松香基荧光衍生物的研究进展

松香是我国重要的天然可再生林业资源,其主要成分是具有三环菲骨架的含有共轭双键和羧基的树脂酸,可进行氢化、歧化、加成、酯化、重排、氧化等多种化学反应。脱氢枞酸是由松香通过催化歧化后提纯得到,骨架中含有一个芳环,基于芳环和羧酸基团可开发多种荧光衍生物,为松香的高值化利用开辟了新途径。本文着重归纳了基于脱氢枞酸芳环改性的几类荧光衍生物,如酰基化、芳胺、杂环、席夫碱等化合物,基于树脂酸羧酸改性的荧光衍生物,如脱氢枞胺、杂环化合物、脱氢枞酸羧基衍生物等,并对荧光衍生物的荧光性能及其作为发光材料在有机发光器件、荧光探针和细胞成像等领域的应用进行了综述,探讨了松香基荧光衍生物研究目前存在的高发光效率的蓝光和红光化合物较少,在依赖材料固体薄膜发光的有机电致发光器件中发光效率较低,发光机理研究不足等问题,并展望了未来发展的趋势。     

松香树脂酸的改性及应用的研究进展

阐述了近年来松香树脂酸的改性研究进展,对其改性类型进行分类阐述,即双键改性、羧基改性和芳环改性,并展望了树脂酸及其衍生物的发展前景。     

脱氢松香酸甲酯呋咱衍生物的合成与表征

以歧化松香为原料,将其纯化得到脱氢松香酸,用硫酸二甲酯酯化后,通过12位溴代、7位氧化、13位硝化得到7-羰基-12-溴-13-硝基脱氢松香酸甲酯(Ⅴ),Ⅴ经过与叠氮化钠反应后,在甲苯中回流关环得到7-羰基-12,13-氧化呋咱脱氢松香酸甲酯(Ⅶ),Ⅶ再用三苯基膦脱氧得到7-羰基-12,13-呋咱脱氢松香酸甲酯Ⅷ,这两种产物的产率分别为83%和76%;产物经IR、1HNMR1、3CNMR和MS进行了表征。     

中国塑料专利

正专利名称:含羧基侧基超支化聚芳醚共聚物固化改性环氧树脂组合物及其制备方法和应用申请公布号:CN108276736A申请公布日:2018.07.13本发明提供含羧基侧基超支化聚芳醚共聚物固化改性环氧树脂组合物,主要包括含羧基侧基聚芳醚共聚物,环氧树脂,固化剂,固化促进剂。本发明还提供了该环氧树脂组合物的制备方法和应用,包括将含羧基侧基聚芳醚共聚物、环氧树脂、固化剂和固化促     

脱氢枞胺及其衍生物的应用研究进展

脱氢枞胺是歧化松香胺的主要成分,具有三环菲骨架结构,是松香重要的改性产品之一。本文综述了脱氢枞胺及其衍生物的应用研究进展,包括脱氢枞胺在手性化合物分离方面的应用和脱氢枞胺衍生物在抑菌、防腐、缓蚀、金属离子浮选、催化、抗癌、抗氧化、抗溃疡、可与雄性激素结合等方面的应用。指出目前脱氢枞胺成盐衍生物及脱氢枞胺N-C衍生物的研究较为广泛,脱氢枞胺B环和C环改性衍生物的研究仍需加强,而且对于B环和C环改性衍生物的深入研究,将进一步促进脱氢枞胺衍生物在生物活性方面的应用。最后对脱氢枞胺衍生物在生物医学工程上的应用前景进行了展望。     

离子液体[bmim][dca]中脱氢松香酸β-环糊精酯的合成及其性能研究

以离子液体[bmim][dca]作为绿色反应溶剂,4-二甲基氨基吡啶(DMAP)为催化剂,通过脱氢松香酸酰氯与β-环糊精的O-酰化反应,合成了脱氢松香酸β-环糊精酯(CDDA),最佳合成条件为:摩尔比3∶1(脱氢松香酸酰氯∶β-环糊精葡萄糖单元羟基),催化剂DMAP用量为脱氢松香酸酰氯质量的5％,反应温度90℃,反应时...     

三种脱氢松香酸甲酯噻二唑衍生物的荧光性质研究

以脱氢松香酸甲酯为原料,合成了三种脱氢松香酸甲酯噻二唑衍生物,其结构经NMR、MS确证,并对其荧光光谱性质进行了初步的研究。     

12-溴-13,14-脱氢松香酸甲酯氧化呋咱的合成与表征

以脱氢松香酸为起始原料合成了一种新型的12-溴-13,14-脱氢松香酸甲酯氧化呋咱。其结构经IR、NMR、MS、元素分析及其单晶结构确证。     

脱氢松香酸含氮衍生物的合成及其抗肿瘤活性研究

以天然林化资源脱氢松香酸为原料,合成了5个脱氢松香酸12位含氮衍生物,所有化合物的结构经IR和1HNMR确证,并对4种人体肿瘤细胞株进行了初步体外抗肿瘤活性评价。结果表明部分化合物具有良好的抗肿瘤活性。     

手性7-氨基脱氢松香酸乙酯的合成及表征

以脱氢松香酸为起始原料,通过酯化、氧化、手性辅剂亚胺化、还原以及酸解脱除手性辅剂等反应获得光学纯的 7 -（S）- 氨基脱氢松香酸乙酯 6a 和 7 -（R）- 氨基脱氢松香酸乙酯 6b。产物结构通过 1H NMR、13C NMR、MS 和 HRMS 进行表征,绝对构型经 X-ray 单晶衍射确定。     

L-3-氟-酪氨酸的合成研究

以L-酪氨酸为原料,经由羧基、氨基保护后,在其苯环上3-位直接硝化,硝化后的产物在铁粉和醋酸的作用下还原成3-位氨基的衍生物,再重氮化、光照下发生氟代反应,最后,氟代完成后的产物盐酸水解除去保护基后,即得到光学纯的L-3-氟-酪氨酸.经熔点、旋光度、1H-NMR及MS检测,结果与文献值一致.本文方法是合成L-3-氟-酪氨酸的理想方法.     

Self-assembly of 2,6-naphthalenedicarboxylic acid and 4,4′-biphenyldicarboxylic acid on highly oriented pyrolytic graphite and Au(1 1 1) surfaces

Self-assemblies of 2,6-naphthalenedicarboxylic acid (NDC) and 4,4′-biphenyldicarboxylic acid (BDC) molecules on the highly oriented pyrolytic graphite (HOPG) and reconstructed Au(1 1 1) surfaces has been, respectively, studied by using scanning tunneling microscopy (STM). The NDC molecules form an incommensurate structure, while BDC molecules form a commensurate structure on the HOPG surface. The aromatic rings take the same orientation with that of the underlying HOPG substrate to gain optimum adsorbate-substrate interactions. On the Au(1 1 1) surface, both molecules form incommensurate structures. The orientations of aromatic ring locate about 20° with respect to the gold rows, the 〈1 1 0〉 direction. On the HOPG surface, the whole carboxyl groups are invisible, while the carbon atoms of the carboxyl groups may appear bright on the gold surface.     

Highly functionalized polystyrene by direct metalation—carboxylation

Summary Polystyrene was directly metalated using 1:1 mixture of n-butyllithium (n-BuLi) and potassium-t-butoxide (t-BuOK) in cyclohexane/hexanes at ambient temperature. The metalated polymer on reaction with solid carbon dioxide followed by a metal-proton exchange gave a carboxylated polymer containing 6.38–6.57 mmol acid/g polymer which corresponds to the introduction of carboxyl groups on 94–97% of the repeat units of polystyrene.Based on ¹³C nMR spectra meta, para and ortho aromatic ring substitution was proposed. No detectable backbone carboxylation occurs. the distribution of carboxylated sites on the aromatic ring: 9% ortho, 58% meta and 33% para. Quantitative ¹³C NMR analyses indicates essentially quantitative functionalization.     

针叶木硫酸盐浆中残留木素的GIF体系仿酶降解机理的研究

由于针叶木硫酸盐浆中的残留木素含有大量难降解的LCC结构及其它缩合型木素结构,所以硫酸盐浆的分离木素可以用作难降解型木素大分子的一种结构模型。文章采用Cu2+/吡啶/过氧化氢组成的GIF仿酶体系对马尾松硫酸盐未漂浆的纤维素酶酶解木素(CEL)进行了仿酶降解,并对降解产物进行了分离和化学组成分析。通过FT-IR以及GC-MS测定,解析了CEL在降解过程中的结构变化,并对CEL的仿酶降解机理进行了探讨。研究结果表明:这种仿酶降解方法对浆中残留木素有较强的降解能力,一部分木素大分子被氧化降解为香草醛和香草酸等低分子化合物,使得降解后的产物中羰基和羟基增多。研究发现木素在仿酶体系中存在苯环及其侧链上C-H键的破坏、木素结构中Ca-Cb连接键的断裂、苯环的开环等反应。因此,该项研究可以为开发纸浆的仿酶漂白技术提供理论依据。     

印尼油砂沥青组成及化学结构分析

利用FTIR和¹³C NMR对印尼油砂沥青中的脂肪烃结构、芳香烃结构、含氧官能团以及碳骨架进行研究,并就印尼油砂样品中较高的硫含量进行XPS分析。结果表明：4个印尼油砂样品沥青中脂肪碳含量均占到了70%左右,脂肪烃主要由亚甲基构成,甲基与次甲基次之,样品中有大量的烷基侧链。FTIR无法准确分辨芳香烃部分的苯环取代结构,通过¹³C NMR发现芳香烃中质子化芳碳的含量较高,桥头芳碳与侧枝芳碳为主要非质子化芳碳,由带质子化芳碳的比例大小可以推断样品芳香环上的取代度为2～4。样品含氧官能团部分以C－O形式存在于醇和醚中,部分以羧基形式存在。样品中硫主要为有机硫,芳香族硫化物含量最高,其次为脂肪族硫化物,存在一定比例亚砜。无机硫以黄铁矿硫与硫酸盐硫形式存在,由于油砂表面被有机质包裹,无机物裸露较少,XPS没有测得硫酸盐硫,黄铁矿硫的检测值也偏低。     

Zur Photolyse von makromolekularen o-Nitrobenzylderivaten

By irradiation with UV-light copolymers with o-nitrobenzylester side groups form the corresponding o-nitrosobenzaldehyde and carboxyl side groups. This reaction is studied in more detail by using poly(o-nitrobenzyl acrylate) and some low molecular o-nitrobenzyl derivates as model compounds. The influence of sensitizers, quenchers and substitution of the aromatic ring on the reactivity is discussed. The photoreaction can be used in “positiv working” photoresist materials.     

基于核磁-能谱实验的中变质烟煤煤尘低润湿性分析

为从微观角度分析中变质烟煤的低润湿特性,以巨野煤田赵楼气肥煤为例,选用核磁共振（NMR）与X射线光电子能谱（XPS）手段对其微观分子结构进行实验,并分析了分子结构参数对其润湿性的影响规律。结果表明,赵楼气肥煤煤尘的芳香度为0.77,芳香结构含量较高,且主要以质子化芳环为主;脂肪链结构中以链状烷烃和环烷烃侧链为主,且存在一定的甲基侧链;煤尘表面含氧官能团主要为醚基（C-O-C）,其次为羰基（C=O）与羟基（C-OH）,含量最少的是羧基（COOH）,上述4种含氧官能团含量之比约为4∶2∶2∶1.5。赵楼气肥煤煤尘不仅芳香度较高,芳香簇尺寸较大,缩合度偏高,而且烷基侧链少而短,导致煤尘分子结构单元表现出较强的疏水性;而对表面亲水性贡献较大的羧基（COOH）和羟基（C-OH）含量却只占表面含氧官能团总量的13.53%、21.45%。因此,受微观分子结构的影响,赵楼气肥煤煤尘总体表现出疏水性的特点,润湿性较差。     

An addition compound of oxidized tocopherol and linoleic acid

There is evidence that an addition compound of oxidizeddl-alpha-tocopherol and linoleic acid is formed when the components are absorbed in mixed monolayer on silica gel at a molecular ratio of 1∶20, and subjected to heating in air at 80C. A relatively nonpolar tocopheryl quinone is also formed in smaller amounts. These are the major tocopherol oxidation products isolated in this system and do not correspond to any known to the authors. The addition compound has about the same mobility as linoleic acid in most thin layer chromatography (TLC) and chromatographic systems, but can be isolated by successive chromatography on silica and gel filtration on Sephadex LH-20. It yields a single spot in TLC in several systems. The elemental analysis is reproducible and consistent with a simple addition compound of linoleic acid and bivalently oxidized tocopherol. The compound has a carboxyl group which can be esterified. The ester has about the same TLC mobility as methyl linoleate. The molecular weight of the ester is 722.6. The UV spectrum shows a single peak, 2_max^ETOH=3000 Å, E=4.74. The IR spectrum shows a very strong chroman ether band at 9.12 μ, a strong methyl band at 7.24 μ and carboxyl but no hydroxyl absorption. The NMR spectrum shows, in contrast to that of tocopherol, a reduction in aromatic methyl protons, a carboxyl proteon exchangeable with deuterium oxide, but no hydroxy proton. The compound does not reduce Emmerie-Engel reagent prior to treatment with concentrated hydriodic acid, nor do the ether-extractable products after such treatment. The present data are consistent with an addition product whose bridging group is a new chroman ring.     

Synthesis and lyotropic behavior of mesogen‐linked cellulose acetates

Three aromatic (p‐carboxyl phenyl) esters, 4‐(benzoyloxy) benzoic acid, 4‐(4′‐methylbenzoyloxy) benzoic acid, and 4‐(4′‐chlorobenzoyloxy) benzoic acid, were synthesized and they showed nematic monotropic or thermotropic behavior. The mesogen‐linked cellulose acetates were first prepared by the reaction of aromatic (p‐carboxyl phenyl) esters with cellulose acetate through esterification in the presence of N,N‐dicyclohexylcarbodiimide (DCC) and 4‐dimethylaminopyridine (DMAP). Their degrees of mesogenic unit substitution (DS_‐meso) were between 0.27 and 0.41. It was found that they can form cholesteric lyotropic phases in dichloroacetic acid and their critical concentration was about 25 wt %. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2693–2697, 2004