FT-IR analysis of single human normal and leukemic lymphocytes

The infrared spectra of single human normal and leukemic lymphocytes have been obtained by means of the microscope-FT-IR system. Substantial differences between the two kinds of cells have been observed at level of the O-P-O vibrations of the DNA and of the proteic components. This determination opens up the possibility in determining the early stages of leukemia, in following the course of patients under therapy, and in evaluation of the residual neoplastic disease.     

A theoretical study on the molecular structure and vibrational (FT-IR and Raman) spectra of a new organic–inorganic compound of 2[N(C3H7)4]SbCl4

The salt bis-tetrapropylammonium tetrachloroantimonate (III) is crystallized in the monoclinic system with the P2₁/c space group. The unit cell dimensions are: a = 18.1973(5) Å, b = 15.7225(4) Å, c = 13.6491(3) Å, β = 91.65(1)° and Z = 4. The vibrational spectra have been measured at room temperature by FT-infrared spectroscopy (4000–400 cm⁻¹) on polycrystalline samples, and by FT-Raman spectroscopy (3500–30 cm⁻¹) on monocrystals. The structure of the 2[N(C₃H₇)₄]SbCl₄ formed by two types of cations (C₃H₇)₄N⁺ and two types of anions [SbCl₄]⁻ was optimized by density functional theory (DFT) using the B3LYP method. Actually the values obtained by the B3LYP/LanL2MB basis with the aid of a calculation of the potential energy distribution (PED) are in good agreement with the experimental data. A root mean square (rms) difference value was calculated and the small differences between experimental and calculated modes have been interpreted by intermolecular interactions with-in the crystal. A comparison between the results of the 2[N(C₃H₇)₄]SbCl₄ compound and the simulated compounds based on the (CH₃)₄N⁺) and (C₂H₅)₄N⁺ fragments, shows an increase in the wavenumber of the bands assigned to the stretching vibration of the (NC) group for the 2[N(C₃H₇)₄]SbCl₄ compound. The comparison between the [N(C₃H₇)₄]Cl ligand and the 2[N(C₃H₇)₄]SbCl₄ compound of the infrared and Raman spectrum shows an increase in the wavenumber for the bands assigned to the stretching vibration of (CH₃) and the bending vibration of (NC₄) groups in the 2[N(C₃H₇)₄]SbCl₄ compound.     

氨酯丙烯酸酯树脂的合成及其固化反应动力学研究

用不同分子量的聚氧化丙烯二元醇合成了一系列氨酯丙烯酸酯齐聚物（ＵＡＯ）以及含硬段／软段结构的ＵＡＯ，并用ＦＴ－ＩＲ跟踪了这类ＵＡＯ的合成过程。通过ＵＡＯ的链端双键测定，以及ＧＰＣ、ＶＰＯ测定的分子量，表征了ＵＡＯ的数均官能团度。进一步通过ＦＴ－ＩＲ研究了由ＵＡＯ与甲基丙烯酸甲酯形成的氨酯丙烯酸酯树脂（ＵＡＲ）固化时的共聚反应动力学，发现其共聚反应速率与体系中的扩散效应密切相关。在这类ＵＡＯ中引入硬段后，共聚合体系呈现出反常的动力学行为，与网络结构形成过程中材料的形态发展有关。     

Synthesis,Spectral, and Structural Characterization of Bisthiocarbohydrazone Derivatives

Abstract

Bisthiocarbohydrazone derivatives of three heterocyclic ketone ligands, having a flexible coordination ability; 1, 5-bis (2-acetylthiophene) thiocarbohydrazone; 1, 5-bis (2-acetylfuran) thiocarbohydrazone; and 1, 5-bis (2-acetylpyrrole) thiocarbohydrazone were synthesized and characterized by elemental analysis, UV-visible, FT-IR, cyclic voltammetry, and ¹H and ¹³C-NMR spectral studies. All bisthiocarbohydrazone exhibited the thioketone—thioenol tautomeric forms, as evidenced by IR spectral data and single crystal X-ray diffraction studies of 1, 5-bis (2-acetylfuran) thiocarbohydrazone and 1, 5–bis (2-acetylpyrrole) thiocarbohydrazone.

Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfer, and Silicon and the Related Elements for the following free supplemental files: Additional figures and tables.     

Time-dependent fluctuations in infrared vsCH2 frequencies in acyl chain membranes of Acholeplasma laidlawii cells

We measured FT-IR spectra of intact Acholeplasma laidlawii cells grown at 37 °C on palmitic acid (C16:0) or on binary palmitic acid-d31/oleic acid (C16:0-d31/C18:1(9)) at an initial mole ratio of 2:3, which have been previously reported to produce significant fluctuations in CH₂ symmetric stretching (ν_sCH₂) and CD₂ asymmetric stretching (ν_aCD₂) frequencies (Biochim. Biophys. Acta 1279 (1996) 49). Time courses for acyl chain ν_sCH₂ and ν_aCD₂ frequencies determined from fourth derivative spectra are presented. Fluctuations were detected with the C16:0 enriched cells at temperatures above 40 °C as well as with the cells enriched in 2:3 C16:0-d₃₁/C18:1(9). These observations at temperatures above 40 °C for the C16:0 enriched cells were not in agreement with the conclusion in the previous work by Moore et al. Our results have suggested that the 2850 cm⁻¹ ν_sCH₂ band comprises two components arising from trans and gauche conformations, and that the fluctuations in ν_sCH₂ frequency are caused by random temporal changes in the relative intensities of these two components.     

Analysis of additives in polymers by thin-layer chromatography coupled with Fourier transform-infrared microscopy

A new, fast and convenient method based on coupled thin-layer chromatography (TLC) and Fourier transform-infrared (FT-IR) microscopy is developed to separate, detect and identify the additives in polymers. After the TLC development, the analytes were transferred on to a barium fluoride (BaF₂) salt plate via a special capillary technique and analysed by FT-IR microscopy. The additives used for stabilization of polypropylene and the plasticisers used for poly(vinyl chloride) were analysed as examples to illustrate this technique. The overall time taken for the experiment including transferring three marked spots and then identifying them was about 20 min. An amount as small as 0.5 μg can be easily detected and identified. It was a very convenient and reliable method to separate and evaluate complex additives for polymers without the interference from TLC adsorbent, because of a special transferring and identifying method, which is suitable to FT-IR microscopy.     

Crystal chemistry of protonated 1,2-bis(di-R-aminomethyl)benzenes. Part V. [1,2-bis(diethylaminomethyl)-3,6-dichlorobenzene:1,2-bis(diethylaminomethyl)-3,4,6-trichlorobenzene]perchlorate mixed crystals

The mixed crystals of 1,2-bis(diethylaminomethyl)-3,6-di- and 3,4,6-trichloro-benzene perchlorate at 0.5:0.5 ratio have been studied using X-ray diffraction and FT-IR spectroscopy. The molecules of di- and tri-chloro derivatives are distributed randomly in the crystal lattice; however, this disorder manifested mainly by a partial occupation of the chlorine atom at C(4) and by relatively big atomic temperature parameters even at 99 K, particularly for the oxygens of the perchlorate anion. The proton in the [NHN]⁺ bond refined close to the equidistant position between the nitrogens. The conformations of the diethylaminomethyl substituents are pseudo-symmetrical relative to the plane and twofold axis passing through the midpoint of the hydrogen bond. The IR spectrum of the crystals shows a broad intense band and an intense continuous absorption indicating relatively high proton polarizability in the intramolecular hydrogen bond. In acetonitrile and in chloroform, the proton in the intramolecular hydrogen bond also shows a very high proton polarizability demonstrated by the continuous absorption in the IR spectrum.     

Phase transitions and molecular motions in [Cd(H2O)6](BF4)2 studied by DSC, H and F NMR and FT-MIR

Two solid phase transitions of [Cd(H₂O)₆](BF₄)₂ occurring on heating at T_C2=183.3 K and T_C1=325.3 K, with 2 K and 5 K hysteresis, respectively, were detected by differential scanning calorimetry (DSC). High value of entropy changes indicated large orientational disorder of the high temperature and intermediate phase. Nuclear magnetic resonance (¹H NMR and ¹⁹F NMR) relaxation measurements revealed that the phase transitions at T_C1 and T_C2 were associated with a drastic and small change, respectively, of the both spin-lattice relaxation times: T₁(¹H) and T₁(¹⁹F). These relaxation processes were connected with the “tumbling” motions of the [Cd(H₂O)₆]²⁺, reorientational motions of the H₂O ligands, and with the iso- and anisotropic reorientation of the BF₄⁻ anions. The cross-relaxation effect was observed in phase III. The line width and the second moment of the ¹H and ¹⁹F NMR line measurements revealed that the H₂O reorientate in all three phases of the title compound. On heating the onset of the reorientation of 3 H₂O in the [Cd(H₂O)₆]⁺², around the three-fold symmetry axis of these octahedron, causes the isotropic reorientation of the whole cation. The BF₄⁻ reorientate isotropically in the phases I and II, but in the phase III they perform slow reorientation only about three- or two-fold axes. A small distortion in the structure of BF₄⁻ as well as of [Cd(H₂O)₆]²⁺ is postulated. The temperature dependence of the bandwidth of the O-H stretching mode measured by Fourier transform middle infrared spectroscopy (FT-MIR) indicated that the activation energy for the reorientation of the H₂O did not change much at the T_C2 phase transition.     

Matrix merging arrangements for the study protein dynamics by time-resolved step-scan Fourier transform infrared spectroscopy and multivariate curve resolution

In this paper, we propose the construction of merging arrangements for combining the information from various runs as a powerful approach to improve the resolution. The bacteriorhodopsin (bR) photocycle has been chosen in this study as an example dealing with the protein dynamics monitored by means of time-resolved step-scan FT-IR spectroscopy. The possibilities of matrix merging are evaluated and results are compared with those from the analysis of individual and augmented matrices. As a conclusion, this strategy provides excellent results for the analysis of this type of time-resolved FT-IR data.