基于上转换荧光共振能量转移的Hg~(2+)侧流检测模型的设计和应用

本工作利用荧光共振能量转移(FRET)过程,以上转换荧光纳米材料(UCNPs)作为能量供体,以金纳米粒子(AuNPs)作为能量受体,通过适配体识别Hg~(2+),在硝化纤维素膜(NC)上制备侧流检测试纸条。Hg2+的参与会拉近能量供受体距离,引起检测区UCNPs的荧光猝灭。通过检测区的荧光猝灭效率,可判断样品中的Hg~(2+)浓度。该传感器在缓冲溶液中的检测线性范围为0.1~100nmol/L;检出限为0.1nmol/L。本研究成功证实了上转换荧光共振能量转移体系在侧流模型应用的可行性。     

富含胞嘧啶单链DNA-银纳米簇荧光探针用于S1核酸酶的灵敏检测

以富含胞嘧啶（C）的单链DNA为模板合成银纳米簇,将其作为功能化探针,建立了一种无标记荧光检测S1核酸酶的方法.S1核酸酶可以特异性识别单链DNA,在最适的酶催化反应条件下,可将其降解为单核苷酸或寡核苷酸片段.当S1核酸酶不存在时,富含C的单链DNA可以有效地合成荧光银纳米簇;当S1核酸酶存在时,单链DNA模板被特异性识别并降解,导致无法形成银纳米簇,使体系荧光信号降低.实验结果表明,银纳米簇的荧光强度随着S1核酸酶浓度的增加而降低.在优化的条件下,体系荧光信号（F/F₀）与S1核酸酶的浓度在5.0×10^-5~4.0×10^-3 U/μL范围内呈线性关系,检出限为2.0×10^-6 U/μL.该荧光探针选择性好,可用于RPMI 1640细胞培养基中S1核酸酶的检测,回收率达到91.8%~109.5%.     

DNA/银纳米簇荧光探针在检测Pb2+中的应用

基于DNA/银纳米簇的荧光特性报道了一种简单、灵敏、高选择性的荧光方法检测Pb²⁺.以茎部为富G结构,环状部分为聚C结构的发夹型DNA为模板合成具有稳定荧光的银纳米簇.当加入Pb²⁺后,发夹型DNA在Pb²⁺诱导下形成G-四链体结构,破坏了发夹型DNA的构型,极大地影响了合成银纳米簇的模板结构,导致银纳米簇的荧光强度降低.Pb²⁺存在和不存在时所产生荧光强度的差异与发夹型DNA的碱基序列和茎部配对碱基数有关.依据这一现象,在优化DNA碱基序列和茎部配对碱基数的基础上,可实现100 μmol/L至100 nmol/L范围内对Pb²⁺的定量检测,检出限为10 nmol/L.该方法对Pb²⁺的检测具有较好的选择性,并可应用于实际水样中Pb²⁺的检测.检测结果与原子吸收光谱进行比对,显示出较好的一致性.     

基于催化发夹组装和荧光共振能量转移的生物传感器检测EV71病毒

以肠道病毒71型(EV71)为检测对象，建立了基于催化发夹组装(CHA)和荧光共振能量转移(FRET)的生物传感器。设计了检测EV71 VP1基因的CHA信号放大策略，该体系由一对发夹探针(H1、 H2)构成，H1和H2分别标记了荧光基团Cy3和Cy5。当体系中有VP1基因时，可引发H1和H2催化自组装反应，从而使得Cy3和Cy5相互靠近并发生FRET,导致Cy3荧光信号降低，Cy5信号增强；当体系中没有VP1基因时，H1和H2则稳定存在于反应体系中，不发生FRET,只检测到Cy3的荧光信号。优化了缓冲液浓度、 H1与H2的比例、反应温度和反应时间。在最优条件下，所构建的传感器的Cy5与Cy3的荧光强度比值与EV71 VP1基因浓度在0.5～20 nmol/L范围内呈良好的线性关系，检出限为73 pmol/L(3σ)。咽拭子样品的加标回收率为99.6%～103.1%,相对标准偏差在0.3%～1.7%之间。本方法具有较好的特异性及抗干扰能力，在EV71监测和手足口病早期诊断方面具有良好的应用前景。     

基于聚多巴胺纳米粒子的荧光共振能量转移法检测microRNA

基于聚多巴胺纳米粒子(PDA NPs)对Cy5标记单链DNA(Cy5-ssDNA)探针的荧光猝灭效应以及脱氧核糖核酸酶Ⅰ(DNaseⅠ)选择性切割DNA/RNA杂合结构中单链DNA的特性,建立了一种用于微小核糖核酸(miRNA)检测的新型恒温信号放大方法.在优化的实验条件下,体系的相对荧光强度(FR)与miR-21浓度的对数值成正比;对miR-21检测的线性范围为10 pmol/L~100 nmol/L,检出限达7 pmol/L.血清加标实验结果表明,该方法可用于生理环境下miR-21的检测.     

基于DNA模板合成的银簇建立“点亮型”荧光法检测卡那霉素

以DNA为模板合成弱荧光的银纳米簇。利用DNA模板中的适配体序列识别目标卡那霉素后,形成发夹结构使适配体序列上的G碱基和C碱基靠近银簇,导致银簇荧光增强。同时,DNA二级结构的改变使银纳米粒子形成小的银纳米簇也促使银簇的荧光增强。据此建立"点亮型"荧光法对卡那霉素进行定量分析。银簇荧光增强比值与卡那霉素浓度在0.075～8.0μmol/L范围内呈线性关系,线性方程为F/F_0=0.616 8C+0.927 6,检出限为36 nmol/L。卡那霉素在牛奶和蜂蜜样品中的回收率为92.4%～112%。此外,随着卡那霉素加入浓度的增加,银簇的橙色荧光逐渐加深,根据荧光颜色深度可对卡那霉素进行可视化半定量检测。该方法具有灵敏度高、选择性好的优点,可用于复杂食品样品中痕量卡那霉素的定量检测。     

以DNA为模板的银纳米簇荧光检测及逻辑门的构建

以DNA为模板, 合成了具有荧光性质的银纳米簇(DNA-Ag NCs), 利用荧光光谱、 紫外光谱和红外光谱等手段对其进行了表征. 基于DNA-Ag NCs与离子相互作用时产生的荧光变化可实现对离子浓度的检测. 实验结果表明, 在最佳实验条件下, Ni ²⁺及Hg ²⁺的浓度与DNA-Ag NCs荧光强度呈线性关系; 并验证了该荧光探针用于检测自来水样品中汞离子和镍离子的实用性. 由于以DNA为模板的DNA-Ag NCs能够响应多种刺激, 如Ni ²⁺, S ^2-, Hg ²⁺和pH等, 利用相应的荧光强度可构建多输入的DNA-Ag NCs逻辑门及其组合逻辑门. 当荧光输出强度(I_output)>初始荧光强度(I_origin)时, 设定输出为1, 采用各种刺激及其组合作为输入, 构建了YES, INH和组合的NOR与INH逻辑门. 而只有当I_output≥I_origin时定义为输出为1, 可建立NOT, NOR, 组合的IMP加上NOR与AND逻辑门. 基于DNA-Ag NCs可以构建响应多元输入的复杂逻辑门, 实现化学信息的转变和传输, 在构建新的分子器件方面有较大应用前景.     

基于铜/银纳米簇检测铜离子的方法研究

通过设计不同富含G碱基的DNA序列,探究了G碱基对核酸-铜/银纳米簇(DNA-Cu/AgNCs)的荧光增强效应,并建立了铜离子的荧光检测方法。结果发现,在富含C碱基序列模板的5'端增加G5序列后,制备得到的铜/银纳米簇的荧光强度显著增强。同时,该DNA-Cu/AgNCs的荧光可被Cu~(2+)和Hg~(2+)猝灭。通过NaBH_4掩蔽Hg~(2+)实现了对Cu~(2+)的特异性检测。该方法检测Cu~(2+)的线性范围为0.01～5.0μmol/L,检出限为5.0 nmol/L。方法具有简单快速、选择性高、成本低等优点,可用于实际样品测定。     

基于DNA银铂双金属纳米簇的电化学传感器用于Hg~(2+)的检测

以DNA为模板,通过一步法合成了一种银铂双金属纳米簇(DNA-Ag/Pt NCs),其粒径为2~4 nm,并表现出较强的过氧化物模拟酶活性,能催化H2O2氧化TMB使溶液变蓝色。基于此特性,结合Hg2+可与胸腺嘧啶碱基形成T-Hg2+-T结构,设计研制了一种非标记的电化学传感器,用于Hg2+的灵敏特异性检测。实验结果表明,在最佳条件下,该传感器的检测范围为0.65~3.5 nmol/L,检出限达0.17 nmol/L,能较好地识别Hg2+。该传感器有望用于实际水样中痕量汞的检测。     

吲哚类菁染料Cy3嵌入的核壳荧光纳米颗粒的制备及其性质研究

以蛋白质或多肽修饰的吲哚类菁染料Cy3为内核, 采用实验条件简单的油包水反相微乳液方法成核, 通过正硅酸乙酯水解形成的网状二氧化硅包壳的方法制备吲哚类菁染料Cy3嵌入的核壳荧光纳米颗粒. 考察了以不同等电点的蛋白质和多肽修饰的Cy3为内核材料对吲哚类菁染料Cy3嵌入的核壳荧光纳米颗粒制备的影响. 结果表明, 分别采用人免疫球蛋白(IgG)或多聚赖氨酸修饰的Cy3为内核材料, 都能制备荧光强度高、荧光稳定性强和染料泄漏极少的Cy3嵌入的核壳荧光纳米颗粒. 进一步对Cy3嵌入的核壳荧光纳米颗粒进行了表征, 并将基于这一新型的荧光纳米颗粒建立起来的生物标记方法初步应用于流感病毒DNA的检测, 其检测线性范围为3.18×10-10～1.27×10-9 mol/L, 检测下限为3.51×10-10 mol/L, 相关系数r为0.986 5.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

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.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Microwave-assisted copper-catalyzed stereoselective ring expansion of three-membered heterocycles with α-diazo-β-dicarbonyl compounds

Microwave-assisted copper-catalyzed ring expansions of three-membered heterocycles with α-diazo-β-dicarbonyl compounds were investigated. Thiiranes generated 3-acyl-5,6-dihydro-1,4-oxathiines in the presence of copper sulfate and trans-3-acyl-5,6-dihydro-1,4-oxathiines as stereospecific products for 1,2-disubstituted cis-thiiranes through an intramolecular S_N2 process. Oxiranes gave rise to 2-acyl-5,6-dihydro-1,4-dioxines under the catalysis of copper hexafluoroacetylacetonate and cis-3-acyl-5,6-dihydro-1,4-dioxines as stereospecific products for 1,2-disubstituted cis-oxiranes via an intimate ion-pair mechanism. The current method provides a direct and simple strategy in efficient preparation of 3-acyl-5,6-dihydro-1,4-oxathiines and 2-acyl-5,6-dihydro-1,4-dioxines, important agents in medicinal and agricultural chemistry, from readily available thiiranes and oxiranes, respectively.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.