微流控纸芯片的加工及其分析应用的实验设计*

设计了一个使用喷墨打印法加工微流控纸芯片的实验,在经烷基烯酮二聚体(AKD)的正己烷溶液浸泡过的滤纸上,以三乙醇胺溶液为打印墨水,用喷墨打印机打印出设计好的芯片图案。滤纸加热后,打印区域呈现亲水性,非打印区域为疏水性,从而制备出纸芯片,用该纸芯片通过数字比色法实现了亚硝酸根离子的定量测定。该实验不使用昂贵仪器设备,易普及。通过实验,促使学生了解微流控芯片这一前沿科学技术,锻炼学生细致、灵巧的动手能力,激发学生科技创新活力。     

基于纳米金催化的血清尿酸纸芯片的构建及应用

建立了一种以纸芯片为平台,利用纳米金(Au NPs)的过氧化物模拟酶特性对血清中尿酸(UA)含量进行快速检测的方法.在改装的中性笔中灌注疏水性材料溶液,直接在滤纸上绘制所需要的图案,经干燥后形成纸芯片.将纳米金、四甲基联苯胺(TMB)和H_2O_2的混合液依次滴加于纸芯片检测区域,无色的TMB被氧化成蓝色,然后将待测样品滴加于蓝色区域,氧化态TMB被还原为无色,根据手机相机记录的检测区域灰度值计算试样中尿酸的浓度.实验优化了纳米金在纸芯片上的用量、反应时间和反应温度等参数,在最优实验条件下,检测尿酸的线性范围为10.6~125 mg/L,检出限为4.64 mg/L,加样回收率为94.8%~108.5%.该方法选择性良好,可用于测定血清样品中尿酸的含量.     

基于无掩膜光刻法的纸基微流控芯片制备与验证研究

为了开发新的纸芯片制备技术制作高精度的纸基微流控芯片,该文提出了一种基于无掩膜光刻技术的新制备方法。以疏水图案的表面接触角和液体在微流控通道内的流动情况为评价标准,研究了曝光、显影等关键工艺对疏水区域疏水强度以及液体流动情况的影响。研究结果表明,仅需2 s曝光时间制备的纸芯片疏水区域的接触角可达100.56°,亲疏水区域具有明显的区分,最小可实现的亲水通道和疏水屏障分别为(68±5)μm和(104±9)μm。将纸基芯片用于亚硝酸盐的检测,溶液浓度与显色区颜色强度之间呈良好的相关性,线性方程为Y=3.450X+34.83,r²=0.977 0。无掩模光刻法制备纸芯片无需制作掩膜版,减少了芯片制作的成本和时间,工艺简便,芯片精度高,为纸芯片制备和应用提供了有效手段。     

普适型纸芯片的研究与应用

纸基分析芯片(纸芯片)具有成本低、便携化、操作和后处理简单无污染等优点,在临床诊断、食品质量控制和环境监测等领域有着广阔的应用前景。然而,由于难以制作性能优异的疏脂性屏障,使得纸芯片在涉及有机溶剂和表面活性剂的分析检测中,其发展受到了限制。针对当前纸芯片开发研究中存在的灵敏度较低、对有机溶剂和表面活性剂敏感等难点问题,研究人员在滤纸基底上制作出了性能优异的疏水隔离图案和高粘附疏水表面,并验证了所制备的纸芯片对涉及有机溶剂和表面活性剂的分析检测具有普适性。本文对此类普适型纸芯片的研究与应用进行评述。     

基于等离子体技术制作微流控纸芯片及其在血糖检测中的应用研究

滤纸经十八烷基三氯硅烷(OTS)疏水化处理以后,用等离子体区域降解滤纸纤维表面的OTS疏水单分子层,使滤纸的局部区域恢复亲水性,得到具有亲疏水图案化的微流控纸芯片. 考察了等离子体处理时间对滤纸表面亲水性、亲水深度(水溶液由滤纸表层下渗至内部的纵向深度)的影响. 优化模具的设计,依据对滤纸亲水深度的不同需求,设计了两种PMMA-PDMS复合片的组合模具. 初步探讨了该亲疏水性变化过程的化学机理. 将制得的纸芯片用于人体全血中血糖含量的测定,线性范围为1.7～17.7 mmol·L^-1,可满足血液样品中血糖的测定.     

点滴分析概况介绍

一、点滴分析发展简史很久以前,分析化学家就知道在纸上或在不渗透的表面上(如玻皿、坩锅等)用一滴溶液来进行简单的化学试验。例如;约在十七世纪初,人们就已经知道用浸有指示剂的纸来测定溶液中的氢离子或氢氧离子浓度。又如,很早就知道用淀粉试纸来试碘或用黄血盐来试被滴定溶液中的铁。到目前为止,在文献上可查考的,第一个在滤纸上进行点滴分析的,可能是席夫(H.Schiff),他在1859年发表了一篇研究论文,在滤纸上以AgNO_3来分析尿中之尿酸。因尿酸使银还原,于是随尿酸的多少,在滤     

纸芯片显色法用于L-半胱氨酸的快速测定

该文以5,5'-二硫硝基苯甲酸(DTNB)为含巯基化合物的衍生化试剂,建立了其纸芯片快速检测新方法。显色剂DTNB和样品在显色区相遇并显色,用手机拍照记录,采用Photoshop软件分析显色强度,进行比色检测,并以L-半胱氨酸(L-Cys)为例,优化得到纸芯片检测L-Cys的最佳显色条件。结果显示,L-Cys浓度在0.01～0.1 mmol/L范围内与显色强度呈良好的线性关系(r=0.999 8),检出限达0.001 mmol/L。多种氨基酸和干扰离子对L-Cys在纸芯片上的测定干扰不超过±5%。采用该方法测得牛血清样品中L-Cys含量为0.013 mmol/L,加标回收率为99.1%～103%,该方法检测L-Cys具有操作简单、耗样量少、检测快速、重现性好等优点。     

氢氧化锰共沉淀分离-催化极谱法测定土壤中有效钼

土壤样品中有效钼用草酸铵-草酸混合溶液(pH 3.3)振摇提取,所得悬浮液用干滤纸过滤,分取部分滤液蒸缩体积后加入10 g.L-1酸性高锰酸钾溶液并蒸发至近干,趁热加0.25 mol.L-1氢氧化钠溶液进行共沉淀分离。分取部分上清液,用硫酸(1+1)溶液酸化后加入混合底液(其中含有二苯基乙醇酸、二苯胍及氯酸钠)及少许钛铁试剂溶液作为与钼(Ⅵ)进行催化反应的试剂体系。用JP-303极谱仪进行测定。在-220 mV峰电位处测得的峰电流值与其相应的钼(Ⅵ)的质量浓度在0.8～20μg.L-1范围内呈线性关系。此方法的检出限(3s/k)为0.002 6μg.g-1。用此方法分析了5个土壤标准物质,所测得有效钼的含量与其认定值相符。     

基于微流控纸芯片-显色法快速测定全血中尿酸的含量

提出了基于微流控纸芯片-显色法快速测定全血中尿酸含量的方法。使用喷蜡打印机将设计的微通道网格打印在色谱纸上,经过加热处理得到微流控纸芯片。在微流控纸芯片I区(样品预处理区)滴加3.2μL 0.10 g·mL^-1乙二胺四乙酸(EDTA)溶液和4.8μL 0.015 g·mL^-1壳聚糖溶液,干燥,得到微流控纸芯片检测平台。全血样品与磷酸盐缓冲液(pH 7.4)按体积比1∶4混合,分取混合溶液13μL滴加至I区,红细胞与血浆在壳聚糖和EDTA的凝集作用下发生分离,血浆流动至II区(显色区);待血浆完全铺满II区后,滴加3μL三氯化铁和邻二氮菲的混合溶液,静置反应2 min,用手机拍照,采用Photoshop CS2软件分析显色区的颜色强度,得到RGB值(红、绿、蓝三色叠加值),根据标准曲线计算尿酸含量。结果表明：全血中葡萄糖等常见还原性物质均不影响尿酸含量的测定;尿酸浓度在0.05～0.85 mmol·L^-1内与RGB值呈线性关系,检出限(3.3s/k)为0.03 mmol·L^-1。方法用于实际全血样品分...     

3D纸基微流控分析器件测定药物中抗坏血酸的研究

本文报道一种新型3D纸基微流控分析器件测定药物中抗坏血酸。采用不同的方法固定试剂于器件显色滤纸,有效地避免了试剂间的影响。以手动折叠,实现了各步反应时间的控制。在优化的实验条件下,测定体系的灰度值(Gray)与抗坏血酸浓度在7~550μmol/L范围内呈线性关系,检出限为6.1μmol/L。该纸基微流控分析器件制备简单,携带方便,成本低廉,可用于药物中抗坏血酸的测定,同时适用于药物及其它样品中抗坏血酸的现场实时测定。     

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.     

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.     

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.     

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.     

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%).     

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.     

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.