Surface Initiated Polymerization from Substrates of Low Initiator Density and Its Applications in Biosensors

Surface initiated polymerization (SIP) has become an attractive method for tailoring physical and chemical properties of surfaces for a broad range of applications. Most of those application relied on the merit of a high density coating. In this study we explored a long overlooked field of SIP. SIP from substrates of low initiator density. We combined ellipsometry with AFM to investigate the effect of initiatior density and polymerization time on the morphology of polymer coatings. In addition, we carefully adjusted the nanoscale separation of polymer chains to achieve a balance between nonfouling and immobilization capacities. We further tested the performance of those coating on various biosensors, such as quartz crystal microbalance, surface plasmon resonance, and protein microarrays. The optimized matrices enhanced the performance of those biosensors. This report shall encourage researches to explore new frontiers in SIP that go beyond polymer brushes.

Carbon transition efficiency and process cost in high-rate, large-area deposition of diamond films by DC arc plasma jet

A new DC plasma torch in which are jet states and deposition parameters can be regulated over a wide range has been built. It showed advantages in producing stable plasma conditions at a small gas flow rate. Plasma jets with and without magnetically rotated arcs could be generated. With straight are jet deposition, diamond films could be formed at a rate of 39 mu m/h on Mo substrates of Phi 25 mm, and the conversion rate of carbon in CH4 to diamond was less than 3%. Under magnetically rotated conditions, diamond films could be deposited uniformly in a range of Phi 40 mm at 30 mu m/h, with a quite low total gas flow rate and high carbon conversion rate of over 11%. Mechanisms of rapid and uniform deposition of diamond films with low gas consumption and high carbon transition efficiency are discussed.

Structural, morphological and optical properties of ZnO thin films grown on gamma-LiAlO2 substrate by pulsed laser deposition

ZnO thin films were deposited on the substrates of (100) gamma-LiAlO2 at 400, 550 and 700 degrees C using pulsed laser deposition (PLD) with the fixed oxygen pressure of 20 Pa, respectively. When the substrate temperature is 400 degrees C, the grain size of the film is less than 1 mu m observed by Leitz microscope and measured by X-ray diffraction (XRD). As the substrate temperature increases to 550 degrees C, highly-preferred c-orientation and high-quality ZnO film can be attained. While the substrate temperature rises to 700 degrees C, more defects appears on the surface of film and the ZnO films become polycrystalline again possibly because more Li of the substrate diffused into the ZnO film at high substrate temperature. The photoluminescence (PL) spectra of ZnO films at room temperature show the blue emission peaks centered at 430 nm. We suggest that the blue emission corresponds to the electron transition from the level of interstitial Zn to the valence band. Meanwhile, the films grown on gamma-LiAlO2 (LAO) exhibit green emission centered at 540 nm, which seemed to be ascribed to excess zinc and/or oxygen vacancy in the ZnO films caused by diffusion of Li. from the substrates into the films during the deposition.

Microstructure and laser-induced damage threshold of ZrO2 coatings dependence on annealing temperature

ZrO2 coatings were deposited on different substrates of Yb:YAG and fused silica by electron beam evaporation. After annealed for 12 h at 673 and 1073 K, respectively, weak absorption of coatings was measured by surface thermal lensing (STL) technique, and then laser-induced damage threshold (LIDT) was determined also. The crystalline phase of ZrO2 coatings and the size of the crystal grain were investigated by X-ray diffraction. It was found that microstructure of ZrO2 coatings was dependent on both annealing temperature and substrate structure, and coatings containing monoclinic phases had higher damage threshold than others. Due to the strong absorption of Yb:YAG, damage threshold of coatings on Yb:YAG was much less than that on fused silica. (C) 2004 Elsevier B.V. All rights reserved.

The temporal and spatial distribution, composition and abundance of Protozoa in Chaohu Lake, China: Relationship with eutrophication

Systematic investigations into the temporal and spatial distribution, composition and abundance of protozoa in two regions with different trophic levels in Chaohu Lake, a large, shallow and highly eutrophic freshwater lake in China, were conducted during 2002-2003. A total of 114 species of protozoa, including phytomastigophorans, zoomastigophorans, amoebae and ciliates, were identified from 120 polyurethane foam unit (PFU) samples exposed at four stations and from various types of natural substrates. Of the 114 taxa, 36 core species were found on PFU substrates and 23 of these were found on natural ones. Protozoan abundance and chemical physical parameters at nine sampling stations, four in the western lake and five in the eastern part, indicate trophic gradient changes along the lake. Seasonal variations in the species composition of major groups at littoral PFU sampling stations illustrate the effect of a severe algal bloom on the protozoan community structure. Temporal and spatial distributions of individual abundance as functions of water temperature and trophic status were revealed. This study demonstrates again that the PFU artificial substrate method samples protozoan communities more effectively than routine natural substrate methods. (c) 2005 Elsevier GmbH. All rights reserved.

Preparation and characterization of Si sheets by renewed SSP technique

Silicon sheets from powder (SSP) ribbons have been prepared by modified SSP technique using electronic-grade (9N purity) silicon powder. The surface morphology, crystallographic quality, composition and electric properties of the SSP ribbons were investigated by surface profiler, X-ray diffraction (XRD), scanning electron microscopy (SEM), metallurgical microscope, Auger electron spectroscopy (AES) and four-point probe apparatus, respectively. The results show that the SSP ribbon made from electronic-grade silicon powder is a suitable candidate for the substrates of crystalline silicon thin film (CSiTF) solar cells, which could meet the primary requirements of CSiTF solar cell process on the substrates, including surface smoothness, crystallographic quality, purity and electric conductivity, etc. (C) 2004 Elsevier B.V. All rights reserved.

Fast plasma sintering deposition of nano-structured silicon carbide coatings

Fast plasma sintering deposition of SiC nano-structured coatings was achieved using a specially designed non-transferred dc plasma torch operated at reduced pressure. Employing the Taguchi method, the deposition parameters were optimized and verified. With the optimized combination of deposition parameters, homogeneous SiC coatings were deposited on relatively large area substrates of Φ50 mm and 50×50 mm with a deposition rate as high as 20 μm/min. Ablation test showed that such coatings can be used as oxidation resistance coatings in high temperature oxidizing environment.

Nanocomposite multilayer film of preyssler-type polyoxometalates with fine tunable electrocatalytic activities

Through layer-by-layer (LBL) assembly technique, iron oxide (Fe3O4) nanoparticles coated by poly (diallyldimethylammonium chloride) (PDDA) and Preyssler-type polyoxometalates (NH4)(14)NaP5W30O110.31H(2)O (P5W30) were alternately deposited on quartz and ITO substrates, and 4-aminobenzoic acid modified glassy carbon electrodes. Thus-prepared multilayer films were characterized by UV-visible spectroscopy, X-ray photoelectron spectroscopy, and cyclic voltammetry. It was proved that the multilayer films are uniform and stable. And the electrocatalytic activities of the multilayer films can be fine-tuned by adjusting the assembly conditions in the LBL assembly process, such as the pH of the assembly solution. The multilayer films fabricated from P5W30 solutions dissolved in 0.1 M H2SO4 exhibit high electrocatalytic response and sensitivity toward the reduction of two substrates of important analytical interests, HNO2 and IO3- whereas the films assembled with P5W30 solutions dissolved in 1.0 M H2SO4 show remarkable electrocatalytic activity for the hydrogen evolution reaction (HER). Furthermore, the electrocatalytic properties of the HER of the latter film can be obtained from the former film upon exposure to 1.0 M H2SO4 for several hours.

Synthesis of tetra-iron substituted sandwich-type pentadecatungstodiarsenate and its multilayers on glassy carbon electrode by self-assembly with electrocatalytic properties

A novel sandwich-type compound, Na-12 [Fe-4 (H2O)(2) (As2W15O56)(2)] . 38H(2)O (denoted as Fe(4)AS(4)W(30)) was synthesized. The compound was well characterized by means of IR, UV-Vis, W-138 NMR and elemental analyses. Redox electrochemistry of the compound has been studied in acid buffer solutions using cyclic voltammetry(CV). The compound containing multilayer films has been fabricated on the 4-aminobenzoic acid(4-ABA) modified glassy carbon electrode(GCE) surface by alternate deposition with a quaternized poly (4-vinylpyridine) partially completed with [Os(bpy)(2)Cl](2+/-) (denoted as QPVP-Os). CV, X-ray photoelectron spectroscopy (XPS) and UV-Vis spectroscopy were used to characterize the asprepared multilayer films. It is proved that the multilayer films are uniform and stable. The electrocatalytic activities of the multilayer films were investigated on the reduction of two substrates of important analytical interest, NO2- and H2O2.

Layer-by-layer assembly of multilayer films consisting of silicotungstate and a cationic redox polymer on 4-aminobenzoic acid modified glassy carbon electrode and their electrocatalytic effects

A novel 4-aminobenzoic acid (4-ABA) monolayer film is formed on glassy carbon electrode (GCE) by amino cation radical method. Silicotungstic heteropolyanion (SiW12O404-, denoted as SiW12)-containing multilayer films have been fabricated on the 4-ABA modified GCE surface by alternate deposition with a quaternized poly(4-vinylpyridine) partially complexed with [Os(bpy)(2)Cl](2+/+) (denoted as QPVP-Os). Cyclic voltammetry (CV), X-ray photoelectron spectroscopy (XPS) and X-ray reflectivity (XR) have been used to characterise the as-prepared multilayer films. It is proved that the multilayer films are uniform and stable. The average thickness for a bilayer of QPVP-Os/SiW12 in the multilayer film is 30.2 Angstrom. The electrocatalytic activities of the multilayer films have been investigated on the reduction of three substrates of important analytical interests, HNO2, BrO3- and H2O2. Especially, the influence of layer number of the multilayer films on the electrocatalytic reduction of HNO2 has been investigated in detail. (C) 2000 Elsevier Science B.V. All rights reserved.

VTE法制备γ-LiAlO2／α-Al2O3复合衬底以及腐蚀和退火对其影响

通过气相传输平衡法(VTE)制备了γ-LiAlO2／α-Al2O3复合衬底，使用5％的稀盐酸对其进行腐蚀并在900℃退火72h。利用X射线衍射、偏光显微镜及扫描电镜对复合衬底进行了分析，发现在白宝石α面(11-20)和γ面(1—102)均获得单相多晶的γ-LiAlO2，且后者的择优取向好于前者。腐蚀可以提高样品的择优取向，在5％的稀盐酸中，时间控制在2min左右可获得较好的结果。退火后γ-LiAlO2颗粒质量得到改善，白宝石α面上γ-LiAlO2的质量优于r面上的γ-LiAlO2，两者都出现颗粒长大现象。

退火对ZrO2薄膜微结构及激光损伤阈值的影响

利用电子束蒸发方法在Yb:YAG晶体和熔融石英衬底上沉积单层ZrO2薄膜,分别在673 K和1 073 K的温度下经过12 h退火以后,通过X射线衍射(XRD)分析了薄膜晶相,计算了薄膜的晶粒尺寸;利用表面热透镜技术获得了薄膜的吸收;测量了退火后薄膜的激光损伤阈值.实验结果表明:两种衬底上的薄膜结构受到退火温度和衬底表面结构的影响,高温退火有利于单斜相的形成,含单斜相的ZrO2薄膜具有较高的激光损伤阈值,而由于衬底的吸收,Yb:YAG晶体上薄膜的损伤阈值远小于石英衬底上薄膜的损伤阈值.

Strong three-level resonant magnetopolaron effect due to the intersubband coupling in heavily modulation-doped GaAs/AlxGa1-xAs single quantum wells at high magnetic-fields

Electron cyclotron resonance CR) measurements have been carried out in magnetic fields up to 32 T to study electron-phonon interaction in two heavily modulation-delta -doped GaAs/Al0.3Ga0.7As single-quantum-well samples. No measurable resonant magnetopolaron effects were observed in either sample in the region of the GaAs longitudinal optical (LO) phonons. However, when the CR frequency is above LO phonon frequency, omega (LO)=E-LO/(h) over bar, at high magnetic fields (B>27 T), electron CR exhibits a strong avoided-level-crossing splitting for both samples at frequencies close to (omega (LO)+ (E-2-E-1)1 (h) over bar, where E-2, and E-1 are the energies of the bottoms of the second and the first subbands, respectively. The energy separation between the two branches is large with the minimum separation of 40 cm(-1) occurring at around 30.5 T. A detailed theoretical analysis, which includes a self-consistent calculation of the band structure and the effects of electron-phonon interaction on the CR, shows that this type of splitting is due to a three-level resonance between the second Landau level of the first electron subband and the lowest Landau level of the second subband plus one GaAs LO phonon. The absence of occupation effects in the final states and weak screening or this three-level process yields large energy separation even in the presence of high electron densities. Excellent agreement between the theory and the experimental results is obtained.

Strong resonant intersubband magnetopolaron effect in heavily modulation-doped GaAs/AlGaAs single quantum wells at high magnetic fields

Electron cyclotron resonance (CR) has been studied in magnetic fields up to 32 T in two heavily modulation-delta-doped GaAs/Al0.3Ga0.7As single quantum well samples. Little effect on electron CR is observed in either sample in the region of resonance with the GaAs LO phonons. However, above the LO-phonon frequency energy E-LO at B > 27 T, electron CR exhibits a strong avoided-level-crossing splitting for both samples at energies close to E-LO + (E-2 - E-1), where E-2, and E-1 are the energies of the bottoms of the second and the first subbands, respectively. The energy separation between the two branches is large, reaching a minimum of about 40 cm(-1) around 30.5 T for both samples. This splitting is due to a three-level resonance between the second LI, of the first electron subband and the lowest LL of the second subband plus an LO phonon. The large splitting in the presence: of high electron densities is due to the absence of occupation (Pauli-principle) effects in the final states and weak screening for this three-level process. (C) 2000 Published by Elsevier Science B.V. All rights reserved.

苯乙酮、氨甲酸酯参与的直接Mannich反应

Mannich反应是有机化学中最重要的碳-碳键形成反应，其产物是合成手性胺的通用中间体。间接Mannich反应使用不稳定的预制烯醇等当体，以未修饰的酮为给体的直接方法将增强Mannich反应的效率。针对低活性苯乙酮、氨甲酸酯参与的直接Mannich反应，研究工作将更具挑战性。 在前期实验中，我们发现Lewis酸-NbCl5可高效催化苯乙酮、芳香醛、芳香胺三组分直接Mannich反应，反应在环境温度下进行，高收率获得Mannich碱。这是以苯乙酮参与的Mannich反应中，实现催化量Lewis酸催化的首次报道。该方法高效且操作简单。但就底物而言，对易去保护、低活性的氨甲酸酯类底物收率较低。我们设想Brønst酸可解决此类底物问题。令人高兴的是，杂多酸可高效催化芳香酮、芳香醛、氨甲酸酯三组分直接Mannich反应，反应在环境温度下进行，高收率获得N-保护的β-氨基酮。该方法底物范围广泛，普适性强且催化剂便宜。 基于杂多酸在苯乙酮、氨甲酸酯为底物直接Mannich反应中的高效性，我们设想杂多酸与功能化的手性有机小分子-手性伯胺组装可解决催化剂回收问题，同时实现不对称催化。实验结果表明，非共价键固载手性伯胺不能有效催化苯乙酮为底物的直接Mannich反应，无论是对映选择性还是收率均较低。随后，我们以丙二酸酯及α-氨基砜为底物，以增强底物活性，同时绕开亚胺的不稳定性。辛可宁伯胺以氢键双活化底物，有效催化原位产生氨甲酸酯类亚胺与丙二酸酯的Mannich反应，高收率获得Mannich碱，ee值中等。 我们采用逐步解决问题的策略解决Mannich反应中的部分问题并在Lewis酸催化、Brønst酸催化、非共价键固载手性伯胺催化及手性伯胺氢键催化的直接Mannich反应中做出了有益探索。 The Mannich reactions are among the most fundamental carbon-carbon bond forming reactions in organic chemistry, and the reaction products are versatile intermediates in the synthesis of chiral amines. The indirect Mannich reaction uses preformed enolate equivalents. However the preformed enolates are unstable. Thus, a direct methodology based on unmodified ketone donors would enhance the efficiency of the Mannich reaction. Especially researches for the directed Mannich reactions of acetophenone, carbamate, which own lower activities, will be more challengeable. In the initial experiments, we found an efficient Lewis acid-NbCl5 which could catalyze three-component Mannich-type reaction of acetophenone, aromatic aldehydes and aromatic amines at ambient temperature in high yields. This is the first report that use catalytic amount of Lewis acid in the Mannich reactions of .acetophenone. The method reported is not only simple to operate but also efficient. However, as far as amines are concerned, the substrates of carbamates which can be deprotected more easily and less reactive than amines give low yields. We envisaged that Brønsted acid would resolve this problem. Pleasingly, heteropoly acids (HPA) efficiently catalyzed one-pot three-component Mannich reactions of aryl aldehydes, aryl ketones, and carbamates at ambient temperature and afforded the corresponding N-protected β-amino ketones in good to excellent yields. This method provides a novel and improved modification of three-component Mannich reactions in terms of a wide scope of aldehydes, ketones and carbamates, economic viability. Based on the high efficiency of heteropoly acids in the Mannich reaction of acetophenone and carbamates, we envisaged that if HPA were combined with functionalized chiral organocatalysts–chiral primary amines the assemblies may be able to act as recoverable asymmetric organocatalysts. The results of exprimentals showed that noncovalently supported heterogeneous chiral primary amine couldn’t effectively catalyze the Mannich reactions which own two the substrate of acetophenone regardless of enantioselectivity and yield. Then, we employed malonates and α-amido sulfones as substrates to enhance reactivity of substrates and circumvent the instability of imines. A moderately enantioselective and highly yield Mannich reaction with in situ generation of carbamate-protected imines from stable α-amido sulfones catalyzed by cinchonine primary amine catalyst was developed. It is noteworthy that cinchonine primary amine can dual activate substrates through H-bond activation and thus promote the reaction. We applied step-by-step-strategy to resolve some problems in the Mannich reactions and did some instructive explorations in Lewis acid catalysis, Brønst acid catalysis, noncovalently supported heterogeneous chiral primary amine catalysis and chiral primary amine as hydrogen-bond catalysis.