Development of a LCST membrane forming system for cellulose acetate ultrafiltration hollow fiber

A novel lower critical solution temperature (LCST) membrane forming system containing cellulose acetate (CA)/poly (vinyl pyrrolidone) (PVP 3 60K)/N-methyl-2-pyrrolidone (NMP)/1,2-propanediol with a weight ratio of 24.0:5.0:62.6:8.4 had been developed. CA hollow fiber ultrafiltration (UF) membranes were fabricated using the dry-wet spinning technique. The fibers were post-treated with a 200 mg/L hypochlorite solution over a period of 6 It at pH 7. The experimental results showed that water flux of a membrane decreased while retention increased with increasing CA concentration in a dope. It was concluded that the membrane pore size decreased with increasing CA concentration. The membrane fouling tendency for BSA was 3 times higher than that for PVP 24K. (C) 2004 Elsevier B.V. All rights reserved.

Adsorption of Components of the Plasma Kinin-forming System on the Surface of Porphyromonas gingivalis Involves Gingipains as the Major Docking Platforms

Enhanced production of proinflammatory bradykinin-related peptides, the kinins, has been suggested to contribute to the pathogenesis of periodontitis, a common inflammatory disease of human gingival tissues. In this report, we describe a plausible mechanism of activation of the kinin-generating system, also known as the contact system or kininogen-kallikrein-kinin system, by the adsorption of its plasma-derived components such as high-molecular-mass kininogen (HK), prekallikrein (PK), and Hageman factor (FXII) to the cell surface of periodontal pathogen Porphyromonas gingivalis. The adsorption characteristics of mutant strains deficient in selected proteins of the cell envelope suggested that the surface-associated cysteine proteinases, gingipains, bearing hemagglutinin/adhesin domains (RgpA and Kgp) serve as the major platforms for HK and FXII adhesion. These interactions were confirmed by direct binding tests using microplate-immobilized gingipains and biotinylated contact factors. Other bacterial cell surface components such as fimbriae and lipopolysaccharide were also found to contribute to the binding of contact factors, particularly PK. Analysis of kinin release in plasma upon contact with P. gingivalis showed that the bacterial surface-dependent mechanism is complementary to the previously described kinin generation system dependent on HK and PK proteolytic activation by the gingipains. We also found that several P. gingivalis clinical isolates differed in the relative significance of these two mechanisms of kinin production. Taken together, these data show the importance of this specific type of bacterial surface-host homeostatic system interaction in periodontal infections.

Investigation into the rheological properties of PES/NMP/nonsolvent membrane-forming systems

From the perspective of a polymer solution, the rheological properties of the popular polyethersulfone (PES)/N-methyl-2-pyrrolidone (NMP)/nonsolvent (NS) membrane-forming system were investigated thoroughly with a controlled stress rheometer (HAAKE RS75, Germany). The scope of the study included measurements of the controlled-stress flow curve, creep recovery, and dynamic oscillation. H2O, 1-butanol, ethylene glycol, and diethylene glycol were used as NS additives. The effects of the polymer concentration and the quality of the solvent mixture, as characterized by the approaching ratio, on the rheological behavior of the dopes were studied. Up to 38 wt % PES and extremely adjacent to the phase separation (i.e., the approaching ratio of the dope was 0.95), the viscous property dominated all the dopes, which behaved as Newtonian fluids. Moreover, all the membrane-forming dopes investigated were in the crossover regime in the semidilute region, in which the chains were overlapping but unentangled. (C) 2001 John Wiley & Sons, Inc.

Characterising material and process variation effects on springback robustness for a semi-cylindrical sheet metal forming process

Variation in the incoming sheet material and fluctuations in the press setup is unavoidable in many stamping plants. The effect of these variations can have a large influence on the quality of the final stamping, in particular, unpredictable springback of the sheet when the tooling is removed. While stochastic simulation techniques have been developed to simulate this problem, there has been little research that connects the influence of the noise sources to springback. This paper characterises the effect of material and process variation on the robustness of springback for a semi-cylindrical channel forming operation, which shares a similar cross-section profile as many automotive structural components. The study was conducted using the specialised sheet metal forming package AutoForm^TM Sigma, for which a series of stochastic simulations were performed with each of the noise sources incrementally introduced. The effective stress and effective strain scatter in a critical location of the part was examined and a response window, which indicates the respective process robustness, was defined. The incremental introduction of the noise sources allows the change in size of the stressstrain response window to be tracked. The results showed that changes to process variation parameters, such as BHP and friction coefficient, directly affect the strain component of the stressstrain response window by altering the magnitude of external work applied to forming system. Material variation, on the other hand, directly affected the stress component of the response window. A relationship between the effective stressstrain response window and the variation in springback was also established.

An extension of the flower pattern diagram for roll forming

The initial process design of a roll forming system is often based on the traditional ‘flower pattern diagram’. In this diagram, the cross sections of the strip at each roll stand are superimposed on a single plane; the diagram is a 2D representation of the 3D process. In the present work, the flower pattern is extended into three dimensions. To demonstrate the method, the forming path or trajectory of a point at the edge of the strip during forming a V-section is considered. The forming path is a surface curve that lies on a cylindrical surface having its axis along the machine axis. This surface is unwrapped to give its plane development and important features of the forming process can be determined and are readily interpreted from this plane curve. It is shown that at any stage in the process, the axial strain and the curvature of the sheet adjacent to the point are dependent on the slope of the trajectory in this plane projection. This new diagram, which apparently has not been used previously, provides a useful initial method of examining the roll forming process and optimising the flower pattern. The model is purely geometric, as is the original flower pattern approach, and does not include the effect of material behaviour. The concept is applied to several cases available in the literature. It shows that the lowest level of shape defect in the part is achieved when the trajectory of the strip edge follows the shortest line length between the start and finish of forming, leading to the least longitudinal strain introduced in the flange. This trend is in agreement with previous experimental observations, suggesting that the analytical model proposed may be applied for early process design and optimisation before time-consuming numerical analysis is performed.

Factors affecting pore structure and performance of poly(vinylidene fluoride-co-hexafluoro propylene) asymmetric porous membrane

Preparation of poly(vinylidene fluoride-co-hexafluoro propylene) (F2.6) flat-sheet asymmetric porous membrane has been studied for the first time. Factors affecting F2.6 membrane pore structure and permeate performance, such as macromolecule pore formers (polyethylene glycol-400, 1000, 1540, 2000 and 6000), the small molecule former (glycerol), swelling agent (trimethyl phosphate) in casting solution, precipitating bath component and temperature, exposure time and ambient humidity, were investigated in detail. Average pore radius and porosity were used to characterize F2.6 membrane structure, and respectively, determined by ultrafiltration and gravimetric method for the wet membrane. Morphology of the resultant membranes was observed by scanning electronic microscopy (SEM). Final test on permeate performance of F2.6 porous membrane was carried out by a direct contact membrane distillation (DCMD) setup. The experimental F2.6 membrane exhibits a higher distilled flux than PVDF membrane under the same operational situations. The determination of contact angle to distilled water also reveals higher hydrophobic nature than that of PVDF membrane.

东天山镁铁-超镁铁岩铜镍硫化物矿床通道式成矿机制与岩体含矿性评价研究

A mafic-ultramafic complex belt well developed in Eastern Tianshan, Xinjiang, NW China, which contains a series of Cu-Ni sulfide deposits. This area is the important production basis for Cu-Ni deposits, including Tulargen deposit, Hulu deposit, Huangshan-Huangshandong deposit, Hulu deposit, Xiangshan deposit, Tianyu deposit, Chuanzhu deposit. In China, especially Eastern Tianshan, it is prevalent that large Cu-Ni deposits occurred in small intrusions, typically including Jinchuan, Kalatongke, et al., so the ore-forming mechanism and evaluation rule for those small intrusions are very meaningful and of universal significance. On the basis of the research to typical Cu-Ni deposits, ore-forming conditions and processes are summarized through which to evaluate the ore-bearing potential for barren intrusions and unexplored mafic-ultramafic intrusions. By the contrast, metallogenic rule and mechanism of ore genesis are concluded, and evaluation system is preliminarily set up on the basis of these conclusions. Quantitatively simulation for the composition of olivine is introduced for the first time in China to discuss the interaction between magma and sulfide, and a new method to calculate the Mg-Fe composition of primitive magma is developed. Interaction between magma and sulfide liquid is used to get the Ni content in sulfide liquid. Sulfur isotopic characteristics in sulfide minerals in country rocks and ores are used to judge crustal sulfur introduction, which is applied for the first time in China. Re-Os isotopic characteristics are related to the ore-forming process, to interpret the process of enrichment of chalcophile elements. On the basis of the evaluation system, Mati, Chuanzhu, Luodong, Xiadong, those intrusions are evaluated to their ore-bearing potential. According to the studies to typical Cu-Ni deposits, conduit-type ore-forming model is set up, and the characteristics of the model are concluded systematically. The evaluation system and conduit-type ore-forming model can be helpful to the evaluation of mafic-ultramafic intrusions in this and similar mafic-ultramafic intrusion belts. The studied typical deposits and mafic-ultramafic intrusion include Tulargen deposit, Hulu deposit, Huangshandong deposit, Chuanzhu deposit, Mati intrusion，Luodong intrusion, Xiadong intrusion, and others. Through studies, there are similar characteristics for Tulargen and Hulu deposits in magma origin, composition of primitive magma（MgO=12.5%, FeO=12% and MgO=11%, FeO=10.5% respectively）, magma evolution, mechanism of sulfide segregation and conduit-type ore-forming process. By Re-Os isotopic system, the ore forming date of Tulargen deposit is 265.6±9.2Ma, which is consistent to regional metallogenic event, but little younger. The Mg-Fe composition of primitive magma of Baishiquan, Huangshandong area, Kalatongke is lower than that of Tulargen and Hulu deposit, showing common basalt composition. The Mg# value（Mg#=(Mg/Mg+Fe）increases gradually from Kalatongke to Baishiquan to Huangshan-Huangshandong East. Baishiquan intrusions show relatively higher crustal contamination by evidence of trace element, which indicates the lower magma original source, from depleted mantle to crust. One break is the discovery of komatiitic intrusion, Xiadong intrusion, which shows characteristics of highly magnesium (Max Fo=96). The primitive magma is calculated of MgO=28%，FeO=9%, belonging to komatiitic magma. Tectonic evolution of Eastern Tianshan is discussed. By the statistics of ore-forming data of porphyry copper deposits, magmatic sulfide Cu-Ni deposits, orogenic hydrothermal gold deposits, we believe that those deposits are the successive products of oceanic subduction, are and back-arc basin collision and post-orogenic extention. And Cu-Ni sulfide deposits and orogenic gold deposits occurred in the stage of post-orogenic extention. According to the conclusions, the conduit-type ore-forming mechanism of magmatic sulfide deposit is set up, and its characteristics and conditions are concluded as well. The conduit-type ore-forming system includes magma generation, sulfide segregation, enrichment of chalcophile elements, interaction of sulfide and magma, sulfide collection in limited space in magma conduit and bottom of the chamber, which make a whole ore-forming system.The ore-forming process of Cu-Ni sulfide deposits is concluded as three steps: 1. mantle derived magma rises upward to the middle-upper crust; 2. magma suffers crustal contamination of different degrees and assimilates crustal sulfur, which leads to sulfur saturation and sulfide segregation. Sulfide liquid interacts with magma and concentrates chalcophile elements; 3. enriched sulfide located in the conduit(Tulargen) or bottom of the chamber (Hulu). Depleted magma rises upward continuously to form barren complexes. For the practical cases, Tulargen deposit represents the feeding conduit, and Hulu deposit represents the bottom of the staging magma chamber. So the deeper of west of Tulargen and southwest of Hulu are the favorite locate for ore location. The evaluation for ore potential can be summarized as follows: (1) Olivine can be served as indicator for magma evolution and events of sulfide segregation; (2) Sulfur isotopic characteristics is an efficient method to judge sulfur origin for magmatic sulfide deposit; (3) Re-Os content of the ores can indicate interaction between sulfide and silicate magma and crustal contamination; (4) PGE mineralization is effected by degree of partial melting of mantle; (5) Cu/Zr is efficient parameter to judge sulfide segregation; (6) The effects of multiple magma fractionation and emplacement are important, for inverse order shows the destruction to previous solid lithofacies and orebodies. Mati, Chuanzhu, Xiadong, Luodong, mafic-ultramafic intrusions are evaluated using evaluation system above. Remarkable Ni depletion is found in olivine of Mati, and southwest of the intrusion can be hopeful location for ore location. Chuanzhu intrusion has remarkable evidence of sulfide segregation, but the intrusion represents the narrow feeder conduit, so the wide part of the conduit maybe the favorite location for sulfide to deposit. The ore potential of Luodong and Xiadong is not good. Both the intrusions show no Ni depletion in olivine, and there is no sulfide in country rocks, so no crustal sulfur is added into the magmatic system. For Sidingheishan, a very large intrusion, the phenomenon of sulfide segregation is found, but there are no favorite places for sulfide to deposit. So the Cu-Ni ore potential maybe not good, but PGE mineralization should be evaluated further.

东营凹陷北部陡坡带砂砾岩体性油气藏形成机理及分布规律研究

The north steep slope zone of Dongying Depression has great potential in oil resource and as the usage of 3-d seismic data in the last decade, the exploration of oil and gas has get into the stage of sandy glavel body lithological oil-gas pool exploration. In this thesis, writer take the north steep slope zone of Dongying Depression as target area and take Sha-III and Sha-[V Menber as purpose stratum, study on sequence stratigraphy, depositional system, reservoir description, emphasesing on analyzing of forming of lithological oil-gas pool, especially the dynamics principle of oil and gas preliminary movement from the source rock to the reservoir form lithological oil-gas pools. The aim of this work is to give some quantitatively explanation for the mechanism of lithological oil-gas pool forming, and set up the theory of pool form with characteristic terrestrial faulted basin. There are main conclusions and views as follow. 1. Applying with principle of sequence stratigrapgy, according to the depositional cycles of Dongying Depression, the sequence stratigraphical partition of Tertiary was finished, stressing on dismembering Sha-III and Sha-IV Menber as 5system tracts. 2. The structure of Dongying Depression especially of the north steep slope zone has accomplished, including the analyzing the structural cortroling to depositional condition of the north steep slope zone of Dongying Depression, discussed relationship between the structure of the north steep slope zone and the pool-forming. 3. The horizontal and vertical exchanges of ancient climates and ancient physiognomy of the all stratum units and studies on characteristic of depositional system distribution have been finished, found that there are five depositional systems in the north steep slope zone of Dongying Depression as fluvial, delta (tan-delta), sub-water fluvial fan lacustrine, gravitive flow, and seven formations of sandy glavel body, and forecasting of all kinds of sandy glavel body has been made. 4. Seismic stratigraphy and log stratigraphy have been made, described and forecasted all kinds of reservoir of objective stratum by means of physical geography method, setup a series means of sandy glavel body description suit to target area. 5. The pool-forming system has been studied, analyzing all the elements in petroleum sub-system of Sha-III and Sha-IV Menber of Dongying Depression with view of source controlling, estimated the petroleum system applying source rock potential index combining with distribution ofreservior. 6.Through studying types of pool, the controlling factors of pool-forming of sandy glavel body were discussed by deposition stages, formation types, structure ect. as a conclusion that the characteristics of pool forming in the north steep slope zone of Dongying Depression are, the controlling factor of the pools is mainly lithology, petrophysics of oil sands vary greatly, with a large heterogeneity, all kind of reservoir with different formation has different pool-forming conditions, and as a result, formed various pools of sandy glavel body along the steep slope with regular combination, distribution and constituted the multiple petroleum accumulative pattern. 7. It's the first time to cauculate and estimate the fluid pressure in source rock of Dongying Depression, set up the stratum fluid pressure in Dongying Depression, and firstly use equivalent charging pressure and reservoir forming index to quantitatively evaluate the pool-forming condition of lithological pool.8. Above all studies, follow up the scent of the exploration combined with practice a lot of explorative targets were found, and got geat economic and social benefit.

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).

下扬子北缘前陆盆地形成演化与油气赋存条件

The foreland basin on the northern margin of the lower reach of the Yangtze river (the lower Yangtze foreland basin) is tectonically situated in the basin-mountain transitional area along the southeastern flank of the Dabie mountains. The early formation and development of the basin is closely related to the open-up of the Mian-Lue paleo-oceanic basin on the southern margin of the Central Orogenic System represented by Qinling-Dabei orogenic belt, while the tectonic evolution of the middle-late stage of the basin is mainly related to development of the Mian-Lue tectonic zone that occurred on the basis of the previous Mian-Lue paleo-suture. The foreland basin of the northern rim of the lower reach of the Yangtze river was formed during the middle-Triassic collision between the Yangtze and North China plates and experienced an evolution of occuirence-development-extinction characterized by marine facies to continental facies and continental margin to intracontinent in terms of tectonic setting.The foreland basin (T2-J2) was developed on the basis of the passive continental marginal basin on the south side of the Mian-Lue paleo-ocean and superimposed by late Jurassic-Tertiary fault basin. The tectonic setting underwent a multiple transformation of rifting-collisional clososing-tensional faulting and depression, which resulted in changes of the property for the basin and the final formation of the superposed compose basin in a fashion of 3-story-building. According to the tectonic position and evolution stages of plate collision happening on the southeastern margin of the Dabie mountains, and tectono-tratigraphic features shown by the foreland basin in its main formational period, the evolution of the foreland basin can be divided into four stages: 1) pre-orogenic passive margin (P2-Ti). As the Mian-Lue ocean commenced subduction in the late-Permian, the approaching of the Yangtze and North China plates to each other led to long-periodical and large-scale marine regression in early Triassic which was 22 Ma earlier than the global one and generated I-type mixed strata of the clastic rocks and carbonate, and I-type carbonate platform. These represent the passive stratigraphy formed before formation of the foreland basin. 2) Foreland basin on continental margin during main orogenic episode (T2.3). The stage includes the sub-stage of marine foreland basin (T2X remain basin), which formed I-type stratigrphy of carbonate tidal flat-lagoon, the sub-stage of marine-continental transition-molasse showing II-type stratigraphy of marine-continental facies lake - continental facies lake. 3) Intracontinental foreland basin during intracontinental orogeny (Ji-2)- It is characterized by continental facies coal-bearing molasses. 4) Tensional fault and depression during post-orogeny (J3-E). It formed tectono-stratigraphy post formation of the foreland basin, marking the end of the foreland evolution. Fold-thrust deformation of the lower Yangtze foreland basin mainly happened in late middle-Jurassic, forming ramp structures along the Yangtze river that display thrusting, with deformation strength weakening toward the river from both the Dabie mountains and the Jiangnan rise. This exhibits as three zones in a pattern of thick-skinned structure involved the basement of the orogenic belt to decollement thin-skinned structure of fold-thrust from north to south: thrust zone of foreland basin on northern rim of the lower reach of the Yangtze river, foreland basin zone and Jiannan compose uplift zone. Due to the superposed tensional deformation on the earlier compressional deformation, the structural geometric stratification has occurred vertically: the upper part exhibits late tensional deformation, the middle portion is characterized by ramp fault -fold deformation on the base of the Silurian decollement and weak deformation in the lower portion consisting of Silurian and Neo-Proterozoic separated by the two decollements. These portions constitutes a three-layered structural assemblage in a 3-D geometric model.From the succession of the lower reach of the Yangtze river and combined with characteristics of hydrocarbon-bearing rocks and oil-gas system, it can be seen that the succession of the continental facies foreland basin overlies the marine facies stratigraphy on the passive continental margin, which formed upper continental facies and lower marine facies hydrocarbon-bearing rock system and oil-gas forming system possessing the basic conditions for oil-gas occurrence. Among the conditions, the key for oil-gas accumulation is development and preservation of the marine hydrocarbon-bearing rocks underlying the foreland basin. The synthetic study that in the lower Yangtze foreland basin (including the Wangjiang-Qianshan basin), the generation-reservoir-cover association with the Permian marine facies hydrocarbon-bearing rocks as the critical portion can be a prospective oil-gas accumulation.Therefore, it should aim at the upper Paleozoic marine hydrocarbon-bearing rock system and oil-gas forming system in oil-gas evaluation and exploration. Also, fining excellent reservoir phase and well-preserved oil-gas accumulation units is extremely important for a breakthrough in oil-gas exploration.

Structural Characterization of Rare-Earth Doped Yttrium Aluminoborate Laser Glasses Using Solid State NMR

The structure of laser glasses in the system (B(2)O(3))(0.6){(Al(2)O(3))(0.4-x)(Y(2)O(3))(x)} (0.1 <= x <= 0.25) has been investigated by means of (11)B, (27)Al, and (89)Y solid state NMR as well as Y-3d core-level X-ray photoelectron spectroscopy, (11)B magic-angle spinning (MAS) NMR spectra reveal that the majority of the boron atoms are three-coordinated, and a slight increase of four-coordinated boron content with increasing x can be noticed. (27)Al MAS NMR spectra show that the alumina species are present in the coordination states four, five and six. All of them are in intimate contact with both the three- and the four-coordinate boron species and vice versa, as indicated by (11)B/(27)Al rotational echo double resonance (REDOR) data. These results are consistent with the formation of a homogeneous, nonsegregated glass structure. For the first time, (89)Y solid state NMR has been used to probe the local environment of Y(3+) ions in a glass-forming system. The intrinsic sensitivity problem associated with (89)Y NMR has been overcome by combining the benefits of paramagnetic doping with those of signal accumulation via Carr-Purcell spin echo trains. Both the (89)Y chemical shifts and the Y-3d core level binding energies are found to be rather sensitive to the yttrium bonding state and reveal that the bonding properties of the yttrium atoms in these glasses are similar to those found in the model compounds YBO(3) and YAl(3)(BO(3))(4), Based on charge balance considerations as well as (11)B NMR line shape analyses, the dominant borate species are concluded to be meta- and pyroborate anions.

Structural studies of NaPO3-WO3 glasses by solid state NMR and Raman spectroscopy

Vitreous samples were prepared in the (100 2 x) NaPO3-x WO3 (0 <= x <= 70) glass forming system using conventional melting-quenching methods. The structural evolution of the vitreous network was monitored as a function of composition by thermal analysis, Raman spectroscopy and high resolution one- and two-dimensional P-31 solid state NMR. Addition of WO3 to the NaPO3 glass melt leads to a pronounced increase in the glass transition temperatures, suggesting a significant increase in network connectivity. At the same time Raman spectra indicate that up to about 30 mol% WO3 the tungsten atoms are linked to some non-bridging oxygen atoms (W-O- or W=O bonded species), suggesting that the network modifier sodium oxide is shared to some extent between both network formers. W-O- W bond formation occurs only at WO3 contents exceeding 30 mol%. P-31 magic angle spinning (MAS)-NMR spectra, supported by two-dimensional J-resolved spectroscopy, allow a clear distinction between species having two, one, and zero P-O-P linkages. The possible formation of some anionic tungsten sites suggested from the Raman data implies an average increase in the degree of polymerization for the phosphorus species, which would result in diminished P-31/Na-23 interactions. This prediction is indeed confirmed by P-31{Na-23} and Na-23{P-31} rotational echo double resonance (REDOR) NMR results, which indicate that successive addition of WO3 to NaPO3 glass significantly diminishes the strength of phosphorus-sodium dipole-dipole couplings.

Structural studies of NaPO3-MoO3 glasses by solid-state nuclear magnetic resonance and raman spectroscopy

Vitreous samples were prepared in the (100 - x)% NaPO3-x% MoO3 (0 <= x <= 70) glass-forming system by a modified melt method that allowed good optical quality samples to be obtained. The structural evolution of the vitreous network was monitored as a function of composition by differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FT-IR), Raman scattering, and solid-state nuclear magnetic resonance (NMR) for P-31, Na-23, and Mo-95 nuclei. Addition of MoO3 to the NaPO3 glass melt leads to a pronounced increase in the glass transition temperatures up to x = 45, suggesting a significant increase in network connectivity. For this same composition range, vibrational spectra suggest that the Mo6+ ions are bonded to some nonbridging oxygen atoms (Mo-O- or Mo=O bonded species). Mo-O-Mo bond formation occurs only at MoO3 contents exceeding x = 45. P-31 magic-angle spinning (MAS) NMR spectra, supported by two-dimensional J-resolved spectroscopy, allow a clear distinction between species having two, one, and zero P-O-P linkages. These sites are denoted as Q(2Mo)((2)), Q(1Mo)((2)), and Q(0Mo)((2)), respectively. For x < 0.45, the populations of these sites can be described along the lines of a binary model, according to which each unit of MoO3 converts two Q(nMo)((2)) sites into two Q((n+1)Mo)((2)) sites (n = 0, 1). This structural model is consistent with the presence of tetrahedral Mo(=O)(2)(O-1/2)(2) environments. Indeed, Mo-95 NMR data suggest that the majority of the molybdenum species are four-coordinated. However, the presence of additional six-coordinate molybdenum in the MAS NMR spectra indicates that the structure of these glasses may be more complicated and may additionally involve sharing of network modifier oxide between the network formers phosphorus and molybdenum. This latter hypothesis is further supported by Na-23{P-31} rotational echo double resonance (REDOR) data, which clearly reveal that the magnetic dipole-dipole interactions between P-31 and Na-23 are increasingly diminished with increasing molybdenum content. The partial transfer of modifier from the phosphate to the molybdate network former implies a partial repolymerization of the phosphate species, resulting in the formation of Q(nMo)((3)) species and accounting for the observed increase in the glass transition temperature with increasing MoO3 content that is observed in the composition range 0 <= x <= 45. Glasses with MoO3 contents beyond x = 45 show decreased thermal and crystallization stability. Their structure is characterized by isolated phosphate species [most likely of the P(OMo)(4) type] and molybdenum oxide clusters with a large extent of Mo-O-Mo connectivity.

Some effects of gamma-irradiated autologous sera on their donors

The present paper is a further step to elucidate the effect of γ-irradiated molecules and their action as immunogens. Rabbits were bled, the total serum was γ-irradiated and reinjected to the autologous donor. Bleeding and reinjection of non-irradiated serum do not produce any alteration hence the animal is able to recognize the autologous unmodified serum proteins as 'self'. Electrophoretic results demonstrate that as an effect of γ-irradiation, alteration of the normal migration properties are occurring. The obtained data are suggesting that due to the possible alteration of the molecular structure, resulting as the effect of γ-rays, the antibody forming system of the animal injected with irradiated autologous serum might recognize the substances as 'not self' what may be the possible reason of antibody formation. The presence of antibodies and probably their complexes with antigens are demonstrated by cutaneous sensibilization technics. The low level of the complement starting from the 7-9 days, the histological alteration of the kidney and the cardiac lesions are tempting to try an interpretation comparing these symptoms to those observed in serum sickness.

Development of organic-inorganic polymeric film formers for controlled drug release and wound care

Film forming polymeric systems represents a new and unexplored technology of systems forskin or wounds protection and for controlled drug release. The aim of this work was to study the use of polymeric organic-inorganic ureasil-polyether hybrids synthesized by the sol-gel process as film forming system containing silver sulfadiazine as model drug. The film formationtime can be controlled by changing the precursor/catalyst ratio used during the step of hydrolysis and condensations. The results showed that the precursor/catalyst proportion influences both the visual characteristics and time required to form the film. The precursor/catalyst ratio equal to 20.8 m/v was considered ideal due to promote the homogeneous and transparent film formation in less than 5 minutes. The release profile of sulfadiazine is dependent on the characteristics of the matrixes: matrix more hydrophobic as ureasil-POP provided a slowed released mainly due to the low swelling of the matrix. The more hydrophilic ureasil-POE matrix presents a large capacity to swell and favors the faster release of the drug. The set of results showed the possibility of future use of these systems for treating wounds caused by burns.