Infrared spectrum of 4-methoxypicolinic acid N-oxide: computation of asymmetric O-H stretching band

In this article we studied the strong intramolecularly hydrogen-bonded system 4-methoxypicolinic acid N-oxide. The potential energy surface V = V(rOH,rOO) and the corresponding dipole moment function were calculated using the DFT B3LYP/6-31+G(d,p) level of approximation. The time-independent vibrational Schr?dinger equation was solved using a rectangular grid basis set and shifted Gaussian basis set. The vibrational spectrum and metric parameters were also calculated. Effects of deuteration were considered. The calculated vibrational spectra were compared with the experimental spectra. The vibrational transition corresponding to asymmetric O-H stretching that occurs at about 1400 cm-1 compares well with the experimentally assigned O-H asymmetric stretching band centered at 1380 cm-1. The corresponding asymmetric O-D stretching band was predicted to be at 1154 cm-1, while the experimental O-D band was not assigned due to its very low intensity. Several overtones and hot transitions of significant intensities were located in the vicinity of the fundamental O-H stretching frequency, effectively broadening the infrared absorption attributed to the O-H stretching mode. This is in a good agreement with the observed broad protonic absorptions found in the infrared spectra of the title compound and its analogs. We have shown that the Gaussian basis set is the method of choice for a two-dimensional vibrational problem that requires several hundreds of vibrational basis functions and when high accuracy of the eigenvalues is required or when extending the calculations to more vibrational degrees of freedom. We have also demonstrated that for a large number of basis functions the Gramm-Schmidt orthogonalization procedure outperforms symmetric and canonical orthogonalization schemes.     

Analysis of sample of highly water-soluble Th-symmetric fullerenehexamalonic acid C66(COOH)12 by ion-chromatography and capillary electrophoresis

Ion chromatography (IC) was used to establish isomer purity of the highly water-soluble sample of fullerenehexamalonic acid, Th-symmetric hexakis-adduct C66(COOH)12. Sharp and symmetric peaks were obtained by IC using 1.0 M potassium hydroxide as eluent and applying gradient elution program. The identity of the two largest peaks in the chromatogram was assigned to Th-C66(COOH)12 and C66H(COOH)11. The developed IC procedure can be used for the semi-quantitative determination of the extent of the partial decarboxylation of the sample. As an alternative analytical technique, a CE procedure was introduced and its performance against IC was compared for this particular case.     

Synthesis of alkyl‐modified poly(sodium glutamate)s for preparation of polymer‐protein nanoparticles in combination with N,N,N‐trimethyl chitosan

The negatively charged, water‐soluble, hydrophobically modified poly(sodium glutamate)s containing different amounts of alkyl grafts were synthesized. First, poly(γ‐benzyl‐L‐glutamate) was prepared by ring‐opening polymerization of the corresponding N‐carboxyanhydride, which was in the next step aminolysed with octylamine. After removal of the remaining benzyl protective groups, the alkyl‐modified poly(sodium glutamate)s [P(Glu‐oa)] were obtained and, together with the oppositely charged N,N,N‐trimethyl chitosan (TMC), used for the preparation of nanoparticles (NPs) of a recombinant granulocyte colony‐stimulating factor (GCSF) protein by polyelectrolyte complexation method. It is observed that, beside electrostatic interaction, the hydrophobic grafts on poly(sodium glutamate)s significantly contribute to association efficiency (AE) with GCSF protein. The addition of TMC solution to the dispersion of GCSF/P(Glu‐oa) complexes results in formation of much more defined NPs with high AE and final protein loading. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2976–2985     

Monolithic chromatography for elemental and speciation analysis

Monolithic supports are increasingly used in the field of chromatography. They are appropriate for different applications (e.g., separation of biomolecules, organic acids and inorganic anions). However, only a few research groups are investigating the potential of using monolithic phases for rapid separation of metal cations and elemental speciation analysis.Monolithic supports based on porous monolithic silica have been successfully applied in separation of alkaline-earth and transition-metal cations in environmental waters and high ionic-strength samples.The present review covers applications of monolithic supports for chromatographic separation of metal cations and the potential for using monolithic chromatography in elemental speciation analysis. We critically evaluate the performances and the advantages of monolithic supports and compare them to conventional particle-packed chromatographic supports.     

Analysis of optodynamic sources generated during laser-induced breakdown in water

We propose a method for evaluating the size of the laser-induced breakdown region in water based on the detection and analysis of optodynamic waves. The breakdown region is an optodynamic source of pressure waves that propagate into the surrounding liquid as an ultrasonic pulse. In the experiment the optical breakdown was generated by a standard ophthalmic Nd:YAG laser with a pulse duration of 10 ns and a maximum energy per pulse of 10 mJ. The pulses were detected inside the liquid with a laser-beam deflection probe. The waveforms were captured in the far-field and analyzed. The analysis provides information about the apparent size of the optodynamic source, which is directly related to the size of the breakdown region. The proposed method can be adapted for online monitoring.     

Fusion and transfer cross sections of 3He induced reaction on Pt and Au in energy range 10–24.5 MeV

In experiments performed by accelerated ion ³He-beam irradiated gold and platinum targets on the cyclotron U-120M of the Nuclear Physics Institute of the Czech Academy of Sciences, ?e?, reactions of complete and incomplete fusion and nucleon transfer reactions in the ³He energy range from 10 to 24.5 MeV have been investigated. To determine the yield of the nuclides resulting from the nuclear reaction, the activation technique has been used. The obtained data are analyzed using models based on statistical calculations and compared with similar results for other light stable particles. Transfer reactions with positive Q values have relatively high cross sections in the energy range below the Coulomb barrier. These cross sections continue to grow with increasing ³He energy, and, in the case of capturing neutron from target nucleus by a nucleus of ³He, the excitation functions of these reactions reach their maximum almost at the Coulomb barrier of the reactions.     

New Methods for Detection of 14N NQR Frequencies

Nitrogen atoms are present in a number of solid explosives and illicit substances. The nuclear quadrupole resonance (NQR) spectra and spin?Clattice relaxation of the nitrogen atomic nucleus ¹⁴N can be used to characterize these compounds and to distinguish between possible crystal polymorphs. After the characteristic ¹⁴N NQR frequencies and spin?Clattice relaxation rates in a compound are determined, NQR can be used to detect this compounds and, in case of crystal polymorphs, also to determine the method of preparation. The ¹⁴N NQR frequencies and spin?Clattice relaxation rates are measured either by pulse NQR or by nuclear quadrupole double resonance (NQDR) based on magnetic field cycling. Here, we discuss several ¹H?C¹⁴N NQDR techniques which can be used to measure the ¹⁴N NQR frequencies and spin?Clattice relaxation rates under various experimental conditions. Some characteristic applications of these techniques are presented and discussed in details.     

The synthesis of 12-membered macrocycles containing a C1–C8 alkene unit via ring-closing metathesis

Model cross and ring-closing metathesis strategies toward the C1–C8-linear carbon skeleton are presented. The introduction of a four-atom tether enables the formation of 12-membered rings in good-to-excellent yields and stereoselectivity. Furthermore, the study revealed that the cross-metathesis approach and the formation of medium ring sizes via ring-closing metathesis are much less favorable.     

Sorption of water vapor by poly(vinyl acetate)

Summary The sorption property of water vapor by poly(vinyl acetate) (PVAc) of relatively low glass transition temperature (T _g) was studied at temperatures nearT _g.Tc_g of humidity-controlled samples of various moisture contents was measured and its variation with the moisture content was determined.T _g of the dry sample was estimated by dilatometry and DSC methods, and to confirm the value, the temperature dependence of mutual diffusion coefficient of the system of water vapor + PVAc was determined. A difference between the sorption mechanisms of water vapor by PVAc at 20 and 30 °C was observed: two sorption mechanisms are involved at 30 °C, while three mechanisms at 20 °C are involved which include the above two and another intermediate one. In earlier stage of sorption, at both 20 and 30 °C, water molecules sorbed by PVAc showed a tendency towards aggregation, while a mixing effect was found at higher stage of the sorption.

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Zusammenfassung In der Arbeit werden Wasserdampfsorptionseigenschaften von Polyvinylacetat mit relativ niedriger Glastemperatur (T _g) in der Nähe vonT _g untersucht. Es wurden Plastizitätseinflüsse und Veränderungen vonT _g mit dem Wassergehalt studiert. Es wurde gefunden, daß bei 30 °C ein 2-Stufen-Sorptionsmechanismus, bei 20 °C ein 3-Stufen-Mechanismus existiert.

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With 7 figures     

声光调Q激光器所需最小衍射效率的研究

以四能级系统为例, 研究了在输出脉冲能量一定的情况下,声光调Q激光器所需要的最小衍射效率如何确定的问题.通过对调Q反转粒子数密度的求解,获得了调Q激光器输出的一定脉冲能量与腔内损耗、所需最小Q开关的衍射效率和输出镜的反射率等的关系公式.这一结果为声光调Q激光器Q开关衍射效率的设计提供了简便的估算方法.