2016 Volume 79 Issue 5

Research Progress in the Probes Targeting DNA G-quadruplex
Zhang Suge , Sun Hongxia , Tang Yalin
2016, 79(5): 387-394
[Abstract](701) [FullText HTML] [PDF 1133KB](0)
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G-quadruplexes are non-canonical secondary DNA/RNA structure formed by guanine-rich oligonucleotide sequences, which widely exist in eukaryotic genomes, such as telomeric DNA, rDNA, and promoter regions of oncogenes. G-quadruplex structure may play a pivotal role in the control of a variety of cellar processes including telomere maintenance, replication, transcription, and translation. Detection of the quadruplex structures using the probes with high specificity and sensitivity will help us to explore the distribution, function, and mechanism of G-quadruplexes in human cells, and may also provide new diagnostic and therapeutic approaches of cancer via targeting G-quadruplex. In the last two decades, various targeting G-quadruplex probes which have high selectivity and sensitivity have been designed, and these probes have been used to recognize different G-quadruplex topologies in solutions. A few probes have also been applied to recognize G-quadruplex in vivo. This article reviews the typical probes targeting G-quadruplexes as well as their application in detection G-quadruplexes in chromosome and cell level. Authors hope this paper can provide a certain reference for design of G-quadruplex-targeting probes and further realization of G-quadruplex detection in living cells.
Reactions of Noble Metal Species with Methane in Gas-Phase
Zhang Meiqi , Zhao Yanxia , He Shenggui
2016, 79(5): 395-402
[Abstract](549) [FullText HTML] [PDF 1785KB](9)
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Noble metals have been identified to exhibit excellent performance in methane chemistry. Gas phase study of chemical reactions between noble metal species and methane permits to uncover the active sites and elementary reaction mechanisms involved in condensed-phase catalytic reactions at a strictly molecular level. In this review, we summarize the recent progress in activation and transformation of methane by noble metal species including single atoms, atomic ions, cluster ions, hydrides, halides, oxides, metal-methyl complexes, and heteronuclear clusters. The mechanistic difference of methane activation by different noble metal systems is also discussed in detail.
Recent Advances in CO2 Adsorption and Separation of MOFs Decorated with Polar Functional Groups
Liu Shuang , Liu Lantao
2016, 79(5): 403-406,411
[Abstract](323) [FullText HTML] [PDF 1225KB](0)
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Based on the urgent practical needs for removal and recovery of CO2 from the exhaust gas, it is one of research hotspots to construct functional MOFs with water resistance, high capacity and separation for CO2 adsorption. In this paper, the high pressure CO2 adsorption of MOFs materials is briefly summarized, and taking into account the actual industrial application conditions, recent progress in low pressure CO2 adsorption and separation by MOFs which have been decorated with nitrogen or heteroatom-containing polar functional groups is highlighted.
Progress in Oilfield Scale Removers
Liu Jianghong , Wang Qi , Ren Jingwei , Lu Yan
2016, 79(5): 407-411
[Abstract](951) [FullText HTML] [PDF 894KB](1)
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Oilfield scale removers are employed for clearing scales adsorbed on the surface of devices and stratum in the process of oilfield production by using chemical methods. This paper summarizes the main factors affecting formation of oilfield scale and introduces the main types of scale removers and their advantages and disadvantages. Types, effects and main problems existed of various new oilfield scale removers are analyzed. Furthermore, the future research direction and development of oilfield scale removers are prospected.
First-Principles Calculations of Electronic Structure of LiFePO4 with Vacancy and Impurity
Xu Chenghao , Wang Li , He Xiangming , Shang Yuming
2016, 79(5): 412-417
[Abstract](311) [FullText HTML] [PDF 1460KB](1)
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The electronic structures of LiFePO4 crystal with various vacancy defects and anion doping were studied by the first-principles method based on DFT. To providing theoretical basis for the studies of LiFePO4 modification experiments, the effects of defects on the electrochemical performance were illustrated by the analysis of the band structure, the density of states and the population distribution. The results showed that Li, Fe and O-site vacancy defects almost have no effect on the band structure of LiFePO4, no new conduction band appears in the band gap though the forbidden band width decreases, and the rise in total energy indicates the instability of structure; P-site vacancy defects introduce two new conduction bands in the band gap, the decrease in forbidden band width is obviously in favor of the electronic conductivity, the increased total energy results in the instability of structure, however, it may be work to get high performance LiFePO4, due to the small amount of impurity phase produced during annealing; F-doping defects show significant effect on the band structure of LiFePO4 which makes the transform from n-type semiconductor into p-type semiconductor, indicating of tremendous improvement in the electronic conductivity. Besides, the improvement in the stability of structure can also be deduced according to the declined total energy.
Theoretical Studies on the Gas-Phase SNAr Reactions of Halobenzenes and Halide Anions
Li Qianggen , Mao Shuang , Cai Wanfei , Zheng Yan , Liu Liuxie
2016, 79(5): 418-424
[Abstract](805) [FullText HTML] [PDF 1474KB](0)
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The gas-phase SNAr reactions of halobenzenes and halide anions (ArY + X-=ArX + Y-, X, Y=F, Cl, Br and I) were investigated by the B3LYP and MP2 methods with the 6-311+G** basis set. Calculated results indicate that the SNAr reactions of halobenzenes and halide anions in the gas-phase proceed via a concerted mechanism, while a two-step addition-elimination pathway is founded with the formation of a stable σ-complex for X=Y=F. In view of thermodynamics and kinetics, the gas-phase SNAr reactions of halobenzenes attacked by fluoride ion are easy to proceed (overall barrier ΔGb=9.0~17.3 kJ/mol), whereas it would be hardly possible to observe the reactions for X=Cl-, Br- and I- due to the higher overall barriers (ΔGb=91.3~202.5 kJ/mol). In addition, the reactivities of the titled reactions can be analyzed by proton affinity (PA), the highest occupied orbital energy (EHOMO) and Mulliken electronegativity (χ) of the halide as well as the Wiberg bond order (BO) and NPA charges (Q). The break of the C-Y bond in transition state (TS) is mainly responsible for the reaction barriers, and the nucleophilicity of the halide anion is mainly dominated by EHOMO, while the leaving-group ability of halogen anion is governed by PA or χ.
Synthesis of BaxWO4-Sr(0.985-x)MoO4:0.01Sm3+ Red Phosphors by Molten Salt Method and Their Luminescence Performance
Li Hui , Li Yan , Liang Yaqin
2016, 79(5): 425-429
[Abstract](431) [FullText HTML] [PDF 1441KB](0)
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A series of BaxWO4-Sr(0.985-x)MoO4: 0.01Sm3+ red phosphors were synthesized by molten salt method with different calcining temperatures, and their luminescence properties were investigated for their application in white light-emitting diodes (WLEDs). The phase structure, luminescence properties and micro-morphology of the as-synthesized powders were characterized by XRD, PL and SEM, respectively. The influences of the different ratios of Ba2+ and Sr2+ and the different calcining temperatures on the phase structure, luminescence properties and micro-morphology of the powders were studied. The results showed the phosphors have pure phase of tetragonal structure, good luminescent properties, and good micro-morphology synthesized under the optimum calcining condition of temperature 900℃, holding time 4h and the Ba/Sr ratio of 7:2.85. The emission peaks of the phosphors locate at 565nm, 602nm, and 648nm under exciting of near ultraviolet light (404 nm), So the synthesized phosphors may be a potential luminescent material for LED applications.
Interaction of Thiophene-Appended Ruthenium Complexes with Yeast-RNA
Liu Xiaoyuan , Zhao Xiaolong , Sang Qian , Du Junlan , Li Zhilin , Wang Kezhi
2016, 79(5): 430-437
[Abstract](261) [FullText HTML] [PDF 2317KB](0)
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The interaction of thiophene-appended ruthenium complexes [Ru(bpy)2(Htip)]Cl2(1) [Ru(Htip)2(dppz)]Cl2(2), [Ru(Htip)3]Cl2(3) and [Ru2(bpy)4(H2bipt)]Cl4(4) {bpy=2,2'-bipyridine, Htip=2-(thiophen-2-yl)-1H-imidazo[4,5-f][1,10] phenanthroline, H2bipt=2,5-bis[1,10] phenanthrolin[4,5-f]-imidazol-2-yl) thiophene, dppz=dipyrido[3,2-a:2',3'-c] phenazine} with yeast-RNA had been investigated by UV-Vis and emission spectroscopy titrations, steady-state emission quenching and salt effect studies, and the RNA and calf thymus DNA (ct-DNA) binding properties of the complexes had also been compared. The results suggested that this kind of thiophene-containing complexes is the strong intercalators of RNA, and in particular, the RNA binding constants of complex 2 and 3 were obtained to be (2.48±0.02)×107L/mol and (4.04±0.04)×107L/mol, which are larger than their reported DNA binding constants and demonstrate the higher RNA binding affinity of the complexes than that of DNA. These complexes could bind to RNA with high strength not only at low salt concentration but also at high salt concentration, with the binding constants as large as (1.07±0.33)×105, (5.62±0.19)×106, (2.11±0.03)×107 and (3.74±0.45)×105L/mol for complex 1, 2, 3 and 4 at the concentration of 100mmol/L NaCl, respectively. Notably, in contrast to the significant increase of emission intensities for DNA binding of the complex 1 and 2, the fluorescence intensity of 1 decreases evidently upon binding to RNA, and there is almost no fluorescence when 2 is free in aqueous solution or bound to RNA, which indicates that complex 1 and 2 display favorable fluorescence recognition property between RNA and DNA.
The Carbon Deposition Characteristics of Propylene in Oil Shale Retorting Gas on Different Heat-Resistant Alloys
Bai Jingru , Zhang Benxi , Zhang Wei , Yue Mingbo
2016, 79(5): 438-442
[Abstract](250) [FullText HTML] [PDF 1370KB](0)
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An experimental research for the carbon deposition characteristics of propylene in oil shale retorting gas was carried out under different conditions including temperatures (700, 750 and 800℃), gas flow (20, 30 and 40 mL/min) and constant time (20min) by a home-made continuous flow reactor system. Different reactors made by 2520 and 316L stainless steel tubes were used. The results showed that the initial carbon deposition temperature range was 630~650℃ and 670~690℃ for 2520 and 316L, respectively. The carbon deposition morphology observed by SEM indicated that no matter 2520 or 316L there were two species of carbon, i.e. filamentous carbon and amorphous carbon. The amount analysis of carbon deposition under different conditions by TPO methods showed that 316L had a characteristic of metal powder resistance. The results of the TG/DSC analyses for carbons stripped proved that the carbon deposition activity of 316L stainless steel is higher than that of 2520 stainless steel.
Study on the Polymerization Process of Polyaniline in Acetone/Water System
Fei Yang , Jin Lei , Song Hongwei , Huang Hui , Guo Zhongcheng
2016, 79(5): 443-447
[Abstract](395) [FullText HTML] [PDF 1185KB](0)
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Polymerization process of polyaniline (PAn) in acetone/water system was investigated. The reaction mechanism was obtained from analyses of open circuit potential, polymerization temperature, intrinsic viscosity and molecular structure of the intermediates. The results showed that the particle size and molecular weight of synthesized PAn can be effectively controlled in acetone/water system. When volume ratio of acetone/H2O is 0.2, the synthesized PAn has better performance. In acetone/water system, high potential time, chain growth time and the acceleration response time have been greatly extended in the polymerization process. As-synthesized PAn is head-to-tail structure. In the chain-terminating step, the high oxidation state in termediates gradually transformed to PAn products.
Synthesis and Complexing Capacity of Two Triptycene-Based Molecular Tweezers
Peng Xiaoxia
2016, 79(5): 448-452
[Abstract](234) [FullText HTML] [PDF 1254KB](1)
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Triptycene-based molecular tweezers 1 and 2 have been synthesized, their structure were characterized by 1H NMR, 13C NMR, MALDI-TOF, Elemental analysis and X-ray crystallography. The interactions between hosts and seven electron-deficient guests in solution were studied by 1H NMR titration and ESI-MS. The results showed that: 1) 1:1 complexes were formed between most of the hosts and guests; 2) host 1 has better binding ability than host 2; 3) the hosts would selectively bind with the electron-deficient guests. Moreover, the complexing behavior of 1·G1 was simulated by the program ORTEP 1.076, which suggested that the noncovalent interactions play important roles in the formation of sandwich-type host-guest complexes.
Efficient Synthesis of 4-Aminobutan-1-ol
Zhao Hui , Su Duomeng , Liu Yujun , Wang Kai
2016, 79(5): 453-454
[Abstract](374) [FullText HTML] [PDF 1036KB](1)
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4-aminobutan-1-ol was synthesized from 2,3-dihydrofuran by hydrolysis of the starting material, condensation with hydroxylamine and reduction with Renay-Ni in turn. The process exhibits advantages such as cheap starting materials simple operation, high yield. It processes a potential for industrial applications in future.
Synthesis of New Asymmetric Pentamethine Cyanine Dye Containing Carboxypentyl and Protein Labeling
Zhang Pengchao , Wang Sheng , Wu Pin , Tang Kun , Zhang Fuli
2016, 79(5): 455-458
[Abstract](473) [FullText HTML] [PDF 1223KB](0)
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2,3-Dimethyl-3-carboxypentyl-3H-indol-5-sulfonic acid was synthesized with 4-hydrazinyl-benzenesulfonic acid and 7-methyl-8-oxo-nonanoic acid. 1-sulfopropyl-2,3,3-trimethyl-3H-indol-5-sulfonic acid was synthesized with 2,3,3-trimethyl-3H-indol-5-sulfonic acid and 1,3-propane sultone. A new water-soluble asymmetric pentamethine indocyanine dye Cy5 was prepared by hemicyanine syntheticism and separated by the self-made C18 reversed-phase chromatographic column with the yield of 57%. The structures of target compound and intermediates were confirmed by 1H NMR and HRMS. The spectral properties and biological labeling application of Cy5 was detected and explored. The water-solubility and photostability of the dye are excellent, and the maximum absorption and fluorescence emission wavelengths in water are 646 nm and 666 nm respectively. The fluorescence quantum yield reaches 0.2, and the D/P of protein labeling is 1.56 when the molar ratio of dye to BSA was 2:1.
FeCl3·6H2O-Mediated Deacetylation/Decarboxylation of α-Carbonyl-α-aceto/Carboxyl Cyclic Ketene Dithioacetals
Zhang Xueyu , Yu Haifeng , Diao Quanping , Yin Jianan , Xi Chunmei , Wu Yue
2016, 79(5): 459-462
[Abstract](392) [FullText HTML] [PDF 1250KB](0)
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An inexpensive and environmentally friendly FeCl3·6H2O-mediated deacetylation/decarboxylation of α-carbonyl-α-aceto/carboxyl cyclic ketene dithioacetals had been developed. The procedure was characterized by mild reaction condition, environmentally benign and simplicity.
The Improvement of Synthesis of 3-Aminoindolin-2-one
Zheng Chenglong , Liu Yizhou , Kang Congmin
2016, 79(5): 463-465
[Abstract](337) [FullText HTML] [PDF 1181KB](0)
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The titled compound was synthesized by the hydrogenation reduction of 3-(hydroxyimino) indolin-2-one, which was synthesized by the reaction of isatin and hydroxylamine hydrochloride. Using Pd/C hydrogenation reduction method, the product yield can be increased to 82.8%, higher than the 71.0% reported in literature. The synthesis has the advantages of high yield, good operability, easy post-processing, low cost and environmental benign, so it is suitable for mass production of the titled compound.
Optimization on Design of Andes Virus Inhibitory Peptides
Lu Yongzhong , Kang Daole
2016, 79(5): 466-469
[Abstract](298) [FullText HTML] [PDF 1335KB](0)
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Andes virus (ANDV) belongs to the genus Hantavirus and can cause hantavirus cardiopulmonary syndrome, which is a serious threat to human health and life, but no specific therapy is available now. The ANDV inhibitory peptides are of potential value for the therapy. In this work, quantitative structure-activity relationships (QSAR) research on a group of ANDV inhibitory peptides was conducted with the whole molecular descriptors of peptides, and the QSAR models established were applied to optimize the inhibitory peptides. The results showed that the genetic algorithm-partial least squares(GA-PLS) models exhibited good performance in stability and predictability (R2>0.80,Qext>20.58); and peptides with higher activity than the original ones were designed based on the models, which laid foundation for further synthesis and experimental test.
《Detective Conan and Explore of the Secrets of Chemistry》——Practice and Demonstration of Humanistic Literacy in Scientific Education
Zhao Siqi , Luo Yiming , Fu Ganghua , Wang Xiang , Xu Hai
2016, 79(5): 470-473
[Abstract](1031) [FullText HTML] [PDF 1243KB](1)
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A new course《Detective Conan and Explore of the Secrets of Chemistry》combined with famous cartoon 《Detective Conan》 has been offered since 2012 in Central South University, and has been well received in campus and society because of its excellent teaching effects. This paper introduces the status of this course as a new and successful education mode of humanistic literacy in scientific education and proposes the parts for needing improvement of this mode.
Victor Moritz Goldschmidt: Founder of Modern Geochemistry and of Crystal Chemistry
Zhang Qingjian
2016, 79(5): 474-479
[Abstract](1599) [FullText HTML] [PDF 1454KB](0)
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Victor Moritz Goldschmidt (1888-1947), founder of modern geochemistry, discovered the laws determining the distribution of the chemical elements on earth. His work on the relative abundances of the elements, atomic and ionic radii, inter-ionic distances, the effect of radius ratio on coordination number in crystals, and the lanthanide contraction had provided the basis for modern crystal chemistry. Herein his life and work are introduced.
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