ZnS量子点荧光探针对Pb~(2+)的检测研究

以L-半胱氨酸修饰ZnS量子点为荧光探针,测定火腿肠中Pb~(2+)含量。对ZnS量子点进行了UV、IR、荧光性能表征。研究了酸度、ZnS量子点浓度对体系荧光强度的影响,最佳测定条件为pH 8,L-半胱氨酸-ZnS量子点(L-ZnS量子点)浓度为1.0×10~(-6)mol/L。基于Pb~(2+)浓度对体系的荧光猝灭效应,实现对Pb~(2+)的定量检测,Pb~(2+)浓度在1.0×10~(-7)~4.5×10~(-5)mol/L范围内与体系的荧光强度线性关系良好,R2=0.984 7,检出限(3σ/S)为3.7×10~(-8)mol/L。线性方程为F0/F=88.14-14.05cPb~(2+),RSD=5.4%(n=6)。该方法简便、灵敏度高,可应用到检测Pb~(2+)诸多方面。     

三乙醇胺包覆的CdTe量子点用于尿样中三聚氰胺的荧光传感

利用三聚氰胺对乙酰半胱氨酸-三乙醇胺复合包覆的碲化镉量子点荧光的猝灭作用,建立了快速测定尿样中三聚氰胺的荧光传感新技术。研究结果表明,三聚氰胺浓度在0.1~1.0μmol/L范围内,量子点的荧光强度猝灭值(ΔF)与三聚氰胺的浓度呈线性关系,线性方程为ΔF=202.89cMA+38.26,相关系数(r)为0.9959,方法检出限0.05μmol/L。本方法用于尿液加标样品中三聚氰胺的检测,RSD为2.67%,三聚氰胺的平均回收率为98%~106%。     

谷胱甘肽包覆的碲化镉量子点荧光探针法快速测定多巴胺

利用多巴胺(DA)对谷胱甘肽包覆的碲化镉量子点荧光的猝灭作用,建立了快速测定多巴胺的荧光探针分析法。实验结果表明,在Tris-HCl(p H=7.0)溶液中,多巴胺浓度在0.06~2.1μmol/L范围内,碲化镉量子点荧光强度的猝灭值(ΔF)与多巴胺的浓度呈线性关系,线性方程ΔF=165.43cDA+9.57,相关系数(r)0.998 6,方法检出限0.03μmol/L。将本方法应用于样品中DA的分析,RSD为4.2%,DA的加标回收率为95.2%~104.8%。     

11-巯基烷酸修饰的核/壳量子点CdSe/ZnS的合成及分析应用研究

以11-巯基烷酸作为修饰剂,在水相中合成了CdSe/ZnS量子点荧光探针(QDs),并将其用于测定牛血清白蛋白.从透射电子显微镜看到该量子点外观近似球形,粒径约为15 nm.该核/壳量子点紫外吸收峰为460 nm,荧光发射峰为548nm,其荧光强度比单核量子点增强2.1倍.而且在至少40 d里,荧光强度基本保持稳定.在最佳条件下,实验表明了CdSe/ZnS QDs-BSA体系的荧光强度与BSA浓度呈线性关系,线性响应范围为10.0～50.0 mg/L,线性方程为△F=141.29 1.259c(c:mg/L),r=0.999 1.该方法应用于合成样品的测定中得到满意的结果.     

荧光碳量子点测定替硝唑的应用研究

替硝唑对碳量子点的荧光具有明显的猝灭作用,在pH值=7.10的PBS缓冲溶液中,碳量子点的荧光猝灭强度与替硝唑浓度在8.0×10~(-7)～2.0×10~(-5) mol/L范围内呈线性,相关系数为0.9992,方法检出限为2.3×10~(-7) mol/L。该方法用于样品中替硝唑的测定,回收率为96.2%～101.8%。通过比对碳量子点和碳量子点-替硝唑体系的荧光寿命和吸收光谱的变化以及改变温度环境后体系猝灭常数的变化趋势,确定该碳量子点与替硝唑的猝灭机理为动态猝灭。     

碳量子点的合成及对水体中Cr(Ⅵ)的测定

以姜粉为碳源,通过一步水热法合成了水溶性碳量子点(CDs),通过荧光、紫外和红外光谱、荧光寿命对其发光特性进行了研究。实验发现,在pH为2.21时,Cr(Ⅵ)能使该CDs荧光强烈猝灭,提出了以姜粉CDs为荧光探针测定Cr(Ⅵ)的新方法。Cr(Ⅵ)在1.0×10~(-6)~1.0×10~(-4)mol/L范围内与荧光猝灭值ΔF线性关系良好,方法检出限为5.0×10~(-7)mol/L,RSD=0.85%(n=5,c=2.5×10~(-5)mol/L)。采用该方法测定了水样中Cr(Ⅵ)的含量,结果满意。对CDs和Cr(Ⅵ)间的猝灭机理进行了研究。     

基于核桃壳碳量子点的制备及在痕量Hg~(2+)检测中的应用

采用核桃壳为碳源,尿素为氮源,通过一步水热法制备出水溶性好的氮掺杂碳量子点,并建立了氮掺杂碳量子点为荧光探针测定Hg~(2+)的方法。方法:在pH值为7. 0的PBS缓冲溶液中,控制量子点浓度为10 mg/L,在常温下与Hg(Ⅱ)反应20 min,根据体系的荧光猝灭程度测定Hg~(2+),结果:F/F0与Hg~(2+)浓度在4～100 nmol/L和1～60μmol/L范围内线性关系良好,方法检出限为3. 0 nmol/L和0. 25μmol/L,相对标准偏差为1. 9%～2. 4%,加标回收率为95. 4%～104%,结论:方法可用于河水水样中Hg~(2+)的测定,结果与原子荧光光谱法基本一致。     

NAC修饰的CdS测定盐酸帕罗西汀片剂含量的研究

以N-乙酰半胱氨酸(NAC)为修饰剂,简便,无毒,快速合成了CdS量子点,并基于盐酸帕罗西汀对该量子点的荧光猝灭作用,建立了盐酸帕罗西汀片剂的含量测定方法。结果显示,在pH=7.22,Tris-HCl缓冲液浓度为0.06 mol/L,量子点浓度为0.35 mmol/L,反应25 min的最佳条件下,该系统荧光强度变化值与盐酸帕罗西汀在(0.0033~0.1810 mg/m L)范围内线性关系良好,ΔF=682.06C+19.115为线性回归方程,检测限为0.32μg/m L。结果满意。     

基于Mn掺杂ZnS量子点室温磷光检测头孢克肟

在室温下,利用巯基丙酸(MPA)包裹Mn掺杂ZnS量子点的磷光信号,建立一种检测头孢克肟(CEF)的新方法。在最佳条件下(0.4 mg/L量子点溶液和pH=7.4磷酸缓冲液),CEF的加入使MPA包裹的Mn掺杂ZnS量子点的室温磷光发生猝灭,磷光强度(ΔRTP)与CEF呈现良好的线性关系,其线性范围1.2²4μmol/L,最低检出限0.49μmol/L,相关系数0.993,实际样品的检测回收率为93.7%24μmol/L,最低检出限0.49μmol/L,相关系数0.993,实际样品的检测回收率为93.7%¹01.3%。该方法简便快速、成本低、选择性好等,能够用于人体液中CEF含量的分析。     

基于Mn掺杂ZnS量子点室温磷光检测头孢克肟

在室温下,利用巯基丙酸(MPA)包裹Mn掺杂ZnS量子点的磷光信号,建立一种检测头孢克肟(CEF)的新方法。在最佳条件下(0.4 mg/L量子点溶液和pH=7.4磷酸缓冲液),CEF的加入使MPA包裹的Mn掺杂ZnS量子点的室温磷光发生猝灭,磷光强度(ΔRTP)与CEF呈现良好的线性关系,其线性范围1.2~24μmol/L,最低检出限0.49μmol/L,相关系数0.993,实际样品的检测回收率为93.7%~101.3%。该方法简便快速、成本低、选择性好等,能够用于人体液中CEF含量的分析。     

Insect antifeedant properties of anthranoids from the genusVismia

Vismiones and ferruginins, representatives of a new class of lypophilic anthranoids from the genusVismia were found to inhibit feeding in larvae of species ofSpodoptera, Heliothis, and inLocusta migratoria.     

Direct observation of freeze-thaw instability of latex coatings via high pressure freezing and cryogenic SEM

Despite its industrial importance, the subject of freeze-thaw (F/T) stability of latex coatings has not been studied extensively. There is also a lack of fundamental understanding about the process and the mechanisms through which a coating becomes destabilized. High pressure (2100 bar) freezing fixes the state of water-suspended particles of polymer binder and inorganic pigments without the growth of ice crystals during freezing that produce artifacts in direct imaging scanning electron microscopy (SEM) of fracture surfaces of frozen coatings. We show that by incorporating copolymerizable functional monomers, it is possible to achieve F/T stability in polymer latexes and in low-VOC paints, as judged by the microstructures revealed by the cryogenic SEM technique. Particle coalescence as well as pigment segregation in F/T unstable systems are visualized. In order to achieve F/T stability in paints, latex particles must not flocculate and should provide protection to inorganic pigment and extender particles. Because of the unique capabilities of the cryogenic SEM, we are able to separate the effects of freezing and thawing, and study the influence of the rate of freezing and thawing on F/T stability. Destabilization can be caused by either freezing or thawing. A slow freezing process is more detrimental to F/T stability than a fast freezing process; the latter actually preserves suspension stability during freezing. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004 in Chicago, IL. Tied for first place in The John A. Gordon Best Paper Competition.     

Many Drugs of Abuse May Be Acutely Transformed to Dopamine,Norepinephrine and Epinephrine In Vivo

It is well established that a wide range of drugs of abuse acutely boost the signaling of the sympathetic nervous system and the hypothalamic–pituitary–adrenal (HPA) axis, where norepinephrine and epinephrine are major output molecules. This stimulatory effect is accompanied by such symptoms as elevated heart rate and blood pressure, more rapid breathing, increased body temperature and sweating, and pupillary dilation, as well as the intoxicating or euphoric subjective properties of the drug. While many drugs of abuse are thought to achieve their intoxicating effects by modulating the monoaminergic neurotransmitter systems (i.e., serotonin, norepinephrine, dopamine) by binding to these receptors or otherwise affecting their synaptic signaling, this paper puts forth the hypothesis that many of these drugs are actually acutely converted to catecholamines (dopamine, norepinephrine, epinephrine) in vivo, in addition to transformation to their known metabolites. In this manner, a range of stimulants, opioids, and psychedelics (as well as alcohol) may partially achieve their intoxicating properties, as well as side effects, due to this putative transformation to catecholamines. If this hypothesis is correct, it would alter our understanding of the basic biosynthetic pathways for generating these important signaling molecules, while also modifying our view of the neural substrates underlying substance abuse and dependence, including psychological stress-induced relapse. Importantly, there is a direct way to test the overarching hypothesis: administer (either centrally or peripherally) stable isotope versions of these drugs to model organisms such as rodents (or even to humans) and then use liquid chromatography-mass spectrometry to determine if the labeled drug is converted to labeled catecholamines in brain, blood plasma, or urine samples.     

Ethanol and (−)-α-Pinene: Attractant Kairomones for Bark and Ambrosia Beetles in the Southeastern US

In 2002–2004, we examined the flight responses of 49 species of native and exotic bark and ambrosia beetles (Coleoptera: Scolytidae and Platypodidae) to traps baited with ethanol and/or (−)-α-pinene in the southeastern US. Eight field trials were conducted in mature pine stands in Alabama, Florida, Georgia, North Carolina, and South Carolina. Funnel traps baited with ethanol lures (release rate, about 0.6 g/day at 25–28°C) were attractive to ten species of ambrosia beetles (Ambrosiodmus tachygraphus, Anisandrus sayi, Dryoxylon onoharaensum, Monarthrum mali, Xyleborinus saxesenii, Xyleborus affinis, Xyleborus ferrugineus, Xylosandrus compactus, Xylosandrus crassiusculus, and Xylosandrus germanus) and two species of bark beetles (Cryptocarenus heveae and Hypothenemus sp.). Traps baited with (−)-α-pinene lures (release rate, 2–6 g/day at 25–28°C) were attractive to five bark beetle species (Dendroctonus terebrans, Hylastes porculus, Hylastes salebrosus, Hylastes tenuis, and Ips grandicollis) and one platypodid ambrosia beetle species (Myoplatypus flavicornis). Ethanol enhanced responses of some species (Xyleborus pubescens, H. porculus, H. salebrosus, H. tenuis, and Pityophthorus cariniceps) to traps baited with (−)-α-pinene in some locations. (−)-α-Pinene interrupted the response of some ambrosia beetle species to traps baited with ethanol, but only the response of D. onoharaensum was interrupted consistently at most locations. Of 23 species of ambrosia beetles captured in our field trials, nine were exotic and accounted for 70–97% of total catches of ambrosia beetles. Our results provide support for the continued use of separate traps baited with ethanol alone and ethanol with (−)-α-pinene to detect and monitor common bark and ambrosia beetles from the southeastern region of the US.     

Novel polyurethane coating technology through glycidyl carbamate chemistry

Glycidyl carbamate chemistry combines the excellent properties of polyurethanes with the crosslinking chemistry of epoxy resins. Glycidyl carbamate functional oligomers were synthesized by the reaction of polyfunctional isocyanate oligomers and glycidol. The oligomers were formulated into coatings with several amine functional crosslinkers at varying stoichiometric ratios and cured at different temperatures. Properties such as solvent resistance, hardness, and impact resistance were dependent on the composition and cure conditions. Most coatings had an excellent combination of properties. Studies were carried out to determine the kinetics of the curing reaction of the glycidyl carbamate functional oligomers with multifunctional and model amines. Detailed kinetic analysis of the curing reactions was also undertaken. The results indicated that the glycidyl carbamate functional group is more reactive than a glycidyl ether group. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, on October 27–29, 2004, in Chicago, IL.