黑色圆珠笔油墨的高效液相色谱法分析

建立了黑色圆珠笔油墨字迹色痕的高效液相色谱法的分析条件和实验方法,采用乙腈-NH4HCO3溶液（10mmoL／L）（体积60：40）为流动相,检测波长580nm,同时利用质谱法作为佐证。在此条件下对市售的51支不同生产厂家和品牌黑色圆珠笔油墨的字迹色痕进行了分析,根据油墨中所含染料成分的差异将其分为6大类,考察了纸张的影响及在该分析条件下结果的精密度和重复性。     

蓝色圆珠笔字迹色痕傅里叶变换显微红外光谱法的无损分析

利用傅里叶变换显微红外光谱法中的微区衰减全反射采样技术无损测定了纸张上圆珠笔油墨所形成的字迹色痕,获得了１０种不同圆珠笔字迹的显微红外光谱图。结果表明,笔迹色痕的微区衰减全反射谱图可明显地识别色料和溶剂的结构组成;快速地分辨各生产厂家油墨的差异。同时,纸张的不同,字迹书写的深浅均可快速,准确地进行无损分析。     

蓝色圆珠笔油墨紫外光照射变化的研究

在紫外光照射下，通过对蓝色圆珠笔字迹色痕ＦＴ－ＩＲ显微光谱的研究。发现溶剂挥发迅速。其次是环氧树脂的聚合、交联；三苯甲烷染料的分解比较缓慢；而醇酸树脂相对稳定。该研究为字迹色痕的进一步分辨提供了新方法，同时为字迹色痕的“年龄”推断奠定了基础。选用相关峰的相对峰高比来描述这一变化，并进行曲线拟合，消除了因笔力不同而引起的油墨流出量不同造成的误差，这在实际工作中是很有意义的。     

薄层色谱法分析圆珠笔色痕形成时间

 利用薄层色谱法对 70种市售的蓝色圆珠笔油墨的染料成分进行了研究。通过与染料标样的薄层色谱数据比较 ,发现国内圆珠笔厂生产的圆珠笔所用的油墨中的染料主要包括碱性紫、碱性蓝及铜酞菁 ,只是不同厂家的油墨中几种染料的配比不同。根据薄层扫描仪对油墨各斑点的扫描结果 ,确定了圆珠笔油墨成分中碱性紫和铜酞菁染料的峰高比值随着书写时间变化的关系 ,从而为法庭科学工作中鉴定圆珠笔字迹的色痕形成时间提供了可靠的依据。     

蓝色圆珠笔字迹色痕ATR谱与模式识别研究

圆珠笔字迹色痕的鉴定一直是法庭科学领域中十分注目而又棘手的研究课题之一[1,2 ] .曾有人用溶剂萃取和色谱法进行研究 ,但因损坏试样而存在一定的局限性 [3～ 7] .尽管 FTIR用于字迹色痕的鉴定收到了一定效果 ,但因样品制备非常苛刻 ,实际应用存在困难 [8～ 10 ] .本文在用 ATR(AttenuatedTotal Reflection)技术对 1 0 8种蓝色圆珠笔油墨的字迹色痕进行了系统分析 (区分为 1 8类 )基础上 ,又采用了模式识别[11,12 ] 进行研究 ,不仅实现了种类区分 ,而且达到了生产厂家、牌号及批次的认定 (进一步分为 5 3种 ) .该系统的实现 ,为蓝色圆…     

气相色谱法确定蓝色圆珠笔油墨字迹的形成时间

选择适当的内标物,利用气相色谱法测定蓝色圆珠笔油墨中展色剂苯甲醇和苯氧基乙醇这两种组分的含量(以峰面积计),以展色剂的峰面积、内标物的峰面积与紫外-可见光谱测得的参比物墨水中的染料的吸光度值这三者之比为纵坐标,以字迹形成时间为横坐标,确定了字迹形成曲线,从而建立了确定字迹形成时间的方法。选择了不同种类的蓝色圆珠笔油墨进行检测,获得了良好的实验效果,为圆珠笔油墨字迹形成时间的推断建立了一种可靠而又系统的方法。该方法适用于实际办案。     

薄层色谱法鉴别黑色中性笔色痕的种类

中性笔外型类似圆珠笔,它与圆珠笔的不同在于其笔芯内所灌注的材料.圆珠笔芯内灌注的是油性的圆珠笔油墨,而中性笔灌注的则是非油性的胶状物或果冻状物质.由于中性笔芯内的胶状物通常为非油性的,形成的字迹类似钢笔墨水字迹,同时其外型和字迹形成方式又与圆珠笔相似,兼有钢笔墨水字迹和圆珠笔的特点,故称其为"中性"笔[1].中性笔以其书写流利、价格适中和使用方便等特点而被广泛使用,近年来发展迅速,大有取代圆珠笔、钢笔之势.     

非水毛细管电泳法区分蓝色圆珠笔油墨的研究

建立了一种基于非水毛细管电泳法区分蓝色圆珠笔油墨的方法.确定了笔迹中碱性染料(结晶紫、甲基紫、碱性品蓝、罗丹明6G、碱性艳蓝B和碱性艳蓝BO)的分离条件:缓冲溶液为1.00 mmol/L醋酸-100 mmol/L醋酸铵的甲醇-水(体积比90 ∶ 10)体系,分离电压和温度分别为25 kV和25 ℃,检测波长为214 nm.通过该方法分析了96支蓝色圆珠笔中的油墨,并依据油墨中所含的染料种类对圆珠笔进行分类,同一类笔又通过聚类分析计量学方法再次进行区分.该法重复性好,结果准确可靠,为圆珠笔字迹鉴定提供了一种科学的方法.     

基于多变量-系统聚类分析法区分蓝色圆珠笔色痕

综合应用不同的检验方法对110支不同产地、品牌的蓝色圆珠笔油墨进行检验及种类鉴定。采用气相色谱-质谱法和薄层色谱法分别研究了圆珠笔油墨中的溶剂组成和染料组成。通过数据预处理,分别建立了不同样品气相色谱法和薄层色谱法的共有谱图,采用二值法对特征数据进行提取,将定性信息数量化,将欧氏距离的平方作为样品之间差异的量度进行系统聚类分析,并将分类结果用于判别分析,建立相应的判别式函数。结果表明,基于多变量的系统聚类结果由于同时考察油墨的溶剂和染料在组成上的差异,将110支不同品牌、产地的蓝色圆珠笔分为了29类,可以达到品牌之间的区分和认定,较依据单一检验手段得到的分类结果更为精确、系统。尝试结合判别式函数对未知色痕进行分类,由于样本量较少,因此交叉验证得到的分类正确率仅为47.7%,但通过本实验将化学计量学中的相关算法引入到油墨种类的鉴别中,为添改文件、文件形成时间的检验提供了更加准确的结果,为建立油墨样本库提供了数据支持。     

高效液相色谱法鉴别黑色签字笔墨水字迹形成时间的研究

签字笔携带方便、书写流畅,现已成为常用的书写工具之一。在许多刑事及民事案件中,尤其在呈明显上升趋势的各类贪污、受贿案件中,经常会遇到由签字笔墨水形成的契约、合同、收据、借条等可疑文件中关于签字笔墨水字迹色痕的鉴定。对于字迹色痕形成时间的鉴定工作一直是困扰法庭     

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%.     

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.     

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.     

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.     

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.     

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.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.