     

In-situ cation exchange enhances room temperature phosphorescence of a family of metal-organic frameworks

The rational designability and chemical tunability of metal-organic frameworks(MOFs)are enabling tributes to efficaciously enhance their room temperature phosphorescence(RTP)performance.A family of stable anionic MOFs,[Zn₂(4,5-ImDC)₂]M₂(NKU-132,M=(CH₃)₂NH₂or(CH₂CH₃)₂NH₂),featuring significant RTP have been synthesized.By rational cation selection and in-situ replacement from dimethylammonium to diethylammonium,the phosphorescence lifetime is increased from 30.88 to126.3 ms,along with less sensitivity to air.This work provides an anti-quenching and lifetime tuning example for RTP-MOFmaterials via facile host-guest chemistry.     

Silicon-substituted rhodamines for stimulated emission depletion fluorescence nanoscopy

As an essential part in the toolbox of super-resolution microscopy, stimulated emission depletion(STED)nanoscopy has been widely explored in revealing the substructure and bioactivities in fluorescence imaging. Among the applied STED fluorophores, silicon-substituted rhodamines(SiRs) belong to one of the most extensively employed fluorophores. The carboxy-SiR was favored in STED bioimaging with many advantages, including reliable photostability, cell permeability, tunable fluorogenicity, feasibl...     

石墨烯玻璃透明薄膜加热特性

Graphene has become a research focus in recent years owing to its excellent characteristics, and glass is a commonly used material with high transparency and low cost. Graphene glass combines the excellent properties of both graphene and glass; graphene glass has not only high thermal conductivity, high electrical conductivity, and good surface hydrophobicity but also exhibits superior electrothermal conversion and wide-spectrum high-light-transmittance characteristics. Therefore, the study of graphene glass films is of theoretical value and practical significance. In this study, a high-purity glass-based (JGS1 quartz glass) multilayer graphene film was developed based on an atmospheric-pressure chemical vapor deposition (APCVD) method, and its electrical characteristics, light transmittance, and electrical heating characteristics were experimentally investigated in detail. The results show that graphene glass with different surface resistance values obtained through direct growth on a high-purity quartz glass substrate using the APCVD method, not only has excellent uniformity and quality, but also has considerably flat and high transmittance across the entire visible light region and exhibits excellent heating performance and fast response time. For graphene glass with a surface resistance of 1500 Ω·sq^-1, the light transmittance can reach 74%, and the saturation temperature can rise to 185 ℃ by applying a bias voltage of 40 V. In addition, when the resistance value of the graphene glass is 420 Ω·sq^-1, the graphene glass reaches a high saturation temperature of 325 ℃ in 40 s, and the corresponding heating rate can exceed 18 ℃·s^-1, achieving a significantly higher heating rate than other heating films at the same voltage. Compared with the polyethylene-terephthalate- (PET-) based and silicon-based graphene films obtained by the transfer, graphene glass has a higher saturation temperature, shorter thermal response time, and faster heating rate. Furthermore, graphene glass exhibits better heating cycle stability and longer-term heating stability at a constant voltage. In addition, an experiment using the graphene glass to thermally tune the wavelength of a vertical-cavity surface-emitting laser was conducted and gave good results. The position of the laser peak controlled by the graphene glass was red-shifted by 1.78 nm by applying a voltage of 20 V, and the wavelength tuning efficiency reached 0.059 nm·℃^-1. Compared with PET-based and silicon-based graphene films, the actual electrical heating capacity of graphene glass increased by 195%. These experimental findings demonstrate that graphene glass transparent films with excellent electric heating characteristics can be used in various transparent electric heating fields and have relatively wide application prospects.     

基于混酸回流制备碳点的中和过程

Carbon dots (C dots) are relatively novel carbon nanomaterials that have attracted significant interest due to their unique photoluminescence, good biocompatibility, and stability. The preparation methods of C dots was usually summarized into "top-down" and "bottom-up", and mixed acid reflux is a top-down strategy that can be used to synthesize C dots, during which neutralization is a necessary step that can significantly influence the properties and potential applications of the final product. Previously, this research area mainly focused on tuning the properties of C dots by changing the starting materials and/or varying the reaction conditions; the influence of the reagents used during neutralization has been largely ignored. As the previously reported C dots prepared by mixed acid reflux were obtained from different starting materials under varied conditions, a meaningful comparison is difficult. Herein, yellow-emitting C dots were prepared by mixed acid-refluxing a carbon-rich material derived from fullerene carbon soot. For the same batch of as-prepared C dots, the influences of four reagents, i.e., NaOH, Na₂CO₃, K₂CO₃, and NH₃·H₂O, during neutralization on the structures and photoluminescence of the resulting C dots were investigated in detail. The results of thermogravimetric analysis, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy clearly showed that the reagent used during neutralization can affect the degree of dissociation of the acidic functional groups on the C dots. This is further supported by examination of the C dot/surfactant mixtures where subtle changes in the phase behavior were observed. Structural changes of the C dots cause variations in their surface states, ultimately altering the optical characteristics, including UV-vis absorption and fluorescence. Among the treated C dots, the sample prepared with Na₂CO₃ showed the strongest emission under the same excitation wavelength, while that prepared with NH₃·H₂O exhibited a distinct red shift (~8 nm) in the emission curve. The results presented herein provide clear evidence that neutralization reagent selection is important for optimizing the properties of the resulting C dots obtained by mixed acid reflux. In addition, the photoluminescence of the C dots can be influenced by their counterions, providing a novel method for tuning the properties of C dots while explaining their behavior in saline solutions. In short, the basicity of the neutralizing reagent and the type of counterions affect the structure of the C dots surface, which brings different performances. This work reminds researchers that it is necessary to use the type of neutralizing reagent as an experimental condition when preparing C dots in the future.     

金属衬底在石墨烯化学气相沉积生长中的作用

以过渡金属为催化衬底的化学气相沉积法(Chemical Vapor Deposition,CVD)已经可以制备与机械剥离样品相媲美的石墨烯,是实现石墨烯工业应用的关键技术之一。原子尺度理论研究能够帮助我们深刻理解石墨烯生长机理,为实验现象提供合理的解释,并有可能成为将来实验设计的理论指导。本文从理论计算的角度,总结了各种金属衬底在石墨烯CVD生长过程中的各种作用与相应的机理,包括在催化碳源裂解、降低石墨烯成核密度等,催化加快石墨烯快速生长,修复石墨烯生长过程中产生的缺陷,控制外延生长石墨烯的晶格取向,以及在降温过程中石墨烯褶皱与金属表面台阶束的形成过程等。在本文最后,我们对当前石墨烯生长领域中亟需解决的理论问题进行了深入探讨与展望。     

离子选择电极阵列土壤中硝态氮测定

土壤硝态氮反映土壤短期氮素供应水平,实时了解土壤硝态氮的含量为精准农业和农业面源污染防控提供支撑,因此,在线实时检测土壤硝态氮方法突破就显得十分迫切。土壤硝态氮中的硝酸根离子在土壤中的高水溶性和流动性为全固态硝酸根离子选择电极高敏感检测土壤中硝态氮提供了条件,固态硝态氮离子选择电极的离子选择膜反应硝酸根离子在被测溶液中的浓度。采用全固态硝酸根离子选择电极,且与温度电极和pH电极融合组成电极阵列对土壤饱和溶液中的硝态根离子进行检测。设计了高输入阻抗运算放大电路对电极信号进行采集,并通过微处理控制蠕动泵完成土壤硝态氮待测溶液连续流动测量及实时传输结果。实验结果表明,电极响应时间≤15 s,斜率-51.63 mV/decade,线性范围10-5-10-2.2 mol/L,最低检测限10-5.23 mol/L。相对标准差在0.78%-4.47%范围内,加标回收率均在90%-110%以内。与国家标准紫外可见分光光度法测试结果相比,相关系数（R2）为0.9952,为土壤硝态氮在现场检测奠定技术基础。     

槲皮素-3-O-丙基衍生物的合成及生物活性研究

槲皮素是具有丰富生物活性的黄酮类化合物,药理活性显著。本文以槲皮素为先导物,选择性对C环3位羟基进行修饰,以廉价的芦丁为原料,经苄基保护、Williamson成醚反应,再经Pd/C催化加氢脱苄基得到28个未见文献报道的槲皮素-3-O-丙基衍生物,其结构经¹H NMR、¹³C NMR、ESI-MS进行确证。采用MTT法考察了所合成化合物对人食管鳞癌（EC109）、人胃癌（HGC27）、人乳腺癌（MCF-7）、小鼠黑色素瘤（B16-F10）的增殖抑制作用。结果显示,通过化学方法对槲皮素结构进行修饰后,其体外抗肿瘤活性增强。其中,化合物F3(IC₅₀=5.23±0.37μmol/L)、F5(IC₅₀=2.63±0.09μmol/L)对小鼠黑色素瘤（B16-F10）抑制作用比5-氟尿嘧啶(IC₅₀=14.38±0.27μmol/L)好,值得进一步研究。     

Calorimetric studies on the electrorefining process of copper

Calorimetric measurements were carried out on the electrorefining of copper using different current densities with a Calvet type microcalorimeter at room temperature. The ratio (R) of the measured heat (Q _m orW _m) to the input electric energy (Q _in orW _in) and the excess heat (Q _ex orW _ex), i.e. the difference betweenQ _m (orW _m) andQ _in (orW _in) during the electrorefining process were discussed in terms of general thermodynamics. It was found thatR andQ _ex were related to the current density employed in the experiment and varied as a logarithmic function. The results obtained here indicate that the heat generation under different conditions, such as different currents or voltages, may be caused partially by the irreversibility of the process or by some unknown processes.Dedicated to Prof. Menachem Steinberg on the occasion of his 65th birthdayThe authors would like to acknowledge the extreme encouragements and help of Professor Shuyi Liu (University of Science and Technology of China) and Professors Fu Tan and Guoquan Liu (Institute of Chemistry, Academia Sinica).This study was supported by the National Nature Science Foundation of China.