基于Nafion/碳纳米粒子修饰的葡萄糖传感器

采用滴涂法制备了Nafion/碳纳米粒子复合物修饰玻碳电极,该电极对H2O2具有良好的电催化氧化性能。还利用滴涂法制备了Nafion/碳纳米粒子复合物包裹的葡萄糖酶电化学生物传感器,该生物传感器对葡萄糖有着良好的电催化作用。应用该传感器对葡萄糖进行了检测,检测线性范围为2.0×10-6～6.0×10-3mol/L,检出限为1.6×10-6mol/L(S/N=3),实验结果表明该传感器具有良好的稳定性、重现性和抗干扰能力。对小鼠血清样品中的葡萄糖进行检测,结果令人满意。     

L-AlaC4NTf2手性离子液体作为新型气相色谱固定相的性能研究

合成了一种手性离子液体L-丙氨酸叔丁酯双三氟甲烷磺酰亚胺(L-AlaC4NTf2), 将其作为新型气相色谱固定相, 并与OV-1701按不同比例混合, 考察了它们的色谱性能. 研究结果表明, 该离子液体作为手性固定相的热稳定性高于175 ℃; 平均McReynolds常数为665; 在容量因子为1.02时, 理论塔板数可达每米1095块; 其对烷烃、醇类、酮类、芳香族化合物、位置异构体以及一些手性化合物具有良好的分离效果.     

Carbon nanoparticles from corn stalk soot and its novel application as stationary phase of hydrophilic interaction chromatography and per aqueous liquid chromatography

Carbon nanoparticles (CNPs) (6–18 nm in size) were prepared by refluxing corn stalk soot in nitric acid. The obtained acid-oxidized CNPs are soluble in water due to the existence of carboxylic and hydroxyl groups. ¹³C NMR measurement shows the CNPs are mainly of sp² and sp³ carbon structure different from CNPs obtained from candle soot and natural gas soot. Furthermore, these CNPs exhibit unique photoluminescence properties. Interestingly, the CNPs might be exploited to immobilize on the surface of porous silica particles as chromatographic stationary phase. The resultant packing material was evaluated by high-performance liquid chromatography, indicating that the new stationary phase could be used in hydrophilic interaction liquid chromatography (HILIC) and per aqueous liquid chromatography (PALC) modes. The separation of five nucleosides, four sulfa compounds and safflower injection was achieved by using the new column in the HILIC and PALC modes, respectively.     

一个新的分子电性距离矢量(MEDV)

有机化合物通常由电性各异的碳、氢、氧、氮、硫等元素以共价键相互连接而成。我们提出了一个称为分子电性距离矢量(简称MEDV)的新描述来表征有机分子结构。以含有环、饱和与不饱和键及碳氧氮等元素的色氨酸分子为例,说明构建MEDV的基本方法。开发设计了计算有机MEDV分子的TrueBASIC语言程序。不借用其他任何描述子,仅用MEDV建立了烷、醇、多环芳烃等多种有机化合物包括沸点、密度、保留指数等多种性质的定量结构-性质相关(QSPR)模型,相关系数均达0.98以上。     

Synthesis and catalysis of location-specific cobalt nanoparticles supported by multiwall carbon nanotubes for Fischer-Tropsch synthesis

Cobalt nanoparticles located on the concave internal surface of multiwalled carbon nanotubes (Co-in-MW-CNTs) and the convex external surface of MW-CNTs (Co-on-MW-CNTs) were synthesized. Their catalytic performances in Fischer-Tropsch synthesis (FTS) were investigated. A correlation between the location, pretreatment, and surface chemistry of the cobalt nanoparticles and the catalytic selectivity in FTS was built. It is found that the selectivity in production of C(5+) molecules through FTS on cobalt catalysts supported by MW-CNTs depends on activation temperatures and surface chemistry of the cobalt nanoparticles. A pretreatment at 300 °C in H(2) flow results in a different surface chemistry for Co-in-MW-CNTs than for Co-on-MW-CNTs, which leads to a difference in selectvity to the production of C(5+) molecules. Pretreatment at a relatively high temperature, 400 °C, in H(2) flow produces completely reduced Co nanoparticles in Co-in-MW-CNTs and Co-on-MW-CNTs. There is no signifcant difference in catalytic selectivity between the two catalysts upon pretreatment at 400 °C. The absence of a significant difference in catalytic selectivity of metallic Co-on-MW-CNTs and metallic Co-in-MW-CNTs suggests that the electronic effect of the MW-CNT support does not significantly affect the C(5+) selectivity of cobalt catalysts in FTS.     

多壁碳纳米管作为气相色谱固定相的性能研究

将甲烷催化裂解法生产的经过纯化的多壁碳纳米管(PMWCNTs)、活性炭、石墨 化碳黑(Carbopack B)分别填装成气相色谱填充柱,比较它们分离烷烃、芳香烃、 卤代烃、醇、酮、醚、酯类的性能。分别在PMWCNTs和Carbopack B上涂清5%(w/w) 的Carbowax 20M,填装成气相色谱填充柱后,比较它们分离醇、酮、醚、酯、有机 酸类的性能。结果表明,PMWCNTs是一种性能优异的气相色谱固定相。与相同比表 面积的Carbopack B石墨化碳黑相比较,它有更强的保留能力,适合于分析沸点相 对较低的化合物;具有更均匀的表面,表现为极性化合物亦可得到对称的峰形;理 论塔板数较小。此外,和Carbopack B一样,PMWCNTs涂清5% (w/w) Carbowax 20M 后可用来分离极性化合物,甚至是强极性的小分子有机酸。     

Preparation of highly luminescent nitrogen and sulfur co-doped carbon nanoparticles for iron(Ⅲ) ions detection and cell imaging

Highly photoluminescent nitrogen and sulfur co-doped carbon nanoparticles (CNPs) ca. 56 nm have been prepared through a green one-step hydrothermal synthesis route by using millet powder as carbon sources, in which the nitrogen and sulfur co-doping improves the photoluminescent efficiency of the CNPs. The as-prepared CNPs display excellent fluorescent properties and low biotoxicity with a relatively high quantum yield of 30.4%, which have been applied for bioimaging and highly sensitive and selective detection of iron (Ⅲ) ions.     

用选择离子流动管质谱测定汽油和柴油蒸汽成分

采用选择离子流动管质谱(SIFT／MS)装置，以H30^ 、N0^ 为初始离子对汽油和柴油蒸汽进行了研究，质谱分析表明，汽油和柴油主要由C—H化合物组成，包括烷烃、环烷烃、烯烃、炔烃、二烯烃以及芳香烃。在这几种成分中，烷烃都占有最大的比例；汽油蒸汽和柴油蒸汽最大的区别是柴油蒸汽中长链大分子的挥发性C—H化合物所占的比例远远高于汽油蒸汽。文中还给出了以H30^ 、N0^ 为初始离子所得到的汽油蒸汽的质谱图，以及汽油、柴油蒸汽中各种成分的定量分析结果。     

Evaluation of multi-walled carbon nanotubes as gas chromatographic column packing

Purified multi-walled carbon nanotubes (PMWCNTs), activated charcoal and graphitized carbon black (Carbopack B) were used as column packing materials to compare their separation ability and other gas chromatographic behavior for aromatic hydrocarbons, alkanes, halogenated hydrocarbons, alcohols, ketones, esters, and ethers. The results show that PMWCNTs can be an excellent gas chromatographic packing material. Compared to Carbopack B with the same surface area, PMWCNTs had a stronger retention ability, a more homogenous surface and smaller theoretical plate numbers. Polar compounds can present symmetric peaks on PMWCNTs. PMWCNTs were found to be an interesting alternative adsorbent to activated charcoal and Carbopack B as gas chromatographic column packing material for volatile compounds, especially those with relatively low boiling points.     

On the gas-phase reactivity of complexed OH+ with halogenated alkanes

OH(+) is an extraordinarily strong oxidant. Complexed forms (L--OH(+)), such as H(2)OOH(+), H(3)NOH(+), or iron-porphyrin-OH(+) are the anticipated oxidants in many chemical reactions. While these molecules are typically not stable in solution, their isolation can be achieved in the gas phase. We report a systematic survey of the influence on L on the reactivity of L--OH(+) towards alkanes and halogenated alkanes, showing the tremendous influence of L on the reactivity of L--OH(+). With the help of with quantum chemical calculations, detailed mechanistic insights on these very general reactions are gained. The gas-phase pseudo-first-order reaction rates of H(2)OOH(+), H(3)NOH(+), and protonated 4-picoline-N-oxide towards isobutane and different halogenated alkanes C(n)H(2n+1)Cl (n=1-4), HCF(3), CF(4), and CF(2)Cl(2) have been determined by means of Fourier transform ion cyclotron resonance measurements. Reaction rates for H(2)OOH(+) are generally fast (7.2x10(-10)-3.0x10(-9) cm(3) mol(-1) s(-1)) and only in the cases HCF(3) and CF(4) no reactivity is observed. In contrast to this H(3)NOH(+) only reacts with tC(4)H(9)Cl (k(obs)=9.2x10(-10)), while 4-CH(3)-C(5)H(4)N-OH(+) is completely unreactive. While H(2)OOH(+) oxidizes alkanes by an initial hydride abstraction upon formation of a carbocation, it reacts with halogenated alkanes at the chlorine atom. Two mechanistic scenarios, namely oxidation at the halogen atom or proton transfer are found. Accurate proton affinities for HOOH, NH(2)OH, a series of alkanes C(n)H(2n+2) (n=1-4), and halogenated alkanes C(n)H(2n+1)Cl (n=1-4), HCF(3), CF(4), and CF(2)Cl(2), were calculated by using the G3 method and are in excellent agreement with experimental values, where available. The G3 enthalpies of reaction are also consistent with the observed products. The tendency for oxidation of alkanes by hydride abstraction is expressed in terms of G3 hydride affinities of the corresponding cationic products C(n)H(2n+1) (+) (n=1-4) and C(n)H(2n)Cl(+) (n=1-4). The hypersurface for the reaction of H(2)OOH(+) with CH(3)Cl and C(2)H(5)Cl was calculated at the B3 LYP, MP2, and G3(m*) level, underlining the three mechanistic scenarios in which the reaction is either induced by oxidation at the hydrogen or the halogen atom, or by proton transfer.     

A homogeneous fluorescence sensing platform with water-soluble carbon nanoparticles for detection of microRNA and nuclease activity

Based on the high efficiency of fluorescence quenching and the different affinities of water-soluble carbon nanoparticles (CNPs) towards single-stranded DNA (ssDNA) and double-stranded DNA/RNA hybrid, a novel, rapid and cost-effective assay for detection of microRNA and nuclease activity was developed. The fluorescein-labeled ssDNA probe (FAM-P) could be adsorbed on the surface of CNPs through π-π stacking interaction giving rise to fluorescence quenching. By introduction of microRNA complementary to the DNA probe, the double-stranded DNA/miRNA hybrid could be formed and released from the surface of CNPs resulting in the fluorescence recovery. Thus, microRNA was successfully detected in homogenous fashion without any amplification or enzyme-involving reactions. Moreover, we demonstrated that the nuclease activities of RNase H and DNase I could also be sensitively monitored by using CNPs based on the fluorescence changing of the DNA probe. So, the CNPs provide an excellent homogeneous sensing platform for studying molecular diagnosis and therapeutics.     

Mo_2N/Zr-MCM-41新型催化剂的制备、表征及其麻疯树油加氢脱氧的催化性能

采用水热法合成载体MCM-41与不同初始n(Si)/n(Zr)的Zr-MCM-41,由(NH_4)_6Mo_7O_(24)与载体经过共浸渍、高温焙烧、氨气程序升温氮化制备了Mo_2N/Zr-MCM-41新型加氢脱氧催化剂。采用XRD、BET、XPS、TEM以及吡啶红外等手段对催化剂进行了表征,并采用高压反应釜评价了不同n(Si)/n(Zr)的Mo_2N/Zr-MCM-41催化麻疯树油加氢脱氧反应的性能。结果表明,Zr改性后的载体与纯硅MCM-41同样具有良好的孔道结构,且L酸、B酸酸值提高。Mo_2N作为活性组分体现出了优异的加氢脱氧性能,在反应温度350℃、氢气分压3.0 MPa条件下催化的产品油组成主要为直链烷烃与芳香族化合物,占产品组分的90%(质量分数)以上;不同n(Si)/n(Zr)的新型催化剂脱氧率可高达100%;芳香族化合物含量高于直链烷烃,最高可占组成的72.09%(质量分数),主要以单环、双环芳香烃为主,碳链长度分布在C_(8-16);直链烷烃碳链长度分布在C_(8-17)。通过Mo_2N/Zr-MCM-41催化后的麻疯树油经分馏处理后可制备生物燃料。     

Side chain liquid crystal polyurethanes with azobenzene mesogenic moieties: Influence of spacer length on hydrogen bonding at different temperatures

A series of side chain liquid crystal polyurethanes (CnCNPs), in which the spacer length was varied from 2 to 12 methylene units, were synthesized by the addition polymerization of α-[bis(2-hydroxyethyl)amino]-ω-(4-cyanoazobenzene-4′-oxy)alkanes (CnCN-diols) with hexamethylene diisocyanate. The liquid crystalline properties of CnCNPs were characterized by means of differential scanning calorimetry, polarizing optical microscopy, and X-ray diffraction. Polyurethanes with spacer length 4 or higher exhibited mesomophic properties. C4CNP and C5CNP exhibited an enantiotropic nematic mesophase, while C6-C12CNPs exhibited enantiotropic bilayer smectic mesophases. CnCNPs have a high tendency to crystallize; crystallization is kinetically controlled. Polyurethane's backbone crystallization is closely related to hydrogen bonding. To establish the role of hydrogen bonding in mesophase formation as well as crystallization, Fourier transform infrared spectroscopy studies of CnCNPs were carried out at different temperatures focusing on H-bonds between the N H and CO groups of the urethane backbone. With increasing temperature, CO and N H stretching bands were evenly shifted to higher wavenumbers, with two exceptions (C4CNP and C5CNP) discussed in detail in the text. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2135–2146, 1998     

Kinetics of Reactions of CCN Radical with Alcohols

The reaction kinetics of cyanomethylidyne radical, CCN( eX2Π), with a series of primary alcohols were studied at about 1.33 kPa total pressure and room temperature using pulsed laser photolysis/laser-induced fluorescence (LP/LIF) technique. The CCN radical was produced via laser photolysis of CCl3CN with the fourth harmonic output of a Nd: YAG laser (266 nm). The relative concentration of the CCN( eX2Π) radical was monitored by LIF in the (0, 0) band of the CCN( ~ A2￠? eX2Π) transition at 470.9 nm. Under pseudofirst-order conditions, the reaction rate constants of CCN( eX2Π) with a series of primary alcohol molecules (n-CnH2n+1OH, n=1-6) were determined by measuring the time evolution of the relative concentration of CCN( eX2Πi). The measured rate constants increased monotonously with the number of carbon atoms in the alcohols, and the values for reactions of CCN( eX2Π) with alcohols were larger than those for reactions of CCN( eX2Π) with alkanes (C1-C5). Based on the bond dissociation energies and linear free energy correlations, it was believed that the reactions of CCN( eX2Π) with alcohols proceeded via a hydrogen abstraction mechanism that was analogous to CCN( eX2Π) with alkanes. The experimental results indicated that the H atoms on the C-H bonds were activated at the presence of the OH group in alcohol molecules and the hydrogen abstraction from the C-H bonds in the alcohol molecules was the dominant reaction pathway. The relation between the rate constants and the long-distance attractive potentials between the CCN radical and the alcohol molecules was discussed.     

One‐Step Synthesis of Graphitic Nanoplatelets that are Decorated with Luminescent Carbon Nanoparticles as New Optical‐Limiting Materials

Graphitic nanoplatelets (GNPs) and luminescent carbon nanoparticles (CNPs) are simultaneously synthesized by controlling the laser parameters and the size of the graphite flakes. Because luminescent CNPs are attached onto GNPs, a new carbon nanostructure is obtained. Compared with carbon black, GNPs, and luminescent CNPs alone, this nanostructure shows better optical‐limiting (OL) effects. The OL mechanism of GNPs that are decorated with luminescent CNPs can mainly be attributed to nonlinear scattering. The role of luminescent CNPs is to promote the formation and growth of nonlinear scattering bubbles, thereby enhancing their optical‐limiting effects.     

Ionic liquid‐bonded polysiloxane as stationary phase for capillary gas chromatography

Ionic liquid (IL) stationary phase is especially suitable for separation of complex samples, owing to the “dual nature” of IL. In this study, a synthetic method of ionic liquid‐bonded polysiloxane (PSOIL) as stationary phase of GC was proposed. Then, the PSOIL was used to prepare an 8 m capillary column by static method. The column efficiency was measured to be about 4000 plates/m (k=3.55, naphthalene) after the column had been conditioned at 210°C. The durability of PSOIL column was better than that of the mixed stationary phase of IL and OV‐1. Moreover, the Abraham solvation parameter model was employed to characterize the PSOIL. The result revealed that the PSOIL had stronger dispersion force (l) than neat IL and stronger hydrogen bond basicity (a) than DB‐1. That meant the PSOIL might offer good selectivity for both polar and non‐polar analytes. The column exhibited unique selectivity for various organic substances, such as the homologous compounds of alkanes, esters, alcohols and aromatic compounds. It was also found that some aromatic positional isomers could be separated better on the PSOIL column than on the DB‐1 column. Furthermore, the stationary phase was suitable for separation of high‐boiling point compounds such as polycyclic aromatic hydrocarbons, phthalic esters, etc. All of these demonstrated that the PSOIL offered good selectivity and high separation efficiency for a wide range of analytes.     

Vapor pressures of pure compounds using the Peng–Robinson equation of state with three different attractive terms

Accurate representation of pure compounds vapor pressures is required to increase the robustness of equations of state when predicting phase equilibria for mixtures. Using cubic equations of state, this representation largely depends on improving the temperature-dependent attractive term of the equation of state (EOS) to cover data from the triple to critical points. With this purpose, the Peng–Robinson equation of state is applied with three different attractive terms: Mathias, Mathias–Copeman, and Carrier–Rogalski–Péneloux. Experimental vapor pressures for 311 pure compounds (9000 experimental values) have been fitted. The studied compounds include nitrogen compounds, oxides, sulfides, chlorides, oxyhalides, inorganic compounds, alkanes, cycloalkanes, alkenes, alkadienes, alkynes, aromatic hydrocarbons, halogenated alkanes, halogenated cycloalkanes, halogenated alkenes, halogenated aromatic hydrocarbons, alcohols, ethers, aldehydes, ketones, alkanoic acids, esters, phenols, heterocyclic oxygen compounds, heterocyclic nitrogen compounds, hydrocarbon nitrogen compounds, and sulfur compounds. Overall average absolute deviations of 0.416, 0.214 and 0.276% have been found for the resulting Peng–Robinson–Mathias (PRM), Peng–Robinson–Mathias–Copeman (PRMC), and Peng–Robinson–Carrier–Rogalski–Péneloux (PRCRP) equations of state, respectively.     

固态发光碳纳米粒子的制备及在潜指纹成像中的应用

采用热分解法, 以柠檬酸钠和尿素为前驱体, 通过控制反应温度制备了不需要结合任何固体分散基质即可呈现明亮固态发光的碳纳米粒子(CNPs). 利用X射线衍射(XRD), 透射电子显微镜(TEM), X射线光电子能谱(XPS)、 紫外-可见吸收光谱(UV-Vis)和光致发光光谱(PL)等对CNPs的物相、 形貌和粒径、 表面基团及光学特性进行了表征. 结果表明, 该CNPs为无定形碳结构, 准球形形貌, 粒径分布在5~15 nm范围, 其表面存在C=O, C=N和O=C—N等基团. CNPs的水溶液和固体粉末在365 nm紫外光辐射下, 均呈现明亮的蓝绿色发光. 将该CNPs粉末用作荧光试剂可直接显现不同非渗透性客体表面的潜指纹(LFPs). 在365 nm紫外光激发下, CNPs粉末刷显后的LFPs细节特征清晰可辨, 强荧光背景客体表面的LFPs获得了高对比度的显现效果. 同时, 老化30 d的LFPs利用CNPs粉末也能够显现出可识别的指纹细节. CNPs发光粉末作为指纹试剂在刑侦领域具有潜在的应用前景.     

Palladium(II) chelate of tetradentate Schiff base as mixed stationary phase for gas chromatography

Bis(acetylacetone)ethylenediiminepalladium(II) (PdAA2en) was examined as a mixed stationary phase with OV-1 on Chromosorb G/NAW 60-80 mesh size for the GC separation of aromatic hydrocarbons, heteroaromatics, alcohols, aldehydes, ketones, esters, and nitro compounds. Forty-two compounds were examined and the GC results were compared with those obtained with 3% OV-1 on Chromosorb G/NAW 60-80 mesh size under similar operating conditions. Improved resolution, peak asymmetry, theoretical plate numbers, and Kovats indices were obtained on the mixed stationary phase of 3% OV-1 + 5% PdAA2en compared to 3% OV-1 column. The stability constant (Km), enthalpies (deltaH), entropies (deltaS), and Gibbs free energies (deltaG) of the GC elution on the column (2 m x 3 mm id) packed with 3% OV-1 + 5% PdAA2en on Chromosorb G/NAW 60-80 mesh size have been calculated. Donor-acceptor complexation in the gas phase is indicated by negative values of enthalpy (-deltaH) within 5.81 to 10.89 kcal/mol and Gibbs free energy (-deltaG) from 1.34 to 4.08 kcal/mol. The retention time transformations on both the phases were calculated and the ratios obtained from the stationary phases 3% OV-1 and 3% OV-1 + 5% PdAA2en were plotted on the x-axis and the y-axis, respectively, and the coefficients of determination for alkanes, aromatic and heteroaromatics, ketones, and alcohols were observed to lie within 0.5253 to 0.9742, indicative of some different kinds of interaction of the two stationary phases with the solutes.