DNA network structures on various solid substrates investigated by atomic force microscopy

We have fabricated DNA network structures on glass and sapphire substrates. As a comparison, we also formed the network structure on mica substrate. For titanate strontium substrate, however, DNA network can not be obtained even if it is wet-treated by Na2HPO4 solution to make it hydrophilic. We also discuss the factors that affect the DNA networks formed on various substrates.

Synthesis, characterization and crystal structure of a new layered heterometallic coordination polymer {[(CuL) Sr-2(H2O)center dot Sr-2(H2O)(7)]center dot 2H(2)O center dot 0.5CH(3)OH}(n)

A copper-strontium heterometallic coordination polymer was synthesized and characterized by elemental analysis and IR spectra. The crystal structure was determined by single-crystal X-ray diffraction analyses. The title complex is a 2 D coordination polymer with the chemical formula [[(CuL)(2)Sr (H2O) center dot Sr-2 ((HO)-O-2)(7)]center dot 2H(2)O center dot 0.5CH(3)OH](n), where H4L = N-(2-hydroxybenzamido)-N'-(3-carboxylsalicylidene) ethylenediamine. Its structural unit is comprised of two adjacent units, which polymerized with each other to form a new layered heterometallic coordination polymer.

Local structure and valences of samariurn in SrB4O7 : Sm and SrB6O10 : Sm prepared in-air

The coordination numbers for the samarium atoms and the Sm-O bond distances in SrB4O7:Sm and SrB6O10:Sm prepared in air were determined by means of Sm-L-3 edge EXAFS. The coordination. was found to be nine-folded for both these hosts and the bond distance was 2.40-2.42 Angstrom in SrB4O7:Sm and 2.42-2.44 Angstrom in SrB6O10:Sm. For SrB4O7:Sm the coordination number is coincident with that of the strontium. atoms suggesting the substitution of the samarium atoms at the strontium sites. The coordination number of the strontium atoms in SrB6O10 was also suggested to be nine assuming the same type of substitution. The valences of samarium were determined from the luminescent spectra. Both divalent and trivalent ions were present in both SrB4O7:Sm and SrB6O10:Sm, while the fraction of Sm2+ was higher in the former than in the latter. This difference has been assigned to the difference in rigidity between the B-O networks in these structures.

UV-VUV excited luminescence of SrBPO5 : Sm phosphor prepared in air

The high-resolution luminescent spectrum of divalent samarium excited by 355 nm UV light at 77 K, the VUV excitation spectra, the VUV excited emission spectra and EXAFS at Sm-L-3 edge were reported for samarium doped strontium borophosphate, SrBPO5:Sm prepared by solid state reaction in air at high temperature. The high-resolution luminescent spectrum showed that the divalent samarium ions occupied the C-2upsilon lattice sites. The VUV excitation spectra indicated that the sample exhibited absorption bands with the maxima at 129 and 148 nm, respectively. The performance of EXAFS at Sm-L3 absorption edge suggested that the samarium ions were nine-coordinated and the mean distances of bond Sm-O were 2.38 Angstrom.

Preparation of divalent rare earth ions in air by aliovalent substitution and spectroscopic properties of Ln(2+)

When alkaline earth ions in borates, phosphates or borophosphates [SrB4O7, SrB6O10, BaB8O13, MBPO5 (M=Ca,Sr)] are substituted partially and aliovalently by trivalent rare earth ions such as Sm3+, Eu3+, these rare earth ions can be reduced to divalent state by the produced negative charge vacancy V-M". The matrices must have appropriate structure containing a rigid three-dimensional network of tetragonal AO(4) groups (A=B,P). These groups can surround and isolate the produced divalent RE2+ ions from the reaction with oxygen. Therefore, this reduction reaction can be carried out even in air at high temperature. The produced divalent rare earth ions can be detected by luminescence and XANES methods and their spectroscopic properties are discussed.

Preparation of borates doped with divalent rare earth ions (RE2+) in air and spectroscopy of divalent rare earth ions (RE2+ = Sm, Eu, Tm, Yb)

The spectroscopic feature of divalent Sm2+, Eu2+, Tm2+ and Yb2+ is discussed in this paper. Especially the spectroscopic properties of some berates containing tetrahedral BO4 group such as SrB4O7, SrB6O10 and BaB8O13 doped with these divalent ions are reported. When the divalent alkaline earth ion in these berates is replaced partially by the above trivalent rare earth ion, the charge carried in the produced defects can be used as reductant to reduce the doped rare earth ion into divalent state at high temperature even in air. Therefore, a convenient and safe method is provided to prepared phosphors doped with these divalent rare earths.

Luminescence of RE2+ (RE = Sm, Yb) in barium octoborate

The reduction process from trivalent to divalent state for Sm3+ and Yb3+ ions in barium berates (BaB8O13) prepared in air was observed. The luminescence properties of these divalent rare-earth ions were studied. Yb2+ shows an f-d broad emission band, due to the 4f(14) --> 4f(13)5d transition, while the Sm2+ ion shows an f --> f transition. From the spectra of Yb2+, and using the D-5(0) --> F-7(0) transition of Sm2+ as a structural probe, two crystallographic sites were found to be available for the cations in the host. Vibronic transitions of Sm2+ were observed at low temperature. BaB8O13 was found to be a good host for reducing the trivalent rare-earth ions to divalent state and to exhibit interesting spectroscopic properties,

The reduction of RE3+ in SrB6O10 prepared in air and the luminescence of SrB6O10 : RE2+ (RE=Eu, Sm, Tm)

The reduction of RE3+ to RE2+ (RE=Eu, Sm and Tm) in SrB6O10 prepared in air by high-temperature solid state reaction was observed. The luminescent properties of Eu2+ and Tm2+ show f-d transition and Sm2+ shows f-f transition at room temperature. Three crystallographic sites for Sm2+ in matrix are available. Vibronic transition of D-5(0)-F-7(0) of Sm2+ was studied. The coupled phonon energy about 108 cm(-1), was determined: from the vibronic transition. Due to the thermal population from D-5(0) level, (D1-FJ)-D-5-F-7 (J=0, 1, 2) transitions of Sm2+ were observed at room temperature. A charge compensation mechanism is proposed as a possible explanation.

Luminescence properties of Sm2+ in barium octaborates (BaB8O13 : Sm2+)

The luminescence of Sm2+ in BaB8O13 are studied as a function of temperature. At 10 K, several crystallographic sites for Sm2+ ions with inversion symmetry are possible and D-5(0) --> F-7(1) transition show predominant intensities, whereas above 50 K two crystallographic sites without inversion symmetry are clearly observed for Sm2+ in BaB8O13 and the D-5(0) --> F-7(0) transition show strongest intensity. The vibronic transitions and the non-radiative transitions of Sm2+ are studied and a coupled-phonon energy about 50 cm(-1) is obtained. The thermal effects on the line shift, emission intensities, half-width and lifetime of the D-5(0) --> F-7(0) transition are also studied. The decay curves at different temperatures are all in single exponential and are temperature-independent with lifetime around 3.5 ms. (C) 1999 Elsevier Science B.V. All rights reserved.

STUDIES ON THE REACTION AND STRUCTURE OF THE COMPLEXES OF ALKALINE-EARTH METAL WITH CHLOROPHOSPHONAZO-DBC

In this paper, the reaction and structure of the complexes of alkaline earth metal (Ca, Sr, Ba) with 2-(4'-chloro-2'-phosphonazo)-7-(2', 6'-dibromo-4'-chlorophenylazo 1, 8-dihydroxy-3, 6-naphthalene disulfonic acid (Chlorophosphonazo-DBC) have been studied. This ligand has eight forms under different acidity. The protonation reactions take place at [H+] > 0.36 mol.dm-3. The ligand begins dissociations at pH > 0.5. Two protons are released in the complexes formation reactions(Me2+ + 2HI half-arrow-pointing-left and half-arrow-pointing-right MeL2 + 2H+). The stability constants of the complexes of Calcium, Strontium and Barium have been determined by Yoe-Jone method, Majumder-Chakrabartty method and calculation method. The order of the stability of complexes is as follows: Sr > Ba > Ca. The structure of the complexes have also been studied by infrared spectroscopy, Laser Raman spectroscopy, NMR, and EPR. The results show that these groups of N = N, PO3H2 and OH are active groups in the complex reactions. The structure of the complexes of Strontium, Barium and Calcium with chlorophosphonazo-DBC are represented and the reaction and the complex bonds are discussed in this paper.

ISOTOPIC CHARACTERISTICS AND AGE DATING OF THE PUMICE IN OKINAWA TROUGH

The data on the isotope compositions of rubidium, strontium and oxygen in the pumice of Okinawa Trough are reported for the first time. The ages of the pumice were successfully dated with the method of U-series disequilibrium. Then, the material source, crystallization evolution of magma and activity cycles of volcanos are explored. Isotopic data show that pumice magma was originally from the mantle, but had undergone a full crystallization differentiation and had been contaminated to a fair extent by crust-derived materials before the magma was erupted out of the sea floor. According to the dating results available so far, the earliest volcanic eruption in Okinawa Trough occurred about 70,000 a ago and the latest eruption was about 10,000 a B.P. During this period, there were three volcanic eruption cycles which were respectively corresponding to the middle Late Pleistocene, the late Late Pleistocene and the Early Holocene.

中国北方表沙无机碳储量及次生碳酸盐固碳潜力研究

This paper selected the Taklamakan Desert and the Badain Jaran Desert as the research areas, tested the carbonate content of surface-sand samples of dunes using Eijkelkamp carbonate goniophotometer, and analyzed the spatial-distribution characteristics of carbonate and estimated the carbonate-stock and secondary carbonate-stock in 1m depth of surface sand in the Taklamakan Desert and the Badain Jaran Desert. In addition, the paper test XRD, SEM, TDA, stable carbon isotope and radioactive strontium isotope of lacustrine deposits in the Taklamakan Desert and carbonates, such as kunkar, root canal, lacustrine deposits, sinter and calcrete, in the Badain Jaran Desert. Resting on the achievements by our predecessors, it analyzed the mineral-composition differences of the carbonates, calculated the contents of secondary carbonate and, furthermore, evaluated their potential of sequestration of CO2 in the atmosphere. The overall goal of this study was to increase our understanding of soil carbonate in the context of carbon sequestration in the arid region in China. That is, to advance our understanding about whether or not secondary carbonate in desert is a sink for atmospheric CO2. The following viewpoints were obtained: 1 Carbonate contents of surface-sand samples decend from the south to the north of the Taklamakan Desert. The minimum lies in the south and the maxmum in the mid. Carbonate content of surface-sand of megadunes in the Badain Jaran Desert has low value generally in the dune-crest and the base of slope, and large value in the mid. The average of Carbonate contents of all sorts of collected samples in the same area of the Taklamakan Desert has small diffetences. The average is about 9%. 2 Using carbonate contents as key parameters, calculate the carbon-stock of carbonates in 1m depth of surface sand in the Taklamakan Desert and the Badain Jaran Deser.They are 1.13Pg and 0.19 Pg respectively. There are 0.53Pg and 0.088Pg carbon-stock of secondary-carbonates in 1m depth of surface sand in the Taklamakan Desert and the Badain Jaran Desert. 3 Through testing data from XRD （X-ray diffraction）and TAD ( Thermal Analysis Data), the most significant conclusion derived from is that the main mineral ingredient is calcite in different carbonate substances in arid regions, From the SEM(Scanning electron microscopy ) images, can obtains the information about the micro environment of different carbonate forms in which they can grow. 4 Selected gas by termal cracking and traditional phosphoric acid method, their δ13C show that δ13C is a good parameter to indicate the micro environment in which different secondary carbonate forms. From the δ13C of the same type samples, if the redeposit degree is hard, theδ13C is light, the redeposit degree is weak, the δ13C is heave. and the δ13C of the different type samples, δ13C is mainly controlled by the micro environment in which secondary formed. if the procedure is characterized by redeposit and dissolve of marine facies carbonate, δ13C is heavy, it is characterized by CO2 which produced by plant respiration,δ13C is light. 5 From the δ13C of lacustrine deposit in the different grain size, there exsit certain differences in their micro environment and secondary degree among different grain size in the same grade. 6 The secondary carbonate content of lacustrine deposits in Taklimakan Desert is 47.26%. And those of root canal, sinter, calcrete, kunkar, lacustrine deposit and surface sand in Badain Jaran Desert are 91.74%, 78.46%, 76.26%, 87.87%, 85.37%and 46.49%, respectively. Of different grain size samples, the secondary carbonate contents of coarse fraction (20-63μm), sub-coarse fraction (5-20μm) and fine fraction (<5μm) are 80.10%, 47.2%and 50.07%, respectively. 7 There is no obvious relevance betweenδ13C of secondary carbonate and the content of secondary carbonate,theδ13C of secondary carbonate mainly reflects the parameters of secondary process, the content of secondary carbonate reflects difference of secondary degree.. 8 Silicates potentially supply 3.4 pencent calcium source during forming process of lacustrine deposits in Taklimakan Desert. If calcium source is mainly supplied by goundwater, it can be calculated that about 5.18 %, 6.13%, 5.68%, 5.64 % and 6.82% silicates supply calcium source respectively for root canal, kunkar, lacustrine deposit, calcrete and sinter, during the forming process of different kinds of carbonates in Badain Jaran Desert.

塔里木盆地柯坪-巴楚露头区白云岩成岩作用机理研究

Through field outcrop dolomite observation, laboratory petrography (macroscopy, microscopy, cathodeluminescence and scan electronic microscopy), geochemistry (carbon-oxygen-strontium isotopes and trace elements) and fluid inclusion microthermometry study in Keping-Bachu area of Tarim Basin, it can be inferred that there are existing eight dolomite texture types within four evolution phases in Keping-Bachu area of Tarim Basin. The paragenesis of different dolomite texture types and associated minerals in Keping-Bachu area has been established. The carbon and oxygen isotopes of saddle dolomites and matrix dolomites overlap greatly. The Strontium isotopes results of Keping-Bachu outcrop area show that the strontium isotopes differentiation of the matrix and saddle dolomites is not obvious, the reason of which is that there is thousands of Cambrian-Ordovician dolomite strata below the stratum bearing the saddle dolomite. In the process of the heat flow upward migration, the isotopes of the heat interacts with the host rock, which leads to the similarity betwwen the strontium of the saddle dolomite and matrix dolomite. The strontium isotope of the saddle dolomite is not very radiogenic. the six types samples within four phases in the study area show Eu negatively. Comparing to the other types of samples, the δEu of saddle dolomite is relatively high falling into the range of 0.510-0.874, which shows that the saddle dolomite forms in the hydrothermal setting and is affected by the hydrothermal activity to some extend.The Lan/Ybn of saddle dolomite is high up to 15.726, which means that the HREE is very rich. It belongs to the typical hydrothermal genesis model. The δCe of saddle dolomite is positive anomaly, which is the result of high effect from the land source debris. The homogeneous temperature of the saddle dolomite falls into two ranges 110-120℃ and 125-160℃, after pressure correction, they are 141-152℃，157.5-196℃, the salinity of the saddle dolomite can reach to 20-25%. With the comparing with the burial history, the Th of the saddle dolomite is high than the ambient strata temperature, these data show that the saddle dolomite is of hydrothermal origin. The evolution trend of different dolomite and associated minerals is from matrix dolomite, dolomite cementation, saddle dolomite, quartz to calcite. Alonging with this evolution trend, the temperature of the diagenetic flow initiated from 80-100℃, after rising to 135-160℃, then gradually declined. Finally, a structurally-controlled dolomitization model is established in Keping-Bachu area of Tarim Basin.

河北寿王坟铜矿成矿定年及同位素地球化学特征

Samples from carbonate wall-rocks, skarn, ore of skarn type, later calcite vein, and ore of porphyry type in Shouwangfen copper deposit district were collected. Systematic study was carried out on carbon, oxygen, rubidium, strontium and sulfur isotope compositions of carbonates and sulfides in these samples. The first Isochron dating by the Rb-Sr isotopes in chalcopyrite of ore sub-sample was done as well. The following conclusions were obtained. The age (113.6±4.3Ma), obtained by Rb-Sr isotope isochron dating of chalcopyrite and pyrite from sub-sample of skarn ores, probably represents the true mineralization age of skarn ores. That demonstrates the genetic relationship between granodiorite in Shouwangfen complex and skarn copper ores. On the other hand, the Rb-Sr isochron age (73±15Ma) of chalcopyrite from porphyry ores is a little incredible because of bad synthesizing evaluation. But combined with other age data of igneous rocks, it implies the possibility of hydrothermal mineralization in connection with magma activity during the fourth period of Yanshanian in Hebei Province, even in the whole northern edge of Huabei continental block. Together from structure analysis of sulfide sub-samples, from pretreating preccedure of Rb-Sr isotope isochron and its' valuating, we found out that Rb-Sr isotope isochron of sulfide sub-samples is influenced by the crystal structure of sulfides. That is, sulfide ores with very big crystals are not suitable for sub-sample isochron. Carbon, oxygen, sulfur and strontium compositions, of different minerals in these two kinds of ores, imply that the ore-forming hydrothermal fluids were probably derived from magma deep under the crust. The calcite ~(87)Sr/~(86)Sr ratios from the porphyry are consistent to the initial 87Sr/86Sr ratio of the Rb-Sr isochron of chalcopyrite and pyrite in the skarn ore, indicating that these two kinds of ores have the same source characteristic, although the porphyry deposit was formed probably 40 million years later than the skarn one according to our dating results. Skarn and skarn ores are usually considered as interaction product between carbonate wall-rocks and magmatic fluids, but the carbon of the sedimentary carbonate seems not involved in the skarn ores. Considering the connection of magmatic processes and hydrothermal ore formation in the Shouwangfen district, particularly, the spatial distribution of skarn-type and porphyry-type ores, it is possible that the Shouwangfen ore district corresponds to a hydrothermal ore-forming system, which was promoted by high-intruding magmatic rocks. Systematic stable isotopic research can help to reveal the upper part of this hydrothermal ore-forming system, which mainly related to heated and circulating meteoric water, and the lower part principally related to ascending magmatic fluids. Both skarn and porphyry ore-bodies are formed by up-intruding magmatic fluids (even more deep mantle-derived fluids).

矾山杂岩体成因及其与磷（铁）矿的成矿关系

The Fanshan complex consists of layered potassic ultramafic-syenite intrusions. The Fanshan apatite (-magnetite) deposit occurs in the Fanshan complex, and is an important style of phosphorus deposit in China. The Fanshan complex consists of three (First- to Third-) Phases of intrusion, and then the dikes. The First-Phase Intrusive contains ten typical layered rocks: clinopyroxenite, biotite clinopyroxenite, coarse-grained biotite clinopyroxenite, pegmatitic orthoclase-biotite clinopyroxenite, variegated orthoclase clinopyroxenite, interstitial orthoclase clinopyroxenite, biotite rock, biotite-apatite rock, biotite rock and magnetite-apatite rock. This layered intrusive consists of nine rhythmic units. Each rhythmic unit essentially comprises a pair of layers: clinopyroxenite at the bottom and biotite clinopyroxenite at the top. The apatite (-magnetite) deposit is situated near the top of rhythmic Unit no. 6 of the First-Phase Intrusive. The Second-Phase Intrusive contains three typical rocks: coarse-grained orthoclase clinopyroxenite, . coarse-grained salite syenite and schorlomite-salite syenite. The Third-Phase Intrusive includes pseudo-trachytic salite syenite, porphyritic augite syenite, fine-grained orthoclase clinopyroxenite and fine-grained salite syenite. The origin of the Fanshan complex is always paid attention to it in China. Because most layered igneous intrusion in the world not only have important deposit in it, but also carry many useful information for studying the formation of the intrusion and the evolvement of magma. Two sketch maps were drawn through orebodies along no. 25 cross-cut on 425 mL and no. 1 cross-cut on 491 mL in the Fanshan mine. Through this mapping, a small-scaled rhythmic layering (called sub-rhythmic layering in the present study) was newly found at the top of the rhythmic Unit no. 6. The concept of sub-rhythmic layering is defined in this article. The sub-rhythmic layering is recognized throughout this apatite-rich part, except for magnetite-apatite rock. Presence of the layered magnetite-apatite rock is one of the characteristics of the Fanshan apatite (-magnetite) deposit. Thus, from this layer downwards six units of sub-rhythmic layering are recognized in the present study. Each unit consists of biotite clinopyroxenite (or biotite rock and biotite-apatite rock) layer at the bottom and apatite rock layer at the top. To study this feature in detail is an important work for understanding the origin of the Fanshan complex and apatite (-magnetite) deposit. The origin of the Fanshan complex and the relation of the formation of the apatite(-magnetite)deposit will be interpreted by the study of sub-rhythmic layering on the basis of previous research works. The magma formed the Fanshan complex was rich in K2O, early crystallized pyroxene, and after this phase more biotite crystallized, but no amphibole appeared. This indicated that the activity of H2O in the magma was low. Major element compositions of biotite and clinopyroxene (on thin sections) in the sub-rhythmic layering were analyzed using electron microprobe analyzer. The analytical results indicate Mg/(Mg+Fe*+Mn) atomic ratios (Fe*, total iron) of these two minerals rhythmically changed in sub-rhythmic layering. The trends of Mg/(Mg+Fe*+Mn) atomic ratio (Fe*, total iron) of biotite and clinopyroxene indicate that the magma evolved markedly from relatively magnesian bottom layer to less magnesian top layer in each sub-rhythmic unit. A general trend through the sub-rhythmic layering sequence is both minerals becoming relatively magnesian upwards. The formation temperatures for sub-rhythmic layering yield values between 600 and 800 ℃, were calculated using the ratio of Mg/(Mg+Fe+Mn) in the salite and biotite assemblage. The equilibrium pressures in the rhythmic layers calculated using the contents of Al in the salite were plotted in the section map, shown a concave curve. This indicates that the magma formed the First-Phase Intrusive crystallized by two vis-a-vis ways, from its bottom and top to its centre, and the magnetite-apatite rock was crytallized in the latest stage. The values of equilibrium pressures in the sub-rhythmic layering were 3.6-6.8(xlO8) Pa with calculated using the contents of Al in the salite. The characteristics of geochemistry in various intrusive rocks and the rocks or apatite of sub-rhythmic layers indicated that the Fanshan complex formed by the comagmatic crystallization. The contents of immiscible elements and REEs of apatite rock at the top of one sub-rhythmic unit are more than biotite clinopyroxenite at the bottom. The contents of immiscible elements and REEs of apatite of biotite clinopyroxenite at the bottom of one sub-rhythmic unit are higher than apatite rock at the top. The curves of rocks (or apatite) in the upper sub-rhythmic units are between two curves of the below sub-rhythmic unit in the primitive mantle-normalized trace element abundance spider diagram and the primitive mantle-normalized REE pattern. The trend for the contents of immiscible elements and REEs inclines to the same contents from the bottom to the top in sub-rhythmic layering. These characteristics of geochemistry of rocks or apatites from sub-rhythmic layering indicate that the latter sub-rhythmic unit was produced by the residual magma after crystallization of the previous sub-rhythmic unit. The characteristics of petrology, petrochemistry, geochemistry in the Fanshan complex and sub-rhythmic layers and the trends of Mg/(Mg+Fe+Mn) atomic ratio of biotite and clinopyroxene in sub-rhytmic layering rejected the hypotheses, such as magma immiscibility, ravitational settling and multiple and pulse supplement of magma. The hypothesis of differentiation by crystallization lacks of evidences of field and excludes by this study. On the base of the trends of formation temperatures and pressures, the characteristics of petrology, petrochemistry, geochemistry for the Fanshan complex and the characteristics of geochemistry for the rocks (or apatites), the trends of Mg/(Mg+Fe+Mn) atomic ratio of biotite and clinopyroxene in sub-rhytmic layering, and the data of oxygen, hydrogen, strontium and neodymium isotopes, this study suggests that the magma formed the Fanshan complex was formed by low degree partial melting of mantle at a low activity of H2O, and went through the differentiation at the depth of mantle, then multiply intruded and crystallized. The rhythmic layers of the First-Phase Intrusive formed by the magma fractional crystallized in two vis-a-vis ways, from the bottom and top to the centre in-situ fractional crystallization. The apatite (-magnetite) deposit of the Fanshan complex occurs in sub-rhythmic layering sequence. The the origin of the sub-rhythmic layering is substantially the origin of the Fanshan apatite (-magnetite) deposit. The magma formed the rhythmic layers of First-Phase Intrusive was rich in H2O, F and P at the later stage of its in-situ fractional crystallization. The Fanshan apatite (-magnetite) deposit was formed by this residual magma in-situ fractional crystallization. The magnetite-apatite rock was crystallized by two vis-a-vis ways at the latest stage in-situ fractional crystallization in the rhythmic layers. The result was light apatite layer below heavy the magnetite-apatite layer, formed an "inversion" phenomenon.