采用微流注射法在光纤端面制备单层胶体微球薄膜

提出了一种在光纤端面制备单层胶体晶体薄膜的新方法——微流注射法,利用针尖微量注射胶体微球溶液,该方法可以在气/液界面直接形成大面积六角密排的周期纳米球阵列,面积达到平方厘米级别,再利用二维胶体单层膜的可转移性,将薄膜转移至到光纤端面衬底上,形成单层胶体微球有序薄膜.采用扫描电子显微镜和光谱分析仪对样品形貌、结构以及光学特性进行了表征和分析.电子显微镜图像表明,光纤端面的胶体晶体为六角密排阵列结构.透射光谱表明,该结构具有光子晶体的带隙特征,带隙的中心波长约为700和850 nm,与分析软件FDTD Solutions仿真结果相吻合.结合溅射沉积方法,得到了银纳米球壳阵列结构,检验了其局域表面等离子体共振效应(LSPR).对比讨论了溶液浓度、弯月面的形成及注射速度等因素对微流组装胶体微球薄膜质量的影响.     

胶体晶体

简要综述胶体晶体的研究进展情况,主要介绍胶体粒子的简单自组装、模板引导下的自组装和二元胶体晶体组装等几类主要的胶体晶体制备技术,并概述胶体晶体在光子晶体、传感器、光子纸张、三维有序大孔材料、二维纳米结构阵列等方面的应用。     

碗形胶体颗粒/阵列薄膜的制备及性能研究进展

随着科学技术和应用需求的快速发展, 对胶体颗粒形貌、尺寸和组分提出了越来越高的要求, 简单组成的球形颗粒已经难以满足需求. 微/纳米碗形胶体颗粒/阵列薄膜由于具有比表面积大、结构对称性下降等特点, 在纳米反应器、药物运载、高灵敏度传感器、数据储存、自组装等方面有着广阔的应用前景, 其研究、开发和应用已经成为微／纳米材料研究领域的热点. 概述了近十年来国内外碗形胶体颗粒/碗形阵列薄膜的研究进展, 按照无机和金属、聚合物两大类分别对碗形材料的各种制备方法进行了详细介绍, 目前主要有单层胶体晶体模板法、碗形阵列薄膜模板法、诱导生长法、异形颗粒法、中空微球内陷法、种子聚合法、溶剂处理法等; 按照材质种类, 分别对TiO₂, ZnO, Fe_xO_y, 贵金属、聚合物等碗形颗粒/阵列薄膜的结构与性能研究进行了概述, 指出了其潜在的应用领域; 并进一步展望了该领域未来的发展趋势.     

胶体马达

胶体马达亦称微纳米马达、微纳米泳体或游动纳米机器人,是研究复杂系统的绝佳非平衡态物理模型,同时因其具有额外的自推进力、自主导航等独特优势,有望为靶向药物递送等生物医学应用带来颠覆性变革.作为一个新兴的多学科交叉领域,胶体马达拓展了胶体与界面化学的研究范畴,带来了新的现象、理论与应用,是以胶体科学为核心的国际前沿交叉学科研究的热点领域.本文系统地阐述了胶体马达以及基于胶体马达的超分子胶体马达和游动纳米机器人的新概念,同时以本课题组在胶体马达领域取得的研究成果为例,详细综述了胶体马达的结构设计与可控制备、驱动机理及运动行为的界面调控策略、集群行为规律与重构方法以及突破各种生物屏障实现药物主动靶向递送等方面的最新进展,在此基础上展望了胶体马达对于胶体科学发展所带来的新机遇与新挑战.     

胶体刻蚀——纳米结构化表面的构筑与应用

综述了近年来胶体刻蚀领域的研究进展, 分别讨论了基于胶体微粒和胶体晶体为模板的可控沉积与可控刻蚀及在固体平面基质、曲面基质和气液界面等不同基质上构筑结构化表面的方法. 同时还探讨了利用胶体刻蚀方法形成的微纳结构在光、电、磁以及表面润湿和生物学等方面的应用.     

TiO2掺杂调控聚苯乙烯微球折射率及胶体光子晶体结构色

胶体光子晶体由于其可调变的结构色在绿色印刷、印染等领域备受关注,而其光子带隙的宽度和位置由光子晶体的晶格参数(晶面间距,通常受胶体微球尺寸影响)和介质的折射率决定。现有人工胶体光子晶体主要基于SiO_2和高分子(如聚苯乙烯(PS)等)微球的组装制备,由于胶体微球材质种类有限,折射率调控受限,因而目前调控胶体光子晶体结构色主要靠改变胶体微球的尺寸来实现。本文首先制备高折射率(2.6)的TiO_2纳米晶,在乳液聚合制备单分散的PS(折射率1.6)微球过程中,将所制备的TiO_2纳米晶掺杂于PS微球中,通过TiO_2的掺杂量有效调控胶体微球的折射率,进而实现胶体光子晶体的结构色调控。以多色胶体光子晶体微球的水溶液为墨水,采用彩色喷墨打印技术打印了电脑设计的光子晶体彩画。本文发展的光子晶体结构色调控新技术拓展了胶体光子晶体的应用。     

蒸发自组装法制备聚苯乙烯胶体晶体

采用乳液聚合法制得亚微米级聚苯乙烯单分散微球,并用蒸发自组装法在乳液气-液界面进行自上而下的层层组装,制得了厚度在450μm以上的三维有序胶体晶体。结果表明,影响胶体晶体有序性的关键因素是对蒸发速度的控制,促使胶体晶体规则排列的最主要作用力为溶液的毛细管力。在胶体晶体组装末期,随着溶剂量的减少,空间阻力逐渐增大,微球对流能力下降,造成胶体晶体的有序性降低。     

基于胶体晶体刻蚀构筑含金纳米碗的柱状结构阵列

以二氧化硅微球为掩板,利用各向异性等离子体刻蚀技术对光固化树脂薄膜进行选择性刻蚀,制备出微纳级的顶端带凹陷的柱状结构.在材料表面蒸镀一层金后,得到微纳米级柱顶端带有金纳米碗的特殊结构.通过调整刻蚀时间可以改变光固化树脂薄膜表面的柱状结构的高度.随着柱状结构高度的增加,材料的特征峰从500 nm红移至760 nm.运用时域有限差分(FDTD)方法对这种含贵金属结构的电场分布进行模拟,发现在金纳米碗状结构的边缘处存在高强度的电场,这是材料特征峰产生的原因.这种由材料表面结构变化导致材料在光谱中特征峰迁移的现象在传感、光通讯及小型化光学器件和药物筛选等领域具有潜在应用的价值.     

简单对流自组装制备层数可控有序阵列

利用简单的方法和较少的胶体乳液,在没有任何特殊设备的情况下制备出了二维和三维的有序阵列.通过控制胶体乳液浓度获得了层数可控的胶体晶体有序阵列.通过使用现有成膜模型模拟沉积行为揭示胶体晶体阵列在生长过程中控制冷凝蒸发过程的机理,对自组装过程中颗粒转移和溶剂蒸发之间的平衡细节进行了详细的讨论.利用阵列横截面的SEM显微照片来观测样品的厚度和均匀性,通过反射光谱来观察样品的光学性质.     

悬浮液气-液界面二元胶体颗粒的漂浮组装机理

提出一种在悬浮液气-液界面漂浮组装亚微米单分散聚苯乙烯(PS)微球和纳米SiO2颗粒二元胶粒晶体的新方法, 并系统研究了漂浮组装机理. 研究表明, 聚苯乙烯微球和二氧化硅两种胶体颗粒在悬浮液气-液界面的漂浮组装是以PS微球的组装为主导的. 在一定PS微球相浓度范围内, 悬浮液中PS 微球与SiO2颗粒的初始体积配比基本不影响PS微球有序组装的形成. PS微球粒径在150-500 nm时易于形成有序排列, 较小或较大粒径的PS微球难以形成有序排列. SiO2颗粒的组装是一种以PS微球为“基底”的沉积过程. 二元胶粒晶体中SiO2颗粒的体积分数由其在混合悬浮液中的相浓度所决定.     

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%.     

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.     

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.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Copper catalyzed/mediated synthetic methodology for ebselen and related isoselenazolones

Scope of the copper catalyzed/mediated selenium-nitrogen coupling reaction has been studied for the synthesis of isoselenazolones. It is noticed that the 2-chloro, 2-bromo-, and 2-iodo-aryl amides substrates can be exploited in the selenium-nitrogen coupling reaction by employing 25-100 mol % of CuI/1,10-phenanthroline (L) and potassium carbonate as a base in DMF. Furthermore, electron rich 2-chloro-arylamides also underwent selenium-nitrogen coupling reaction to give biologically important selenium-nitrogen heterocycles. Also, copper-catalyzed selenium-nitrogen coupling reaction has been meticulously applied for the synthesis of diaryl diselenides having methoxy, amine, and amide functionality from respective aryl iodides in the presence of stoichiometric amount of succinimide as an external Se-N coupling partner.     

Knoevenagel condensation catalyzed by novel Nmm-based ionic liquids in water

A series of novel N-methyl morpholine (Nmm) based ionic liquids with 1,2-propanediol group were synthesized and used as catalysts for Knoevenagel condensation at room temperature in water. Under the effect of the catalyst, various aldehydes or aliphatic ketones could react with a wide range of activated methylene compounds well, including malononitrile, alkyl cyanoacetate, cyanoacetamide, β-diketone, barbituric acid, 2-arylacetonitrile and thiazolidinedione. Furthermore, most of the products could be separated just by filtrating and washing with water. Additionally, the catalyst is recyclable and applicable for the large-scale synthesis.     

Construction of polyheterocyclic spirotetrahydrothiophene derivatives via sulfa-Michael/aldol cascade reaction

A series of polyheterocyclic spirotetrahydrothiophene derivatives were obtained in moderate to excellent yields via a catalyst-free sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 under mild conditions. We also present the first asymmetric sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 with moderate to good enantioselectivities catalyzed by readily available chiral phase-transfer catalysts (PTCs).     

Suzuki-Miyaura reactions of the soluble guanylate cyclase inhibitor NS2028: a non-product specific route to C-8 substituted analogues

Both soluble guanylate cyclase (sGC) inhibitors ODQ 1 and NS2028 2 are synthesized via improved protocols. In the former case treating 3,4-dihydroquinoxalin-2(1H)-one oxime 8, which can be prepared in two steps from 1,2-benzenediamine, with 1,1′-carbonyldiimidazole (CDI) gives the dihydro-ODQ 10 that in the presence of KMnO₄ oxidises to give ODQ 1 in an overall yield of 46% starting from 1,2-benzenediamine. In the latter case, the synthesis affords NS2028 2 from 2-amino-4-bromophenol 3 in three steps with an overall yield of 85% and avoids the need for chromatography. Furthermore, Suzuki-Miyaura reaction conditions are described that enable the preparation of 8-aryl and 8-heteroaryl derivatives of NS2028 directly from NS2028 2. Finally, demethylation of the 8-(methoxyphenyl) substituted analogues afforded the 8-(hydroxyphenyl) derivatives 40-42. All new products are fully characterised.