REE AND Sr, Nd, Pb ISOTOPIC GEOCHEMISTRY OF HUANGYISHAN BASALT, KUANDIAN, LIAONING, NORTHEAST CHINA

In the light of major element geochemistry, mineral chemistry and REE and isotopic data, the small but apparent isotopic differences between the Cenozoic volcanic rocks east and west of the Tancheng-Lujiang fault are believed to be caused by the mixing and metasomatism of crustal and mantle material in tho mantle source region in response to Pacific plate subduction. The presence of phlogopite and pargasite in mantle xenoliths lends strong support to mantle metasomatism.     

Source Rocks of the Caledonian-Age Granitoid Rocks in Wanyanshan-Zhuguangshan, Southeast China (Ⅱ)——Topological Analysis in Isotopic Multispace

Topological analysis in Sr-Nd-O-Pb_3 six-dimensional isotopic space suggests that the source rocks of the Caledonian-age granitoid rocks in Wanyangshan-Zhuguangshan, southeast China, comprise three end-member components. Isotopic mixing model discrimination indicates that the granitoid rocks were produced through mixing of the three componentsin varying proportions. Comprehensive study of multiple isotopic systems and geochemistry of the granitoid rocks suggests that the three end-member components were crustal rocks which are continent-derived sediments, geosycline sediments and altered basic volcanic rocks.     

Creation of crosslinkable interphases in polymer blends

A new type of bi- and trifunctional coupling agents containing 2-oxazoline and/or 2-oxazinone as well as hydrosilane moieties has been prepared by hydrosilylation of the corresponding allyl ether containing precursors with poly(methylhydro)siloxanes. In heterogeneous model blends based on mono-carboxylic acid terminated polystyrene (PS) and mono-amine terminated polyamide 12 (PA), the oxazoline and oxazinone units can selectively react with the carboxylic groups or amino groups, respectively. Under this mixing conditions the hydrosilane partially crosslinks. The morphology development of the three-component blends under melt mixing conditions is a rather complex process. We have shown that the coupling agents are immiscible with the polymers and form their own phase. Under proper processing conditions they locate at least partially at the PS/PA interface and can be used for further modification of the blend interphase, e.g. for crosslinking by hydrolysis. This crosslinking can be accelerated by the addition of a Pt-catalyst during the melt mixing.     

Effects of reprocessing of oxobiodegradable and non-degradable polyethylene on the durability of recycled materials

The use of plastics is steadily increasing in our daily lives, and plastics are the fastest-growing component of the waste stream. Although the efficiency of plastic recycling is increasing, plastics are often seen as a permanent environmental problem because of littering. The introduction of oxobiodegradable polyolefins (OBDs), containing prodegradant additives, is considered to be a way to reduce this problem by enabling the fast degradation of plastics in the environment. The prodegradant additives form radicals that attack the polymer chains, causing chain scissions and generation of low molecular mass oxidation products that can be consumed by microorganisms. There is, however, a concern that the prodegradant additives will present a problem if OBD materials end up in the conventional plastic recycling streams. The present study therefore highlights the impact of mixing OBD materials with conventional polyolefins to evaluate the impact on the remaining service life of the recyclates.The study included the use of two different OBDs, mixed in different proportions (10% and 20%) in a conventional polyethylene. The remaining service life of the mixtures was evaluated by monitoring the reduction in tensile strain after exposure to thermo-oxidative degradation at 70 °C, compared with a pure polyethylene. The impact of stabilizer content in the mixtures was also evaluated together with the effect of mixing partially degraded OBDs into the recyclate.The results show that the incorporation of minor fractions of OBD materials in the existing recycling streams will not create a severe effect on the service life of the recyclates as long as the polymer mixture possesses a reasonable degree of stabilization.     

Reaction rates as a function of scale within ionic liquids: microscale in droplet microreactors versus macroscale reactions in the case of the Grieco three-component condensation reaction

Task-specific ionic liquids (TSILs) and more specifically binary task-specific ionic liquids (BTSILs), a unique subclass, have been shown to be excellent supports for solution-phase chemistry. The negligible volatility of ionic liquids enables their use as stable droplet microreactors in atmospheric environments without oil protection or confinement. These droplets can be moved, merged and mixed by electrowetting on a chip. Solution-phase synthesis can be performed on these open digital microfluidic labs-on-a-chip as illustrated by a study of the Grieco three-component reaction in [tmba][NTf(2)]-droplet (tmba=N-trimethyl-N-butylammonium NTf(2)=bis(trifluoromethylsulfonyl)imide) microreactors. A detailed study of matrices and scale effects on conversion and kinetic rates of this three-component condensation is presented in this paper. Reactions have been shown to be slower in droplets than in batches in the absence of additional mixing. Also, a significant influence of the ionic-liquid matrix has been observed. Finally, an increase of droplet's temperature resulted in a kinetics enhancement so as to reach macroscale reaction rates, probably because of a much better mixing of reaction's components involving a Marangoni's effect.     

不对称Kabachnik-Fields反应合成研究进展

不对称三组分Kabachnik-Fields反应合成光学活性的α-氨基膦酸酯,由于其多组分反应自身所具有的独特优势,近年来已成为一个非常有吸引力的研究领域.从手性催化剂催化和光学活性底物诱导两方面综述了不对称Kabachnik-Fields反应合成手性α-氨基膦酸酯及其衍生物的最新研究进展,重点介绍了手性催化剂与手性底物构型对反应立体选择性的影响及其有关反应机理.最后提出了不对称多组分Kabachnik-Fields反应研究中存在的一些问题,并对其今后的发展方向进行了展望.     

郯庐断裂带鲁皖段新生代玄武岩形成机制的稀土判别

根据郯庐断裂带鲁皖段早第三纪、中新世以及更新世玄武岩的稀土元素特征的研究，应用稀土判据探讨了区内玄武岩的形成机制。稀土元素和常量元素的相关关系显示，郯庐断裂带新生代3个阶段玄武岩成岩过程中分离结晶作用不明显，其形成机制应该为上地幔部分熔融作用。通过多种稀土元素联合协变关系也同样反映了这些玄武岩的形成机制为上地幔部分熔融作用，同时也显示区内新生代玄武岩的稀土元素特征继承了其源区物质的稀土元素特征。这一结论与区内Sr，Nd同位素研究的结果相吻合。     

6,6′-Thiobis(methylene)-β-cyclodextrin dimer as a dimeric host and reusable promoter for synthesis of chromenones in water

Herein, two unit of β-cyclodextrin linked by thiomethylene bridge was synthesized and employed as a novel efficient supramolecular host for the synthesis of biologically active chromenones templates via three-component single-pot reaction. A possible reaction mechanism through molecular complexation is suggested based on 2D ROESY NMR spectroscopic analysis. Moreover, the catalyst could be easily recycled, while a 94% yield and 89% rate of catalyst recovery could be achieved after four cycles of catalyst recycling. Environmentally benign reaction conditions, excellent yields, and avoidance of organic solvent and conventional isolation as well as purification are the noteworthy credits of this developed protocol.     

Sputtering induced recombination of nitrogen isotopes on tungsten

Adsorbed isotopic mixtures of ¹⁴N₂ and ¹⁵N₂ at low coverages on polycrystalline tungsten have been used as model systems for studying sputtering induced recombination during secondary ion mass spectrometry (SIMS). Earlier studies have shown that N₂ is completely dissociated on a W surface at low coverage. Thermal desorption spectroscopy (TDS) has been employed here to confirm this fact; our results show that complete isotopic mixing occurs. Adsorbed nitrogen can be sputtered as both atoms and molecules and sputtering induced recombination of adsorbate atoms increases as primary ion energy increases. Sputtering induced recombination is detected through isotopic mixing in SIMS. The data show that the dominant mechanism for sputtering of dimers (N₂) is not direct emission from the surface but rather a sputtering induced recombination mechanism.     

Measurements of water vapor isotope ratios with wavelength-scanned cavity ring-down spectroscopy technology: new insights and important caveats for deuterium excess measurements in tropical areas in comparison with isotope-ratio mass spectrometry

The new infrared laser spectroscopic techniques enable us to measure the isotopic composition (δ(18)O and δ(2)H) of atmospheric water vapor. With the objective of monitoring the isotopic composition of tropical water vapor (West Africa, South America), and to discuss deuterium excess variability (d=δ(2)H - 8δ(18)O) with an accuracy similar to measurements arising from isotope-ratio mass spectrometry (IRMS), we have conducted a number of tests and calibrations using a wavelength-scanned cavity ring-down spectroscopy (WS-CRDS) technique. We focus in this paper on four main aspects regarding (1) the tubing material, (2) the humidity calibration of the instrument, (3) the water vapor concentration effects on δ, and (4) the isotopic calibration of the instrument. First, we show that Synflex tubing strongly affects δ(2)H measurements and thus leads to unusable d values. Second, we show that the mixing ratio as measured by WS-CRDS has to be calibrated versus atmospheric mixing ratio measurements and we also suggest possible non-linear effects over the whole mixing ratio range (~2 to 20 g/kg). Third, we show that significant non-linear effects are induced by water vapor concentration variations on δ measurements, especially for mixing ratios lower than ~5 g/kg. This effect induces a 5 to 10‰ error in deuterium excess and is instrument-dependent. Finally, we show that an isotopic calibration (comparison between measured and true values of isotopic water standards) is needed to avoid errors on deuterium excess that can attain ~10‰.     

Polymer-colloid complexes in three-component system: poly(styrene-alt-maleic acid)-poly(ethylene oxide)-silica sol in aqueous medium

Complex formation in the model three-component system, including polymer-polymer complex of poly(styrene-alt-maleic acid) (PSMA) and poly(ethylene oxide) (PEO), and also silica sol (SiO₂) in aqueous solution as a function of molecular weight of PEO and the order of component mixing, were investigated. The degree of binding of PSMA links with PEO and SiO₂ as well as the Gibbs energy of formation of the polymer-polymer complex and polymer-colloid complexes were defined. It was shown that the main factor of stabilization of the structure is hydrogen bonds. The conditions of three-component polymer-colloid system are practically independent of the order of component mixing. The spontaneous formation of polymer-colloid complexes between chemically complementary polymers and small dispersed particles is considered as the main reason for the abnormally high binding ability of colloid particles to the polymer-polymer complex.     

A laboratory comparison of two methods used to estimate the isotopic composition of soil delta13CO2 efflux at steady state

The stable isotopic composition of soil (13)CO(2) flux is important for monitoring soil biological and physical processes. While several methods exist to measure the isotopic composition of soil flux, we do not know how effective each method is at achieving this goal. To provide clear evidence of the accuracy of current measurement techniques we created a column filled with quartz sand through which a gas of known isotopic composition (-34.2 per thousand) and concentration (3,000 ppm) diffused for 7 h. We used a static chamber at equilibrium and a soil probe technique to test whether they could identify the isotopic signature of the known gas source. The static chamber is designed to identify the source gas isotopic composition when in equilibrium with the soil gas, and the soil probe method relies on a mixing model of samples withdrawn from three gas wells at different depths to identify the gas source. We sampled from ports installed along the side of the sand column to describe the isotopic and concentration gradient as well as to serve as a control for the soil probe. The soil probe produced similar isotopic and concentration values as the control ports, as well as Keeling intercepts. The static chamber at equilibrium did not identify the source gas but, when applied in a two end-member mixing model, did produce a similar Keeling intercept produced from the control ports. Neither of the methods was able to identify the source gas via the Keeling plot method probably because CO(2) profiles did not reach isotopic steady state. Our results showed that the static chamber at equilibrium should be used only with a Keeling plot approach and that the soil probe is able to provide estimates of uncertainty for the isotopic composition of soil gas as well as information pertinent to the soil profile.     

Palladium-catalyzed alkylation-hydride reduction sequence: synthesis of meta-substituted arenes

A new three-component, palladium-catalyzed domino reaction which gives access to meta-substituted arenes using aryl iodides and primary alkyl halides is reported. Various functional groups are tolerated on both the aryl iodide and alkyl halide. In addition, isotopic labeling studies provide insight into the mechanism of this Catellani-type reaction. [reaction: see text]     

Isotopic analysis of lead present in the cinnabar of Roman wall paintings from the Xth Regio "(Venetia et Histria)" by ICP-MS

The analysis of Roman wall paintings coming from Verona, Vicenza, Padova, Pordenone and Trieste evidentiated the presence of cinnabar. In this work, the isotopic composition (206)Pb, (207)Pb and (208)Pb of trace of lead present in cinnabar is reported, via ICP-MS measurements. The isotopic ratio values are compared with the values obtained from samples coming from Roman wall paintings of Pompeii and from the mines of Almaden (Spain) Monte Amiata (Grosseto Italy) and Idria (Slovenia). All the isotopic data can be represented by a "field" ranging from Huelva, to Almeria Spanish provinces. This trend could be due to the mixing of cinnabar products treated in Rome.     

Review on Applications of 17O in Hydrological Cycle

The triple oxygen isotopes (¹⁶O, ¹⁷O, and ¹⁸O) are very useful in hydrological and climatological studies because of their sensitivity to environmental conditions. This review presents an overview of the published literature on the potential applications of ¹⁷O in hydrological studies. Dual-inlet isotope ratio mass spectrometry and laser absorption spectroscopy have been used to measure ¹⁷O, which provides information on atmospheric conditions at the moisture source and isotopic fractionations during transport and deposition processes. The variations of δ¹⁷O from the developed global meteoric water line, with a slope of 0.528, indicate the importance of regional or local effects on the ¹⁷O distribution. In polar regions, factors such as the supersaturation effect, intrusion of stratospheric vapor, post-depositional processes (local moisture recycling through sublimation), regional circulation patterns, sea ice concentration and local meteorological conditions determine the distribution of ¹⁷O-excess. Numerous studies have used these isotopes to detect the changes in the moisture source, mixing of different water vapor, evaporative loss in dry regions, re-evaporation of rain drops during warm precipitation and convective storms in low and mid-latitude waters. Owing to the large variation of the spatial scale of hydrological processes with their extent (i.e., whether the processes are local or regional), more studies based on isotopic composition of surface and subsurface water, convective precipitation, and water vapor, are required. In particular, in situ measurements are important for accurate simulations of atmospheric hydrological cycles by isotope-enabled general circulation models.     

Environmentally sound manufacturing and polymer industry for the 21st century

Life cycle assessments to protect global environment and to control waste in the polymer industry are reviewed. It focused on 1) the environmentally sound technology, 2) the energy conservation, and 3) recycling of industrial products. The competitiveness of a nation depends on how to balance between economic development of sustainable growth and responsible care of global environment in borderless economy. It fully depends on the development of both the environmentally sound manufacturing and the effective products recycling technologies. Current environmental issues of the Japanese chemical industries as well as Toray's performance and new products development for environment business are reviewed; 1) Energy conservation and technology of Japanese manufacturing industry. 2) Development of environmentally sound technology. 3) Effective products recycling technologies, and 4) Sustainable growth of the new chemical age. The future issues of life cycle assessment and environmental protection in manufacturing industries are discussed.     

共聚物混溶性热力学-分子内排斥作用与附加共聚焓

基于聚合物分子间物理相互作用和统计平均场理论,引入附加共聚焓定义,使聚合物分子间的作用得到量化,同时推导出二元共混体系相互作用参数和三元共混体系混合焓关系式.利用所导出的公式解释一些常见聚合物共混体系和增溶体系.导出的关系式很好地解释了聚合物的热力学混溶性,但不能解释聚合物共混增溶作用.     

聚己内酯和酚氧树脂共混物的结晶行为和熔融转变

通过采用不同变温程序对溶液铸膜PCL与酚氧共混物进行了热分析。实验结果显示,在准平衡状态下,对PCL含量大于30％的共混对,PCL均可从混合物熔体中降温结晶出来。进一步研究发现熔融温度随PCL含量减少而下降,此现象可籍结晶、非晶聚合物之间的热力学混容解释,并应用由Scott方程推导出的关系式计算,发现对该聚合物对,相互作用参数在320K时为-0.155。从熔融态等速降温,对PCL含量大于50％的共混对均观察到结晶转变,转变温度强烈依赖于组成和降温速率,主要原因在于对这种“动力学”实验,熔体中PCL链段向晶体表面的扩散过程控制结晶,任何使PCL链段扩散能力减弱的因素,都将降低结晶温度。在等速降低温度过程中还发现,共混物产生双结晶峰。     

Life Cycle Assessment in Polymer Industry Toward the 21st Century

Abstract

Life cycle assessments to protect global environment and to control waste in the polymer industry are reviewed. The focus is on 1) environmentally sound technology, 2) energy conservation, and 3) recycling of industrial products. The competitiveness of a nation depends on how it balances economic development of sustainable growth and responsible care of the global environment in a borderless economy. It fully depends on the development of both environmentally sound manufacturing and effective recycling technologies for the products. Current environmental issues of the Japanese chemical industries as well as Toray's performance and new products development for environment business are reviewed: 1) Energy conservation and technology of the Japanese manufacturing industry, 2) Development of environmentally sound technology, 3) Effective products recycling technologies, and 4) Sustainable growth in the new chemical age. The future issues of life cycle assessment and environmental protection in manufacturing industries are discussed.     

Measurements of the order parameter by proton N.M.R. on N-(4-alkoxybenzylidene)4'-toluidines

N-(4-alkoxybenzylidene)4'-toluidines are a family of organic compounds which present a nematic and (depending on the chain length) a smectic mesophase. We have performed proton spin echo measurements on some members of the family in these mesophases. N.M.R. spectra present well-defined structures that can be assigned to one of the two end methyl groups on the basis of phenomenological as well as analytical discussion, despite the large number of protons contributing to the total line shape. The order parameter derived from this analysis is compared with optical data on the same compounds.