手持式拉曼光谱仪结合双金属Au@AgNPs聚集体检测环境水中结晶紫

构建了一种基于手持式拉曼光谱仪,结合双金属银包金粒子(Au@AgNPs)聚集体的现场快速检测结晶紫的表面增强拉曼光谱(SERS)方法。首先制备了“核-壳”粒径分别约为30 nm和6 nm的双金属银包金粒子(Au@AgNPs),并以NaCl作为聚集剂,获得了具有SERS活性的Au@AgNPs聚集体。结合激发光源785 nm的手持式拉曼光谱仪,实现了结晶紫的快速检测。以结晶紫位于1621 cm^-1处的特征峰进行定量分析,方法检出限为8.20μg/L,对河水和湖水中结晶紫的加标回收率为71.0%～128.4%。本文所构建的方法可用于监测结晶紫的非法使用。     

基于柔性SERS基底拉曼光谱法快速检测水果表面的福美双

采用海胆状金纳米粒子(GNUs)柔性表面增强拉曼散射(SERS)基底,检测了水果表皮的福美双残留。GNUs表面尖锐的突起能够极大增强周围电磁场,提高检测灵敏度。与普通柔性基底相比,这种高粘性的SERS基底具有不易老化和不易脱胶等优点。评估了SERS基底的灵敏度、重现性和稳定性。通过简单的"粘贴-剥离"法,利用组装的柔性基底对雪花梨表面的福美双残留进行了原位检测。在1×10~(-10)～1×10~(-4)mol/L范围内,雪花梨表面的福美双浓度的对数与SERS强度呈线性关系,GNUs柔性基底对福美双的检测限为92 pmol/L,方法可用于食品安全、环境检测、公共安全等领域。     

现场制备表面增强拉曼光谱基底法快速检测药片中盐酸阿米洛利的含量

利用加热贴(暖宝贴)作为热源现场合成银溶胶,并用其作为表面增强拉曼光谱(SERS)基底。使用罗丹明6G(R6G)作为探针分子,对合成的银溶胶的SERS性能进行评价。结果显示,银溶胶的制备方法简便、快速,制备时间在15 min内,具有较好的SERS增强效果,且在4 h内具有较好的稳定性。将现合成的银溶胶用于药片中盐酸阿米洛利的SERS检测,在0.8～8 mg/L范围内盐酸阿米洛利的质量浓度与拉曼峰强度有较好的线性相关系,线性方程为:y=1 395ρ-76.40,r~2=0.999 2。检出限(LOD)为0.2 mg/L,其加标回收率为104%～106%,相对标准偏差为0.35%～3.5%。该方法简单快速、稳定性好,为药片中盐酸阿米洛利的快速检测和鉴别提供了新途径。     

银纳米片在无纺布纤维上的可控组装及其SERS效应

以无纺布(NWF)为支撑基体, 采用两步化学合成法在NWF上原位构建了由间隙为20~110 nm Ag纳米片(AgNS)组装成的AgNS@NWF微纳结构. 扫描电子显微镜(SEM)分析表明, AgNS@NWF具有特殊的层级结构, 该结构可用于表面增强拉曼散射(SERS)研究. 实验结果表明, AgNS@NWF微纳结构具有良好的SERS灵敏度和优异的信号可重现性. 将罗丹明6G(R6G)作为SERS探针分子, 发现R6G的SERS特征峰强度的对数值与R6G水溶液的浓度对数值呈良好的线性关系, 最低检测限可达1×10^?10 mol/L, 表明AgNS@NWF微纳结构具有良好的SERS灵敏度; 当R6G水溶液的浓度为1×10^?5, 1×10^?6和1×10^?7 mol/L时, 610 cm^?1处谱带拉曼散射强度的相对标准偏差分别为3.57%, 3.67% 和8.46%, 优于或接近于以往研究, 表明AgNS@NWF微纳结构具有优异的信号可重现性. 将3-巯基丙酸和三聚氰胺作为SERS的检测分子, 最低检测限分别为1×10^?5和1×10^?6 mol/L. 本文为制备灵敏度高、 信号可重现性优异的SERS基底提供了一种简单、 快速、 成本低廉的方法, 在生物检测和环境监测中具有潜在的应用价值.     

构筑内标化表面增强拉曼散射基底用于梨汁中福美双的检测

本文基于表面增强拉曼光谱(SERS)技术，以内嵌有4-巯基苯甲腈(4-MBN)的银包金核壳纳米粒子(Au@4-MBN@AgNPs)为SERS基底，结合高通量疏水纸基，建立了一种免标记、高灵敏的福美双检测方法。内标探针4-MBN的引入显著提高了SERS基底的重现性；疏水纸基的使用进一步提高了检测的灵敏度。结果表明：福美双与内标探针的SERS信号强度比值(I_R=I₁₃₈₁/I₁₅₈₂)与不同浓度福美双之间具有较好的线性关系，相关系数R²为0.9990,检出限(LOD)为2.70×10^-10 mol/L。梨汁中加标回收率为85.36%～89.15%,与高效液相色谱-串联质谱法的检测结果(86.21%～91.68%)具有较好的一致性。本文提出的福美双检测方法操作简单、成本低、普适性强，为农残的快速、准确定量检测提供了新的可能。     

Au@Ag纳米粒子在农药SERS光谱分析中的应用

随着现代农业的发展,多种农药被广泛应用于农田,果园和温室等场所。由于大多数农药对生态环境、动物和人类健康都有害,因此建立快速、灵敏和实时检测环境与食品中农药含量的技术显得越来越重要。本文论述了用作表面增强拉曼散射(SERS)光谱基底的金核银壳纳米粒子(Au@AgNPs)的制备方法,以及将其用于苹果表面农药百草枯Paraquat(PQ)残留量的检测分析,检测限为4.69×10~(-9) M。研究工作表明,相对于单纯的金溶胶(AuNPs)或者银溶胶(AgNPs),Au@AgNPs在该农药的SERS光谱分析中表现出更好的SERS增强效应和检测效果。Au@AgNPs在浓度为1.3×10~(-7) M的低浓度条件下仍可检测到PQ。因此,具备核壳结构的Au@Ag溶胶可用于实时和灵敏检测果皮表面的农药残留,这为相关检测技术的建立提供了有益的信息。     

表面增强拉曼光谱法测定牛奶中青霉素G钠的残留量北大核心CSCD

青霉素G钠(NaBP)溶液的常规拉曼光谱信号微弱.将制备的浓缩银纳米粒子(AgNPs)20μL与不同浓度(1×10^(-9)~1×10^(-1)mol·L^(-1))的青霉素G钠溶液(pH 6)20μL混合,所得混合液的表面增强拉曼光谱(SERS)信号显著增强,在上述混合液中加入1×10^(-2)mol􀅰L^(-1)硫酸镁溶液8μL,青霉素G钠SERS增强效果最佳.据此,提出了以AgNPs为基底,硫酸镁为凝聚剂,采用SERS测定青霉素G钠含量的方法,并用于加标牛奶样品的检测.结果表明,青霉素G钠浓度为1×10^(-8)~1×10^(-3)mol·L^(-1)时,其浓度的对数值与相应的SERS信号强度呈线性关系,检出限(3s/k)为8.2×10^(-9)mol·L^(-1).按标准加入法进行回收试验,回收率为80.0%~96.0%,测定值的相对标准偏差(n=5)为2.3%~6.5%.     

Au@PVP核壳纳米粒子作为表面增强拉曼散射基底检测孔雀石绿

采用水热法合成了粒径均一、壳层厚度可控的Au@PVP核壳纳米粒子,利用壳层PVP分子分散纳米粒子的特性,使其形成均一、排列致密的单层结构,利用其内核金纳米粒子的等离子共振效应实现了孔雀石绿( MG)分子的表面增强拉曼检测。通过优化吸附时间与壳层厚度,在致密的、均匀的核壳纳米粒子表面增强拉曼散射(SERS)基底上实现MG分子高灵敏分析检测,检测线性范围1×10-10~1×10-5 mol/L,线性相关系数R2达到0.98,检出限可达1×10-12 mol/L。将本方法用于罗非鱼鱼肉中MG含量检测,样品未检出,样品加标回收率为70.8％~126.0％。结果表明,本方法快速准确、操作简单,可用于鱼肉中MG的快速检测。     

树枝状银微纳结构的表面增强拉曼散射效应研究

利用两电极电化学沉积法制备出一种树枝状银微纳结构基体.扫描电子显微镜(SEM)的表征结果证实所制备的银基体呈现出完整的树枝状结构,具有对称性的树枝和树干,且树叶清晰可见.实验结果表明,树枝状银微纳结构的表面增强拉曼散射(Surface-enhanced Raman scattering,SERS)可以检测到超低浓度的罗丹明6G(Rhodamine 6G,R6G,10-10 mol/L)光谱信号,即树枝状银微纳结构作为SERS基体表现出较好的灵敏性;当R6G的浓度在10-5~10-10 mol/L范围依次降低一个数量级时,谱带610 cm-1处的拉曼散射强度的相对标准偏差分别为12.1%,12.0%,11.7%,10.9%,13.2%和14.3%,表明所制备银基体的SERS"热点"(Hot spots)分布较均一,树枝状银微纳结构作为SERS基体具有较好的重现性;当低SERS活性的3-巯基丙酸(3-Mercaptopropionic acid,3MPA)的检测浓度为10-5 mol/L时,利用树枝状银基体能检测到3MPA的SERS光谱,说明所制备的银基体对低活性物质也具有较好的SERS灵敏性.     

流动注射-化学发光法测定猪饲料中的吡喹酮

基于吡喹酮对Luminol-NaIO_4化学发光体系有较强的抑制作用,并结合流动注射分析技术,建立了测定吡喹酮的流动注射-化学发光(FI-CL)新方法。在最佳实验条件下,吡喹酮在4.0×10~(-8)～1.0×10~(-6) mol/L浓度范围内与相对化学发光强度呈良好的线性关系,该方法对测定吡喹酮显示出较高的灵敏度,检出限(LOD,3σ)为9.9×10~(-9) mol/L。对2.0×10~(-7) mol/L的吡喹酮平行测定11次,其相对标准偏差(RSD)为1.4%。采用该方法对猪饲料样品进行加标实验,回收率为98.5%～100%。该方法已经成功用于猪饲料样品中吡喹酮的测定。     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.