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51.
52.
A novel set of light-responsive polyelectrolytes has been developed and studied, to control and tune surface wettability by introducing various types of substituted R head-groups of azo polyelectrolytes in self-assembled multilayer (SAMU) films. As part of a larger project to develop polymer surfaces where one can exert precise control over properties important to proteins and cells in contact, photo-reversibly, we describe here how one can tune quite reliably the contact angle of a biocompatible SAMU, containing a photo-reversible azo chromophore for eventual directed cell growth. The azo polyelectrolytes described here have different substituted R head-group pairs of shorter-ionized hydrophilic COOH and SO3H, shorter non-ionized hydrophobic H and OC2H5, and larger non-ionized hydrophobic octyl C8H17 and C8F17, and were employed as polyanions to fabricate the SAMU onto silicon substrates by using the counter-charge polycation PDAC. The prepared SAMU films were primarily characterized by measurement of their contact angles with water. The surface wetting properties of the thin films were found to be dependent on the type of substituted R-groups of the azo polyelectrolytes through their degree of ionization, size, hydrophobicity/hydrophilicity, solubility, conformation, and inter-polymeric association and intra-polymeric aggregation. All these factors appeared to be inter-related, and influenced variations in hydrophobic/hydrophilic character to different extents of aggregates/non-aggregates in solution because of solvation effects of the azo polyanions, and were thus manifested when adsorbed as thin films via the SAMU deposition process. For example, one interesting observation is significantly higher contact angles of 79° for SAMU films of larger octyl R groups of PAPEA-C8F17 and PAPEA-C8H17 than for others with contact angles of 64° observed for non-polar R-groups of OC2H5 and H. Furthermore, lower contact angle values of 59° for SAMU films with polar R-groups of COOH and SO3H relative to that of non-polar R-groups are in accordance with their expected order of the hydrophilicity or hydrophobicity. It is possible that the large octyl groups are more effective in shielding the ionic functional groups on the substrate surface, and contributed less to the water drop-molecule interactions with ionic groups of the PDAC and/or AA groups. In addition, higher hydrophobicity of the SAMU films may be due to the incorporation of bulky and hydrophobic groups in these polyelectrolytes, which can produce aggregates on the surfaces of the SAMU films. Through understanding and controlling the complex aggregation behavior of the different substituted R-groups of these azo polyelectrolytes, and hence their adsorption on substrates, it appears possible to finely tune the surface energy of these biocompatible films over a wide range, enhance the photo-switching capabilities of the SAMU films, and tailor other surface properties for the development and application of new devices in diverse areas of microfluidics, specialty coatings, sensors, and biomedical sciences. 相似文献
53.
Encapsulation and Enhanced Luminescence Properties of IrIII Complexes within a Hexameric Self‐Assembled Capsule
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Dr. Shinnosuke Horiuchi Hirotaka Tanaka Prof. Dr. Eri Sakuda Prof. Dr. Yasuhiro Arikawa Prof. Dr. Keisuke Umakoshi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(49):17533-17537
Encapsulation and luminescence studies of [Ir(ppy)2(bpy)]Cl (ppy=2‐phenylpyridinate, bpy=2,2′‐bipyridine) within a hexameric resorcinarene capsule are reported. One IrIII complex cation was encapsulated within the capsule, as demonstrated by NMR and dynamic light scattering (DLS) studies. The emission color of the IrIII complex was drastically changed from orange to yellow by encapsulation, in contrast with the lack of significant changes in the absorption spectrum. The hexameric capsule effectively hampers the non‐radiative pathway to increase both the luminescence quantum yield and the exited state lifetime. The luminescent properties of the encapsulated IrIII complex depend on the ratio of IrIII complex to the resorcinarene monomer as well as the concentration of resorcinarene monomer owing to the reversible process of self‐assembly of the hexameric capsule. Quenching experiments revealed that the IrIII complex in the capsule was effectively separated from quenchers. 相似文献
54.
Gi-Seong Ryu 《Molecular Crystals and Liquid Crystals》2017,652(1):207-212
Most of the merit of organic thin film transistors (OTFTs) is that they can be manufactured using cost effective processes. However, expensive gold (Au) electrodes have usually been used as a source/drain (S/D), due to their benign energy level matching, high air stability, and easy patternability. In this article, we report a simple method for improving the charge injection from a low cost molybdenum (Mo) electrode to organic semiconductors in OTFTs by incorporating a dodecanoic acid (DA)–based self-assembled monolayer (SAM). The OTFT performance is remarkably improved when compared to the devices with a pristine Au electrode. The hole carrier mobilities (hole μFET) were ~0.13 (rr-P3HT), ~0.55 (PC12TV12T) and ~0.72 (P2100) cm2/V·sec. 相似文献
55.
Silver electrodes were modified by the adsorption of α-, β-, and γ-cyclodextrin dithiocarbamates (2α–γ) and characterized by reductive desorption experiments. Their molecular recognition properties were studied by cyclic voltammetry using three families of positional isomers of aromatic nitro compounds. Electrodes modified with 2α and 2β were selective for meta and para isomers while 2γ showed little selectivity. These observations are explained in terms of cavity sizes and guest structure. Computational studies suggest that the main reason for the observed selectivity is the different position of the NO2 group in ortho and para isomers with respect to the CD cavity. 相似文献
56.
11,11′-Dithiobis[1-(2-bromo-2-methylpropionyloxy)undecane], a conventional initiator for grafting polymers from gold surfaces, was synthesized in two steps from 11-mercapto-1-undecanol in 88–92% overall yield. Oxidative dimerization of 11-mercapto-1-undecanol with a catalytic amount of sodium iodide and 30% hydrogen peroxide in ethyl acetate proceeded in 96% yield. Esterification with 2-bromoisobutyryl bromide in dichloromethane was clean and almost quantitative (92% yield) with pyridine used as base, whereas triethylamine gave a messy reaction (64% yield). Alternatively, esterification with 2-bromo-2-methyl-propanoic acid in dichloromethane occurred readily under Steglich's conditions with N,N′-dicyclohexylcarbodiimide (DCC) and a catalytic amount of dimethylaminopyridine (DMAP; 88% yield). 相似文献
57.
Maryam Zohri Alireza Nomani Tarane Gazori Ismaeil Haririan Seyed Saeed Mirdamadi Seyed Kazem Sadjadi 《Journal of Dispersion Science and Technology》2013,34(4):576-582
The aim of this study was to evaluate the effect of the polymeric ratios on the characteristics of chitosan/alginate (ch/alg) self-assembled nanoparticles and their potential as protein delivery vehicle. The nanoparticles were prepared using proper mixing of polymers in presence or absence of bovine serum albumin (BSA) as a protein model. Three formulations of nanoparticles comprising ch/alg ratios of 2:1, 1:1, and 1:2 were prepared. Size, shape and zeta potential of the formulations were studied by scanning electron microscopy (SEM) and nanosizer instruments. FTIR, and differential scanning calorimetery (DSC) studies were performed to investigate polymer-polymer or polymer-protein interactions. Release profiles and entrapment efficiencies of the nanoparticles were determined by calorimetric technique using appropriate techniques. Entrapment efficiency was 70% for ch/alg ratio of 1:1, 65% for 1:2, and 60% for 2:1. The z-average size of the nanoparticles were 403, 205, and 318 nm for ch/alg ratios of 2:1, 1:1, and 1:2, respectively. Average zeta potentials were ?47, +15, ?25 mV for 2:1, 1:1, and 1:2 as well. Considering the favorable features required for protein delivery systems, ch/alg (1:1) due to its smallest size, highest loading, and most homogenous shape was regarded as the best ratio. 相似文献
58.
Electropolymerization is one of the most important methodologies to synthesize and develop conducting polymers. The complexity of the polymerization mechanism, ion doping processes and structural defects are considered to be symbiotic and unavoidable, making the stagnant state and huge band gap with advanced interdisciplinary research fields and important applications in the last three decades. Herein, we provide a point of view into controlled electropolymerization by regioselective activation reactions of monomers, where self-dimerizations instead of self-electropolymerizations were utilized. The resulting dimers play a role in the connections between functional building blocks to form functional polymers on demand. This account highlights the typical findings in controlled electropolymerizations as a forum for discussing new opportunities in exploiting novel designs and applications. 相似文献
59.
K-ion batteries (KIBs) attract considerable attention due to the abundance of K, high-working voltages, and chemical similarity with Li, enabling the utilization of mature Li-ion technology. However, shortage of high-performance anode materials is a critical obstacle for the development of KIBs. Through first-principles swarm-intelligence structural search, we identify a potential anode material, the C6S monolayer, which provides not only a remarkably high specific capacity of 1546 mAh/g but also a low diffusion barrier of 0.11 eV and a low open-circuit voltage of 0.21 V. Inherent metallicity originates from delocalized π electrons. 相似文献
60.
Hao Huang Cuicui Du Hongyan Shi Xun Feng Jin Li Yanlei Tan Wenbo Song 《Particle & Particle Systems Characterization》2015,32(1):72-79
Uniform water‐soluble monolayer MoS2 quantum dots (MQDs) with lateral sizes of ≈2.1 nm, a clearly zigzag‐terminated edge, and a hexagonal lattice structure are achieved using ammonium molybdate, thiourea, and N‐acetyl‐l ‐cysteine (NAC) as precursors and the capping reagent in a facile one‐pot hydrothermal approach. MQDs have good dispersity and high stability in aqueous suspension and exhibit a significantly larger direct bandgap (3.96 eV) compared to monolayer MoS2 nanosheets (1.89 eV). Pronounced blue‐shifts in the wavelengths of both the excitonic absorption and intrinsic state emission with activated strong luminescence at room temperature beyond monolayer MoS2 nanosheets is demonstrated. Unusual upconversion photoluminescence is also observed and is caused by two successive transfers of energy from the near‐infrared (NIR) absorption generated by the NAC capping reagent to the hexagonal structure of MQDs. Additional optical properties of MQDs may provide numerous exciting technological applications. Here, MQDs are demonstrated as a highly selective fluorescent reagent for detecting tetracycline hydrochloride under UV and NIR irradiation. 相似文献