Studies on the organometallic palladium coordinated carbosillane liquid crystalline dendrimer

A novel complex - palladium-coordinated ate-type liquid crystalline dendrimer was synthesized by a divergent approach, The product showed liquid crystalline properties from 115 degrees C to 187 degrees C, and it belonged to dinuclear species, containing two palladium centers linked by two bridging Cl, each palladium atom completes its coordinations with N atom and a sigma bond to an ortho-carbon in the phenyl ring. The microanalytical values obtained for the product are in agreement with those of compound containing ligand, palladium:and chlorine in a molar ratio of 1 : 1 : 1 and 12 palladium atoms for every scaffold.

Spectroscopic study of luminescence and energy transfer of binary and ternary complexes of rare earth with aromatic carboxylic acids and 1,10-phenanthroline

A series of rare earth (Gd, Eu, Tb) complexes with different substituent group carboxylic acids (ortho-hydroxylbenzioc acid, ortho-aminobenzoic acid and ortho-methoxy benzoic acid) and 1,10-phenanthroline were synthesized. The spectroscopic studies of the photophysical properties such as luminescence properties, energy match and intramolecular energy transfer were carried out. The lowest triplet state energies of ligands and the intramolecular energy transfer efficiencies were determined with the measurement of low phosphorescence spectra and lifetimes of Gd complexes.

Synthesis, luminescence properties and energy transfer of binary and ternary rare earth complexes with aromatic acids and 1,10-phenanthroline

A series of binary and ternary rare earth (Gd, Eu, Tb) complexes with ortho hydroxyl benzoic acid, pam aminobenzoic acid, nicotinic acid and 1,10-phenanthroline were synthesized. Phosphorescence spectra and lifetimes of Gd complexes were measured and the lowest triplet state energies of gadolinium binary complexes end the intramolecular energy transfer efficiencies were determined. The luminescence properties and energy transfer process of Eu3+ and Tb3+ complexes were discussed.

The synthesis, luminescence and energy transfer of the binary and ternary complexes of rare earth with aminobenzoic acids and 1,10-phenanthroline

Thirteen kinds of binary and ternary complexes of rare earth (Gd, Eu,Tb) with ortho (para) aminobenzoic acid and 1.10--phenanthroline were synthesized and characterized. The phosphorescence spectra and lifetimes of gadolinium complexes were measured and the lowest triplet state energies of ligands and the energy transfer efficiencies between ligands were determined. The luminescence properties and intramolecular energy transfer of these complexes were studied in details.

CHEMICAL-IONIZATION MASS-SPECTROMETRY OF SOME NITRO-CONTAINING BIFUNCTIONAL AROMATIC-COMPOUNDS - LOCATION OF PROTONATION SITE

It is found that the nitro substituent of some aromatic bifunctional compounds shows unusual reactivity towards protonation. In the chemical ionization mass spectra of nitrobenzoic acids and their esters and amides, and of nitrophenols and their ethers, protonations on the carboxyl, ester, amide, hydroxyl or alkoxyl groups are highly suppressed by that on the nitro group. As a result, fragmentations based on protonation on these groups unexpectedly become negligible. Ortho effects were observed for all the ortho isomers where the initial protonation on the nitro group is followed by an intramolecular proton transfer reaction, which leads to the expected 'normal' fragmentations. Protonation on the nitro substituent is much more favourable in energy than on any of the other substituents. The interaction of the two substituents through the conjugating benzene ring is found to be responsible for this 'unfair' competitive protonation. The electron-attracting nitro group strongly destabilizes the MH+ ions formed through protonation on the other substituent; although the COR (R = OH, OMe, OEt, NH2) groups are also electron-withdrawing, their effects are weaker than that of NO2; thus protonation on the latter group produces more-stable MH+ ions. On the other hand, an electron-releasing group OR (R = H, Me, Et) stabilizes the nitro-protonated species; the stronger the electron-donating effect of this group the more stable the nitro-protonated ions.

SOLUTION PROPERTIES OF POLYANILINE AND ITS DERIVATIVES

Solutions of polyaniline (PAn), poly(ortho-toluidine) (POT) and poly(ortho-anisidine) (PAs) in N-methyl pyrrolidinone (NMP) were examined by viscometric, gel permeation chromatographic (GPC) and theological methods. Strong intermolecular interaction and molecular aggregation are shown.

SYNTHESIS AND PROPERTIES OF POLY(ANILINE-CO-ANISIDINE)

Aniline and ortho-anisidine were chemically copolymerized at various temperatures and monomer compositions. Copolymers completely soluble in THF are prepared and characterized.

STUDIES ON OLEFIN-COORDINATING TRANSITION-METAL CARBENE COMPLEXES .20. SYNTHESIS OF 1,3-CYCLOHEXADIENE(DICARBONYL) [ETHOXY(ARYL)-CARBENE]IRON COMPLEXES AND THEIR PHOSPHINE ADDUCTS - CRYSTAL-STRUCTURE OF C6H8(CO)2FEC(OC2H5)C6H4CH3-O

Reaction of 1,3-cyclohexadiene(tricarbonyl)iron (1) with ortho-substituted aryllithium reagents ArLi (Ar=o-CH3C6H4, o-CH3OC6H4, o-CF3C6H4) in ether at low temperature, and subsequent alkylation of the acylmetalates formed with Et3OBF4 in aqueous solution at 0-degrees-C or in CH2Cl2 at -60-degrees-C gave the 1,3-cyclohexadiene(dicarbonyl)[ethoxy(aryl)carbene]iron complexes (eta4-C6H8)(CO)2FeC(OC2H5)Ar (3, Ar = o-CH3C6H4; 4, Ar = o-CH3OC6H4), and the isomerized product (eta3-C6H8)(CO)2FeC(OC2H5)C6H4CF3-o (5), respectively, among which the structure of 3 has been established by an X-ray diffraction study. Complex 3 is monoclinic, space group P2(1) with a = 8.118(4), b = 7.367(4), c = 14.002(6) angstrom, beta = 104.09(3)-degrees, V = 812.2(6) angstrom3, Z = 2, D(c) = 1.39 g cm-3, R = 0.056, and R(w) = 0.062 for 976 observed reflections. Complexes 3 and 5 were converted into the chelated allyliron phosphine adducts(eta3-C6H8)(CO)2(PR31)FeC(OC2H5)Ar (6, Ar = o-CH3C6H4, R1 = Ph; 7, Ar = o-CH3C6H4, R1 = OPh; 9, Ar = o-CF3C6H4, R1 = Ph), by reaction with phosphines in petroleum ether at low temperatures.

Axial growth of hexactinellid spicules: Formation of cone-like structural units in the giant basal spicules of the hexactinellid Monorhaphis

The glass sponge Monorhaphis chuni (Porifera: Hexactinellida) forms the largest bio-silica structures on Earth; their giant basal spicules reach sizes of up to 3 m and diameters of 8.5 mm. Previously, it had been shown that the thickness growth proceeds by appositional layering of individual lamellae; however, the mechanism for the longitudinal growth remained unstudied. Now we show, that the surface of the spicules have towards the tip serrated relief structures that are consistent in size and form with the protrusions on the surface of the spicules. These protrusions fit into the collagen net that surrounds the spicules. The widths of the individual lamellae do not show a pronounced size tendency. The apical elongation of the spicule proceeds by piling up cone-like structural units formed from silica. As a support of the assumption that in the extracellular space silicatein(-like) molecules exist that associate with the external surface of the respective spicule immunogold electron microscopic analyses were performed. With the primmorph system from Suberites domuncula we show that silicatein(-like) molecules assemble as string- and net-like arrangements around the spicules. At their tips the silicatein(-like) molecules are initially stacked and at a later stay also organized into net-like structures. Silicatein(-like) molecules have been extracted from the giant basal spicule of Monorhaphis. Applying the SDS-PAGE technique it could be shown that silicatein molecules associate to dimers and trimers. Higher complexes (filaments) are formed from silicatein(-like) molecules, as can be visualized by electron microscopy (SEM). In the presence of ortho-silicate these filaments become covered with 30-60 nm long small rod-like/cuboid particles of silica. From these data we conclude that the apical elongation of the spicules of Monorhaphis proceeds by piling up cone-like silica structural units, whose synthesis is mediated by silicatein(-like) molecules. (C) 2008 Elsevier Inc. All rights reserved.

Geochemical properties of the variolitic andesite from Susong in the Dabie orogenic belt, China

The variolitic andesite from the Susong County in the Dabie Mountains implies that it was erupted in water. The mineralogy of the varioles is primarily radiate plagioclase (albite sind oligoclase), with little pyroxene, hornblende and quartz (derived from alteration). The pyroxene, hornblende and quartz are in the interstices between plagiocalse. The matrix consists of glass, hornblende, chlorite, epidote and zoisite. It is clearly subjected an extensive alteration. The andesite has an uncommon chemical composition. The SiO2 content is about 56.8%, TiO2 = 0.9%, MgO = 6.4%, Fe2O3 (tot) = 6.7%similar to 7.6%, 100Mg/(Mg + Fe) = 64.1 similar to 66.2. Mg-# is significantly high. The andesite has high abundances of large-lithophile trace elements (e.g. K, Ba. Sr, LREE), e.g. La/Nb = 5.56 similar to 6.07, low abundances of high-strength-field elements (HFSE e.g. Ta, Nb, P, Ti), particularly Ta and Nb strongly depleted. These are consistent with the characteristics of subduction-related magmas. In the spider diagram of trace elements, from Ce to right hand, the abundances of elements decrease quickly, showing a character of the continental margins. There has a strong punishment of light-rare-earth elements, with a significant diffraction of REEs (the mean value of (La/Yb)(N) is 32.84). No Eu anomaly, but there are anomaly high (La/Yb)(N) = 28.63 similar to 36.74, (La/Y)(N) = 70.33 similar to 82.4. The elements Y and Yb are depleted greatly, Y<20 g/g, Y-N = 2.74 similar to 2.84, Yb-N = 2.18 similar to 2.35. From the La-(La/Sm) diagram, the andesite is derived from partial melting. But the epsilone value of Nd is - 18.7 similar to -19.2, so that the material source may be the mantle materials affected by the crustal materials. The Nd model age is 1.9 Ga indicating that the variolitic basaltic andesite was resulted from the mantle wedge of North China block, which had the Nd model age of 2.5Ga, when the Yangze block which had the Nd model age of 1.7Ga subducted beneath it. So the variolitic andesite has characteristics of the island-are volconic rocks oil a continental basement in the vicinity of the destructive continental margin.

Mineral chemistry and its genetic significance of olivine in Cenozoic basalts from the South China Sea

We dredged lots of Cenozoic basalts from areas covered from the northern sub-slope to the southern sub- slope of the South China Sea. Based on the study on mineral chemistry of clinopyroxenes in these Cenozoic hasalts, this paper indicates that pyroxenes are mostly enstatite and a few of augite, sahlite and Ca-rich pyroxene. Pyroxene microlite has higher content in, Ca, Ti and Fe than pyroxene phenocryst, it may reflect that the evolution trend of host magma of pyroxene is coincidence with that of alkali rock series. The depth of magma chambers which calculated from equilibrium temperatures and pressures between clinopyroxene and melt are as follows, that of magma of tephrite is about 49km, that of magma of trachybasalt is about 25km, and that of magma of basalt is about 15km. Correspondingly, Equilibrium temperatures( K) of three types rocks mentioned above gradually decrease from 1535 1498 to 1429 to 1369. By using discriminant plot which developed from pyroxene and alkali discriminant diagram of host rock, Cenozoic basalt from the South China Sea belongs to intraplate alkali basalt. The results suggest that alkali basalt series in the study area may be the products of continuous evolution of mantle plume, which result from some physical and chemistry process including partial melting and fractional crystallization of mantle plume during the course of its ascent to the surface.

海洋红藻多管藻和松节藻的化学成分及抗氧化活性研究

海洋生物具有产生丰富多样的次生代谢产物的能力，其中红藻门松节藻科海藻卤代次生代谢产物以其结构新颖、生物活性独特引起了天然产物化学家的重视。 本论文对海洋红藻多管藻和松节藻进行了化学成分研究，综合利用各种色谱学方法 (硅胶柱层析、反相硅胶柱层析、凝胶Sephadex LH-20柱层析、半制备高效液相色谱以及重结晶等) 和现代波谱学技术 (IR、UV、EI-MS、FAB-MS、HR-ESI-MS、CD、1H-NMR、13C-NMR、DEPT、1H-1H COSY、HSQC、HMBC等)，共分离鉴定了100个化合物，发现25个新化合物。 从多管藻中分离鉴定38个化合物 (24个溴酚化合物)，其中7个新化合物 (均为溴酚化合物)，包括1个菲并呋喃结构溴酚 (P1), 2个二氢菲结构溴酚 (P2, P3)，1个含 5,7-dihydrodibenzo[c,e]oxepine 结构溴酚 (P4)和3个简单溴酚 (P5, P6, P7)。P1 (urceolatin) 属首例报道的具有菲并呋喃结构的天然产物，从该种中分离的化合物P12 和 P13 可能是其生源合成的前体。P2和P3为第二例报道的具有二氢菲结构的溴酚化合物。 从松节藻中分离并鉴定了62 个化合物，其中18 个为溴酚类新化合物，44 个为已知化合物。化合物具有多变的取代基团，包括2 个脲基吡咯烷酮溴酚化合物 (R1, R2), 4 个γ-脲基丁酸溴酚化合物 (R3-R6)，5 个酰胺溴酚化合物 (R7, R8, R9, R13, R14)，1 个溴酚砜化合物 (R12), 1 个Xanthene 溴酚化合物 (R10)和5 个简单溴酚化合物 (R11, R15, R16, R17, R18)。R1、R2 是首例报道的含有脲基吡咯烷酮片段的天然产物，R10 为首次报道的溴代Xanthene 类天然产物。 对分离到的化合物进行了清除DPPH 和ABTS两种自由基活性的筛选。结果发现溴酚类天然产物具有显著的DPPH自由基清除活性，其中R3 的IC50 仅为3.3 μM, 其活性强度约为阳性对照BHT (IC50 为82.1 μM) 的24倍。另外，溴酚类天然产物对ABTS自由基有较强的清除活性，R2 的TEAC（Trolox efficency activity capacity）值为5.2 mM，约为阳性对照 (ascorbic acid, 1.02 mM) 的 5 倍。初步的构效关系研究发现，稠环分子、多羟基和邻位甲氧基等结构特点能有效增强DPPH 自由基清除活性；特殊取代基如脲基、吡咯烷酮等含有氮原子的基团，能有效增强ABTS 自由基清除活性，多羟基、溴代等结构特点也使其活性有所增强。 本研究结果丰富了海藻卤代化合物的结构类型，为多管藻和松节藻的合理利用提供了一定的科学依据。

Study of a new derivatizing reagent that improves the analysis of amino acids by HPLC with fluorescence detection: application to hydrolyzed rape bee pollen

A simple and sensitive method for evaluating the chemical compositions of protein amino acids, including cystine (Cys)(2) and tryptophane (Try) has been developed, based on the use of a sensitive labeling reagent 2-(11H-benzo[alpha]-carbazol-11-yl) ethyl chloroformate (BCEC-Cl) along with fluorescence detection. The chromophore of the 1,2-benzo-3,4-dihydrocarbazole-ethyl chloroformate (BCEOC-Cl) molecule was replaced with the 2-(11H-benzo[alpha]-carbazol-11-yl) ethyl functional group, yielding the sensitive fluorescence molecule BCEC-Cl. The new reagent BCEC-Cl could then be substituted for labeling reagents commonly used in amino acid derivatization. The BCEC-amino acid derivatives exhibited very high detection sensitivities, particularly in the cases of (Cys)(2) and Try, which cannot be determined using traditional labeling reagents such as 9-fluorenyl methylchloroformate (FMOC-Cl) and ortho-phthaldialdehyde (OPA). The fluorescence detection intensities for the BCEC derivatives were compared to those obtained when using FMOC-Cl and BCEOC-Cl as labeling reagents. The ratios I (BCEC)/I (BCEOC) = 1.17-3.57, I (BCEC)/I (FMOC) = 1.13-8.21, and UVBCEC/UVBCEOC = 1.67-4.90 (where I is the fluorescence intensity and UV is the ultraviolet absorbance). Derivative separation was optimized on a Hypersil BDS C-18 column. The detection limits calculated from 1.0 pmol injections, at a signal-to-noise ratio of 3, ranged from 7.2 fmol for Try to 8.4 fmol for (Cys)(2). Excellent linear responses were observed, with coefficients of > 0.9994. When coupled with high-performance liquid chromatography, the method established here allowed the development of a highly sensitive and specific method for the quantitative analysis of trace levels of amino acids including (Cys)(2) and Try from bee-collected pollen (bee pollen) samples.

Docking and molecular dynamics studies toward the binding of new natural phenolic marine inhibitors and aldose reductase

Phenolic marine natural product is a kind of new potential aldose reductase inhibitors (ARIs). In order to investigate the binding mode and inhibition mechanism, molecular docking and dynamics studies were performed to explore the interactions of six phenolic inhibitors with human aldose reductase (hALR2). Considering physiological environment, all the neutral and other two ionized states of each phenolic inhibitor were adopted in the simulation. The calculations indicate that all the inhibitors are able to form stable hydrogen bonds with the hALR2 active pocket which is mainly constructed by residues TYR48, HIS110 and TRP111, and they impose the inhibition effect by occupying the active space. In all inhibitors, only La and its two ionized derivatives La_ion1 and La_ion2, in which neither of the ortho-hydrogens of 3-hydroxyl is substituted by Br, bind with hALR2 active residues using the terminal 3-hydroxyl. While, all the other inhibitors, at least one of whose ortho-sites of 3- and 6-hydroxyls are substituted by Br substituent which take much electron-withdrawing effect and steric hindrance, bind with hALR2 through the lactone group. This means that the Br substituent can effectively regulate the binding modes of phenolic inhibitors. Although the lactone bound inhibitors have relatively high RMSD values, our dynamics study shows that both binding modes are of high stability. For each inhibitor molecule, the ionization does not change its original binding mode, but it does gradually increase the binding free energy, which reveals that besides hydrogen bonds, the electrostatic effect is also important to the inhibitor–hALR2 interaction.

青岛晚白垩世岩石圈结构特征：劈石口晚白垩世基性脉岩及其捕虏体提供的证据

The occurrence of Late Cretaceous mafic dykes and their entrained peridotite and granulite xenoliths as well as clinopyroxene xenocrysts in the Qingdao region provide us a precious opportunity to unveil the nature and characteristics of the Late Mesozoic lithospheric mantle and lower crust beneath the Jiaodong region, and the change of the magma sources. These studies are of important and significant for understanding the lithospheric evolution in the eastern North China Craton. There were two periods of magma activities in Late Mesozoic in Qingdao Laoshan region, one was around 107Ma in the Early Cretaceous and the other around 86Ma in the Late Cretaceous according to the whole rock K-Ar age determination. The Early Cretaceous mafic dykes and the Late Cretaceous mafic dyke (i.e. Pishikou mafic dike) have completely different geochemical characteristics. The Early Cretaceous mafic dykes are enriched in LILE, strongly depleted in HFSE (Nb, Ta, Zr, Hf) and characterized by the highly radiogenic Sr and Nd isotopic compositions. These geochemical features indicate that the Early Cretaceous mafic dykes were derived from an enriched lithospheric mantle. In contrast, the Late Cretaceous mafic dyke is enriched in LILE, without HFSE depletion (Nb, Ta, Zr, Hf) and has less radiogenic Nd and Sr isotopic compositions. These geochemical features indicate that the Late Cretaceous mafic dyke was derived from the asthenosphere modified by subducted pelagic sediment contamination. The intrusive age of the Late Cretaceous mafic dyke provides further information for the termination of the lithosphere thinning for the eastern North China Crtaon. Pishikou Late Cretaceous mafic dyke contains abundant peridotitic xenoliths, granulite xenoliths and clinopyroxene xenocrysts. The peridotitic xenoliths can be divided into two types: high Mg# peridotites and low Mg# peridotites, according to their textural and mineral features. The high-Mg# peridotites have high Fo (up to 92.2) olivines and high Cr# (up to 55) spinels. The clinopyroxenes in the high# peridotites are rich in Cr2O3 and poor in Al2O3. The low-Mg# peridotites are typified by low Mg# (Fo <90) in olivines and low Cr# (Cr# <0.14) in spinels. The clinopyroxenes in the low-Mg# peridotites are rich in Al2O3 and Na2O and poor in Cr2O3. These two type peridotites have similar equilibrated temperatures of 950C-1100C. The Clinopyroxenes in the high-Mg# peridotites generally have high and variable REE contents (REE = 5.6-84 ppm) and LREE-enriched chondrite-normalized patterns ((La/Yb)N>1). In contrast, the clinopyroxenes in the low-Mg# peridotites have low REE contents (REE = 12 ppm) and LREE-depleted patterns ((La/Yb)N<1). The textural, mineral and elemental features of the low-Mg# peridotites are similar to those of the low-Mg peridotites from the Junan, representing the newly-accreted lithospheric mantle. However, the mineralogical and petrological features of the high-Mg# peridotites are similar to those of the high-Mg# peridotites from the Junan region, representing samples from the old refractory lithospheric mantle that was strongly and multiply affected by melts of different origins Late Cretaceous mafic dike in the Qingdao region also contains two types of granulite xenoliths according to the mineral constituents: the pyroxene-rich granulites and the plagioclase-rich granulites. Equilibrated temperatures calculated from the cpx-opx geothermometers are in a range of 861C - 910C for the pyroxene-rich granulites and of 847C - 890C for the plagioclase-rich granulites. The equilibrated pressure for the plagioclase-rich granulites is in a range of 9.9-11.7 kbar. Combined with the results of the peridotitic xenoliths, a 40C temperature gap exists between the peridotite and the granulite. The petrological Moho was 33~36 km at depths, broadly consistent with the seismic Moho estimated from the geophysical data. This indicates that there was no obvious crust-mantle transition zone in the Qingdao region in the Late Mesozoic. Pishikou Late Cretaceous mafic dyke entrained lots of clinopyroxene xenocrysts which are characterized by the chemical zoning. According to the zoning features, two types of clinopyroxene xenoliths can be classified, the normal zoning and the revise zoning. The normally-zoned clinopyroxene xenocrysts have LREE-depleted REE patterns in the cores. In contrast, the revisely-zoned clinopyroxenes have LREE-enriched REE patterns in the cores. According to the rim and core compositions of xenocrysts, all the rims are balanced with the host magma. Meanwhile, the origins of the cores were complicated, in which the normally-zoned clinopyroxenes were derived form the lithospheric mantle and some of the reversely-zoned clinopyroxnes were originated from the lower crust. Other revisely-zoned clinopyroxenes had experienced complex geological evolution and need to be further investigated. According to the above results, a simplified lithospheric profile has been established beneath the Qingdao region and a constraint on the nature and characteristics of the lithospheric mantle and lower crust has been made.