Spectroscopic study on the photophysical properties of chlorine substituted tetraphenylporphyrin-histidine and its zinc(Ⅱ)complexes

The photophysical properties of ortho-CI,meta-CI and para-CI substituted tetraphenylporphy-rin-histidine and their zinc (II) complexes have been studied by means of steady-state absorption and fluo-rescence spectroscopies, as well as time-resolved fluo-rescence spectroscopy. For the cases of both free-base and zinc complexes, it was found that the ortho-chlorine substitution onto the phenyl rings significantly altered the fluorescence quantum yield, thefluorescence lifetime and the ratio between radiative and nonradiative deactivation rates of the porphyrin chromophore, i.e. the photophysical parameters were quite different from those of meta- and para-substituted compounds. On the other hand, however, the introduction of covalently-linked histidine did not exert much effects on the photophysical behavior of the porphyrin chromophore. The results are interpreted interms of the steric effect and the heavy-atom effect from the chlorine atoms substituted onto the phenyl rings.     

Theoretical study on tetrazole and its derivatives (Ⅰ)──Ab initio study on chlorotetrazole

Molecular geomitries and electronic structures of four chlorotetrazoles are calculated with ab initio method at MP2/6-311G ** level. The results show that all the titled compounds are planar and aromatic. The skeletal bond lengths of the ring tend to be uniformized. Compared with 1- and 2-substituted chlorotetrazoles, 5-substituted chlorotetrazoles are more acidic and lower in total energy. 5-chloro-2H-tetrazole has the lowest energy and is the most stable.     

Theoretical study on photophysical property of C_(60)M(CO)_5 (M=Cr,Mo and W)

Configurations of three η2 models of transition-metal 60 fullerene derivatives C60M(CO)5(M=Cr,Mo and W) have been optimized at B3LYP/LanL2DZ level.On the basis of the optimized geometrical structures,their electronic spectra and the frequency dependence of third-order nonlinear optical polarizabilities γ in different optical processes of third-harmonic generation(THG),electric-field-induced sec-ond-harmonic generation(EFISHG) and degenerate four-wave mixing(DFWM) are calculated by using TDB3LYP model based on LanL2DZ level coupled with the SOS(sum-over-state) method.The obtained results show that their electronic spectra have a red shift compared with that of 60 fullerene and dif-ferent transition-metal functional groups added to C60 cage may result in different spectrum properties.For the three studied species,(η2-C60)Mo(CO)5 has the largest third-order nonlinear optical polarizability.     

Equilibrium dialysis study on the interaction between Cu(Ⅱ) and HSA or BSA

The interaction of Cu(Ⅱ) and human serum albumin (HSA) or bovine serum albumin (BSA) at physiological pH is studied by equilibrium dialysis. The successive stability constants are obtained by non-linear least square methods fitting Bjerrum formula. For both the Cu(Ⅱ)-HSA and Cu(Ⅱ)-BSA systems, the order of magnitude of K 1 and K 2 was found to be ≈10 4 mol -1·dm 3. There are about twenty stoichiometry binding sites found in one HSA or BSA molecule. They can be divided into two or three sets. Results of equilibrium dialysis experiments suggest that there exists one strong metal binding site in both Cu(Ⅱ)-HSA and Cu(Ⅱ)-BSA. It is the imidazol group nitrogen atoms of His 3 that are primarily concerned with copper binding site. After reaching dialysis equilibrium, there is the interaction among the different binding sites, the values of K all deviate from the simple statistical effect except for K-1 and K-2 in both Cu(Ⅱ)-HSA and Cu(Ⅱ)-BSA systems, and the positive cooperative effect is found.     

Great progress in study on aerosol and its impact on the global environment

The transport from atmosphere is a more important pathway than that from rivers for certain elements and compounds in the remote ocean. The desert and those arid/semi-arid areas in the northwest of China and the Loess Plateau are the sources of those aerosols over the Pacific. Atmospheric iron is the limiting factor of the productivity in certain ocean regions. The dust storms must now be seen as repeated sources of pollution elements as well as soil elements to the East China Sea and, farther out, to the North Pacific Ocean and even to the USA. The long-range transport of aerosols, especially the dust storm, from China and the positive feedbacks of iron coupled with sulfur in atmosphere might be one of the important mechanisms that would affect the primary productivity in the Pacific and/or the global climate change and deserve to be further studied. It can be seen clearly that the dust storms would affect not only the health of human beings and the local or regional climate, but also the global climate change that has been the focus of environmental study internationally.     

Synthesis and magnetic properties of one-dimensional Mn(II) complexes linked by dithiooxalato

Three dithiooxalato (Dto) bridging one-dimensional Mn(II) complexes [Mn(L)Dto](L = Phen (1), Bpy (2) and en (3)) were synthesized. All of the complexes have the similar one-dimensional structure through Dto bridge. The measurement of the variable temperature magnetic susceptibility of complex 1 showed that there are weak antiferromag-netic interactions between the Mn(II) ions.     

Effect of calcium ions on the secondary structures of photosystemⅡ and its relations with photoinhibition

Calcium ions play an important role in the oxygen_evolving process of photosystem Ⅱ as demonstrated in many experiments. The changes of the secondary structures of PS Ⅱ induced by the depletion of Ca 2+ were reported. The results indicated that the removal of Ca 2+ led to the transition of α helix to turns and sheet structures. While Ca 2+ was re_added to the media, only the structures changed to turns could be recovered. The protein conformational changes of PS Ⅱ during the donor side photoinhibition induced by the depletion of Ca 2+ were also studied. This showed that the protein conformational changes differed between the control and Ca 2+ _depleted samples in a short period of illumination (within 10 min). However, the changes became similar when the illumination time was increased.     

Bioinformatical study on the proteomics and evolution of SARS-CoV

A novel coronavirus has been identified as the causative agent of the severe acute respiratory syndrome (SARS). For all the SARS-CoV associated proteins derivated from the SARS-CoV genome, the physiochemical properties such as the molecular weight, isoelectric point and extinction coefficient of each protein were calculated. The transmembrane segments and subeellular localization (SubLoeation) prediction and conserved protein motifs search against database were employed to analyze the function of SARS-CoV proteins. Also, the homology protein sequence alignment and evolutionary distance matrix calculation between SARS-CoV associated proteins and the corresponding proteins of other coronaviruses were employed to identify the classification and phylogenetic relationship between SARS-CoV and other coronaviruses. The results showed that SARS-CoV is a novel coronavirus which is different from any of the three previously known groups of coronviruses, but it is closer to BoCoV and MHV than to other coronaviruses. This study is in aid of experimental determination of SARS-CoV proteomics and the development of antiviral vaccine.     

Synthesis and magnetic properties of one-dimensional Mn（Ⅱ） complexes linked by dithiooxalato

Three dithiooxalato (Dto) bridging one-dimensional Mn(Ⅱ) complexes [Mn(L)Dto](L=Phen (1), Bpy (2) and en (3)) were synthesized. All of the complexes have the similar one-dimensional structure through Dto bridge. The measurement of the variable temperature magnetic susceptibility of complex 1 showed that there are weak antiferromagnetic interactions between the Mn(Ⅱ) ions.     

Effects of Ag addition on the microstructures and properties of Al-Mg-Si-Cu alloys

Effects of Ag addition on the microstructures, aging characteristics, tensile properties, electrochemical properties, and intergranular corrosion (IGC) properties of Al-1.1Mg-0.8Si-0.9Cu-0.35Mn-0.02Ti alloy were investigated using scanning electronic microscopy and transmission electronic microscopy. The aging process of Al-Mg-Si-Cu alloys was accelerated by the addition of Ag. The strength of peak-aged Al-Mg-Si-Cu alloys was enhanced by Ag addition because of the high density of β"- and L-phase age-hardening precipitates. The corrosion performance of the Al-Mg-Si-Cu alloy is closely related to the aging conditions and is independent of the Ag content. The IGC susceptibility is serious in the peak-aged alloy because of the continuous distribution of Cu-rich Q-phase precipitates along grain boundaries. Ag addition reduces the size of the grain-boundary-precipitate Q phase and the width of the precipitate-free zone and thus results in decreased IGC susceptibility of Al-Mg-Si-Cu alloys.     

Researching on the Digital Information Systems of Mine and its Applications

The development in science and technology, such asinformation,communication,controlling,etc .has offered theopportunityfor constructing the digital information systemofmine .The population,resource ,environment arethree majordifficult problems in the 21st century, among them thequestion of mineral resources is outstanding particularly .Tosettle the contradictions which happened between the limitedresource andthe increasing demand of mineral resources ,thecrisis of mineral resource andthe waste…     

Landscape Change and its effect on the environment of Daqing City

In this paper, we will study the temporal-spatial landscape change from 1978 to 2001 in Daqing City, based on the multi spectral scanner (MSS) and thematic mapper (TM) images of remote sensing (RS) of 1978, 1988, 1992, 1996 and 2001. In order to explain the effects of the component change on the whole landscape, we make a statistic analysis about the transfer probability matrix of the component types of the landscape by using the ARCGIS platform through the overlay analysis of different landscape components. Based on the transfer probability matrix, we calculate the in-transfer ratio, the out-transfer ratio and the contributor ratio of the special transfer process of the main landscape components. The results illustrate that the cultivated-land, grassland, swamp, and alkaline land are the main contributors resulting in the landscape change: the out-transfer ratios of grassland and swamp are much higher than the in-transfer ones; the in-transfer ratio of alkaline land is much higher than the out-transfer one; the in-transfer ratio of the land-lot is always higher than its out-transfer with the highest rate per year, although there is a small difference among the in-transfers and the out-transfers per year. The main landscape changing processes are the salination of cultivated-land, salination or desertification of grassland, salination and degeneration of swamp. Results in this paper can provide scientific basis for investigating the landscape change mechanism of resources-based city.     

Isolation of tomato proteinase inhibitor Ⅱ gene and the function of its intron

The genomic DNA sequence of tomato proteinase inhibitor Ⅱ gene (named tin2i, whose accession number in GenBank is AF007240) was isolated by PCR techniques. The intron sequence (TPI), with a length of 109 bp, owns typical structures of GT/AG dinucleotides at both ends and high content of AT base pairs which accounts for 80.7% of the total nucleotides. As shown by recombination experiment, the TPI sequence could efficiently promote the expression of the reporter gene gusA and this effect was independent of the position and orientation of the intron, thus showing its role as an enhancer. Such experiments as gel retardation assays, GUS histochemical staining and GUS fluorometric assays further demonstrated that TPI sequence maybe has promoter-like activity.     

Formation of the Yazi Spring Stream and its significance on tectonics-climate on the northern slope of Kunlun Mountains

The sequences of fluvial terraces in the Yazi Spring Stream are signs of the stepwise uplift of the Kunlun Mountains in the northern part of the Tibetan Plateau since the Late Pleistocene. Geomorphic and sedimentary features of the terraces reveal that they have resulted from the phased tectonic uplift and the consequent river incision in the northern plateau. Using the method of Single-aliquot Regenerative-dose （SAR） Protocol and Radiocarbon ^14C dating, the deposit ages of three-grade terraces were obtained, which are 57.5, 12.8 and 5.7 kaBP, respectively. The features and ages of terraces reveal that the incision rate of the stream accelerated at the beginning of the Holocene. The incision rate changed suddenly at 12.8 KaBP, from 0.43±0.07 mm/a to 1.59±0.55 mm/a. This implicates that uplift of the Kunlun Mountains is intensive at the first onset of the Holocene, corresponding to the obvious change of slip-rate on the AItyn Tagh Fault. But its uplift rate is much lower than that of the latter, which suggests that growth of the northern margin of the Tibetan Plateau is stronger than its interior.     

Corrosion properties of bio-oil and its emulsions with diesel

Bio-oil is a new liquid fuel but very acidic. In this study, bio-oil pyrolyzed from rice husk and two bio-oil/diesel emulsions with bio-oil concentrations of 10 wt% and 30 wt% were prepared. Tests were carried out to determine their corrosion properties to four metals of aluminum, brass, mild steel and stainless steel at different temperatures. Weight loss of the metals immersed in the oil samples was recorded. The chemical states of the elements on metal surface were analyzed by X-ray photoelectron spectroscopy （XPS）. The results indicated that mild steel was the least resistant to corrosion, followed by aluminum, while brass exhibited slight weight loss. The weight loss rates would be greatly enhanced at elevated temperatures. Stainless steel was not affected under any conditions. After corrosion, in- creased organic deposits were formed on aluminum and brass, but not on stainless steel. Mild steel was covered with many loosely attached corrosion materials which were easy to be removed by washing and wiping. Significant metal loss was detected on surface of aluminum and mild steel. Zinc was etched away from brass surface, while metallic copper was oxidized to Cu20. Increased Cr203 and NiO were presented on surface of stainless steel to form a compact passive protection film. The two emulsions were less corrosive than the bio-oU. This was due to the protection effect of diesel. Diesel was the continuous phase in the emulsions and thus could limit the contact area between bio-oil and metals.     

Synthesis of Calix[4] arene Thia Derivative and Extraction Effect of Substituents on Mercury( Ⅱ) and Lead( Ⅱ)

Calix[4]arene derivatives have been reported to possess high selectivity for metal ions.In order to analyze the extraction effect of substituents on Hg~(2+)and Pb~(2+),calix[4]arene derivatives containing hydroxyl,bromoethoxy and 1,11-dioxa-4,8-dithiahendecene were successfully synthesized,with their extraction effectiveness towards Hg~(2+)and Pb~(2+)were evaluated respectively.The results indicated that the phenolic hydroxyl in calix[4]arene improved the extraction ability on Hg~(2+)by promoting the formation of the negative oxygen ions that could bind with Hg~(2+)by coordination and ionic bonds.The extraction ability of 5,17-dinitro-26,28-(1’,11’-dioxa-4’,8’-dithiahendecene)-calix[4]arene(calix[4]arene thia derivative)was improved slightly due to the better coordination capacity for metal ions after introduction of 1,11-dioxa-4,8-dithiahendecene,which was a chelate-binding centre.Regarding to Pb~(2+),only 1,11-dioxa-4,8-dithiahendecene on molecule contributed to extraction due to the coordination bond.Since the metal ion with higher charge-to-radius ratio could coordinate with one ligand more stably,Pb~(2+)with higher charge-to-radius ratio than Hg~(2+)was coordinated and extracted by the calix[4]arene thia derivative more easily.Furthermore,extraction rates of the calix[4]arene thia derivative on both ions(Hg~(2+)and Pb~(2+))increased with the increase of pH value in acidic aqueous system(pH7).     

Effect of bromization on the properties of a series of sub-stituted 1,8,15,22-tetra(2,4-ditertbutylphenoxy) phthalocyanines

As a novel kind of functional dyes, phthalocyanines and metallophthalocyanines have been attracting the at-tention of many scientists for many years. Recently, the chemistry of Pcs has been undergoing a renaissance because Pcs and many of their derivatives exhibit theirproperties for potential application in materials science[1,2 One of the main questions in the field of phthalocya-nines research is to modify the molecular structure re-placing the benzene-spherical hydrogen atoms by various s…