Gas-phase isothermal chromatography with short-lived technetium isotopes

In order to study the gas-phase chemical behavior of transactinides, an on-line isothermal chromatography apparatus has been developed and applied to separate short-lived technetium isotopes in the form of TcO3 from fission products. The fission products from a Cf-252 source were continuously and rapidly transported through the capillary to the isothermal chromatography apparatus using the N-2/KBr gas-jet techniques. Volatile oxide molecules were formed at the reaction zone kept at 900 degrees C since a trace amount of oxygen existed in the N-2 carrier gas. With the new developed isothermal chromatography apparatus, a selective separation of Tc from fission products was achieved. After isothermal chromatographic separation, Tc-101,Tc-103,Tc-104,Tc-105,Tc-106,Tc-107,Tc-108 were dominantly observed together with their Ru daughters in the gamma-spectrum, The chemical yields of Tc-101, and Tc-104 and Tc-105 isotopes with longer half-lives are about 55-57%, and those of Tc-103, Tc-106 and Tc-108 isotopes with shorter half-lives dropped down to 25-28%. The adsorption enthalpy of the investigated compounds on quartz surfaces was determined to be -150 +/- 5 kJ/mol by fitting the measured retention curves with a Monte Carlo model. The observed species of technetium oxide is attributed to TcO3, which is in good agreement with previous experimental results. That means our system worked properly and it can be used to investigate the gas-phase chemical behavior of transactinides.

Molecular dynamics and control following excitation with an ultra-short intense laser pulse

Vibronic excitations of the tri-atomic molecule OClO (A(2)A(2)(nu(1), nu(2), nu(3)) <-- (XB1)-B-2 (0, 0, 0)) with weak and strong ultra-short laser fields are studied within full quantum wavepacket dynamics in hyperspherical coordinates. Different dynamics is observed following excitation with laser pulses of different intensities. With a strong laser pulse, many vibrational states are excited and a spatially more localised wavepacket arises. The numerical results show that the population of different vibrational states of the wavepacket on the excited potential energy surface is altered by the intensity of the laser pulse. The numerical results also suggest a related effect on the phase of the wavepacket. These interesting phenomena can be understood by an analysis of the corresponding results for two model diatomic molecules. The possible physical mechanisms of control of chemical processes using strong laser fields are discussed. (C) 2004 Elsevier B.V. All rights reserved.

Short columns with molecularly imprinted monolithic stationary phases for rapid separation of diastereomers and enantiomers

Three molecularly imprinted monolithic columns with different length but almost identical column volume had been prepared. It was observed that the separation factors of diastereomers and enantiomers were almost unaffected by column length. However, the short column with dimension of 38 mm x 8 mm W. showed much lower resistance to flow rate so that it could be operated at much higher flow rates. By combining stepwise gradient elution with elevated flow rate, the diastereomers of cinchonine and cinchonidine and the enantiomers of Cbz-DL-Trp and Fmoc-DL-Trp were successfully separated within 3 min on the short column with dimension of 38 mm. x 8 mm i.d.. Based on the above results, a cinchonine imprinted monolithic disk with dimension of 10 mm x 16 mm W. was further developed. The SEM image and the pore size distribution profile showed that large flow-through pores are present on the prepared monolith, which allowed mobile phase to flow through the disk with very low resistance. Chromatographic performances on the monolithic disk were almost unchanged compared with the long columns. A rapid separation of cinchonine and cinchonidine was achieved in 2.5 min at the flow rate of 9.0 ml/min. Furthermore, it was observed that there was almost no effect of the flow rate on the dynamic binding capacity at high flow rates. In addition, the effect of the loading concentration of analytes on the dynamic binding capacity, namely adsorption isotherm, was also investigated. A non-linear adsorption isotherm of cinchonine was observed on the molecularly imprinted monolith with cinchonine as template, which might be a main reason to result in the peak tailing of template molecule. (C) 2004 Elsevier B.V. All rights reserved.

Short-term effect of increasing nitrogen deposition on CO2, CH4 and N2O fluxes in an alpine meadow on the Qinghai-Tibetan Plateau, China

National Key Research and Development Program [2010CB833500]; Natural Science Foundation of China [30590381]; Knowledge Innovation Project of Chinese Academy of Sciences [KZCX2-YW-432]

Self-assembly of a hydrophobic polypeptide containing a short hydrophilic middle segment: Vesicles to large compound micelles

This report describes a facile route to prepare the vesicles and large compound micelles (LCMs) from a series of poly(epsilon-benzyloxycarbonyl L-lysine)-block-poly[diethylene glycol bis(3-amino propyl) ether]-block-poly(epsilon-benzyloxycarbonyl L-lySine) (PZLL-DGBE-PZLL) in their water solution, depending on molecular weight of the polypeptides. A pyrene probe is used to demonstrate the aggregate formation of PZLL-DGBE-PZLL in solution, and also to measure their critical micelle concentration as a function of molecular weight of the polymer.

Synthesis and Characterization of Short-chain Branched Polyethylene

Two kinds of ethylene copolymers with controllable structures were synthesized and the molecular parameters were characterized by FTIR, GPC, H-1 NMR and C-13 NMR systematically. Effects of molecular and the content of branched short chains on the crystalline properties of the resultant ethylene copolymers were investigated by DSC, respectively. First, polybutadienes with M-w ranging from 20000 to 110000, low polydispersity index(PDI = 1.1) and almost the same content of vinyl (molar fraction about 7%) were synthesized by anionic polymerization. After hydrogenation, the melting point and crystallinity of the obtained model ethylene/1-butene copolymers decreased with the increase in M-w of the copolymers.

Short-capillary electrophoresis with electrochemiluminescence detection using porous etched joint for fast analysis of lidocaine and ofloxacin

Fast analysis of ofloxacin and lidocaine, as bactericide and analgesic or anesthetics, is of clinic importance for understanding the patient's medical process. This paper presented a high throughput, simple analysis method of lidocaine and ofloxacin by capillary electrophoresis coupled with electrochemiluminescence (ECL) using porous etched joint. To shorten the analysis time and to improve the analytical performance, a capillary with 10 cm in length was used as the separation channel. The cyclic voltammograms of Ru(bpy)(3)(2+) with different capillary length at same field strength showed that the porous etched joint eliminated the effect of electrophoretic current on the ECL detection. Following micro total analysis systems (muTAS), some advantages of which this approach has, the fabrication of channel in chip was not needed. Compared with capillary electrophoresis with 40-cm-long capillary, the high sample throughput and low zone broadening may be the main advantage of the present system. Under optimal condition, the detection limits of lidocaine and ofloxacin based on peak height were 3.0 x 10(-8) and 5.0 x 10(-7) mot L-1 and a 60 h(-1) of sampling frequency was obtained.

Enthalpy/entropy compensation: Influence of DNA flanking sequence on the binding of 7-amino actinomycin D to its primary binding site in short DNA duplexes

The effect of the context of the flanking sequence on ligand binding to DNA oligonucleotides that contain consensus binding sites was investigated for the binding of the intercalator 7-amino actinomycin D. Seven self-complementary DNA oligomers each containing a centrally located primary binding site, 5'-A-G-C-T-3', flanked on either side by the sequences (AT)(n) or (AA)(n) (with n = 2, 3, 4) and AA(AT)(2), were studied. For different flanking sequences, (AA)(n)-series or (AT)(n)-series, differential fluorescence enhancements of the ligand due to binding were observed. Thermodynamic studies indicated that the flanking sequences not only affected DNA stability and secondary structure but also modulated ligand binding to the primary binding site. The magnitude of the ligand binding affinity to the primary site was inversely related to the sequence dependent stability. The enthalpy of ligand binding was directly measured by isothermal titration calorimetry, and this made it possible to parse the binding free energy into its energetic and entropic terms.

Effect of DNA flanking sequence on charge transport in short DNA duplexes

Several factors can influence charge transport (CT)-mediated DNA, such as sequence, distance, base stacking, base pair mismatch, conformation, tether length, etc. However, the DNA context effect or how flanking sequences influence redox active drugs in the DNA CT reaction and later in DNA enzymatic repair and synthesis is still not well understood. The set of seven DNA molecules in this study have been characterized well for the study of flanking sequence effects. These DNA duplexes are formed from self-complementary strands and contain the common central four-base sequence 5'-A-G-C-T-3', flanked on both sides by either (AT)(n) or (AA)(n) (n = 2, 3, or 4) or AA(AT)(2). UV-vis, fluorescence, UV melting, circular dichroism, and cyclic voltammetry experiments were used to study the flanking sequence effect on CT-mediated DNA by using daunomycin or adriamycin cross-linked with these seven DNA molecules. Our results showed that charge transport was related to the flanking sequence, DNA melting free energy, and ionic strength. For (AA)(n) or (AT)(n) species of the same length, (AA)(n) series were more stable and more efficient CT was observed through the (AA)(n) series. The same trend was observed for (AA)(n) and (AT)(n) series at different ionic strengths, further supporting the idea that flanking sequence can result in different base stacking and modulate charge transport through these seven DNA molecules.

Non-isothermal crystallization behavior and kinetics of metallocene short chain branched polyethylene

The non-isothermal crystallization behavior and kinetics of metallocene short chain branched polyethylene were investigated via DSC at cooling rates from 2.5 to 20 degreesC/min, and subsequent heating at rate of 10 degreesC/min. To verify the effect of molecular weight and branching content on crystallization, three group samples were chosen: (1) linear polyethylene with low molecular weight and high molecular weight; (2) low molecular weight polyethylene with low branching content and high branching content; (3) high molecular weight polyethylene with low branching content and high branching content. The results show that crystallization temperature, crystallinity, melting temperature and crystallization rate are highly branching content-dependent. Molecular weight effect is less important, compared to branching content. A dramatic decrease of crystallization temperature, crystallinity, crystallization rate and melting temperature was observed for branched samples. The non-isothermal kinetics was analyzed via the methods, developed by Gupta and Mo Zhi-shen, and good agreement was obtained.

The polydispersity of ethylene sequence in metallocene ethylene/alpha-olefin copolymers III: crystallization and melting behavior of short ethylene sequence

Crystallization and melting behavior of short ethylene sequence of metallocene ethylene/alpha -olefin copolymer with high comonomer content have been studied by standard DSC and modulated-temperature differential scanning calorimetry (M-TDSC) technique. In addition to high temperature endotherm around 120 degreesC, a low temperature endotherm is observed at lower temperatures (40-80 degreesC), depending on time and temperature of isothermal crystallization. The peak position of the low temperature endotherm T-m(low) varies linearly with the logarithm of crystallization time and the slope, D, decreases with increasing crystallization temperature T-c. The T-m(low) also depends on the thermal history before the crystallization at T-c, and an extrapolation of T-m(low) (30.6 degreesC) to a few seconds has been obtained after two step isothermal crystallization before the crystallization at 30 degreesC. The T-m(low) is nearly equal to T-c, and it indicates that the initial crystallization at low temperature is nearly reversible. Direct evidence of conformational. entropy change of secondary crystallization has been obtained by using M-TDSC technique. Both the M-TDSC result and the activation energy analysis of temperature dependence suggest that crystal perfection process and conformational entropy decreasing in residual amorphous co-exist during secondary crystallization.

Crystallization kinetics of narrow molecular weight distribution metallocene short-chain-branched polyethylene

Isothermal and non-isothermal crystallization kinetics of three metallocene-catalysed short-chain-branched polyethylene (SCBPE) fractions with different degree of branching were investigated by using differential scanning calorimetry (DSC). Narrow molecular weight fractions (M-w = 20,000 and M-w/M-n < 1.15) are used and the degree of branching (CH3 per 1000C) are 1.6, 10.4, 40 respectively. The regime I - II transition temperature are 119.8C, 115.9 degreesC, 113.3 degreesC with the decreasing of degree of branching. Increasing the branch content decreases the rate of secondary nucleation, i,relative to the rate of surface spreading and so increases the range of supercooling over which regime I exists. The rate of bulk crystallization for both isothermal and non-isothermal crystallization decreases with the increasing of degree of branching. Both Ozawa Equation and Kissinger Equation are invalid for non-isothermal crystallization kinetics of SCBPE fractions,that means the effects of the branched chain on crystallization process are more complex than expected.

Lateral habits of single crystals of metallocene-catalyzed low molecular weight short chain branched polyethylene from the melt

The lateral habits of low molecular weight short chain branched polyethylene single crystals from the melt were studied. Three crystallization temperatures (102, 104 and 106 degrees C) were selected for single crystal growth. It was found that the lateral habits of single crystals were asymmetric at all the crystallization temperatures selected. The electron diffraction patterns and tilting series experiments evidenced that there existed chain tilting in all the lamellae. It was the chain tilting that lead to the asymmetry of the growth rate and of lateral habits of the single crystals about the b-axis. The lateral habits substantially changed from the growth at 102 degrees C where the truncated lozenge single crystals formed with straight (110) faces to the growth at 104 degrees C where the lenticular single crystals appeared. This change occurred at 20 degrees C lower than that in a low molecular weight linear polyethylene with the same molecular weight. Furthermore, kinetics theory analysis evidenced that the change of lateral habits from truncated lozenge to lenticular shape resulted from the transition of growth regime. The results were the same as that of high molecular weight linear polyethylene but different to that of low molecular weight linear polyethylene. It may be attributed by the existence of short branched chains. (C) 2000 Elsevier Science Ltd. All rights reserved.