Experimental and modeling study on decomposition kinetics of methane hydrates in different media

The decomposition kinetic behaviors of methane hydrates formed in 5 cm3 porous wet activated carbon were studied experimentally in a closed system in the temperature range of 275.8-264.4 K. The decomposition rates of methane hydrates formed from 5 cm3 of pure free water and an aqueous solution of 650 g x m(-3) sodium dodecyl sulfate (SDS) were also measured for comparison. The decomposition rates of methane hydrates in seven different cases were compared. The results showed that the methane hydrates dissociate more rapidly in porous activated carbon than in free systems. A mathematical model was developed for describing the decomposition kinetic behavior of methane hydrates below ice point based on an ice-shielding mechanism in which a porous ice layer was assumed to be formed during the decomposition of hydrate, and the diffusion of methane molecules through it was assumed to be one of the control steps. The parameters of the model were determined by correlating the decomposition rate data, and the activation energies were further determined with respect to three different media. The model was found to well describe the decomposition kinetic behavior of methane hydrate in different media.     

The application of C-N.M.R. spectroscopy to the determination of the stereochemistry of Diels-Alder adducts

Long-range (³J) ¹³C-H coupling is a reliable probe to evaluate the stereochemistry of cycloaddition products. The method is best applied to carbonyl containing adducts but not restricted to them. Several structures have been revised and new ones evaluated.     

Crystal structures of the complexes of rare earth picrates with N, N, N′, N′-tetraphenyl-3, 6-dioxaoctanediamide

The complexes of rare earth picrate with N, N, N′, N′-tetraphenyl-3, 6-dioxaoctanediamide (TDD), [Eu(pic)₃(TDD)]-2CH₃CN and [Y(pic)₃(TDD)], have been synthesized. The crystal structures reveal that TDD acts as a tetradentate ligand, forming a ring-like coordination structure with its oxygen atoms together with one oxygen atom of the bidentate picrate. In the Eu (III) complex, the europium ion with a larger ionic radius lies out of the ring, while in the Y (III) complex, the yttrium ion with a smaller ionic radius enters the cavity of the ligand. The structures of the complexes are greatly affected by the ionic radii due to participation of the picrates in coordination. Project supported by the National Natural Science Foundation of China, the Doctoral Foundation of the State Education Commission of China, and the Climb Plan Foundation of the State Science and Technology Commission of China.     

Determining the folding and unfolding rate constants of nucleic acids by biosensor. Application to telomere G-quadruplex

Nucleic acid molecules may fold into secondary structures, and the formation of such structures is involved in many biological processes and technical applications. The folding and unfolding rate constants define the kinetics of conformation interconversion and the stability of these structures and is important in realizing their functions. We developed a method to determine these kinetic parameters using an optical biosensor based on surface plasmon resonance. The folding and unfolding of a nucleic acid is coupled with a hybridization reaction by immobilization of the target nucleic acid on a sensor chip surface and injection of a complementary probe nucleic acid over the sensor chip surface. By monitoring the time course of duplex formation, both the folding and unfolding rate constants for the target nucleic acid and the association and dissociation rate constants for the target-probe duplex can all be derived from the same measurement. We applied this method to determine the folding and unfolding rate constants of the G-quadruplex of human telomere sequence (TTAGGG)(4) and its association and dissociation rate constants with the complementary strand (CCCTAA)(4). The results show that both the folding and unfolding occur on the time scale of minutes at physiological concentration of K(+). We speculate that this property might be important for telomere elongation. A complete set of the kinetic parameters for both of the structures allows us to study the competition between the formation of the quadruplex and the duplex. Calculations indicate that the formation of both the quadruplex and the duplex is strand concentration-dependent, and the quadruplex can be efficiently formed at low strand concentration. This property may provide the basis for the formation of the quadruplex in vivo in the presence of a complementary strand.     

Modification of a packed column gas chromatograph/mass spectrometer

A packed-column gas-chromatograph/mass-spectrometer (GC/MS), Hewlett-Packard 5982, was modified to accommodate fused silica capillary columns. The original GC/MS interface and chemical-ionization sample-line in the ion-source were changed to allow the end of a fused silica capillary column to enter the ion-chamber directly. For chemical-ionization operation, the reagent gas was brought into the MS through the direct-insertion probe port. The calibration compound was introduced through the electron-impact sample-inlet, which simplified the operation. The modified system yields higher sensitivity and more efficient separation, as well as simpler operation, without sacrificing any original instrument functions.     

Reduction and methyl transfer kinetics of the alpha subunit from acetyl coenzyme a synthase

Stopped-flow was used to evaluate the methylation and reduction kinetics of the isolated alpha subunit of acetyl-Coenzyme A synthase from Moorella thermoacetica. This catalytically active subunit contains a novel Ni-X-Fe4S4 cluster and a putative unidentified n = 2 redox site called D. The D-site must be reduced for a methyl group to transfer from a corrinoid-iron-sulfur protein, a key step in the catalytic synthesis of acetyl-CoA. The Fe4S4 component of this cluster is also redox active, raising the possibility that it is the D-site or a portion thereof. Results presented demonstrate that the D-site reduces far faster than the Fe4S4 component, effectively eliminating this possibility. Rather, this component may alter catalytically important properties of the Ni center. The D-site is reduced through a pathway that probably does not involve the Fe4S4 component of this active-site cluster.     

稀土金属硼氢化物的研究(Ⅸ)——N,N''''-双(邻羟基苯叉)-1,3-丙二胺合稀土(Ⅲ)十氢十硼酸盐的合成

我们曾报道过含闭式氢硼駿根的二齿配体的稀土螯合物的合成及性质。为了解不同配体的稀土配合物在结构及性质上的差异,又合成了四齿(ONNO)配体N,N′-双(邻羟基苯叉)-1,3-丙二胺(salpr),并通过两种方法(模板合成法及配体合成法)合成了稀土配合物的闭式十氢十硼酸盐。化合物均为黄色粉末固体,室温下它们对光、空气、潮汽均稳定。     

通过教学过程和互动设计保障在线教学的效果

Based on the analysis of the courses and the investigation of students' online learning needs, an online teaching mode of "Tencent Classroom" and "Rain Classroom" with "split screen" is designed. This mode is used for the online teaching of "Foundation of Innovation and Entrepreneurship" and "Chemical Instrumentation and Automation". After two months of teaching practice, the teaching and learning were reflected and summarized, aiming to improve the performance of online teaching.     

Plasmid DNA isolation using amino-silica coated magnetic nanoparticles (ASMNPs)

A simple and efficient approach for the rapid isolation of plasmid DNA from crude cell lysates has been described. The approach took advantage of the amino-modified silica coated magnetic nanoparticles (ASMNPs) with positive zeta potential at neutral pH and superparamagnetism under the external magnetic fields. As a demonstration, the pEGFP-N3 plasmid has been concentrated and isolated from the E. coli DH5α transformed with pEGFP-N3 plasmid through electrostatic binding between the positive charge of the amino group of ASMNPs and the negative charge of the phosphate groups of the plasmid DNA. Then the pEGFP-N3 plasmid has been released easily and quickly from the pEGFP-N3 plasmid-ASMNPs complexes with 3 M NaCl. The entire procedure could be carried out by the aid of external magnetic fields in 15 min and eliminate the need of phenol, cesium chloride gradients or other noxious reagents and complexes operation. Moreover, the pEGFP-N3 plasmid obtained by this approach retains biological activity that can be suitable for restriction enzyme digestion and cells transfection with expression of green fluorescence protein.     

Molecular basis for antifreeze activity difference of two insect antifreeze protein isoforms

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.