α-蒎烯的光氧化反应研究

α-蒎烯和氧能在基态条件下形成CCT复合物,在与CCT复合物吸收相应波长的光辐照下,有利于促进蒎烯的光氧化反应。在氧化反应中,存在着明显的溶剂极性的影响,极性愈大,反应的速度愈快。这一切都说明电荷转移在反应中起着重要的作用。此外,正由于存在着基态的CCT复合物,因此α-蒎烯的氧化反应也能在暗的条件下进行。根据蒎烯光氧化和暗氧化反应产物的分析,可以肯定蒎烯在本工作实验条件下的氧化反应是通过自由基机理而进行的。     

基于金属有机框架水凝胶的一步式快速富集检测养殖水体中孔雀石绿北大核心CSCD

孔雀石绿是一种三苯甲烷类化合物,在水产品饲养中对疾病的防治有着不错的疗效,但因对人体健康有危害而被列为禁用药。由于实际样品中成分复杂,对于此类染料的检测方法难以同时兼具富集性好、灵敏度高且方便快速的优点。该工作制备了金属有机框架材料(MOF),采用MOF纳米材料掺杂的水凝胶(PAAM-SA/MOF)对养殖水体中的孔雀石绿进行吸附研究。采用一系列表征手段对MOF、PAAM-SA和PAAM-SA/MOF的微观形貌进行分析,结果表明吸附材料已成功合成。通过优化水凝胶吸附剂用量、吸附时间、孔雀石绿溶液pH、吸附温度、孔雀石绿溶液初始浓度等吸附萃取条件,使溶液中的孔雀石绿基本完全吸附在水凝胶中,在最优条件下,吸附效率最高可达97%。此外,采用不同极性的有机溶剂对吸附的孔雀石绿进行洗脱,通过优化洗脱液体积,脱附率最高达99%。在最佳条件下,该方法在高、中、低3个水平下的样品加标回收试验中回收率达到84.8%~118.1%,相对标准偏差小于5.1%,方法的检出限为0.083μg/L(S/N=3),定量限为0.25μg/L(S/N=10)。该方法简化了前处理过程,结合了MOF和水凝胶这二者各自的优点,添加的MOF材料可以在水凝胶体系中发挥其良好的吸附性,既解决了传统的MOF材料因粒径太小而回收率低的难题,便于吸附后直接提取,同时也解决了纯水凝胶吸附效率较低的问题,整体上提高了吸附效率和可回收性。实际样品测试表明该新型水凝胶吸附材料可用于养殖水体中孔雀石绿的快速萃取和检测,在食品检测领域具有很大潜力。     

Cell Membrane-camouflaged Multi-functional Dendritic Large Pore Mesoporous Silica Nanoparticles for Combined Photothermal Therapy and Radiotherapy of Cancer

Combining photothermal therapy and radiotherapy(PTT-RT) with reducing tumor hypoxia acts as an important antitumor modality. However, it is a great challenge to realize photothermal therapy, radiotherapy and exogenous oxygen supply in one nanosystem. To realize a combination of the three functions, we fabricated a red blood cell membrane(RBCm)-camouflaged, red blood cell content(RBCc) and the copper sulfide(CuS) co-loaded dendritic large pore mesoporous silica nanoparticle(DLMSN/CuS/RBCc/ RBCm). The cell membrane coating endowed the nanoparticles with good stability in the physiological environment, and CuS allowed the nanoparticle exhibiting good photothermal and radiosensitization properties. RBCc loaded nanoparticle DLMSN/CuS/RBCc enhanced superior anti-tumor effect than DLMSN/CuS during combined PTT-RT therapy because the introduction of RBCc increased the exogenous oxygen supply. The in vitro study further demonstrated that the combination of photothermal therapy and radiotherapy induced superior antitumor efficacy than single therapy. Our work thus presents a unique multifunctional nanoscale platform favorable for combined PTT and RT.     

Catalytic Hydration of Aromatic Alkynes to Ketones over H-MFI Zeolites

The hydration of alkyne represents the most straightforward and simplest route toward the synthesis of ketone. Herein, Brønsted acidic zeolites are explored as potential catalysts for the liquid-phase phenylacetylene hydration. The topology structure and Si/Al ratio are disclosed to be key factors controlling the catalytic activity of zeolites. Typically, H-MFI zeolite with a Si/Al molar ratio of 13 exhibits the highest catalytic activity, with turnover frequency of 6.0 h^-1 at 363 K. Besides, H-MFI zeolite shows good catalytic stability and recyclability in the reaction of phenylacetylene hydration, and the substrate scope can be simply extended to other soluble aromatic alkynes. The reaction mechanism of phenylacetylene hydration is investigated by means of kinetic and spectroscopic analyses. The Markovnikov electrophilic addition of phenylacetylene by hydrated protons is established as the rate-determining step, followed by deprotonation and enol isomerization to derive acetophenone product.     

Development of the Self-doping Porous Carbon and Its Application in Supercapacitor Electrode

The massive discharge of biomass wastes not only causes waste of resources, but also pollutes the environment. Therefore, converting biomass wastes into carbon materials is an effective way to solve the above problems. Here, using biomass waste pig nails as raw materials and K₂CO₃ as chemical activators, the N-doped porous carbon(KPNC) is prepared by direct pyrolysis. As an electrode for supercapacitors, the electrochemical tests of KPNCs showed that they exhibited good electrochemical performance and excellent cycling stability. When the current density is 0.2 A/g, the specific capacitance is up to 344.6 F/g. Moreover, it still maintains 97.6% initial capacitance retention after 2000 cycles at a high current density of 5 A/g. Above exceptional electrochemical performances may be ascribed to an appropriate porous structure(S_micro/S_total=80.31%, V_micro/V_total=76.19%), high nitrogen contents(4.44%, atomic fraction), oxygen contents(9.13%, atomic fraction) as well as small internal resistance. The above experimental results show that the conversion of pig nails to porous carbon can reduce the waste of resources and alleviate environmental pollution.     

Progress in DNA Aptamers as Recognition Components for Protein Functional Regulation

Proteins play a central role in all domains of life, and precise regulation of their activity is essential for understanding the related biological processes and therapeutic functions. Nucleic acid aptamers, the molecular recognition components derived from systematic evolution of ligands by exponential enrichment(SELEX), can specifically identify proteins with antibody-like recognition characteristics and help to regulate their activity. This minireview covers the SELEX-based selection of protein-binding aptamers, membrane protein analytical techniques based on aptamer-mediated target recognition, aptamer-mediated functional regulation of proteins, including membrane receptors and non-membrane proteins(thrombin as a model), as well as the potential challenges and prospects regarding aptamer-mediated protein manipulation, aiming to supply some useful information for researchers in this field.     

Surface Organometallic Chemistry for Single-site Catalysis and Single-atom Catalysis

Although driven by different research interests, single-site catalysts and single-atom catalysts are both believed to be model systems bridging homogeneous and heterogeneous catalysis. The two concepts are similar but different. In this review, we will first explain the difference between single-atom catalysis and single-site catalysis, in terms of their goals, synthetic methods and coordination structures of corresponding catalysts. Then, we will introduce the surface organometallic chemistry method, a method traditionally used for synthesizing single-site catalyst. We will explain why it might benefit the single-atom catalysis community. At last, the choice of support to accommodate the method for synthesizing single-atom catalysts will be discussed.     

基于i-motif的生物医学应用纳米系统:pH成像、药物控释和肿瘤诊疗

I-motif作为一种新型pH敏感元件,因其在不同pH条件下可以进行快速的构象转变,以及具有自动化合成、优异的生物相容性和灵活的功能化整合等优点,在生物医学领域引起了广泛的关注和研究热潮.该文介绍了i-motif的基本性能,综述了基于i-motif的纳米系统在细胞pH成像、pH控制的药物释放和pH响应型肿瘤诊疗一体化等...     

表层取样法结合气相色谱-串联质谱测定竹木砧板中19种防腐防霉剂残留

建立了表层取样/气相色谱-串联质谱(GC-MS/MS)测定竹木砧板中19种防腐防霉剂残留的方法。通过表层取样法制备样品后先进行酸化,然后利用乙酸乙酯-正己烷(2∶8,体积比)混合溶剂提取,经方法优化后无需进行衍生化反应及净化操作,采用多反应监测扫描(MRM)模式检测,基质匹配溶液外标法定量。结果表明,19种组分在0.005～200.0μg/mL范围呈良好的线性关系(r²> 0.990),检出限(LOD,S/N=3)为0.001～0.17 mg/kg,定量下限(LOQ,S/N=10)为0.003～0.55 mg/kg;在低、高2个不同加标水平下,19种目标物的回收率为65.8%～97.2%,相对标准偏差(RSD,n=6)为4.3%～13%。利用该方法对市售竹木砧板和一次性筷子样品进行检测,发现非定型包装竹木砧板中存在五氯酚残留量高的风险隐患,可为相关部门提供风险预警。     

固相萃取/气相色谱-质谱法测定燃香烟气中9种大麻素类新精神活性物质

建立了同时测定燃香烟气中9种大麻素类新精神活性物质的气相色谱-质谱（GC-MS）分析方法。样品在燃香烟气收集装置中经溶剂提取,浓缩离心后,采用HLB固相萃取小柱净化,毛细管色谱柱Agilent HP-5MS毛细管柱（30 m×0.25 mm×0.25μm）分离,使用电子轰击电离（EI）源检测,SIM模式进行质谱监测,内标法对9种大麻素类化合物进行定量。结果表明,9种大麻素类化合物在27 min内完成分离分析,并在0.01～4.0 mg/L范围内具有良好的线性关系,相关系数（r2）均不小于0.999 5,方法的检出限（LOD,S/N=3）和定量下限（LOQ,S/N=10）分别为0.003～0.06 mg/L和0.01～0.2 mg/L。在阴性样品中进行1、2和10倍定量下限的加标回收实验,9种大麻素类化合物的回收率为74.8%～114%,相对标准偏差（RSD,n=6）为1.6%～9.1%。采用该方法对10种市售的燃香样品进行测定,均未检出大麻素类化合物。建立的方法操作简便,可快速对燃香烟气中大麻素类化合物进行定性和定量分析,且能满足发烟量大燃香的检测需求。该方法的建立为我国燃香中大麻素类...