低能氮离子诱发丙酮与重水溶液的反应机理

利用氮气火花放电产生离子,其中的正离子在阴极位降的加速下“注入”到丙酮的重水溶液中,诱发其中的化学反应.利用气相色谱 质谱（GC MS）分析离子注入后的样品,证实有氘代产物（CH3COCH2D）、氘羟基取代产物（CH3COCH2OD）生成,这表明低能N＋诱发重水溶液中的反应主要是由于重水分子分解产生的自由基引起的,其中氘自由基和氘羟基自由基起重要作用;同时,产物中还检测到氘代乙酸（CH3COOD）和氘氨基丙酮（CH3COCH2ND2）,说明反应是在氧化性氛围中进行的,氮离子俘获重水中的氘形成氘氨基可能是氘氨基取代产物生成的主要原因,也是氮“沉积”在溶液中的重要形式.这些结果对初步揭示低能离子诱发水溶液的反应机理具有一定的意义.     

110 keV Fe＋离子束对氨基酸衍生物的辐射分解

用200 kV离子注入机提供的110 keV Fe＋离子束注入L(＋)-半胱氨酸盐酸盐单晶水合物薄膜样品,离子注量为2.5×1016 ions•cm－2.离子注入后刮下薄膜进行简单固态混和,在傅里叶变换红外光谱仪、高效液相色谱仪和电喷雾电离-傅里叶变换质谱仪上对离子注入前后的样品分别进行了测试.对离子注入样品的两次红外光谱分析结果有所不同,表明薄膜样品不同部位受低能铁离子束辐照后可发生不同的辐射分解,但二者又具有一定的相似性,都反映了原分子中氨基、羧基和巯基等基团的受损和新的硝基的生成.高效液相色谱和傅里叶变换质谱分析表明,离子注入样品中产生了多种不同分子量的新分子,证实110 keV Fe＋离子束能够引起氨基酸衍生物的辐射分解.     

水溶液中磷酰基促进的成肽反应研究

水溶液中磷酰基促进的成肽反应研究沙耀武，巨勇，赵玉芬（清华大学化学系，北京，１０００８４）关键词磷酰化组氨酸，成肽，水溶液一些氨基酸在前生化时期的条件下，就可以由甲烷、氨和水通过高压放电生成［１，２］。如果向该反应体系中加入三氢化磷，生成的氨基酸的种...     

低能氮离子注入乙醇重水溶液的GC-MS分析

将氮气常压弧光放电产生的N⁺在放电间隙电场的加速下“注入”到乙醇的重水溶液中,利用气相色谱-质谱(GC-MS)分析样品,证实有氘代产物(DCH₂CH₂OH)和羟基取代产物(DOCH₂CH₂OH)生成,这表明低能N⁺诱发水溶液中的反应与水分子分解产生的自由基有关.同时,产物中还检测到乙酸(CH₃COOD )和氨基乙醇(HOCH₂CH₂ND₂),说明反应是在氧化性氛围中进行的,而这种氧化作用可能亦与水分子分解产生的氢氧根自由基有关.氨基乙醇则可能是氮离子俘获重水中的氘形成氨基继而与乙醇反应生成的,这也是氮“沉积”在溶液中的重要形式.这些结果对初步揭示低能离子与水溶液体系反应的机理具有一定的意义.     

升温速率对氨基酸裂解生成含氮气体的影响研究

为进一步阐明卷烟烟气中含氮有害气体的形成机理,以甘氨酸、天冬酰胺和天冬氨酸为研究对象,采用TG-FTIR技术对其在不同升温速率下热解时含氮气体的释放特性进行了研究。结果表明:(1)随着升温速率增加,三种氨基酸TG和DTG曲线各个失重阶段的起始和终止温度向高温侧移动;(2)氨基酸结构不同,HCN、NH3、HNCO的生成温度及生成量不同;(3)增加升温速率,三种氨基酸热解过程中HCN、NH3、HNCO的生成量均增加,但三种氨基酸氮转化的选择性不尽相同。甘氨酸和天冬酰胺热解过程中氮主要转化为NH3,而天冬氨酸在低升温速率下热解时,氮主要转化为HCN和NH3,在高升温速率下主要生成HNCO。     

镨和铕离子注入硅的快速热退火研究

利用离子注入技术将稀土Ｐｒ和Ｅｕ离子引入外延硅片中，经快速热退火使注入层再结晶和电激活。对Ｐｒ离子注入样品，在较低温度９４０℃下退火，样品具有电子导电性，注入离子起施主作用，而在较高强度１２４０℃下退火，则具有穴穴导电性，注入离子起受主作用，即有两种导电行为。     

氨基酸的提纯方法

本发明提供一种从氨基酸的碱金属盐的水溶液中提纯氨基酸的方法，所述方法包括下列步骤：（1）阳离子交换步骤，其中，用包含阳离子交换树脂的移动床式连续离子交换装置对氨基酸的碱金属盐的水溶液进行脱盐提纯处理，以得到粗氨基酸的水溶液；（2）阴离子交换步骤，其中，用弱碱性阴离子交换树脂从所得的粗氨基酸的水溶液中吸附除去作为共存的副产物的亚氨基二羧酸，并且甚至在对所述亚氨基二羧酸的吸附达到所述弱碱性阴离子交换树脂的突破点之后，仍使所述粗氨基酸的水溶液流过。     

水溶液中磷酰化组氨酸与其它氨基酸的交叉成肽研究

水溶液中磷酰化组氨酸与其它氨基酸的交叉成肽研究沙耀武，赵玉芬（清华大学化学系，北京１０００８４）一些氨基酸在前生化时期的条件下，就可以由甲烷、氨和水通过高压放电生成［１，２］。如果向该反应体系中加入三氢化磷，生成的氨基酸的种类增多、结构的复杂性也提高...     

UHPLC-Quadrupole/Orbitrap MS同步检测十字花科植物中的游离氨基酸

采用超高效液相色谱-四极杆/静电场轨道阱高分辨质谱联用技术(UHPLC-Quadrupole/Orbitrap MS)结合柱前衍生法建立了可同时测定28种游离氨基酸的分析方法,并对十字花科植物中的游离氨基酸进行检测和分析。样品用超纯水提取后,经6-氨基喹啉基-N-羟基琥珀酰亚胺基甲酸酯(AQC)衍生,采用Waters BEH C18柱作为色谱柱,以pH 5.0乙酸铵缓冲溶液和80%乙腈水溶液作为流动相进行梯度洗脱。质谱检测器采用电喷雾离子源,在正离子模式下进行检测。实验结果表明,十字花科植物中含有25种以上游离氨基酸,其中包括人体必需的8种氨基酸。25种氨基酸在线性范围内相关性良好,平均加标回收率为80.5%~104.4%,相对标准偏差为0.6%~4.4%。不同氨基酸检测灵敏度不同,定量下限为0.01~1.45μmol/L。该方法杂质干扰小,分析速度快,灵敏度高,适用于植物样品中游离氨基酸的同步检测。     

人体汗液中氨基酸的测定

人体汗液是皮肤的排泄分泌物,它的主要成分有水、无机盐和有机物,其中包括微量的蛋白质及氨基酸。我们应用“DNS-氨基酸聚酰胺薄膜层析”的方法对人体汗液中的氨基酸进行了定性和定量的分析,所得结果可供汗痕或生理研究的参考。DNS(Dansyl-Chloride 即二甲基氨基萘磺酰氯)是一种荧光试剂,它能与大多数氨基酸进行反应生成各种衍生物,简称“DNS-氨基酸”。     

Preliminary study on the way of formation of amino acids on primitive earth under non-reducing conditions

Low energy ions were produced by N₂ glow discharge. The positive ions were accelerated into three kinds of carboxylate solution to induce chemical reactions. HPLC analysis showed that N was deposited into the solution, ammonia and amino acids were produced by such kind of implantation. The time-response of amounts of amino acids was given. The results presented a new way for the production of ammonia and amino acids under primitive earth conditions.     

低能离子与生物有机小分子相互作用机制的初步研究

利用低能离子束(N^+,Ar^+离子)辐照固态羧酸钠(甲酸钠)、(乙酸钠)、(苯甲酸钠)和固态嘧啶碱基两类样品,经电子顺磁共振谱(EPR)、富里叶红外光谱(FT-IR)的检测,结果发现,三种低能离子辐照后的甲酸钠样品中产生了[COO]^.^-自由基和亚甲基(CH2),氮离子辐照乙酸钠和苯甲酸钠样品后,形成了新的化学基团氰基(CN);同时,结合茚三酮反应,证明了辐照后的羧酸钠和碱基样品中还含有新的基团氨基(NH2),给出了氨基的产生量与注入离子的剂量的相关曲线。     

N-磷酰化氨基酸与核糖核苷反应的研究

研究了Ｎ－磷酰化氨基酸与核苷在水溶液中的反应，反应中能够同时生成小肽和小的寡核苷酸；不同的Ｎ－磷酰化氨基酸与不同的核苷之间的反应具有一定的选择性。     

杯［4］芳烃硼酸与氨基酸配位作用的荧光光谱研究

用荧光光谱滴定法研究了10种杯[4]芳烃硼酸与4种氨基酸的配位作用,根据扩展的Hilderbrand-Benesi公式,计算出配合物的稳定常数和配位反应的Gibbs自由能变化,杯[4]芳烃硼酸与L－丙氨酸的配位能力和配位选择性均较,可以使用杯[4]芳烃硼酸通过荧光光谱法鉴别D－丙氨酸。     

Enantioselective separation of amino acids as biomarkers indicating life in extraterrestrial environments

Traces of prebiotic amino acids, i.e., the building blocks of proteins, are excellent biomarkers that could provide evidence of extinct or extant life in extra-terrestrial environments. In particular, characterization of the enantiomeric excess of amino acids gives relevant information about the biotic or abiotic origin of molecules, because it is generally assumed that life elsewhere could be based on either l or d amino acids, but not both. The analytical procedures used in in-situ space missions for chiral discrimination of amino acids must meet severe requirements imposed by flight conditions: short analysis time, low energy consumption, robustness, storage for long periods under extreme conditions, high efficiency and sensitivity, automation, and remote-control operation. Such methods are based on gas chromatography, high-pressure liquid chromatography, and capillary electrophoresis, usually coupled with mass spectrometry; of these, gas chromatography–mass spectrometry (GC–MS) is the only such combination yet used in space missions. Preliminary in-situ sample derivatization is required before GC–MS analysis to convert amino acids into volatile and thermally stable compounds. The silylation reagent most commonly used, N-(tert-butyldimethylsilyl)-N-methyltrifluoroacetamide, is unsuitable for detection of homochirality, and alternative derivatization techniques have been developed that preserve the stereochemical configuration of the original compounds and are compatible with spaceflight conditions. These include the reagent N,N-dimethylformamide dimethylacetal, which has already been used in the Rosetta mission, a mixture of alkyl chloroformate, ethanol, and pyridine, a mixture of perfluorinated anhydrides and perfluoro alcohols, and hexafluoroacetone, the first gaseous derivatizing agent. In all the space instruments, solvent extraction of organic matter and chemical derivatization have been combined in a single automatic and remote-controlled procedure in a chemical reactor. Liquid-based separation systems have been used in space missions. In particular, microchip capillary electrophoresis, based on microfluidic lab-on-a-chip systems, enables high-performance chemical analysis of amino acids with low mass and volume equipment and low power and reagent consumption. Coupling with laser-induced fluorescence detectors results in ultra-low limits of detection. This critical review describes applications of the on-board instruments used in the Rosetta mission to comets and in the more recent Mars exploration program, i.e., the Mars Science Laboratory and ExoMars missions.

七氟丁酰氨基酸正丁酯的GC/MS分析

本文报道了19种蛋白质氨基酸的七氟丁酰正丁酯衍生物的GC/MS分析方法;优选了衍生反应条件;建立了GC分离、定量分析方法,最小检测量为0.1ng;研究了衍生物的EI质谱数据,确定了可作为定性依据的特征离子;测定了儿童用复方氨基酸注射液及儿童血清样品,得到了满意的结果。     

棉籽饼粉中氨基酸含量的测定

利用高效液相色谱法对国内外３种棉籽饼粉的氨基酸组成进行了测定和比较,为充分利用国内棉籽饼粉资源提供了依据。结果表明,国内棉籽饼粉的加工工艺尚需完善,并需严格控制质量,以达到用棉籽饼粉做药用培养基的目的。     

An activated O --> N acyl transfer auxiliary: efficient amide-backbone substitution of hindered "difficult" peptides

Overcoming the phenomenon known as "difficult" synthetic sequences has been a major goal in solid-phase peptide synthesis for over 30 years. In this work the advantages of amide backbone-substitution in the solid-phase synthesis of "difficult" peptides are augmented by developing an activated N(alpha)()-acyl transfer auxiliary. Apart from disrupting troublesome intermolecular hydrogen-bonding networks, the primary function of the activated N(alpha)()-auxiliary was to facilitate clean and efficient acyl capture of large or beta-branched amino acids and improve acyl transfer yields to the secondary N(alpha)()-amine. We found o-hydroxyl-substituted nitrobenzyl (Hnb) groups were suitable N(alpha)()-auxiliaries for this purpose. The relative acyl transfer efficiency of the Hnb auxiliary was superior to the 2-hydroxy-4-methoxybenzyl (Hmb) auxiliary with protected amino acids of varying size. Significantly, this difference in efficiency was more pronounced between more sterically demanding amino acids. The Hnb auxiliary is readily incorporated at the N(alpha)()-amine during SPPS by reductive alkylation of its corresponding benzaldehyde derivative and conveniently removed by mild photolysis at 366 nm. The usefulness of the Hnb auxiliary for the improvement of coupling efficiencies in the chain-assembly of difficult peptides was demonstrated by the efficient Hnb-assisted Fmoc solid-phase synthesis of a known hindered difficult peptide sequence, STAT-91. This work suggests the Hnb auxiliary will significantly enhance our ability to synthesize difficult polypeptides and increases the applicability of amide-backbone substitution.     

Multicanonical Monte Carlo calculation of the free‐energy map of the base–amino acid interaction

The specific interactions between base pairs and amino acids were studied by the multicanonical Monte Carlo method. We sampled numerous interaction configurations and side‐chain conformations of the amino acid by the multicanonical algorithm, and calculated the free energies of the interactions between an amino acid at given C_α positions and a fixed base pair. The contour maps of free energy derived from this calculation represent the preferred C_α position of the amino acid around the base, and these maps of various combinations of bases and amino acids can be used to quantify the specificity of intrinsic base–amino acid interactions. Similarly, enthalpy and entropy maps will provide further details of the specific interactions. We have also calculated the free‐energy map of the orientations of the C_α C_β bond vector, which indicates the preferential orientation of the amino acid against the base. We compared the results obtained by the multicanonical method with those of the exhaustive sampling and canonical Monte Carlo methods. The free‐energy map of the base–amino acid interaction obtained by the multicanonical simulation method was nearly identical to the accurate result derived from the exhaustive sampling method. This indicates that a single multicanonical Monte Carlo simulation can produce an accurate free‐energy map. Multicanonical Monte Carlo sampling produced free‐energy maps that were more accurate than those produced by canonical Monte Carlo sampling. Thus, the multicanonical Monte Carlo method can serve as a powerful tool for estimating the free‐energy landscape of base–amino acid interactions and for elucidating the mechanism by which amino acids of proteins recognize particular DNA base pairs. © 2000 John Wiley & Sons, Inc. J Comput Chem 21: 954–962, 2000     

Application of Hadamard transformation to MEKC

The Hadamard transform (HT) technique, which permits the S/N in CE to be improved, was applied to MEKC. Multiple sample injection of fluorescent analytes according to a Hadamard code sequence was performed using an optically gated sample injection technique, in which a sample plug was produced based on photodegradation by irradiation with an intense laser beam. The capillary and reservoirs were filled with a sample solution containing buffer components and SDS as a pseudostationary phase. A preliminary study confirmed that fluorescein ion could be photobleached in the presence of SDS. The optically gated sample injection technique was then applied to multiple sample injection, based on a Hadamard matrix. The S/N in the electropherogram obtained by HT-MEKC was improved substantially compared to that obtained by a single injection method. When the technique was applied to the separation of several amino acids labeled with FITC, the S/N ratio for each amino acid was enhanced, without any evidence of degradation in separation resolution. Moreover, HT-MEKC was applied to the analysis of amino acids contained in a Japanese beverage, resulting in improved S/Ns for the amino acids.