石墨烯纳米网电导特性的能带机理：第一原理计算

通过第一原理电子结构计算来研究有序多孔纳米网的电导特性变化的能带机理.能带结构分析结果表明:石墨烯纳米网超晶格(3m,3n)(m和n为整数)的电子本征态在布里渊区中心点发生四重简并;碳空位孔洞规则排列形成的石墨烯纳米网具有由简并态分裂形成的宽度可调带隙,无论石墨烯的两个子晶格是否对等.在具有磁性网孔阵列的石墨烯纳米网中,反铁磁耦合使对称子晶格的反演对称性增加了一项量子限制条件,导致能带结构在K点的二重简并态分裂成带隙.通过控制网孔密度能够有效调节石墨烯纳米网的带隙宽度,为实现新一代石墨烯纳米电子器件提供了理论依据.     

Second harmonic magnetoacoustic responses of magnetic nanoparticles in magnetoacoustic tomography with magnetic induction

Due to the unique magnetic, mechanical and thermal properties, magnetic nanoparticles(MNPs) have comprehensive applications as the contrast and therapeutic agents in biomedical imaging and magnetic hyperthermia. The linear and nonlinear magnetoacoustic responses determined by the magnetic properties of MNPs have attracted more and more attention in biomedical engineering. By considering the relaxation time of MNPs, we derive the formulae of second harmonic magnetoacoustic responses(2H-MARs) for a cylindrical MNP solution model based on the mechanical oscillations of MNPs in magnetoacoustic tomography with magnetic induction(MAT-MI). It is proved that only the second harmonic magnetoacoustic oscillations can be generated by MNPs under an alternating magnetic excitation. The acoustic pressure of the 2H-MAR is proportional to the square of the magnetic field intensity and exhibits a linear increase with the concentration of MNPs. Numerical simulations of the 2H-MAR are confirmed by the experimental measurements for various magnetic field intensities and solution concentrations using a laser vibrometer. The favorable results demonstrate the feasibility of the harmonic measurements without the fundamental interference of the electromagnetic excitation, and suggest a new harmonic imaging strategy of MAT-MI for MNPs with enhanced spatial resolution and improved signal-to-noise ratio in biomedical applications.     

Ultrasound-assisted immersion freezing reduces the structure and gel property deterioration of myofibrillar protein from chicken breast

The effects of air freezing (AF), immersion freezing (IF) and ultrasound-assisted immersion freezing (UF) at different power levels (125, 165, 205 and 245 W) on the structure and gel properties of the myofibrillar protein (MP) of chicken breast were investigated. UF at 165 W (UF-165) had no obvious negative impact on the primary structure of the MP and effectively reduced the change in the secondary and tertiary structure. In addition, UF-165 significantly reduced the losses in the elastic modulus (G′), gel strength, and gel water holding capacity (P < 0.05). According to low field nuclear magnetic resonance analysis, the T₂₁ and T₂₂ of the UF-165 MP gels were shorter than those of the AF and IF samples, which meant that the UF-165 reduced the mobility of the immobilized water and free water in MP gel. A scanning electron microscopy analysis showed that the appropriate ultrasonic power promoted the formation of a compact and homogeneous protein gel network. These results suggested that the appropriate ultrasonic power maintained the MP structure and reduced the loss of gel quality.     

新郑西亚斯东周玉器材料属性与加工工艺的科技分析

中国玉文化源远流长，治玉工艺经过各个时代的不断发展和完善，在一定程度上能反映古代社会生产力发展水平及文化、贸易、技术交流等信息。利用能量色散型X射线荧光光谱（EDXRF）、激光拉曼光谱（LRS）、超景深光学显微系统（OM）等分析技术，结合硅胶覆膜微痕复制技术，对河南省新郑西亚斯东周墓地出土的一批玉器进行科技分析。首先利用化学成分和物相结构分析技术确定了玉器材质的矿物属性，其次利用显微分析技术表征了玉器表面及穿孔内部和印模的加工痕迹，特别是阴刻纹饰和穿孔微痕特征，最后探讨了玉器样品的材料属性和加工工艺两者之间的联系。化学成分和物相结构分析结果表明，所分析的西亚斯东周玉器材质丰富，主要矿物组成有滑石、透闪石、水晶、云母等。玉器表面纹饰微痕特征分析表明，所分析玉器阴刻工艺采用了两种加工工具，分别是砣具和手持硬质工具。穿孔微痕分析特征表明，钻孔包括单面钻孔和双面/多面钻孔两种方式，钻孔工艺则有实心钻、管钻等。部分玉器钻孔形状和内部微痕特征表明，尽管均采用了实心钻工艺，但所采用的实心钻头在形状上存在差异，同时，也存在是否配合解玉砂进行钻孔的差异。不同材料属性的玉器采用了不同的加工工艺。滑石质玉器，莫氏硬度1，器型主要为玉片饰，其表面阴刻纹饰主要采用手持硬质工具进行刻画，钻孔主要采用了双面钻孔方式，并使用了实心钻头未添加解玉砂进行加工，钻头形状可能为圆锥状；云母质玉器，莫氏硬度2~3，器型主要为玉玦片饰，纹饰采用了砣具添加解玉砂的加工工艺，钻孔方式为单面钻孔，采用了管钻工艺。透闪石型玉器，莫氏硬度5~6，器型主要为玉片饰，表面纹饰采用砣具配合解玉砂砣刻，以双面钻孔的方式为主，钻孔工艺为实心钻头配合解玉砂工艺，钻头形状与滑石类样品一致，为圆锥状。水晶质玉器，莫氏硬度7，均为珠饰，表面无纹饰，钻孔方式为双面/多面钻孔，钻孔工艺为实心钻配合解玉砂工艺，且钻头可能为圆柱形。研究结果表明，玉器表面纹饰所采用的阴刻工艺和钻孔工艺，与玉器本身的材料属性、器型等存在密切关系。     

O-Alkyldithiophosphate Nickel Complexes with dcpf Ligand as Efficient Electrocatalysts for Hydrogen Evolution

Six new O-alkyldithiophosphate nickel complexes with dcpf ligand, [(dcpf)Ni(S₂P{O}OR)] (dcpf = 1,1′-bis (dicyclohexylphosphino)ferrocene, R = CH₃ ( 1 ), CH₃CH₂ ( 2 ), Ph ( 3 ), 4-MeC₆H₄ ( 4 ), PhCH₂ ( 5 ) and PhCH₂CH₂ ( 6 )), have been synthesized by the treatment of dcpf with ((RO)₂PS₂)₂Ni in satisfactory yields. These complexes were characterized by elemental analysis, spectroscopy (FTIR, UV–vis, ¹H, ¹³C, and ³¹P NMR), thermogravimetric analysis and single crystal X-ray diffraction. The nickel atom in 1 , 2 ·CH₂Cl₂, 3 ·CH₂Cl₂, 4 ·2CH₂Cl₂·THF, and 2( 5 )·hexane adopts a slightly distorted square-planar coordination environment finished by two phosphorus atoms of dcpf ligand and two sulfur atoms of O-alkyldithiophosphate ligand. Furthermore, the electrochemical properties for complexes 1 – 6 were also investigated by cyclic voltammetry. With the addition of 120 mM trifluoroacetic acid (TFA), the turnover frequency (TOF) values for 1 – 6 are estimated to be 1243.83, 1046.54, 1331.71, 2545.29, 1899.03, and 1191.37 s⁻¹, with the overpotential (η) values of 0.62, 0.58, 0.71, 0.67, 0.60, and 0.56 V, respectively. The result of electrochemical studies indicates that all complexes can be used as efficient molecular eletrocatalysts for the reduction of protons to hydrogen in the presence of TFA in MeCN.     

Atomic Hydrogen Induced Chemical Vapor Deposition of Silicon Oxycarbide Thin Films Derived from Diethoxymethylsilane Precursor

Amorphous silicon oxycarbide (a-SiOC:H) films produced by remote plasma RPCVD from diethoxymethylsilane (DEMS) were characterized in terms of their basic properties related to the coatings deposited using conventional plasma enhanced PECVD method. The effect of substrate temperature (T_S) on the growth rate, chemical composition, structure, and properties of resulting a-SiOC:H films is reported. Film growth is an adsorption-controlled process, wherein two mechanisms can be distinguished with a transition at about T_S=70°C. Depending on the temperature, films of different nature can be obtained, from polymer-like to highly crosslinked material with C-Si-O network. The chemical structure of a-SiOC:H films was characterized by FTIR, ¹³C and ²⁹Si solid-state NMR, and X-ray photoelectron spectroscopes. The a-SiOC:H films were also characterized in terms of their density, refractive index, surface morphology, conformality of coverage, hardness, adhesion to a substrate, and friction coefficient. The films were found to be morphologically homogeneous materials exhibiting good conformality of coverage and small surface roughness. Their refractive index exhibits anomalous effect revealing a minimum value at T_S=125°C. Due to their exceptional physical properties a-SiOC:H films produced by RPCVD from DEMS precursor seems to be useful as potential dielectric materials or coatings for various encapsulation applications.     

Chirality and Magnetic Properties of One-dimensional Ln (Ln = Gd,Dy) Polymers

The usage of the achiral ligand, in lanthanide chemistry, successfully obtained two series of chiral lanthanide complexes, formulated d - and l -{Gd[IN][HIN][CH₂OCH₂O]}_n (abbreviated as Gd ) and d - and l -{Dy[IN][HIN][CH₂OCH₂O]}_n (abbreviated as Dy , HIN = isonicotinic acid). Crystallographic researches determined that four compounds are all one-dimensional (1D) chain structures and crystallized in a chiral space group. In addition, CH₂OHCH₂OH acts as not only solvent but also the bridge ligand. Besides, single crystal circular dichroism (CD) spectra conformed compounds Gd-_L and Gd-_D , Dy-_L and Dy-_D are enantiomers respectively. Magnetically, compound Gd showed predominant magnetocaloric effect (MCE) of 26.20 J · kg^–1 · K^–1 at 2.5 K for ΔH = 7 T, while there is ferromagnetic interactions in compound Dy .     

Various solution methods,accompanied by dynamic investigation,for the same problem as a means for enriching the mathematical toolbox

A geometrical task is presented with multiple solutions using different methods, in order to show the connection between various branches of mathematics and to highlight the importance of providing the students with an extensive ‘mathematical toolbox’. Investigation of the property that appears in the task was carried out using a computerized tool.     

Synthesis of Heat-resistant Polymers by Thiol–Ene Reaction of N-Allylmaleimide Copolymers Using Glycoluril Crosslinkers with Rigid Molecular Structures

We carried out the thermal curing of the copolymers of N-allylmaleimide (AMI) and 2-ethylhexyl acrylate (2EHA) using 1,3,4,6-tetra(2-mercaproethyl)glycoluril ( G1 ), 1,3,4,6-tetra(3-mercaptopropyl)glycoluril ( G2 ), 1,3,4,6-tetraallylglycoluril ( G3 ), triallylisocyanurate (TAIC), and pentaerythritol tetrakis(3-mercaptobutyrate) (PEMB) as the crosslinkers. Based on the results for the analysis of thiol–ene reactions monitored by IR spectroscopy, it was confirmed that the curing rate significantly depended on the combination of the used crosslinkers. The insoluble fraction after curing was more than 90% for the systems using the glycoluril crosslinkers, while the conversion of the allyl groups was suppressed due to the rigid structure of these crosslinkers. The heat resistance and the mechanical properties of the crosslinked polymers were investigated by thermogravimetric analysis, differential scanning calorimetry, dynamic mechanical analysis, and mechanical tensile tests. For the products cured using the glycoluril crosslinkers, the glass transition temperature (T_g) and the maximum temperature of thermal decomposition (T_max) were 54–59 °C and 395–409 °C, respectively, being higher than those for the cured product prepared with PEMB and TAIC as the conventional crosslinkers. The elasticity (75–139 MPa), the maximum strength (3.0–4.1 MPa), and the adhesion strength (6.7–10.7 MPa) for the polymers cured with the glycoluril crosslinkers, determined by the mechanical tensile and single lap-shear adhesion tests, were higher than those for cured materials produced with PEMB. Thus, the thermal and mechanical properties of the maleimide copolymers were efficiently enhanced by crosslinking using the rigid glycoluril compounds. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 923–931