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941.
The low-temperature NMR spectra of 1,4-bis(mesitoyl)durene, 1, and of 1,4-bis(mesitylethenyl)durene, 2, reveal the presence of syn and anti rotamers at the equilibrium, their relative proportions depending on the dielectric constant of the solvent. In solution the more stable rotamer of 1 is the anti whereas, in the case of 2, the more stable is the syn. Depending on the crystallization solvent employed the more (anti) and the less stable (syn) rotamers were both observed (X-ray diffraction) in the solid state of 1. On the other hand, only the less stable rotamer (anti) was found to be present in the solid state of 2. As shown by MM calculations, the syn-to-anti interconversion occurs via a correlated process (cogwheel pathway) involving the mesityl-C and durene-C bond rotations: the dynamic NMR technique yields an experimental barrier of 8.2 kcal mol(-)(1) for 1 and 13.1 kcal mol(-)(1) for 2. In the case of derivative 2 a second barrier, due to a second type of correlated rotation process (torsion), was also determined (8.6 kcal mol(-)(1)). As a consequence of the restriction of this second torsional motion the anti rotamer of 2 displays two distinguishable NMR spectra at -133 degrees C, corresponding to a pair of conformers with different symmetry (anti C(i)() and anti C(2)). 相似文献
942.
JongHwa Moon SangHoon Kang YongSam Chung OkHee Lee 《Journal of Radioanalytical and Nuclear Chemistry》2007,271(1):155-158
Instrumental neutron activation analysis was used to assess the concentration of the inorganic trace elements in Korean women’s
blood serums. It was found that a high concentration of Na and Cl incurs an analytical interference, but the 12 elements such
as Br, Ca, Cl, Co, Cr, Cs, Fe, K, Na, Rb, Se and Zn could be determined under the condition of an interference minimization.
Serum samples collected from 63 women were analyzed and the concentration level and range of the elements were evaluated.
NIST SRMs were analyzed simultaneously for quality control. The average values of the Na and Cl determined in the serum samples
were 3,365 and 3,533 mg/l, Ca was 96.4 mg/l and K was 191 mg/l. Besides, Br, Se and Zn have a concentration level of 6.46,
0.13 and 0.98 mg/l, respectively. It was found that there is no significant difference between the present values and the
reported values. 相似文献
943.
Rasa Pauliukaite Mariana Emilia Ghica Madalina Barsan Christopher M. A. Brett 《Journal of Solid State Electrochemistry》2007,11(7):899-908
The polymer redox mediator, poly(neutral red) (PNR), has been synthesised and characterised electrochemically to investigate
the best electropolymerisation and mediation conditions for application in enzyme biosensors and to clarify the mechanism
of action. Neutral red was electropolymerised by potential cycling on carbon film electrode substrates by allowing the monomer
to be oxidised during the full 20 cycles of polymerisation or reducing the positive limit of the potential window after the
first 2 cycles to impede monomer oxidation with a view to obtaining longer polymer chains and a lesser degree of branching.
Comparison was made with glassy carbon substrates. The PNR films on carbon film electrodes were characterised using cyclic
voltammetry and electrochemical impedance spectroscopy, as well as in glucose biosensors prepared with PNR. Glucose oxidase
enzyme was immobilised by encapsulation in silica sol-gel and compared with that obtained by cross-linking with glutaraldehyde.
The biosensors were evaluated by chronoamperometry in 0.1 M phosphate buffer saline solution, pH 7.0, and showed evidence
of electron transfer between the enzyme cofactor flavin adenine dinucleotide and PNR dissolved in the enzyme layer competing
with PNR-mediated electrochemical degradation of H2O2 formed during the enzymatic process.
This paper is dedicated to Professor Dr. Algirdas Vaskelis on the occasion of his 70th birthday. 相似文献
944.
Alessandro?De?Robertis Concetta?De?Stefano Demetrio?Milea Silvio?SammartanoEmail author 《Journal of solution chemistry》2005,34(10):1211-1226
Complex formation constants were determined potentiometrically (by a ISE-H+, glass electrode) in the systems, M2+ – Lz – H+ [M2+ = (C2H5)2Sn2+, Lz = malonate, glycinate and ethylenediamine] at t = 25 ∘C and 0.1 mol-L−1≤ I/ ≤ 1 mol-L−1 in NaClaq (0.1 mol-L−1 ≤ I ≤ 0.75 mol-L−1 for the ethylenediamine system). Thermodynamic values of formation constants, at infinite dilution, are [± 95% confidence
interval, Tβpqr refer to the equilibrium, pM2+ + qLz + rH+ = MpLqHr(2+z+r)]: for malonate, log10 Tβ110 = (5.47 ± 0.10); for glycinate, log10 Tβ110 = (9.54 ± 0.08), log10 Tβ111 = (12.97 ± 0.10); and for ethylenediamine, log10 Tβ110 = (10.47 ± 0.10), log10 Tβ120 = (16.17 ± 0.12) and log10 Tβ111 = (15.46 ± 0.10). The dependence on ionic strength of the formation constants was modeled by a simple Debye–Hückel type equation
and by the SIT approach. By analyzing the stability of the species in the three different systems we found a simple additivity
rule that can be expressed by the relationship: log10 K = 6.46 nN + 3.96 nO − 0.60 (nN2+ nO2), with a mean deviation, ε(log10 K) = 0.15 (K = equilibrium constant for the interaction of the organometal cation with the unprotonated or protonated ligand, nN = number of amino groups and nO = number of carboxylic groups of the ligand(s) involved in the formation reaction of complex species). 相似文献
945.
Ana C. D. Medeiros Lidiane P. Correia Mônica O. da S. Simões R. O. Macêdo 《Journal of Thermal Analysis and Calorimetry》2007,88(2):311-315
A number of disintegrants
are available on the market. They improve tablets’ disintegration. The
objective of this work is the comparison of the technological quality parameters
of disintegrants using different analytical techniques. Three batches of disintegrants
and their binary mixtures (water:disintegrants) were investigated. Cooling
experiments were used from –30 up to 200°C. The data obtained showed
calorimetric differences between the samples. In the binary mixtures water
showed different crystallization behaviour from the one found in the literature.
According to the results DSC technique helped the quality control of different
disintegrants. 相似文献
946.
J. Orbán Sz. Halasi G. Papp Szilvia Barkó Beáta Bugyi 《Journal of Thermal Analysis and Calorimetry》2005,82(1):287-290
Summary The thermodynamic properties of the cardiac and skeletal a-actin isoforms were studied to characterize the molecular bases
of the functional differences between them with the method of differential scanning calorimetry (DSC). The thermal properties
of the actin filaments were described in the presence of calcium and magnesium ions as well. Based on the calculated free
energy changes the α-cardiac actin filaments appeared to be more stable in its physiologically more relevant, magnesium saturated
form. The magnesium saturated form of the α-cardiac actin filaments seemed to be more stable compared to the calcium saturated
form of it. The enthalpy and entropy changes could differentiate between the α-cardiac and α-skeletal actin isoforms and between
the calcium and magnesium saturated cardiac actin isoforms as well. Our results can demonstrate that the few differences between
the amino acid sequences of the α-actin isoforms have an influence on the thermal properties and maybe on the function of
these proteins as well. 相似文献
947.
Nine samples of N-acetyl-3,4-methylenedioxyamphetamine (N-acetyl-MDA), prepared according to the most common synthetic procedures, are submitted to (2)H NMR spectroscopy. The relative deuterium content at the various sites of the molecule is shown to depend on its synthetic history. The technique provides a chemical fingerprint of N-acetyl-MDAs and it can be used to trace back the precursor materials and the synthetic pathways employed in the preparation of the samples. 相似文献
948.
949.
Zhou YanXia Tan HongWei Yang ZuoYin Jia ZongChao Liu RuoZhuang Chen GuangJu 《中国科学B辑(英文版)》2007,50(2):266-271
The insect spruce budworm(Choristoneura fumiferana) produces antifreeze protein(AFP) to assist in the protection of the over-wintering larval stage and contains multiple isoforms. Structures for two isoforms,known as CfAFP-501 and CfAFP-337,show that both possess similar left-handed β-helical structure,although thermal hysteresis activity of the longer isoform CfAFP-501 is three times that of CfAFP-337. The markedly enhanced activity of CfAFP-501 is not proportional to,and cannot be simply accounted for,by the increased ice-binding site resulting from the two extra coils in CfAFP-501. In or-der to investigate the molecular basis for the activity difference and gain better understanding of AFPs in general,we have employed several different computational methods to systematically study the structural properties and ice interactions of the AFPs and their deletion models. In the context of intact AFPs,a majority of the coils in CfAFP-501 has better ice interaction and causes stronger ice lattice disruption than CfAFP-337,strongly suggesting a cooperative or synergistic effect among β-helical coils. The synergistic effect would play a critical role and make significant contributions to the anti-freeze activity β-helical antifreeze proteins. This is the first time that synergistic effect and its implica-tion for antifreeze activity are reported for β-helical antifreeze proteins. 相似文献
950.
Jos L. Del Valle Cecilia Polo TomS Torroba Stefano Marcaccini 《Journal of heterocyclic chemistry》1995,32(3):899-901
The sodium salt of TOSMIC reacted with (E)-3,4,5,6,7-penta-O-acetyl-1,2-dideoxy-1-C-nitro-D-galacto- (1) and -D-manno-hept-1-enitol (2) to give 3-(D-galacto- (3) and 3-(D-manno-penta-O-acetylpentitol-1-yl)-4-nitropyrrole (4) , respectively. Compound 1 reacted with diaryl nitrile imines, affording 1,3-diaryl-4-(1,2,3,4,5-penta-O-acetyl-D-galacto-pentitol-1-yl)pyrazoles 5 and 6 . 相似文献