碳纳米管的可控长度拾取及导电性分析

拾取指定长度的半导体性碳纳米管对大规模制造碳纳米管场效应管具有重要意义.本文提出了一种利用原子力显微镜探针和钨针对碳纳米管进行可控长度拾取的方法并进行了碳纳米管导电性分析.在扫描电子显微镜下搭建微纳操作系统,针对切割操作过程中原子力显微镜探针、钨针和碳纳米管的接触情况进行了力学建模和拾取长度误差分析.建立了单根金属性碳纳米管、单根半导体性碳纳米管及碳纳米管束与钨针接触的电路模型,推导了接入不同性质碳纳米管后电路的电流电压特性方程.使用原子力显微镜探针对碳纳米管的空间位姿进行调整,控制钨针对碳纳米管上目标位置进行通电切割,同时获取切割电路中的电流电压数据.实验结果表明,本文提出的方法能够有效控制所拾取碳纳米管的长度,增加碳纳米管与原子力显微镜探针的水平接触长度能够减小碳纳米管形变导致的拾取长度误差,建立的电流电压特性方程能够用于分析碳纳米管的导电性.     

Investigation of Suzuki–Miyaura catalyst‐transfer polycondensation of AB‐type fluorene monomer using coordination‐saturated aryl Pd(II) halide complexes as initiators

Novel triarylamine‐based coordination‐saturated aryl Pd(II) halide complexes ligated by PEt₃, PCy₃, and P(o‐tol)₃ were successfully synthesized by direct oxidative addition of aryl halide to the corresponding Pd(0) precursors. Suzuki–Miyaura coupling polymerization of 2‐(7‐halide‐9,9‐dioctylfluoren‐2‐yl)?1,3,2‐dioxaborinane with these Pd(II) complexes as initiators was investigated for the synthesis of poly(fluorene)s with triarylamine end group. Pd(II) complexes with PCy₃ or P(o‐tol)₃ exhibited catalytic activity and realized the catalyst‐transfer polycondensation at 75 °C and room temperature, respectively, while the polymerization using Pd(II) catalyst ligated by PEt₃ did not proceed, which indicated that the bulky phosphine ligands could facilitate the reductive elimination and further promote the polymerization. In addition, the dimeric Pd(II) complex with P(o‐tol)₃ can convert into monomeric Pd(II) intermediate with an open coordination site, which had a higher activity. The end groups of the afforded polyfluorene were analyzed by matrix‐assisted laser desorption ionization time‐of‐flight (MALDI‐TOF) mass spectrometry, in which the Ar/H end groups are indicative of the catalyst‐transfer polymerization. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1457–1463     

PN结物理特性的开放式测量实验方法研究

开放式、综合性量测实验的设计与应用,在巩固基础理论知识的同时,能够有效培养学生的动手实践能力、数据处理及分析能力,一定程度代表着大学物理实验课程的教学模式改革方向。以PN结物理特性的测量实验为例,基于通用型仪器与元器件的积木式组合,设计出简单、适用的实验电路;t=17.95℃时所采集的原始实验数据经三种模式回归分析,比较验证了PN结扩散电流与电压间遵循的玻尔兹曼分布律;计算出的玻尔兹曼常数与FD-PN-4测定仪的量测值相比,其结果说明了开放式测量实验方法的有效性。     

New soft porous frameworks based on lambda-zirconium phosphate and aliphatic dicarboxylates: Synthesis and structural characterization

New dicarboxylate-functionalized pillared materials with a general formula of λ-ZrPO₄(OH)_1-x(OOC(CH₂)_nCOO)_x/2(dmso) (n=6, 8 and 10) have been prepared by post-synthesis modification of the inorganic layers of λ-zirconium phosphate (λ-ZrP), where the superficial Chloride monovalent anionic ligands of λ-layer are partially exchanged with the divalent anionic ligands of a series of long-chain aliphatic dicarboxylic acids, namely octanedioic acid, decanedioic acid and dodecanedioic acid. The synthesized materials are characterized by X-ray diffractometry, FT-IR spectrophotometry, elemental and thermogravimetric analyses. The X-ray diffraction patterns show that the obtained solid phases are pure. Furthermore, the interlayer distance of λ-ZrP systematically increases from 1.02 to 1.59 nm as a result of the incorporation of the mentioned acids inside the interlayer gallery.     

Synthesis,Crystal Structure,and Magnetic Properties of a New Dinuclear Iron Complex with Schiff Base Ligand

A new dinuclear iron(Ⅲ) complex has been synthesized and structurally characterized by X-ray crystallography: [FeⅢ2(L)(C6H5COO)(SO4)(CH3OH)2]·CH3CN·CH3OH(1, H3 L = N,N'-bis(salicylidene)-1,3-diamino-2-propanol). Complex 1 belongs to orthorhombic space group Pna21 with a = 11.4400(8), b = 22.9705(2), c = 12.5712(9) , V = 3303.5(4) 3, Z = 4, F(000) = 1576, Dc = 1.531 g·cm–3, Mr = 761.36, μ = 1.007 mm–1, S = 1.014, the final R = 0.0505 and wR = 0.1018. The crystal packing is stabilized by intermolecular O–H···O hydrogen bonds, forming an extended one-dimensional chain structure. The temperature dependence of magnetic susceptibility measurement shows that antiferromagnetic interaction is propagated between the metal centers. Fit as dinuclear arrangement gave parameters of J = 19.7 cm-1, g = 1.89 and R2 = 0.9999.     

Experimental and theoretical assessment of Fe-doped indium-oxide-based dilute magnetic semiconductors

Specimens of iron-doped indium oxide (In_1-xFe_x)₂O₃ with x?=?0.015, 0.03, 0.045 and 0.06, amalgamated through a traditional solid-state reaction method followed by H₂/air sintering, were characterised using an X-ray diffractometer (XRD), a vibrating sample magnetometer (VSM), and a scanning electron microscope (SEM) to investigate their structural, magnetic and morphological properties respectively. According to XRD plots, all the specimens exhibit cubic bixbyite structures along with ancillary phases. Magnetic assessment showed that In₂O₃ has a negative susceptibility, exhibiting diamagnetic behaviour at room temperature. The doping of Fe ions induces ferromagnetic (FM) ordering, which is enhanced with increasing doping content. The strength of the magnetisation increases when the specimens are exposed to H₂ but is reduced on further air sintering. A bound magnetic polaron (BMP) model is successfully fitted to the observed FM data involving localised carriers and magnetic cations. A multivariate assessment viz. a hierarchical cluster analysis (HCA) was used to corroborate and strengthen the experimental determined magnetic properties. A homogeneous particle distribution was observed in all SEM micrographs and is validated through MATLAB-based simulation by applying a watershed segmentation algorithm. Surface plots also confirm the change in magnetic properties with increase in doping concentration.     

Novel flame retardant paint based on Co(II) and Ni(II) metal complexes as new additives for surface coating applications

The study is focused on the synthesis of a new Co(II) and Ni(II) metal complexes, which is synthesized by the reaction of the isatin 4‐aminoantipyrine Schiff base ligand with selected divalent Co(II) and Ni(II) ions and their possible applications as flame retardant additives in paint formulations for surface coating application. The prepared metal complexes were characterized using a combination of Fourier transform infrared, elemental analysis, proton nuclear magnetic resonance, ¹³C‐NMR spectra, and mass spectroscopy. The prepared Schiff base ligand metal complexes were physically added to alkyd paint formulation to give coating formulations at a laboratory scale and then applied onto plywood and steel panels using a brush. The ignitability and oxygen index values obtained indicated that the paint which contained the prepared Co(II) and Ni(II) metal complexes as additives exhibited very good flame retardant. The physical and mechanical characteristics of the coatings were studied in order to estimate any disadvantages due to the incorporation of the additives. It was discovered that the added substances did not impact the hardness, flexibility, and adhesion of the prepared coating films. The gloss of the paint formulation film was improved due to the incorporation of the aromatic ring into the formulation and the level of the oil percent.     

Enhanced Performance of Organic/Inorganic Hybrid Nanomaterials bearing Impregnated [PdL2] Complexes as Counter‐Electrode Catalyst for Dye‐Sensitized Solar Cells

N‐coordinate Pd²⁺ complexes [PdL₂] (L: N‐N‐quinoline‐8‐yl‐R‐benzenesulfonamides) ( 6–10 ) and [PdL₂] complexes assembled on multi‐wall carbon nanotubes (MWCNTs) hybrid nanomaterials were fabricated and characterized by various techniques. The [PdL₂] impregnated MWCNTs materials ( 11–15 ) were applied as a counter electrode (CE) catalyst for triiodide to iodide reduction reaction in the dye‐sensitized solar cells (DSSC) and investigated electro‐catalytic activities. The MWCNTs‐supported [PdL₂] CEs ( 11–15 ) are exhibits as Pt‐free CE with good power conversion efficiencies (PCEs), and compared to platinum and bare MWCNTs CEs and the PCE of bare MWCNTs was clearly improved by means of [PdL₂] complexes ( 6–10 ). The DSSCs based on the hybrid counter electrodes (CEs) ( 11–15 ) and bare MWCNTs are indicated a relative efficiency ( ? _rel ) of 64.27%, 54.07%, 53.75%, 51.52% 44.82% and 27.27% concerning a Pt CE control device set at 100%. The report emphasizes that [PdL₂] impregnated MWCNTs type counter electrodes (CEs) ( 11–15 ) are promising as effectively catalyst in working device design, particularly taking into account the eco‐friendly approach of the hybrids.     

In vitro anti‐proliferative and in silico docking studies of heteroleptic copper(II) complexes of pyridazine‐based ligands and ciprofloxacin

Three heteroleptic copper(II) complexes of the type [Cu(L^1–3)(cf)(ClO₄)] ( 1 – 3 ), where cf = ciprofloxacin, have been synthesized using pyridazine‐based ligands 3‐chloro‐6‐(salicylidenehydrazinyl)pyridazine (HL¹), 3‐chloro‐6‐(4‐diethylaminosalicylidenehydrazinyl)pyridazine (HL²) and 3‐chloro‐6‐(5‐bromosalicylidenehydrazinyl)pyridazine (HL³). Electronic spectral data and magnetic moment values suggest octahedral geometry for the synthesized copper(II) complexes. Electrochemical data of the copper(II) complexes present an irreversible one‐electron reduction wave in the cathodic potential region (E_pc) between ?0.631 and ?0.670 V. Frontier molecular orbital calculations were carried out, and the obtained low‐energy gap supports the bio‐efficacy of the complexes. All the complexes were screened for their in vitro cytotoxicity activity against three human cancerous (breast adenocarcinoma (MCF‐7), hepatoma (HepG‐2) and cervical (HeLa)) and one non‐cancerous (non‐tumorigenic human dermal fibroblast (NHDF)) cell lines using MTT assay, in which complex 2 exhibited higher activity. The apoptosis induction by the complexes was analysed using the Hoechst dye staining method with MCF‐7 cell line, which indicates higher apoptotic activity of complex 2 . A molecular docking study was carried out to ascertain the binding affinity of the synthesized heteroleptic copper(II) complexes with phosphoinositide 3‐kinase gamma (PI3Kγ) receptor.     

Finite‐size corrections at the hard edge for the Laguerre β ensemble

A fundamental question in random matrix theory is to quantify the optimal rate of convergence to universal laws. We take up this problem for the Laguerre β ensemble, characterized by the Dyson parameter β, and the Laguerre weight , in the hard edge limit. The latter relates to the eigenvalues in the vicinity of the origin in the scaled variable . Previous work has established the corresponding functional form of various statistical quantities—for example, the distribution of the smallest eigenvalue, provided that . We show, using the theory of multidimensional hypergeometric functions based on Jack polynomials, that with the modified hard edge scaling , the rate of convergence to the limiting distribution is , which is optimal. In the case , general the explicit functional form of the distribution of the smallest eigenvalue at this order can be computed, as it can for and general . An iterative scheme is presented to numerically approximate the functional form for general .