What do titano- and zirconocenes do with diynes and polyynes?

A thorough investigation of the reactions of diynes, R(C&tbd1;C)(2)R, and polyynes, R(C&tbd1;C)(n)()R, with titanocene and zirconocene was performed using the metallocene sources Cp(2)M(L)(eta(2)-Me(3)SiC&tbd1;CSiMe(3)) (M = Ti, L = -; M = Zr, L = THF, pyridine). The conversions show an array of different products generated in complexation, coupling, and cleavage reactions. These results include remarkable structures (e.g., five-membered metallacyclocumulenes) and reactions (e.g., C-C single-bond cleavage). In addition, the first C-C single-bond metathesis in homogeneous solution was discovered. The presented findings have been supported by theoretical studies.     

Malleable and recyclable thermoset network with reversible β-hydroxyl esters and disulfide bonds

By combining bifunctional diglycidyl ether of bisphenol A (DGEBA) and trifunctional tris(4-hydroxyphenyl) methane triglycidyl ether (TMTE) epoxy monomers, along with 4,4′-dithiodibutyric acid (DTDBA) as a carboxylic acid, a variety of novel reprocessable and recyclable thermoset polymers are synthesized. The crosslinked network structures with different crosslinking densities are produced by changing the mixing ratio between DGEBA and TMTE, resulting in changes in mechanical and thermal properties of the final products. The stress relaxation and self-healing experiments confirmed that all of these polymeric materials have covalent adaptable networks in their microstructures and perform reversible transesterification processes inside a polymer network. These thermoset polymers are completely decomposed in solution by disulfide-thiol reduction of DTDBA with reversible cleavage or coupling capability in the presence of reducing agent, allowing chemical recycling capability into the thermoset polymer network.     

Copolymerization of butadiene and isoprene with TMEDA as modifier

以正丁基锂(n-BuLi)为引发剂,N,N,N',N＇-四甲基乙二胺(TMEDA)为调节剂,环己烷为溶剂,通过负离子聚合制备了丁二烯和异戊二烯的共聚物.结果表明,随着TMEDA用量的增加,聚合速度加快,丁二烯单体竞聚率增加,异戊二烯单体竟聚率减少,二者差值逐渐增大,在TMEDA/n-BuLi(摩尔比)不小于0.8时,这种变化趋势变缓,表明共聚物分布不均匀程度增加.     

Nanocomposites prepared with NR and solid-state organic modified montmorillonite

固相法改性蒙脱土及其在天然橡胶中的应用孙玉海,罗远芳,贾德民,傅伟文(华南理工大学材料科学与工程学院,广东广州510640)用丙烯酰胺作改性剂,采用固相法对蒙脱土进行有机改性,用改性的蒙脱土通过机械共混制备了橡胶/蒙脱土纳米复合材料,并将混炼胶在硫化前进行了适当的热处理以提高插层效果。抽提后蒙脱土的红外图谱显示改性剂和蒙脱土之间形成了牢固的化学键合。X射线分析表明改性剂使蒙脱土的层间距由1.52 nm增大到1.88 nm,热处理前后硫化胶中蒙脱土的层间距分别达到了4.19 nm和4.41 nm。     

Replacing fossil oil with fresh oil – with what and for what?

Industrial chemicals and materials are currently derived mainly from fossil‐based raw materials, which are declining in availability, increasing in price and are a major source of undesirable greenhouse gas emissions. Plant oils have the potential to provide functionally equivalent, renewable and environmentally friendly replacements for these finite fossil‐based raw materials, provided that their composition can be matched to end‐use requirements, and that they can be produced on sufficient scale to meet current and growing industrial demands. Replacement of 40% of the fossil oil used in the chemical industry with renewable plant oils, whilst ensuring that growing demand for food oils is also met, will require a trebling of global plant oil production from current levels of around 139 MT to over 400 MT annually. Realisation of this potential will rely on application of plant biotechnology to (i) tailor plant oils to have high purity (preferably >90%) of single desirable fatty acids, (ii) introduce unusual fatty acids that have specialty end‐use functionalities and (iii) increase plant oil production capacity by increased oil content in current oil crops, and conversion of other high biomass crops into oil accumulating crops. This review outlines recent progress and future challenges in each of these areas. Practical applications: The research reviewed in this paper aims to develop metabolic engineering technologies to radically increase the yield and alter the fatty acid composition of plant oils and enable the development of new and more productive oil crops that can serve as renewable sources of industrial feedstocks currently provided by non‐renewable and polluting fossil‐based resources. As a result of recent and anticipated research developments we can expect to see significant enhancements in quality and productivity of oil crops over the coming decades. This should generate the technologies needed to support increasing plant oil production into the future, hopefully of sufficient magnitude to provide a major supply of renewable plant oils for the industrial economy without encroaching on the higher priority demand for food oils. Achievement of this goal will make a significant contribution to moving to a sustainable carbon‐neutral industrial society with lower emissions of carbon dioxide to the atmosphere and reduced environmental impact as a result.     

Drying Kinetics and Energy Consumption in Vacuum Drying Process with Microwave and Radiant Heating

The general objective of this work is to analyze energy input in a vacuum process with the incorporation of microwave heating. Thus, necessary criteria for designing an efficient freeze-drying operation are considered through the analysis of strategies based on the combination of different intensities of radiant and microwave heating. The other aim of this research topic is to study the kinetics of drying in relation to mass transfer parameters. Five freeze-drying strategies using both heating systems were used. Consequently, energy input could be related to diffusivity coefficients, temperature and pressure profiles during dehydration of the product and analyzed in comparison to a conventional freeze-drying process.     

Activated carbon sorbent with thioetheric sites—preparation and characterization

An activated carbon sorbent containing thioetheric sites (ACTS) was prepared by modification of the activated carbon with 2,2′-thiodiethanol. The specific surface area, pore volume, concentration of oxygen-containing groups and sulfur content of the sorbent were determined. The sorption behavior towards ions of some precious metals—Au(III), Pt(IV), Pd(II) and heavy metals—Ni(II), Zn(II), Fe(III), Cu(II), Pb(II), Cd(II) and Co(II) was studied. Selectivity towards gold, palladium and platinum in the pH range 1–9 was observed. The capacity for gold was 80 mg g⁻¹. The sorption of Au(III) at pH 1 is not affected by milligram amounts of Ni(II), Zn(II), Fe(III), Cu(II), Pb(II), Cd(II) and Co(II). The sorbed gold species is Au(0).     

Preparation and characterization of thermo-sensitive microspheres with β-cyclodextrin groups

采用沉淀聚合机理,由一步法和两步法制备聚（N-异丙基丙烯酰胺-甲基丙烯酸缩水甘油酯） [P(NIPAM-co-GMA)]温敏性微球。其中一步法是同时加入所有反应物反应成微球,而两步法是先加NIPAM成微球,再加入GMA,最终均生成P(NIPAM-co-GMA)微球;再将改性的乙二胺代环糊精（EDA-β-CD）通过化学反应引入到P(NIPAM-co-GMA)微球结构中,制备得到聚（N-异丙基丙烯酰胺-甲基丙烯酸-2-羟丙基乙二胺基环糊精） [P(NIPAM-co-GMA/β-CD)]共聚高分子微球。分别用扫描电镜、红外光谱、控温激光粒度仪及光学显微镜对产物的形貌、结构和温敏特性进行了表征。结果表明,两种方法制备的微球均具有良好的单分散性和球形度,均能成功地固载β-环糊精（β-CD）基团,并且都有温度响应特性;但是,同一步法制备的微球相比,两步法制得的微球粒径明显较大,且微球固载有更多的β-CD。     

Random copolymerization of ε-caprolactone and l-lactide with molybdenum complexes

Dioxomolybdenum complexes were examined as catalysts for the copolymerization of ε-caprolactone (ε-CL) and l-lactide (l-LA). The bis-[(5-OMe)salicylaldehydato]dioxomolybdenum complex completed the copolymerization after 20 h at 110 °C with 0.05 mol% of the catalyst to produce a copolymer in high yield. The microstructure of the copolymer was analyzed using ¹H and ¹³C NMR spectroscopy and was determined to have a random structure. The r values calculated from the heterodiad analysis of the ¹H NMR data were r _LA = 0.91 and r _CL = 0.93, and the L values calculated from the triad analysis of the ¹³C NMR data were L _LA = 1.58 and L _CL = 1.81. Other dioxomolybdenum complexes, such as cis-α MoO₂[(3-MeO)DiMeSaltn], MoO₂(acac)₂ and (NH₄)₈[Mo₁₀O₃₄] exhibited comparable or slightly lower reactivity for the copolymerization. Consecutive polymerization of ε-CL followed by l-LA afforded a block copolymer without trans-esterification.     

Shrinkage and mechanical properties of unsaturated polyester reinforced with clay and core–shell rubber

Glassy unsaturated polyester (UP) resin was reinforced using an organically modified montmorillonite (OMMT) and toughened with core?Cshell rubber (CSR) particles. The nanostructure, morphology, and deformation mechanism of composite specimens were studied by small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM) and reflected optical microscopy (ROM). An intercalated nanostructure with partial exfoliation was observed in the UP reinforced by various amounts of OMMT. Locally clustered but globally good CSR particle dispersion in the UP matrix was evident in UP toughened with 5 and 10 wt% CSR particles. Simultaneous presence of OMMT and CSR particles in UP/OMMT/CSR hybrid composites was found to cause partial phase separation with bigger rubber particle agglomerates and lower clay-intergallery height increase. The effects of OMMT and CSR contents on volume shrinkage, impact fracture energy, fracture toughness, and compressive yield strength of UP were investigated. The introduction of OMMT of up to 3?wt% into the UP matrix lowered volume shrinkage to some extent, while further addition increased the shrinkage slightly. In the hybrid nanocomposites, the volume shrinkage decreased to a minimum level of 5.2?% with increases in OMMT level. The impact fracture energy of UP improved with increasing the OMMT level of up to 3?wt%, whereas its further addition decreased the impact fracture energy slightly due to the clay particle agglomeration. The hybrid composites with OMMT level below 3?wt% showed higher impact fracture energy compared to the reinforced UP specimens with the same OMMT levels. Interestingly, a synergism in the fracture toughness (K _IC) was observed in the hybrid composite containing 1?wt% OMMT and 10?wt% CSR particles. The presence of OMMT as reinforcement in the hybrid composites could compensate the lowering of the compressive yield strength caused by low-modulus CSR particles. The clay?Crubber particle interaction in the hybrid systems seems to increase the threshold of shear deformation of the UP matrix to some extent.     

Anaerobic biodegradation of RDX and HMX with different co-substrates☆

Simulated wastewater of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) was treated under anaerobic conditions with co-substrates such as ammonium chloride, dex-trose, sodium acetic, sodium nitrate and sulfate. The results showed that with nitrogen compounds such as ammonium chloride added as co-substrate, no significant change was observed, indicating that the molar ratio of N/C for RDX and HMX is sufficient for biodegradation. With the addition of dextrose and acetate to the system, biodegradation efficiency was enhanced greatly. For example, with dextrose as the co-substrate, degradation efficiency of 99.1%and 98.5%was achieved for RDX and HMX, respectively, after treatment for 7 days. When so-dium acetic was used as the co-substrate, the enhancement of degradation percentage was similar, but was not as high as that with dextrose, indicating the selectivity of RDX and HMX to co-substrate during anaerobic degrada-tion. With sodium nitrate as the co-substrate, the degradation efficiency of RDX or HMX decreased with the increase of salt concentration. Sodium sulfate has no significant effect on the biodegradation of RDX and HMX. A wel-selected co-substrate should be employed in applications for degradation of RDX and HMX wastewaters.     

Interaction of hydrogen and n‐pentane with sulfated zirconia

Interaction of hydrogen with sulfated zirconia catalysts was studied in situ at 473 K. Interaction of hydrogen with the sample evacuated at 673 K leads to the formation of new hydroxyl groups (wide bands near 3330 cm⁻¹) and water (1620 cm⁻¹). In the case of the sample evacuated at 873 K, SOH groups (3660 cm⁻¹) and zirconium hydrides (1555 cm⁻¹) form. Adsorption of n‐pentane on sulfated zirconia catalysts in the range of 253–383 K was studied. It was shown that hydrides and protonated cyclopentadienes form at low temperatures. At higher temperatures, aromatic compounds are formed mainly. The reaction mechanism is discussed. This revised version was published online in August 2006 with corrections to the Cover Date.     

Boron separation by adsorption and flotation with Mg–Al-LDHs and SDBS from aqueous solution

Layered double hydroxides(LDHs) have been shown to be effective adsorbents for boron. However, solid–liquid separation is still a problem when separating boron from industrial radioactive waste liquid. In this research, three types of Mg–Al-LDHs including Mg–Al-LDH(NO₃^–), Mg–Al-LDH(Cl^–) and Mg–Al-LDH(SO₄^2–)were applied to adsorb boron, and moreover sodium dodecylbenzenesulfonate(SDBS) was used to float the LDH particles from aqueous solution...     

Deposition and characterization of nanocrystalline and amorphous Ni–W coatings with embedded alumina nanoparticles

Nanocrystalline and amorphous Ni–W coatings containing Al₂O₃ nanoparticles were electrodeposited from three different ammoniacal citrate baths by direct current (DC) method. The effects of nanoparticles on compositional, structural and morphological features of Ni–W coatings were investigated. The effects of bath chemical composition and current density on codeposition behavior of nanoparticles were also studied. Guglielmi model for particle deposition was applied to identify the kinetics of particle deposition. The presence of nanoparticles may affect on coating grain size, tungsten content and the rate of metal deposition. In addition, nanoparticles can result in more compact coatings with fewer defects. The extent of these effects depends on bath chemical composition and may be influenced by the synergistic effect of Ni on deposition of W. It was also found that the kinetics of particle deposition and the effect of current density on codeposition behavior of nanoparticles are highly dependent on bath chemical composition.     

Characterization of SuperLig® 639 Rhenium and Technetium Resin with Batch Contact and Column Tests

Two new (2013) lots of SuperLig^® 639 ion exchange resin (IBC Advanced Technologies, American Forks, UT) were tested for the first time above typical sodium concentrations (7.8 M sodium, along with typical 5 M concentration) in highly alkaline solutions. Batch contact and ion exchange column tests characterized rhenium (perrhenate) adsorption as a surrogate for pertechnetate. The work supports technetium removal options for Supplemental Low Activity Waste processing at the Hanford River Protection Project Waste Treatment Plant (WTP). The current work found that the resin performs well in the 7.8 M sodium simulant despite complete floating of the beads. A notable difference in performance between the two new resin lots was found. Resin loading overall versus temperature, potassium concentration, and rhenium/nitrate ratios is consistent with previous data and expectations despite the high sodium concentration and floating of the resin beads.     

Study on β-cyclodextrin grafting with chitosan and slow release of its inclusion complex with radioactive iodine

β-CD-2-CTS was synthesized by β-cyclodextrin reacting with p-toluenesulfonyl chloride, then grafting with chitosan. The infrared spectra analysis and ¹³C NMR confirmed that β-cyclodextrin reacted with p-toluenesulfonyl chloride at the 2-position carbon atom in the substituted glucose unit of β-cyclodextrin and formed β-CD-2-OTs. In the ¹³C NMR of β-CD-2-OTs, the characteristic peak of the 2-postion carbon atom in the substituted glucose unit of β-cyclodextrin appeared at 78.43 ppm. β-CD-2-CTS was characterized with infrared spectra analysis and X-ray diffraction. In the infrared spectra of β-CD-2-CTS, the characteristic peak of α-pyanyl vibration of β-CD was at 848.6 cm⁻¹. The characteristic peak of β-pyanyl vibration of CTS was at 894.9 cm⁻¹. The X-ray diffraction analysis showed that the peak at 2θ = 20° decreased greatly in β-CD-2-CTS. The polymer inclusion complex of β-CD-2-CTS with iodine was prepared and its inclusion ability was studied. The experimental results showed that a nice bit of iodine was included with β-CD-2-CTS and formed a stable inclusion complex. After the subcutaneous implantation of the polymer inclusion complex of β-CD-2-CTS with ¹³¹I₂ in rats, ¹³¹I₂ exhibited the property of slow release. ¹³¹I₂ in the blood of rats decreased slowly. ¹³¹I₂ in the blood of rats maintained approximately half of maximum for 70 days later, and maintained much higher radioactivity in the organs of rats compared to the inclusion complex of β-CD with ¹³¹ I₂, too. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2414–2421, 2001     

Inhibitory Activities of Cyanidin and Its Glycosides and Synergistic Effect with Acarbose against Intestinal α-Glucosidase and Pancreatic α-Amylase

Cyanidin and its glycosides are naturally dietary pigments which have been indicated as promising candidates to have potential benefits to humans, especially in the prevention and treatment of diabetes mellitus. We investigated the structure activity relationships of cyanidin and its glycosides to inhibit intestinal α-glucosidases and pancreatic α-amylase in vitro. The results found that cyanidin and its glycosides are more specific inhibitors of intestinal sucrase than intestinal maltase. Cyanidin-3-galactoside and cyanidin-3-glucoside were the most potent inhibitors against intestinal sucrase and pancreatic α-amylase with IC(50) values of 0.50 ± 0.05 and 0.30 ± 0.01 mM, respectively. Our findings indicate that the structural difference between glucose and galactose at the 3-O-position of cyanidin was an important factor for modulating the inhibition of intestinal sucrase and pancreatic α-amylase. The combination of cyandin-3-glucoside, cyanidin-3- galactoside or cyanidin-3,5-diglucosides with a low concentration of acarbose showed synergistic inhibition on intestinal maltase and sucrase. The synergistic inhibition was also found for a combination of cyanidin or cyanidin-3-glucoside with a low concentration of acarbose. The findings could provide a new insight into a use for the naturally occurring intestinal α-glucosidase and pancreatic α-amylase inhibitors for the prevention and treatment of diabetes and its complications.     

Kinetics and mechanism of ethylene homopolymerization and copolymerization reactions with heterogeneous Ti-based Ziegler–Natta catalysts

A detailed kinetic analysis of ethylene homopolymerization reactions and its copolymerization reactions with 1-hexene with a supported Ti-based Ziegler–Natta catalyst (reactions in the absence and the presence of hydrogen) shows a number of distinct kinetic features which are interpreted as a manifestation of multi-site catalysis; the catalyst contains several types of polymerization centers which differ in stability and formation rates, the molecular weight of polymers they produce, and in their response to the presence of α-olefins and hydrogen. All these effects require introduction of a special kinetic mechanism which postulates an unusually low activity of growing polymer chains containing one ethylene unit, the Ti–C₂H₅ group, in the ethylene insertion reaction into the Ti–C bond. This peculiarity of the Ti–C₂H₅ group, which is probably caused by its β-agostic stabilization, predicts two kinetic/chemical features of ethylene polymerization reactions which have not been described yet, the deuterium effect on the homopolymer structure and the activation effect of α-olefins on chain initiation. Both effects were confirmed experimentally. This revised version was published online in June 2006 with corrections to the Cover Date.     

N-Ethylation of aniline with ethanol or diethyl carbonate over alkali and alkaline zeolites Y and β

Vapour phase ethylation of aniline was carried out over alkali and alkaline earth exchanged zeolites Y and β. Reaction conditions were optimised for N-alkylation by varying reaction parameters like temperature, WHSV, mole ratio and time on stream. Over all zeolites, N-alkylation is much higher than C-alkylation. Diethyl carbonate is a better N-alkylating agent than ethanol. Among the catalysts studied, Kβ is a good N-monoalkylating catalyst with 41% aniline conversion and 100% selectivity at 473 K, WHSV 19.8 h⁻¹ and diethyl carbonate/aniline ratio 2.