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.     

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。     

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.     

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.     

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。     

Infrared Absorption Study of Some Cyclic Ureas,Cyclic Thioureas and Their N,N′-Dialkyl Derivatives

Abstract

In his communication on the detection limits for thermal emission spectroscopy of metallic species in flame media, Fassel (¹) attacks our previous statement that detection limits for Al, Be and Mo were available only for turbulent oxygen-supported hydrogen or acetylene flames. It should be borne in mind that he was referring to a preliminary communication (²) which naturally does not carry an extensive bibliography. It should also be noted that we were concerned, in context, with a comparison of the separated flame with conventional flames, not with highly unconventional flames such as those to which he refers. Whilst the point with which he takes issue was a very minor one, incorporated in our preliminary communication mainly as an “aside”, we firmly disagree with his observation. The flame he refers to (³) (⁴) is, in fact, a diluted oxy-acetylene flame which is supported by venting some air (and therefore nitrogen) to dilute the fuel-oxygen mixture. Fassel's communication (¹) erroneously refers to this as a 'premixed oxy-acetylene flame', whereas elsewhere (⁵) it is described more correctly as an oxygen-nitrogen-acetylene flame. The burner he long-pathlength carbonaceous flames (¹⁰). They also allow more sensitive molecular emission spectroscopy of sulphur in an air-hydrogen flame (¹¹), etc. We hope that this unfortunate correspondence will not distract attention from the main issue of our previous or previous preliminary communication on the separated nitrous oxide-acetylene flime.     

Verhältnis des differentiellen (e,N)- zum totalen (γ,N)-Wirkungsquerschnitt

The ratio of the differential cross section for the (e, N)-process to the total (γ,N) -cross section is derived with the use of the relativistic Coulomb Eigenfunctions for the continuous spectrum. For electric and magnetic dipole transitions the Born approximation, the Coulomb correction, the effect of screening and that of finite nuclear size are calculated. In this angular distribution there should be no interference of electron waves scattered by different multipoles, where the inelastically scattered electrons are detected. Numerical calculations have been done for nuclei withZ=6, 29, and 82 and scattering anglesθ=1Ω, 132Ω, 160Ω and 180Ω of the electron. The result of this theory is compared with the experiments of W.C.Barber et al.     

Infrared Spectroscopic Study of N,N‐Dimethylthioformamide Complexes of the Hofmann Type

Four new Hofmanntype complexes, M(DMTF)₂Ni(CN)₄, (where DMTF is dimethylthioformamide, M=Mn, Cd, Co, or Ni) were synthesized and their structure was determined by an elemental analysis and infrared spectroscopy. The IR spectra of DMTF and its nickel tetracyanine complexes with Mn(II), Cd(II), Co(II), and Ni(II) have been investigated within the range 4000–400 cm^–1. The frequency shifts in the metal complexes agree with the assignment of the CS and CN frequencies. The complexes consist of infinite planar polymer layers of |MNi(CN)₄|. Ndimethylthioformamide is coordinated to this layer from above and below; it is a monodentate ligand and is Sbonded through the metal atom in these complexes.     

Synthesis of hydantoins via N,N′-ureas derived from polymer-bound amino acids

Starting from carboxy-linked amino acids on trityl functionalized polystyrene resin a highly efficient solid-phase synthesis of hydantoins via N, N-ureas was elaborated. The polymer-bound hydantoins can be used as scaffolds for further combinatorial transformations, such as alkylation. Cleavage from the resins yielded the corresponding hydantoins in good yields and purities as shown by ESI-MS and HPLC.     

N,N′-二芳基乙二胺的一锅法绿色合成

以芳胺、乙二醛和硼氢化钠为原料,一锅法合成了3种N,N′-二芳基乙二胺,以高于80%的产率得到相应产物,结构均通过核磁氢谱和碳谱表征。与分步法相比,该方法具有操作简单、反应产率高、对环境友好无污染等优点,是一种绿色高效的合成方法。     

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.     

Qweak, N → Δ, and physics beyond the standard model

The data-taking phase of the Qweak experiment ended in May of 2012 at the Thomas Jefferson National Accelerator Facility. Qweak aims to measure the weak charge of the proton, Q _W ^p , via parity-violating elastic electron-proton scattering. The expected value of Q _W ^p is fortuitously suppressed, which leads to an increased sensitivity to physics beyond the Standard Model.     

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.     

基于第一原理拟合Ti,Si,N原子间作用势

为了实现对Ti-Si-N纳米薄膜的原子尺度仿真,本文根据第一原理计算结果,采用Morse势对Ti,Si,N之间作用势进行拟合,并利用TiN二维拉伸模型进行验证。拟合结果表明,采用简单作用势拟合第一原理结果,此方法简单有效,为将来对Ti-Si-N纳米复合材料的仿真奠定了基础。