超声波辐照下N,N,N’,N’-四甲基二氨基二苯 甲烷的合成研究

本文报道了Ｎ,Ｎ,Ｎ’,Ｎ’－四甲基二氨基二苯甲烷的催化合成反应研究,讨论了超声空化场对氨基苯磺酸和阴离子表面活性剂等条件对该反应的催化作用。     

Electric field-induced hole injection-enhanced photoluminescence in a N,N’-bis(3-methylphenyl)-N,N’-bis(phenyl)-benzidine-based emitter

Non-monotonic, asymmetrical electric field dependence of photoluminescence （PL） intensity is observed in a mono- layer sample of tris-（8-hydroxyquinoline） aluminum （A1Q） doped N,N＇-bis（3-methylphenyl）-N,N＇-bis（phenyl）-benzidine （TPD）. A possible model is proposed： the charge separation from the dissociated photoexcited excitons causes energy band bending in the organic films and improves the hole injection from the electrode, which brings about the extra fluorescence. This mechanism is further verified by a series of experiments using a series of samples, variously featuring symmetrical electrodes, block layers, and hosts with lower hole mobilities.     

Birkhoff’s Polytope and Unistochastic Matrices,N = 3 and N = 4

The set of bistochastic or doubly stochastic N×N matrices is a convex set called Birkhoff’s polytope, which we describe in some detail. Our problem is to characterize the set of unistochastic matrices as a subset of Birkhoff’s polytope. For N=3 we present fairly complete results. For N=4 partial results are obtained. An interesting difference between the two cases is that there is a ball of unistochastic matrices around the van der Waerden matrix for N=3, while this is not the case for N=4.     

Vibrational Spectroscopic and Theoretical Studies of Urea Derivatives with Biochemical Interest: N,N′-Dimethylurea,N,N,N′,N′-Tetramethylurea,and N,N′-Dimethylpropyleneurea

Abstract

Mid-infrared, far-infrared, and Raman vibrational spectroscopic studies were combined with density functional theory (DFT) calculations and normal coordinate force field analyses for N,N′-dimethylurea (DMU), N,N,N′,N′-tetramethylurea (TMU), and N,N′-dimethylpropyleneurea (DMPU: IUPAC name 1,3-dimethyltetrahydropyrimidin-2(1H)-one). The equilibrium molecular geometry of DMU (all three conformers), TMU, and DMPU and the frequencies, intensities, and depolarization ratios of their fundamental infrared (IR) and Raman vibrational transitions were obtained by DFT calculations. The vibrational spectra were fully analyzed by normal coordinate methods as well. A starting force field for DMPU was obtained by adapting corresponding force constants for DMU and TMU, resulting after refinements in the stretching force constants C=O (7.69, 7.30, 7.68 N·cm^?1), C–N (5.16, 5.55, 5.05 N·cm^?1), and C-Me (5.93, 4.00, 4.22 N·cm^?1) for DMU, TMU, and DMPU, respectively. The dominating conformer of liquid DMU was identified as trans-trans, strong intermolecular hydrogen bonding was verified in solid DMU, and weak dipole–dipole association was found in liquid TMU and in DMPU. Special attention was paid to analyzing the methyl group frequencies, which revealed deviations from local C_3v symmetry. A linear correlation was found between the CH stretching force constants and the inverse of the CH bond lengths (1/r ²). The averaged NH stretching frequencies of gaseous, dissolved, and solid urea and of DMU, with variations for hydrogen bonding of different strength, are linearly correlated to the NH stretching force constants. Characteristic skeletal vibrations were assigned for a broad variety of urea derivatives and also for pyrimidine derivatives, which all contain the N₂C=O entity. The very strong IR bands of C=O stretching (1,676 ± 40 cm^?1) and asymmetric CN₂ stretching (1,478 ± 60 cm^?1), and the very intense Raman feature of symmetric CN₂ stretching or ring breathing (757 ± 80 cm^?1), can be recognized as fingerprint bands also for the pyrimidine derivatives cytosine, thymine, and uracil, which all are nucleobases in DNA and RNA nucleotides.     

N,N’-邻硝基苯酰基取代苯酰氨基硫脲类化合物的特征红外光谱

研究了N,N’-邻硝基苯酰基取代苯酰氨基硫脲类化合物的芳环、碳硫双键和酰胺等的特征红外光谱,讨论了它们随化学结构而变化的一些规律,特别详细讨论了不同取代基对远程基团特征光谱的影响。结果表明距离取代基直至第五个基团的特征谱带仍然受到影响,并且供电子基所处位置对远程基团特征光谱影响较少,而吸电子基所处的位置影响较大。这对该类化合物和远程光谱的研究是很有启发意义的。     

原子—分子离子反应N‘＋NH^＋（0,0）→N＋N’H＋（v‘,j’）的研究

由多体项展式法导出（ＮＮＨ）＾＋分子离子绵势能函数，用准经典轨线法研究了原子－分子离子反应Ｎ′＋ＮＨ＾＋（０，０）→Ｎ＋Ｎ′Ｈ＾＋（ｖ′，ｊ′）。结果表明，该反应为热中性有阈能的直接交换反应，阈能约为４８ｋｃａｌ／ｍｏｌ。依据对势能面的分析合理地解析了反应机理。     

Synthesis and Spectroscopic Studies of 3,6-Diphenyl-2,5-Dihydropyrrolo[3,4-C]Pyrrole-1,4-Dion’s N,N’-Dialkyl Derivatives

3,6-diaryl-2,5-dihydro-1,4-diketopyrrolo[3,4-c]pyrrole-1,4-dione (DPPD) derivatives are used commercially as red pigments, because of their color strength, brightness, and very low solubility in most common solvents. These products, although highly colored, appear to be of limited value as dyes, since they show a tendency to form an aggregate when incorporated into a solvent. Monoalkyl and dialkyl derivatives of DPPD were synthesized and then characterized with IR, ¹HNMR, UV-Vis absorption and emission spectroscopy. Molar absorption coefficient, singlet energy level and Stokes’ shift values of DPPD derivatives were declared. Monoalkyl and dialkyl derivatives of DPPD’s solubilities were measured from saturated solutions of dimethylformamide (DMF), tetrahydrofuran (THF), dichloromethane (DCM), acetonitrile (ACN) and toluene and they are compared with each other.     

光致变色Schiff碱N,N’-双(水杨醛缩)-1,2-环己二胺的荧光光谱

用稳态和时间分辨荧光光谱研究了Ｎ,Ｎ’ 双水杨醛缩 １,２ 环己二胺（Ｎ,Ｎ’ ｂｉｓ（ｓａｌｉ ｃｙｌｉｄｅｎｅ） １,２ ｃｙｃｌｏｈｅｘａｎｅｄｉａｍｉｎｅ,ＢＳＣ）在固态和四氯化碳、氯仿溶液中的光致变色行为。发现经过光照,ＢＳＣ的荧光光谱发生了明显、快速的改变,并且光致变色过程可重复进行。     

Circular Dichroism and Conformation of Bilirubin Bis N,N, N-Trimethyl α-Phenethylammonium Salts

Analysis of the bisignate circular dichroism spectra of bilirubin-IXα bis-propionate salts of (S)-(-)-N, N, N-trimethyl α-phenethylammonium hydroxide reveals a preference in CHC1₃, (CH₃)₂ CO and CH₃ CN solvents for folded conformations in which the propionate groups are intramolecularly H-bonded to the opposing pyrromethenone units.     

Organic insulator layer influence on the electrical properties of N,N’-di (2-ethylhexyl) - 3, 4, 9, 10-perylene diimide organic thin-film transistors: Experiment and modeling

In this work, n- type organic thin film transistors (OTFTs) based on different kinds of organic dielectrics were fabricated, characterized and theoretically investigated. Three kinds of organic insulators were applied as dielectric gate which are: divinyl tetramethyl disiloxane-bis (benzo-cyclobutene) (BCB), poly(vinylalcohol) (PVA) and poly (4-vinyl phenol) (PVP). Analytical model was applied to describe the electrical behavior of the fabricated OTFTs and to explain the absence of saturation of the drain current for the device based on PVA dielectric. In addition, Meyer–Neldel rule-grain boundary model was applied for the calculation of total resistance of OTFTs based on different dielectrics materials. The theoretical results of output characteristics and total resistance showed an excellent agreement with the experimental measurements. The experimental and theoretical calculations revealed that the n-channel OTFTs based on BCB as an insulator layer exhibited superior electrical characteristics in terms of threshold voltage, mobility and drain current compared with the devices based on PVA and PVP as a gate insulator layer. The device based on BCB organic insulator layer has the largest mobility of 4?×?10^?3 cm² V^?1 s^?1, the smallest leakage current relative to the devices based on PVA and PVP. While, the device fabricated with PVP organic insulator gate has a large trap density on the PVP-EHPDI interface which causes a pronounced decrease in field effect mobility and consequently drain current.     

Poincaré, Einstein,et l’inertie de l’énergie

The mystery surrounding the discovery of the inertia of energy is solved by considering its connection with an older problem: the effect of uniform, global motion on the forces acting in an electric System. From Maxwell's and his disciples’ point of view this effect confirmed the existence of the ether. From Poincaré’ s point of view, it was paradoxical for it contradicted the relativity principle and went with a violation of the principle of reaction. The inertia of energy, as Einstein proposed it in 1905, answered these paradoxes in the framework of special relativity and in Poincaré’s style of reasoning.     

Theoretical study on structures of Ga3N, GaN3, Ga3N2 and Ga2N3 clusters

The structures of Ga_3N, GaN_3, Ga_3N_2 and Ga_2N_3 clusters are studied using the full-potential linear-muffin-tin-orbital molecular dynamics (FP-LMTO MD) method. Four structures for Ga_3 N, five structures for GaN_3, nine structures for Ga_3N_2 and nine structures for Ga_2N_3 have been obtained. The most stable structures of these clusters are planar ones. A strong dominance of the N－-N bond over the Ga－-N and Ga－-Ga bonds appears to control the structural skeletons, supporting the previous result obtained by Kandalam and co-workers. The most stable structures of these small GaN clusters displayed semiconductor-like properties through the calculation of the HOMO－LUMO gaps.     

Fluorescence of N,N′-dimethylaminobenzonitrile in polyvinyl alcohol stretched films

We have demonstrated that the conditions of the charge-transfer (CT) reaction in the N,N′-dimethylaminobenzonitrile (DMABN) molecule in polyvinyl alcohol (PVA) polymer matrices can be considerably changed upon their stretching deformation. The fluorescence spectrum of DMABN in PVA has two characteristic bands in the ultraviolet (UV) and visible spectral ranges, which indicates that a CT reaction proceeds in the excited state. Stretching leads to a strong decrease in the intensity of the UV band, the contribution of which in undeformed samples is comparable with the emission in the violet range. Even single stretching PVA films strongly reduces the emission intensity of the UV band, with this effect being dramatically enhanced upon sixfold stretching. In the latter case, The fluorescence spectrum is characterized by a strong CT band, the relative intensity of which is 3.5 times higher than even in a strongly polar aprotic solvent, such as acetonitrile. The obtained data indicate that, as a result of mechanical stretching, it becomes possible to change basic intermolecular factors that affect the CT rate in PVA samples.     

SAC-CI方法研究甲基乙烯基硅酮分子激发态1 1A’’, 1 1A’, 2 1A’’结构与性质

采用对称性匹配簇/组态相互作用(symmetry adapted cluster－configuration interaction, SAC－CI)方法, 在6-311++g**基组水平上优化了甲基乙烯基硅酮分子的前三个单激发态1 1A’’, 1 1A’, 2 1A’’的平衡几何结构, 比较三个激发态的电荷分布, 最高占据轨道, 最低空轨道, 能隙等结构特性. 研究发现, 1 1A’ 态能隙差最小, 电子容易发生跃迁. 计算了三个单重激发态相应的振动光谱, 得出其振动模式. 从甲基乙烯基硅酮分子激发态结构特性, 电荷分布, 极强位置振动模式等方面分析了其断键机制.     

Bell’s inequality, Einstein, Podolsky, Rosen arguments and von Neumann’s projection postulate

This paper is devoted to analysis of the role of projection postulate in Einstein, Podolsky, and Rosen-EPR [1] argument against completeness of QM. It will be shown that the EPR considerations do not match with von Neumann’s quantum measurement theory (QMT). The root of EPR’s conclusion on incompleteness of QM is the misuse of von Neumann’s projection postulate. EPR applied this postulate to observables with degenerate spectra (which is totally forbidden by von Neumann’s axiomatics of QM). Consequences for Bell’s inequality and quantum information theory are analyzed. This paper might stimulate discussion on the role of projection postulate in quantum information theory, especially quantum cryptography and teleportation.     

Effects of long-wavelength fluorescence excitation in N, N′-dimethylaminobenzonitrile liquid solutions

We have studied the properties of the emission, absorption, and excitation of dual fluorescence of N,N??-dimethylaminobenzonitrile in a set of solvents of different polarity under selective irradiation of solutions by light with different energies of quanta in the range of the long-wavelength absorption band. In all cases, dual fluorescence is observed, which is caused by emission from locally excited Franck-Condon and charge-transfer states. A change in the energy of excitation quanta has no effect on the position of the fluorescence bands; however, the intensity ratio between the bands noticeably changes in favor of the intensity of the long-wavelength band, which belongs to the charge-transfer state. To explain the observed effects, we involve data of quantum-mechanical calculations, which show that there is a considerable probability of occurrence in solutions of these systems of rotational isomers that differ in the orientation of the dimethylamino group with respect to benzonitrile. In the excited state, these rotamers have different charge-transfer reaction rates, which leads to a change in the intensity ratio of the observed fluorescence bands upon using the selective excitation.     

N,N—二甲基苯胺^1H核磁共振溶剂效应的研究

本文研究了Ｎ，Ｎ－二甲基苯胺分子在环已烷和苯混合溶剂中的＾１ＨＮＲＭ谱的溶剂效应，观察到Ｎ，Ｎ－二甲基苯胺分子内的两个甲基和混合溶剂的苯－环已烷的化学位移随苯的摩尔分数增加而逐渐移向高场，ＡＳＩＳ值随苯的摩尔分数增加而增加。得到了所有化学位移植和ＡＳＩＳ值与苯的摩尔分数呈线性关系，尝试用溶剂化作用解释了苯对Ｎ，Ｎ－二甲基苯胺的ＡＳＩＳ效应。     

Lie Symmetries of Einstein’s Vacuum Equations in N Dimensions

Abstract

We investigate Lie symmetries of Einstein’s vacuum equations in N dimensions, with a cosmological term. For this purpose, we first write down the second prolongation of the symmetry generating vector fields, and compute its action on Einstein’s equations. Instead of setting to zero the coefficients of all independent partial derivatives (which involves a very complicated substitution of Einstein’s equations), we set to zero the coefficients of derivatives that do not appear in Einstein’s equations. This considerably constrains the coefficients of symmetry generating vector fields. Using the Lie algebra property of generators of symmetries and the fact that general coordinate transformations are symmetries of Einstein’s equations, we are then able to obtain all the Lie symmetries. The method we have used can likely be applied to other types of equations.