Synthesis and spectroscopic study of mesoporous aluminum methylphosphonate foam templated by dibutyl methylphosphonate

New types of templates and novel interactive mechanisms between template and framework are very important for creating porous materials. In this work, by using neutral dibutyl methylphosphonate as a template, an inorganic-organic hybrid mesoporous material, aluminum methylphosphonate, was prepared. The as-synthesized material was studied by P-31 magnetic angle spinning nuclear magnetic resonance (MAS NMR), Al-27 MAS NMR, C-13 CP/MAS, FT-IR spectroscopy, thermogravimetry (TG), differential thermal analysis (DTA), and transmission electron microscopy. After thermal treatment at 673 K and 10 mmHg for 2 h, hybrid mesoporous foam was obtained. The transformation process was investigated by FT-IR. TG-DTA results indicate that the methyl group bonded to the framework keeps intact up to 792 K under air and 823 K under nitrogen. The characterization results from nitrogen gas adsorption-desorption measurements show that the BET surface area and the Barrett-Joyner-Halenda desorption cumulative pore volume of the foam are 90 m(2) g(-1) and 0.32 cm(3) g(-1) respectively. (C) 2003 Elsevier Inc. All rights reserved.

A simple preparation of stationary phase of alkylamide reversed-phase liquid chromatograph for the separation of basic substances

A simple preparation process of alkylamide phase for reversed-phase HPLC (RP-HPLC) is described. The process includes aminopropyltrimethoxysilane firstly reacted with octanoyl chloride, then the intermediate was coupled onto porous silica. The resultant bonded silica has a reproducible ligand surface concentration and homogenous bonded ligand distribution on the porous silica. Characterization of prepared packing was carried out with elemental analysis, solid-state C-13 NMR and Fourier transform infrared (FT-IR). Chromatographic evaluations were carried out by using a mixture of organic compounds including acidic, basic and neutral analytes under methanol/water as binary mobile phase. The results showed that the stationary phase have excellent chromatographic properties and can be efficiently used for the separation of basic compounds.

Structure of an unexpected trimer from the reaction of ageratochromene II with aluminum chloride

A new trimer from the reaction of ageratochromene [1] (6,7-dimethoxy-2,2-dimethyl-1-benzopyran) with anhydrous aluminum chloride was shown to be 3,4-dihydro-6,7-dimethoxy-2,2-dimethyl-3-(6',7'-dimethoxy-2',2'-di-methyl-2H-1-benzopyran-4'-yl)-4-(3" 4"-dihydro-6", 7"-dimethoxy-2",2"-dimethyl-2H-1-benzopyran-3"-yl)-2H-1-benzopyran. Its structure was confirmed by NMR (H-1, C-13, DEPT-135. COSY, HMBC, HSQC, TOCSY and NOESY), IR, mass spectra and elemental analysis. Copyright (C) 2002 John Wiley Sons, Ltd.

Characterization of stable isotope fractionation during methane production in the sediment of a eutrophic lake,lake dagow,germany

We measured delta C-13 of CO2, CH4, and acetate-methyl in profundal sediment of eutrophic Lake Dagow by incubation experiments in the presence and absence of methanogenic inhibitors chloroform, bromoethane sulfonate (BES), and methyl fluoride, which have different specificities. Methyl fluoride predominantly inhibits acetoclastic methanogenesis and affects hydrogenotrophic methanogenesis relatively little. Optimization of methyl fluoride concentrations resulted in complete inhibition of acetoclastic methanogenesis. Methane was then exclusively produced by hydrogenotrophic methanogenesis and thus allowed determination of the fractionation factors specific for this methanogenic pathway. Acetate, which was then no longer consumed, accumulated and allowed determination of the isotopic signatures of the fermentatively produced acetate. BES and chloroform also inhibited CH4 production and resulted in accumulation of acetate. The fractionation factor for hydrogenotrophic methanogenesis exhibited variability, e. g., it changed with sediment depth. The delta C-13 of the methyl group of the accumulated acetate was similar to the delta C-13 of sedimentary organic carbon, while that of the carboxyl group was by about 12 parts per thousand higher. However, the delta C-13 of the acetate was by about 5 parts per thousand lower in samples with uninhibited compared with inhibited acetoclastic methanogenesis, indicating unusual isotopic fractionation. The isotope data were used for calculation of the relative contribution of hydrogenotrophic vs. acetoclastic methanogenesis to total CH4 production. Contribution of hydrogenotrophic methanogenesis increased with sediment depth from about 35% to 60%, indicating that organic matter was only partially oxidized in deeper sediment layers.

Effects of afforestation on soil carbon turnover in China's subtropical region

Afforestation in China's subtropics plays an important role in sequestering CO2 from the atmosphere and in storage of soil carbon (C). Compared with natural forests, plantation forests have lower soil organic carbon (SOC) content and great potential to store more C. To better evaluate the effects of afforestation on soil C turnover, we investigated SOC and its stable C isotope (delta C-13) composition in three planted forests at Qianyanzhou Ecological Experimental Station in southern China. Litter and soil samples were collected and analyzed for total organic C, delta C-13 and total nitrogen. Similarly to the vertical distribution of SOC in natural forests, SOC concentrations decrease exponentially with depth. The land cover type (grassland) before plantation had a significant influence on the vertical distribution of SOC. The SOC delta C-13 composition of the upper soil layer of two plantation forests has been mainly affected by the grass biomass C-13 composition. Soil profiles with a change in photosynthetic pathway had a more complex C-13 isotope composition distribution. During the 20 years after plantation establishment, the soil organic matter sources influenced both the delta C-13 distribution with depth, and C replacement. The upper soil layer SOC turnover in masson pine (a mean 34% of replacement in the 10 cm after 20 years) was more than twice as fast as that of slash pine (16% of replacement) under subtropical conditions. The results demonstrate that masson pine and slash pine plantations cannot rapidly sequester SOC into long-term storage pools in subtropical China.

萤火虫的荧光素酶基因克隆表达及发光行为的初步研究

本研究围绕萤火虫的荧光素酶克隆表达和发光行为两方面来进行。首先对萤火虫的发光体系和发光行为进行了概述，然后对萤火虫荧光素酶cDNA进行了克隆表达分析，探讨了日行性和夜行性萤火虫荧光素酶的差异。最后通过萤火虫的饲养和发光行为观察研究，对卵发光的意义进行了探讨。本研究克隆了三种云南萤火虫的荧光素酶基因，并成功表达出两种有活性的荧光素酶。其中日行性萤火虫云南窗萤(Pyrocoelia pygidialis)的荧光素酶基因完成了首次克隆，并在大肠杆菌中成功表达出有功能的荧光素酶。测序结果表明：P. pygidialis荧光素酶的cDNA序列有1647个碱基，编码548个氨基酸残基。系统发育分析表明云南窗萤与同属三种发光很亮的萤火虫不形成单系，在一定程度上印证了P. pygidialis以及同属微弱发光的日行性种类与持续发出很亮荧光的夜行性种类构成窗萤属两个分支的观点；并且从发光器官的形态差异初步推断这两个分支之间是独立进化的。荧光素酶的结构模拟分析表明，云南窗萤荧光素酶的N端和C端结构域之间的裂沟处存在着五个多肽环，这是已知荧光素酶推测的活性位点。日行性的云南窗萤和三种夜行性萤火虫的荧光素酶有13个不同氨基酸，位于模拟的分子结构表面。这些氨基酸的差异，有利于进一步分析日行性和夜行性萤火虫荧光素酶结构的不同。对栉角雪萤(Diaphanes pectinealis)的荧光素酶cDNA也完成了克隆表达。结果表明其cDNA序列有1647个碱基，编码548个氨基酸残基，比从基因组中获得基因序列多3个碱基。体外表达产物在底物存在时发出黄绿色光。对雌光萤科Rhagophthalmus sp.的荧光素酶基因进行了克隆和氨基酸序列比对。得出其荧光素酶基因与来自同一科的荧光素酶基因有最高的一致性为90.7％，和鞘翅目另外三个科的物种的一致性在65％以下，显示出雌光萤科独特的分类地位。通过对采自昆明郊区的云南窗萤和一种扁萤属萤火虫的饲养和发光行为的观察，得出萤火虫的卵和蛹阶段持续发微弱的光的结论，且首次发现了卵发光在发育过程中的变化。本文对卵发光行为进行了描述，并在此基础上对萤火虫卵和蛹两阶段发光的原因和意义进行了探讨。

Effect of acetylation on the properties of corn starch

Acetylated corn starches with different degrees of substitution (DS 0.85, DS 1.78, DS 2.89) were synthesized by the reaction of corn starch with acetic anhydride in the presence of acetic acid under varying reaction temperatures. The product was characterized by FTIR spectroscopy, H-1 NMR, X-ray diffraction and contact angle measurement. Acid-base titration and H-1 NMR methods were employed to determine the degree of substitution of product. FTIR spectroscopic analysis showed that the characteristic absorption intensities of esterified starch increased with increase in the degree of substitution, and the characterized peak of hydroxyl group almost disappeared in the spectrum of DS 2.89 acetylated starch. The detailed chemical microstructure of native starch and acetylated starch was confirmed by H-1 NMR, C-13 NMR and C-13-(1) H-1 COSY spectra.

Solution-processable highly efficient yellow- and red-emitting phosphorescent organic light emitting devices from a small molecule bipolar host and iridium complexes

A bipolar transport compound, 2,5-bis(4-(9-(2-ethylhexyl)-9H-carbazol-3-yl) phenyl)-1,3,4-oxadiazole (CzOXD), incorporating both electron-and hole-transport functionalities, was synthesized and fully characterized by H-1 NMR, C-13 NMR, elemental analysis and mass spectrometry. Its thermal, electrochemical, electronic absorption and photoluminescent properties were studied

Synthesis of novel star-like hyperbranched polymers with poly(amido amine) core and poly(L-lysine) shell

Hyperbranched poly(amido amine)s containing vinyl and hydroxyl groups were successfully synthesized via Michael addition polymerization of triacrylamide (TT) and 3-amino-1,2-propanediol (APD) with equal molar ratio in feed. H-1, C-13 and HSQC NMR techniques were used to clarify the structure of hyperbranched polymers and polymerization mechanism.

Synthesis and micellization of star-like hyperbranched polymer with poly(ethylene oxide) and Poly(epsilon-caprolactone) arms

Novel star-like hyperbranched polymers with amphiphilic arms were synthesized via three steps. Hyperbranched poly(amido amine)s containing secondary amine and hydroxyl groups were successfully synthesized via Michael addition polymerization of triacrylamide (TT) and 3-amino-1,2-propanediol (APD) with feed molar ratio of 1:2. H-1, C-13, and HSQC NMR techniques were used to clarify polymerization mechanism and the structures of the resultant hyperbranched polymers

Synthesis, characterization and catalytic properties of chiral BINOL functionalized mesoporous silicas for enantioselective Morita-Baylis-Hillman reaction

Several Chiral BINOL functionalized mesoporous silicas were prepared by post grafting of organosilane derivatives of (S)-BINOL (1,1'-bi-2-naphthol) on SBA-15 and characterized by C-13 CP/MAS NMR, FT-IR, UV-visible absorption spectra, elemental analysis, powder XRD, nitrogen adsorption-desorption isotherms and TEM techniques. Their catalytic properties were demonstrated in enantioselective Morita-Baylis-Hillman reaction of 3-phenylpropanal and cyclohexenone.

Spontaneous volume transition of polyampholyte nanocomposite hydrogels based on pure electrostatic interaction

A circular system is employed in this paper to investigate the swelling behaviors of polyampholyte hydrogels; this circular system can effectively eliminate the disturbance of various factors and keep the surrounding environment constant. It is found that there exists a spontaneous volume transition to the collapsed state of polyampholyte hydrogels, which is attributed to the overshooting effect, and the transition can occur repeatedly under certain conditions. C-13 NMR is employed to investigate the swelling behavior of polyampholyte hydrogels.

Styrene polymerization catalyzed by metal porphyrin complex/MAO for in situ synthesizing polystyrene containing air stable pi cation radicals

A novel catalyst system based on nickel(II) tetraphenylporphyrin (Ni(II)TPP) and methylaluminoxane for styrene polymerization was developed. This catalyst system has a high thermal stability and show fairly good activity. The obtained polystyrene (PS) was isotactic-rich atactic polymer by C-13 NMR analysis, and its molecular weight distribution was rather narrow (M-w/M-n approximate to 1.6, by GPC analysis). ESR revealed that Ni(II)TPP pi cation radicals were formed in the polymerization and could remain in the resulting PS stably. The mechanism of the polymerization was discussed and a special coordination mechanism was proposed. The PS product containing Ni(II)TPP pi cation radicals can be used as a potential functional material.

Synthesis and Characterization of Urea Bridged Hybrid Periodic Mesoporous Organosilica Materials

Urea bridged organic-inorganic hybrid mesoporous SiO2 materials (U-BSQMs) were synthesized through a sol-gel procedure by co-condensation of bis(triethoxysilyl propyl) urea (BSPU) under basic conditions using cetyltrimethylammonium bromide (CTAB) as organic template. X-ray diffraction (XRD) and transmission electron microscopy (TEM) confirmed the mesoporous structure of the sample. Fourier-transform infrared spectroscopy (FT-IR), solid state CP-MAS NMR spectroscopy of Si-29 (Si-29, CP-MAS NMR) and C-13 (C-13 CP NMR) indicated that most of the Si-C bonds are unbroken during the synthesis process.

Band Gap Tunable, Donor-Acceptor-Donor Charge-Transfer Heteroquinoid-Based Chromophores: Near Infrared Photoluminescence and Electroluminescence

A series of D-pi-A-pi-D type of near-infrared (NIR) fluorescent compounds based on benzobis(thia diazole) and its selenium analogues were synthesized and fully characterized by H-1 and C-13 NMR, high-resolution mass spectrometry, and elemental analysis. The absorption fluorescence, and electrochemical properties were also studied. Photoluminescence of these chromophores ranges from 900 to 1600 nm and their band gaps are between 1.19 and 0.56 eV.