腰果酚键合硅胶固定相的制备及其色谱性能北大核心CSCD

天然产物作为一种绿色低毒、来源广泛、功能位点丰富的单体,已被广泛应用于色谱固定相的研制与开发。该文以天然可再生资源腰果酚为配体,通过一步法开环反应将其接枝到由γ-缩水甘油醚氧丙基三甲氧基硅烷(KH-560)修饰的硅胶上,制备得到腰果酚键合硅胶固定相。利用傅里叶红外光谱、元素分析、热失重分析和N_(2)吸附脱附实验对固定相进行表征,结果表明成功制备了腰果酚键合硅胶色谱固定相。采用Tanaka实验试剂、烷基苯、多环芳香烃、苯酚类化合物和芳香族位置异构体为探针评价其分离性能和保留机制,并与C_(18)柱进行对比。研究发现,腰果酚键合固定相除疏水作用外,还具有π-π和氢键作用。基于上述保留作用,腰果酚键合硅胶固定相对测试探针表现出良好的分离性能。重复进样10次,各探针保留时间的RSD为0.052%~0.079%,峰面积的RSD为0.104%~0.847%,峰高的RSD为0.081%~0.272%,表明该色谱柱具有良好的重复性和稳定性。此外,腰果酚键合硅胶色谱柱对中药喜树果和吴茱萸果的粗提物具有良好的分离性能,验证了其在实际样品分析中的巨大潜力。将天然产物腰果酚用于色谱固定相的制备,为分离纯化喜树碱和吴茱萸提供了新的方法,同时拓展了腰果酚在色谱分离材料方面的应用。     

漆酚酯键合硅胶液相色谱固定相的制备与应用

以甲基丙烯酸漆酚酯为色谱配体,制备了一种新型色谱固定相。首先以漆酚和甲基丙烯酰氯为原料制备得到甲基丙烯酸漆酚酯,并通过物理吸附涂覆到由3-（甲基丙烯酰氧）丙基三甲氧基硅烷化学修饰的硅胶上,再通过自由基引发与硅烷化硅胶的双键聚合制得漆酚酯键合硅胶固定相（USP）。对固定相进行傅里叶红外光谱（FT-IR）、热重分析（TGA）、扫描电子显微镜（SEM）和元素分析（EA）表征,结果表明通过共聚反应成功地将漆酚酯固定在硅烷化硅胶上,且制备出的固定相具有良好的单分散性。采用匀浆法装柱,以乙腈-0.05%磷酸溶液（3：97,v/v）为流动相,流速为0.4 mL/min,检测波长为220 nm,考察固定相对天麻浸膏的分离性能。以乙腈-水（50：50,v/v）为流动相,流速为0.5 mL/min,检测波长为290 nm,考察固定相对吴茱萸浸膏的分离性能。结果表明该固定相对天麻浸膏和吴茱萸浸膏均具有良好的分离性能,从天麻浸膏中分离出5个色谱峰,从吴茱萸浸膏中分离出2个色谱峰。与商品化C₁₈ 柱相比,USP柱可以从天麻浸膏中分离出更多的有效组分并实现基线分离,分离吴茱萸浸膏的色谱条件更为环保和安全。采用低流速对天麻浸膏和吴茱萸浸膏进行分离,减少了流动相的使用量,分离结果令人满意。以天然产物漆酚制备色谱固定相,既为分离纯化天麻素和吴茱萸碱提供了一种新的方法,又为液相色谱固定相制备提供了新的思路,还拓展了生漆在色谱分离材料方面的应用。     

多壁碳纳米管键合硅胶固定相的保留机理研究

制备了3种不同键合量的多壁碳纳米管键合硅胶固定相。以芳香族化合物为目标分析物,甲醇-水为流动相,分别考察了其在不同流动相比例、流速、柱温条件下,酸性、中性、碱性化合物的色谱保留行为,并通过计算分离过程中焓变、熵变和吉布斯自由能等热力学参数,探讨了色谱柱的保留机理。结果表明,碳纳米管键合硅胶与未键合的硅胶固定相分离对氨基苯磺酸和尿嘧啶时,因碳纳米管的加入增强了其疏水作用,保留机理与反相色谱柱相似。而分离中性化合物时,因加入的碳纳米管引入π-π作用,增强了对化合物的保留,有效地提高了色谱柱的柱效。碳纳米管的加入使溶质分子在固定相上的保留增强,溶质分子从杂乱无序排列转为有序排列,且溶质分子在不同碳纳米管键合量的色谱柱上的保留并非由单一机理支配,而是由多种作用相互协同的结果,这使碳纳米管键合硅胶固定相在分离和固相萃取领域展现出良好的应用前景。     

溴化1-乙烯基-3-十二烷基咪唑硅胶键合固定相制备及其色谱性能

膜脂作为细胞质膜的主要组成部分,在生命活动中扮演着重要的作用,其涉及多种重要疾病的发生和发展过程。发展适用于膜脂分离分析的新型色谱材料对于其后续结构和生物学功能研究具有重要的意义。该文选用具有潜在生物相容性的离子液体溴化1-乙烯基-3-十二烷基咪唑（1-vinyl-3-dodecylimidazole bromide,VDI）为功能单体,通过一步法点击反应将其接枝到巯基功能化硅球表面,制备得到了新型溴化1-乙烯基-3-十二烷基咪唑硅胶键合固定相（Sil-VDI）。利用傅里叶变换红外光谱仪和热重分析仪对Sil-VDI固定相材料的结构进行表征,结果证明Sil-VDI色谱固定相已被成功制备。保留机制研究显示填充Sil-VDI色谱柱具有典型的反相/离子交换混合模式保留特性。基于此,采用不同疏水性物质烷基苯、多环芳烃、苯胺、苯衍生物和无机阴离子BrO₃ ^- 、NO₃ ^- 和IO₃ ^- 为测试物,对所制备固定相的色谱性能进行了研究。结果表明,该固定相对4类疏水性物质和无机阴离子均有较好的分离选择性和良好的峰对称性。进一步研究了所制备的Sil-VDI色谱柱对鸡蛋黄磷脂和肺腺癌细胞提取膜脂的分离效果,结果显示Sil-VDI色谱柱对2种磷脂样品均显示出了良好的分离能力。该文所制备的Sil-VDI色谱固定相合成方法简便,具有良好的分离分析应用潜能,后续工作会进一步研究该固定相在生物样品中的分离分析性能。     

葫芦[6]脲单轮烷键合固定相的制备、表征及色谱性能

将超分子自组装技术与色谱键合硅胶固定相制备技术相结合,采用γ-[(2,3)-环氧丙氧]丙基三甲氧基硅烷(KH-560)为偶联剂,首次将一种葫芦[6]脲单轮烷(CB6MR)键合到硅胶上,制备了一种新型的葫芦[6]脲单轮烷键合固定相(CB6MRBS)。通过元素分析、红外光谱和热分析对该固定相进行了结构表征。以中性、酸性、碱性化合物和二取代苯位置异构体等溶质为探测因子,分别在反相和正相色谱模式下对固定相的色谱性能和保留机理进行了研究。结果表明：CB6MRBS是一种多模式键合固定相,具有良好的正相和反相色谱性能,对位置异构体具有较高的识别能力,尤其是可有效地用于碱性化合物的分离分析。其保留机理存在氢键、静电、π-π和疏水作用等多种作用力机制,协同作用提高了CB6MRBS对溶质的分离选择性。由于CB6MR配体中含有酰胺基和众多极性羰基,CB6MRBS可能在络合色谱面有应用前景。     

两亲性纤维素接枝聚脱氢枞酸共聚物的制备及性能研究

通过均相原子转移自由基聚合法(ATRP)将生物质基疏水性松香单体(脱氢枞酸(2-甲基丙烯酰氧基乙基)酯,MAEDA)接枝到纤维素骨架上合成了全生物质基两亲性的纤维素-g-聚脱氢枞酸接枝共聚物(cellulose-g-PMAEDA).ATRP反应过程动力学研究表明cellulose-g-PMAEDA接枝共聚物的合成过程是活性可控的;傅里叶红外光谱(FTIR)、核磁共振氢谱(1H-NMR)、凝胶色谱(GPC)和X射线衍射(XRD)结果证实了cellulose-g-PMAEDA接枝共聚物的成功合成;由于聚脱氢枞酸侧链的引入,cellulose-g-PMAEDA接枝共聚物的热稳定性,疏水性能明显提高,并且具有紫外吸收性能;动态光散射仪和透射电镜结果表明两亲性cellulose-g-PMAEDA接枝共聚物能够在水溶液中自组装成平均粒径约为200 nm左右的纳米微球,并且该纳米微球具有以纤维素为壳,聚脱氢枞酸酯为核的核壳结构.     

高效液相色谱法测定胶黏剂中树脂酸的含量北大核心CSCD

样品2.500 g溶解于乙酸乙酯5 mL中,加入甲醇15 mL涡旋0.5 min,再以6 000 r·min^(-1)转速离心10 min,用甲醇冲洗离心管及沉淀,合并上清液和洗涤液,并定容至25 mL。上述所得溶液以Waters XTerra RP18色谱柱为固定相,乙腈-0.4%(体积分数)乙酸溶液(80+20)混合液为流动相进行高效液相色谱分离。脱氢枞酸、枞酸及其同分异构体的检测波长分别为200,216 nm。树脂酸的质量浓度在1.0~100.0 mg·L^(-1)范围内与其峰面积呈线性关系,脱氢枞酸、枞酸及其同分异构体的测定下限(10S/N)分别为3.0,10.0 mg·kg^(-1)。按标准加入法进行回收试验,回收率在91.9%~98.0%之间,相对标准偏差(n=6)在0.26%~2.8%之间。     

高效液相色谱法测定胶黏剂中树脂酸的含量

样品2.500 g溶解于乙酸乙酯5 mL中,加入甲醇15 mL涡旋0.5 min,再以6 000 r·min~(-1)转速离心10 min,用甲醇冲洗离心管及沉淀,合并上清液和洗涤液,并定容至25 mL。上述所得溶液以Waters XTerra RP18色谱柱为固定相,乙腈-0.4%(体积分数)乙酸溶液(80+20)混合液为流动相进行高效液相色谱分离。脱氢枞酸、枞酸及其同分异构体的检测波长分别为200,216 nm。树脂酸的质量浓度在1.0~100.0 mg·L~(-1)范围内与其峰面积呈线性关系,脱氢枞酸、枞酸及其同分异构体的测定下限(10S/N)分别为3.0,10.0 mg·kg~(-1)。按标准加入法进行回收试验,回收率在91.9%~98.0%之间,相对标准偏差(n=6)在0.26%~2.8%之间。     

咪唑键合硅胶液相色谱固定相的正相色谱行为

该文将咪唑键合硅胶液相色谱固定相填充到毛细管中,在自制的微柱液相色谱系统下以碱性(胺类)和酸性(酚类)化合物为溶质对该固定相的正相色谱行为进行考察.结果表明该键合相在正相色谱模式下对碱性化合物具有良好的分离选择性,而酸性化合物在流动相中加入改性剂乙酸的条件下也实现了较好的分离.研究表明,正相模式下该键合相的保留机理存在着氢键、静电吸引及π-π等相互作用机制.     

反相高效液相色谱法分离蛋白质的研究

采用反相高效液相色谱法考察了几种大孔硅胶烷基键合固定相在等度淋洗条件下进行蛋白质分离的色谱性能。研究了冲洗剂中有机溶剂异丙醇的浓度、离子对酸（ＴＦＡ）浓度对蛋白质保留时间的影响。探讨了蛋白质在ＲＰ－ＨＰＬＣ中的保留机理。结果表明,大孔硅胶（２０～３０ｎｍ）短链（Ｃ４和Ｃ８）烷基键合固定相适合蛋白质的分离。     

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.     

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.     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.