Characterization of reduced iso‐α‐acids derived from hops (Humulus lupulus) by NMR

Reduced forms of iso‐α‐acids (isohumulones), used in modern beer brewing were separated and characterized by ¹H and ¹³C NMR spectroscopy. Components from mixtures of rho‐iso‐α‐acids, tetrahydro‐iso‐α‐acids, and hexahydro‐iso‐α‐acids were isolated using high‐performance liquid chromatography (HPLC) and analyzed by use of one‐ and two‐dimensional NMR experiments. The data presented assign the identities of the main peaks in the HPLC traces for the reduced iso‐α‐acids. Previous tentative assignments regarding the cis and trans configurations and the structures of the acyl residues of the reduced iso‐α‐acids were confirmed and extensive NMR assignments were made. Furthermore, the previously unknown stereochemistry in the C‐4 side‐chain of the rho‐ and hexahydro‐iso‐α‐acids was assigned. Copyright © 2003 John Wiley & Sons, Ltd.     

Applications of density functional theory methods in millimeter‐wave spectroscopy

Density functional theory (DFT), using the most common functionals, and ab initio quantum chemistry methods are used to calculate the rotational constants and dipole moments of the astrophysically important molecules HCN, CH₃CN, CH₃CNH⁺, HCCCN, and HCCNC. As far as millimeter‐wave spectroscopy is of interest the DFT methods performed well with most functionals, giving results within ±1% of experiments for rotational constants and ±3% for dipole moments. Analyzing the results obtained with all theoretical models, it may be concluded that the Becke's three‐parameter exchange functional and the gradient‐corrected functional of Lee, Yang, and Paar (B3LYP) and Becke's three‐parameter functional with Perdew–Wang correlational functional [B3PW91/6‐31G(d, p)] give the best performances. A detailed analysis of the electron correlation effects shows that HCCCN is more stable than is HCCNC, by 1.16 eV, with important contribution arising from triple excitations. This result is also compared with those obtained with DFT methods. Despite occasional difficulties, DFT with the currently available functionals are of great utility in quickly assessing spectroscopic parameters of astrophysical interest. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2003     

Foams and surface rheological properties of β-casein, gliadin and glycinin

Interfacial rheological properties and their suitability for foam production and stability of two vegetable proteins were studied and compared to β-casein. Proteins used ranged from flexible to rigid/globular in the order of β-casein, gliadin and soy glycinin. Experiments were performed at pH 6.7. Network forming properties were characterised by the surface dilational modulus (determined with the ring trough) and the critical falling film length (L_still) at which a stagnant protein film will break. Gliadin had the highest dilational modulus, followed by glycinin and β-casein, whereas glycinin formed the strongest film against fracture in the overflowing cylinder. The rate of decrease in the surface tension was studied at the air–water (Wilhelmy plate method) and the oil–water interface (bursting membrane) and the dynamic surface tension during compression and expansion in the caterpillar. Gliadin had the lowest equilibrium interfacial tensions and β-casein the lowest dynamic surface tension during expansion. Hardly any foam could be formed at a concentration of 0.1 g/l by shaking. At a concentration of 1.4 g/l most foam was formed by β-casein, followed by gliadin and glycinin. It seems that in the first place the rate of adsorption is important for foam formation. For the vegetable proteins, adsorption was slow. This resulted in lower foamability, especially for glycinin.     

自由电子激光振荡器的二维数值模拟

在柱二维坐标系中,用数值计算方法求解了摇摆器内电子模拟方程组、光场方程组和无源区(不含摇摆器区)经非自适应方法变换后的无源旁轴波动方程并设计了相应的程序R_2D。用该程序计算的数值结果表明,在有源条件下二维数值模拟结果与高斯光束近似下的数值模拟结果符合较好;取完全相同的计算条件R-2D程序与洛斯阿拉莫斯实验室(LANL)的FELEX程序的计算结果符合较好;初步认为LANL实验数据的物理图象合理,数值结果基本可信;最后给出北京自由电子激光器(BFEL)的一些物理数据。     

Characteristic of a broadband Ti:LiNbO3 optical modulator with buried electrodes and etched grooves in the buffer layer

Traveling wave Ti:LiNbO₃ Mach-Zehnder optical modulators with buried electrodes and etched grooves in the SiO₂ buffer layer are analyzed by the finite element method. The tradeoff between the bandwidth BW and the half-wave voltage Vπ is discussed. The value of BW/Vπ is used to weight the total performance of the modulator. Taking a thick buffer layer and etching deep grooves in the buffer layer are demonstrated as two effective methods to improve the performance of the modulator. A 3-dB optical bandwidth of 18 GHz with half-wave voltage 5V at a wavelength of 1.55 pm could be obtained even though the electrode is not very thick. When the requirement of half-wave voltage is not very critical, a bandwidth of more than 100 GHz can be obtained.     

Theoretical study of cyclization of 2′-hydroxychalcone

The isomerization mechanism of 2′(OH)chalcone (1) in flavanone (2) was studied. The calculations were performed with the semiempirical method AM1, using totally optimized molecular geometries. A 6-step mechanism including several equilibrium states was proposed. It was concluded that: (a) At the conformational equilibrium of 1 there could be 43.9% of s-cis conformer; (b) The acid dissociation of 1 trans-s-trans is considerable; (c) The E_E, ΔH_f and net charges show that the rotation of ring A of 1 and the formation of ring C of 2 occurs without greater impairments; (d) Although the keto structure is the most stable one, the enolate of 2 is present in the reaction medium; (e) The conversion of enol of 2 in the keto form would be the limiting step of the analyzed isomerization rate.     

Contributions to the synthesis of some ferrocene-containing antibiotics

This Review discusses the synthesis and characterization by our Group of new antibiotics belonging to the class of penicillins, cephalosporins and rifamycins with ferrocenyl and 1, 1′-ferrocenilene residues in the molecule. As reactants for 6-aminopenicillanic acid (6-APA) and 7-aminocephalosporanic acid (7-ACA) the following were used: 1, 1-bis(chlorocarbonyl)ferrocene, ferrocenyl sulfochloride, 1, 1′-ferrocenylenedisulfochloride and thioglycolic acids S-modified with ferrocene. In the synthesis of rifamycins, the hydrazides of the thioglycolic acids, S-modified with ferrocene, were employed as nucleophilic agents. The synthesized intermediates were characterized by elemental analysis, TLC, IR, UV and ¹H NMR spectra. The characterization of new antibiotics was made by TLC, IR and UV spectral analysis. Biological activity was tested on Gram-negative and Gram-positive bacteria. Good activity is reported towards Gram-positive bacteria in the case of derivatives containing residues of thioglycolic acid S-modified with ferrocene, the antibacterial activity being similar to that of amoxicillin, carbenicillin and cephalothin. All compounds are inactive towards Gram-negative bacteria.     

Molecular electric field mapping of some anions and cations of 2- aminopurine and 6- thioguanine

Electric fields of the anions, cations and neutral forms of 2-aminopurine and 6-thioguanine have been mapped. Certain important features of the maps are similar to those found earlier in the neutral and ionic forms of adenine and guanine. The computed electric field patterns satisfactorily explain reactive sites and biological activity of the molecules.