基质固相分散-高效液相色谱法测定水稻中痕量异丙威

研究出一种应用基质固相分散 (MSPD) -高效液相色谱法测定水稻中痕量异丙威残留物的新方法。并讨论了应用MSPD技术进行前处理与传统残留分析的区别。本实验将MSPD技术用于水稻中异丙威残留物的高效液色谱分析 ,并对定量检测条件作了详细的研究。

用化学发光体系测定水样中异丙威含量

在酸性介质中,Ce(IV)氧化连二亚硫酸钠产生较弱的化学发光,异丙威可以大大增强此发光强度。并且,增加的发光强度与异丙威的质量浓度在0.3～8.0μg·mL–1范围内呈良好的线性关系。基于此,结合流动注射技术建立了测定异丙威的流动注射化学发光新方法。对3.0μg·mL–1的异丙威连续平行测定11次,其相对标准偏差(RSD)为3.4%。根据IUPAC建议,计算其检出限为0.09μg·mL–1(3σ)。用该法测定水样中加入的异丙威含量,结果良好。

Synthesis of Methyl Isopropyl Ketone and Diethyl Ketone over Ni-Na/ZrO_2-MnO_2-ZnO Catalyst

ZrO2-MnO2-ZnO supports were prepared by the co-precipitation method,and then Ni-Na/ZrO2-MnO2-ZnO catalysts were prepared by the impregnation method.In this paper,the reactions to synthesize methyl isopropyl ketone and diethyl ketone by the one-step synthesis method over this catalyst were studied,and meanwhile,the impact of the catalyst preparation conditions and the reaction conditions on catalyst performance was also investigated.It was observed that under the conditions when Ni loading was 25%,calcination temperature was 400℃ and reduction temperature was 410℃,this catalyst had good catalytic performance on the reaction.The suitable reaction conditions were achieved:reaction temperature was 400℃;reaction at atmospheric pressure;liquid hourly space velocity of raw material of 0.5 h 1 ;and the molar ratio of(methanol)/(methyl ethyl ketone)/(water) was equal to 1/1/1.Under such conditions,the conversion of methyl ethyl ketone could achieve 41.7%,and the overall selectivity of methyl isopropyl ketone and diethyl ketone could achieve 83.3%,which was comparable to the conversion of 38.1% and the selectivity of 82.2% achieved by using palladium as the active material.The good stability made this catalyst have good prospects for industrial application.

Synthesis and Separation Performance of Y-type Zeolite Membranes by Pre-Seeding Using Electrophoresis Deposition Method

Y-type zeolite membranes were synthesized by a two-step approach in which a particle seed layer was prepared by electrophoresis deposition(EPD) at first, followed by densification through secondary growth. The pre-seeding adopted the directing agent for Y-type zeolite synthesis serving as seeds. The effects of aging time of the directing agent, electrophoresis voltage and electrophoresis deposition time on seed layers quality as well as the quality of zeolite membranes were investigated. The results indicated that the zeolite seeds derived from the directing agent could be evenly deposited on substrate under certain EPD conditions. The XRD patterns of the seeded substrates after the secondary growth showed that the pure as-synthesized Y-type zeolite membranes had successfully grown on the substrates. The SEM images indicated that the substrate was covered by the highly intergrown zeolite crystals when the seeding solution employed the directing agent with an aging time of 2 days. The separation performance of zeolite membrane was evaluated using a CO_2/N2 mixture(with a mole ratio of 1:1) at different temperatures. Furthermore, the pervaporation measurements were carried out for the dehydration of isopropanol aqueous solutions with different mass fractions. The as-synthesized Y-type zeolite membranes exhibited a relatively high selectivity of water from isopropanol and sustainable permeation flux.

Efficient approach to thiazolidinones via a one-pot three-component reaction involving 2-amino-1-phenylethanone hydrochloride,aldehyde and mercaptoacetic acid

A highly efficient three-component reaction has been developed for the synthesis of thiazolidinones involving the reaction of 2-amino-l-phenylethanone hydrochloride with an aromatic aldehyde and mercaptoacetic acid in the presence of diisopropylethylamine in a single pot.Critically,this reaction exhibited excellent chemoselectivity,with the nitrogen atom of the 2-amino-l-phenylethanone component reacting selectively with the aromatic aldehyde to give the corresponding Schiff base.Nucleophilic attack at the carbon of the Schiff base by the sulfur atom of mercaptoacetic,followed by a cyclocondensation reaction between the nitrogen and the carboxylic acid moiety afforded the desired thiazolidinones,which were fully characterized by spectroscopic techniques.

Synthesis and characteristics of pH-and temperature-sensitive hydrogels of poly （DMAEMA/NIPAAm）

A kind of novel copolymer hydrogel of poly（N, N-dimethylaminoethyl methacrylate-co-N-isopropylacrylamide） （poly[DMAEMA/NIPAAm]） was synthesized by the initiation of K2S2O8, N, N＇-methylene-bis（acrylamide） （Bis） was used as the crosslinker. The effects of monomer content, pH and temperature on swelling ratio of the hydrogel were investigated; the thermo-sensitivity in deionized water and in physiological saline was determined. It showed that the swelling ratio of the hydrogel could be changed by changing the temperature or pH alternately. Both swelling ratio and LCST （Lower Critical Solution Temperature） of the hydrogel decreased with the increase of NIPAAm in the co-polymer content.

THE FABRICATION OF CARBON AEROGELS BY GELATION IN ISOPROPANOL WITH BASIC CATALYST

A new method for the fabrication of carbon aerogels is reported in this paper. Resorcinol and furfural were gelated in isopropanol with basic catalysts and then dried directly under isopropanol supercritical condition, followed by carbonization under nitrogen atmosphere. The bulk densities of carbon aerogels obtained are in the range of 0.21g/cm3~0.27g/cm3 and the sizes of the interconnected carbon nano-particles are in the range of 20nm^30nm. All of the aerogel samples exhibit high BET surface areas in the range of 730m2/g^900m2/g. The bulk density, micro-pore volume, meso-pore volume and meso-pore diameter can be controlled by gelation conditions such as R/I ratio and R/C ratio.

Reaction kinetics of isopropyl palmitate synthesis

In this study, the kinetics of isopropyl palmitate synthesis including the reaction mechanism was studied based on the two-step noncatalytic method. The liquid-phase diffusion effect on the reaction process was eliminated by adjusting the stirring rate. The results showed that the two-step reaction followed a tetrahedral mechanism and conformed to second-order reaction kinetics. Nucleophilic attack on the carbonyl carbon afforded an intermediate, containing a tetrahedral carbon center. The intermediate ultimately decomposed by elimination of the leaving group, affording isopropyl palmitate. The experimental data were analyzed at different temperatures by the integral method. The kinetic equations of the each step were deduced, and the activation energy and frequency factor were obtained. Experiments were performed to verify the feasibility of kinetic equations, and the result showed that the kinetic equations were reliable. This study could be very signi ficant to both industrial application and determining the continuous production of isopropyl palmitate.

Assessment of mitral valve reserve capacity before and after percutaneous balloon valvuloplasty with isoproterenol stress echocardiography

Objective: To explore whether successful valvuloplasty increases mitral valve reserve capacity in patients with mitral stenosis. Methods: Thirty-eight patients with pure rheumatic mitral stenosis underwent isoproterenol stress echocardiography before and after successful percutaneous balloon valvuloplasty. The mitral valve area (by direct planimetry of two-dimensional echocardiography), mean transmitral pressure gradient (by continuous-wave Doppler echocardiography), and cardiac output (by M-mode echocardiography) were measured at rest and under isoproterenol infusion to achieve heart rate of different stages. Results:Between the measurements before and after valvuloplasty, significant differences were observed in the mitral valve area (0. 91±0. 28 vs 1. 87±0. 23 cm2, P<0. 01), mean transmitral pressure gradient (12. 5±6. 3 vs 3. 9±1. 9 mmHg, P<0. 01) and cardiac output (3. 93±1. 44 vs 4. 73±1. 01 L/min, P<0. 05) at rest. Before valvuloplasty, the mean transmitral pressure gradient increased significantly (P<0. 01) as heart rate increased, but there were no significant differences in the measurements of mitral valve area and cardiac output (both P>0. 05). In contrast, there was a significant increase after valvuloplasty in the mean transmitral pressure gradient (P<0. 01), but both mitral valve area and cardiac output further increased (both P< 0. 01) as heart rate increased. Moreover, valvuloplasty decreased the mean transmitral pressure gradient at peak heart rate from 23. 0±4. 5 to 7. 75±2. 30 mmHg (F<0. 01) under submaximal stress. Conclusion: Successful percutaneous balloon valvuloplasty soon causes a significant increase of mitral valve reserve capacity in patients with mitral stenosis, which is conspicuously manifested under condition of hemodynamic stress. Stress echocardiography provides a safe, feasible and non-invasive means of assessing the reserve capacity.

Synthesis of multifunctional ABC stars with a reduction-labile arm by consecutive ROP, RAFT and ATRP processes

This study aims at versatile synthesis of 3-arm ABC-type （A=poly（c-caprolactone）, PCL; B=poly（N-isopropylacrylamide）, PNIPAM; C=poly（tert-butyl acrylate）, PtBA, or poly（acrylic acid）, PAA） miktoarm star copolymers with a reducible disulfide linkage. Using 2-（（2-（（2-hydroxymethyo-2-（（2-bromo-2-methyl）propionyloxy）methyl）propionyloxy）ethyl）disulfanyl）ethyl 4- cyano-4-（phenylcarbonothioylthio）pentanoate （HBCP） as a heterotrifunctional initiator, consecutive ring-opening polymerization （ROP） of g-caprolactone （CL）, reversible addition-fragmentation chain transfer （RAFT） polymerization of N-isopropy- lacrylamide （NIPAM） and atom transfer radical polymerization （ATRP） of tert-butyl acrylate （tBA） afforded ABC1 star, and followed by a subsequent hydrolysis to give ABC2 star. IH nuclear magnetic resonance （IH NMR） and gel permeation chromatography （GPC） analyses revealed the desired stars and their precursors had well-controlled molecular weight and relatively low polydispersity （PDI≤1. 12）. As confirmed by GPC analysis, the disulfide linkage in ABCI star could be efficiently cleaved upon reductive stimulus, during which the topology was converted from star terpolymer to mixtures of homopolymer （B） and diblock copolymer （AC1）. In addition to acting as nanocarriers for stimuli-triggered drug delivery systems, ABC stars with terminal bromide, dithiobenzoate and hydroxyl functionalities are expected to form other reduction-cleavable multicomponent copolymers such as （BC-graft-A）m and dendritic graft copolymers via postpolymerization modification. Our research affords a straightforward ＂core-first＂ method to construct multifunctional star terpolymers with stimuli-responsive arms and reduction-labile linkage.

Synthetic promoters consisting of defined cis-acting elements link multiple signaling pathways to probenazole-inducible system

Probenazole （3-allyloxy-l,2-benzisothiazole-1,1-dioxide, PBZ）, the active component of Oryzemate, could induce systemic acquired resistance （SAR） in plants through the induction of salicylic acid （SA） biosynthesis. As a widely used chemical inducer, PBZ is a good prospect for establishing a new chemical-inducible system. We first designed artificially synthetic promoters with tandem copies of a single type of cis-element （SARE, JERE, GCC, GST1, HSRE, and W-box） that could mediate the expression of the tS-glucuronidase （GUS） reporter gene in plants upon PBZ treatment. Then we combined different types of elements in order to improve inducibility in the PBZ-inducible system. On the other hand, we were surprised to find that the cis-elements, which are responsive to jasmonic acid （JA） and ethylene, also responded to PBZ, implying that SA, JA, and ethylene pathways also would play important roles in PBZ＇s action. Further analysis demonstrated that PBZ also induced early events of innate immunity via a signaling pathway in which Ca2＋ influx and mitogen-activated protein kinase （MAPK） activity were involved. We constructed synthesized artificial promoters to establish a PBZ chemical-inducible system, and preliminarily explored SA, JA, ethylene, calcium, and MAPK signaling pathways via PBZ-inducible system, which could provide an insight for in-depth study.

Surface-grafted block copolymer brushes with continuous composition gradients of poly(poly(ethylene glycol)-monomethacrylate) and poly(N-isopropylacrylamide)

Surface-grafted block copolymer brushes with continuous composition gradients containing poly(poly(ethylene glycol) monomethacrylate) (P(PEGMA)) and poly(N-isopropylacrylamide) (PNIPAAm) chains were fabricated by integration of the surface-initiated atom transfer radical polymerization (SI-ATRP) and continuous injection method. Three types of copolymer gradients were prepared: (1) a uniform P(PEGMA) layer was block copolymerized with a gradient PNIPAAm layer (PP1); (2) a gradient P(PEGMA) layer was block copolymerized with a uniform PNIPAAm layer (PP2); and (3) a gradient P(PEGMA) layer was inversely block copolymerized with a gradient PNIPAAm layer (PP3). The as-prepared gradients were characterized by ellipsometry, water contact angle and atomic force microscopy (AFM) to determine their alterations in thickness, surface wettability and morphology, confirming the gradient structures. In vitro culture of HepG2 cells was implemented on the gradient surfaces, revealing that the cells could adhere at 37 ℃ and be detached at 20 ℃. Introduction of the PEG chains as an underlying layer on the PNIPAAm grafting surfaces resulted in faster cell detachment compared with the PNIPAAm grafting surface.