Immobilization of modified penicillin G acylase on Sepabeads carriers

An approach to stable covalent immobilization of chemically modified penicillin G acylase from Escherichia coli on Sepabeads® carriers with high retention of hydrolytic activity and thermal stability is presented. The two amino-activated polymethacrylate particulate polymers with different spacer lengths used in the study were Sepabeads® EC EA and Sepabeads® EC HA. The enzyme was first modified by cross-linking with polyaldehyde derivatives of starch in order to provide it with new useful functions. Such modified enzyme was then covalently immobilized on amino supports. The method seems to provide a possibility to couple the enzyme without risking a reaction at the active site which might cause the loss of activity. Performances of these immobilized biocatalysts were compared with those obtained by the conventional method with respect to activity and thermal stability. The thermal stability study shows that starch-PGA immobilized on Sepabeads EC-EA was almost 4.5-fold more stable than the conventionally immobilized one and 7-fold more stable than free non-modified PGA. Similarly, starch-PGA immobilized on Sepabeads EC-HA was around 1.5- fold more stable than the conventionally immobilized one and almost 9.5-fold more stable than free non-modified enzyme.     

双硫腙改性的聚(二甲基丙烯酸乙二醇酯-甲基丙烯酸羟乙酯)微球的制备及其对铜离子的吸附研究

用悬浮聚合法由二甲基丙烯酸乙二醇酯(EGDMA)和甲基丙烯酸羟乙酯(HEMA)共聚制备得到聚(二甲基丙烯酸乙二醇酯-甲基丙烯酸羟乙酯)(PHEMA)微球,考察了NaOH浓度、反应时间等对用双硫腙进行PHEMA改性反应的影响以及铜离子水溶液浓度(5～500mg/L)、pH(2.0～6.5)、吸附时间等对改性后的微球对铜离子吸附性能影响的因素.改性的PHEMA微球对铜离子的最大吸附量为65.6mg铜离子/g双硫腙;而且,吸附有铜离子的改性PHEMA微球用0.1mol/L的硝酸的解吸率可达到90%以上,经过3次吸附-解吸循环后,解吸率仍基本不变,这表明双硫腙改性的PHEMA微球可以多次反复使用,具有良好的应用前景.     

The trajectory and stability of a spiralling liquid jet: Viscous theory

We examine a spiralling slender viscous jet emerging from a rapidly rotating orifice, extending Wallwork et al. [I.M. Wallwork, S.P. Decent, A.C. King, R.M.S.M. Schulkes, The trajectory and stability of a spiralling liquid jet. Part 1. Inviscid theory, J. Fluid Mech. 459 (2002) 43–65] by incorporating viscosity. The effects of viscosity on the trajectory of the jet and its linear instability are determined using a mixture of computational and asymptotic methods, and verified using experiments. A non-monotonic relationship between break-up length and rotation rate is demonstrated with the trend varying with viscosity. The sizes of the droplets produced by this instability are determined by considering the most unstable wave mode. It is also found that there is a non-monotonic relationship between droplet size and viscosity. Satellite droplet formation is also considered by analysing very short wavelength modes. The effects of long wavelength modes are examined, and a wave which propagates down the trajectory of the jet is identified for the highly viscous case. A comparison between theoretical and experimental results is made, with favourable agreement. In particular, a quantitative comparison is made between droplet sizes predicted from the theory with experimental observations, with encouraging agreement obtained. Four different types of break-up are identified in our experiments. The experimentally observed break-up mechanisms are discussed in light of our theory.     

CO2 on a Tightrope: Stabilization,Room‐Temperature Decarboxylation,and Sodium‐Induced Carboxylate Migration

A sterically shielded 3‐substituted zwitterionic N,N‐dimethylisotryptammonium carboxylate has been synthesized by consecutive chemoselective double alkylation of indole. The carboxylate undergoes a quantitative and unusually facile decarboxylation in dimethyl sulfoxide (DMSO) or dimethyl formamide (DMF) at room temperature. The breaking of a nearly equidistant hydrogen bond by solvent molecules initiates heterolytic C? C cleavage. The decarboxylation rate decreases with increasing COub>2ub> partial pressure, proving the competitiveness of protonation and re‐carboxylation of the carbanionic intermediate. Corresponding spiro compounds containing silylene and stannylene moieties show high thermal stability. Addition of an excess of methyllithium to the sodium salt triggers a reaction sequence comprising a deprotonation, carboxylate transfer, and nucleophilic trapping of the rearranged carboxylate by another equivalent of methyllithium. Hydrolytic work‐up of the geminal diolate leads to an acetyl product. The role of the sodium counterion and the mechanism of the rearrangement have been unraveled by deuteration experiments.     

Organocatalyzed Enantioselective Desymmetrization of Diols in the Preparation of Chiral Building Blocks

Desymmetrization of diols is a powerful tool to the synthesis of chiral building blocks. Among the different approaches to perform discrimination between both enantiotopic hydroxyl groups, the organocatalytic approach has gained importance in the last years. A diverse range of organocatalysts has been used to efficiently promote this enantioselective transformation and this Minireview examines the different contributions in this field.     

Full potential x-ray absorption calculations using time dependent density functional theory

We report the implementation of a fully relativistic time dependent density functional theory (TDDFT) method for carrying out x-ray absorption spectroscopy calculations for extended systems. This is the first time that a TDDFT simulation of x-ray absorption in extended systems has featured a full potential ground state calculation. We prove that this unusual feature of the TDDFT implementation unequivocally yields improvement over the previous muffin-tin calculation methods.     

多级离心泵内叶轮出口压力脉动研究

为研究瞬态工况下离心泵叶轮出口处的压力脉动情况,为离心泵泄漏流道流动提供边界条件,建立了包含叶轮和导叶流道的离心泵模型,基于CFD方法计算得到了其在不同工况下的性能参数,利用测试数据对结果进行了验证。分析了瞬态工况下叶轮出口处压力的变化趋势,比较了不同工况对叶轮出口压力脉动的影响,发现叶轮出口压力随叶轮旋转呈周期性变化,压力脉动频率与转速及叶轮数量有关;偏工况时叶轮出口压力脉动趋势与额定工况基本一致,但脉动频率及脉动幅值有较大区别;随离心泵转速增加,叶轮出口处压力脉动的最大值和最小值均呈减小趋势,但幅值随转速增加而增加,且增幅明显。     

Berezin Transform, Mellin Transform and Toeplitz Operators

We consider functions of the form fub>1ub>[`(g)]ub>1ub>+h{f_1\bar g_1+h} in the range of the Berezin transform B, where f ub>1ub> and g ub>1ub> are holomorphic on the unit disk \mathbb D{\mathbb D}, and h is either harmonic or of the form fub>2ub>[`(g)]ub>2ub>{f_2\bar g_2} for some holomorphic functions f ub>2ub> and g ub>2ub> on \mathbb D{\mathbb D}. First, by using the Mellin transform, we complement Ahern’s Theorem (Ahern in J Funct Anal 215:206–216, 2004) by proving that if u ? Lup>1up>{u\in L^1} and B(u) is harmonic, then u is harmonic. Secondly, we extend Ahern’s Theorem when h is harmonic, and give very precise relations between f ub>1ub> and f ub>2ub>, g ub>1ub> and g ub>2ub> when h=fub>2ub>[`(g)]ub>2ub>{h=f_2\bar g_2} and g ub>2ub>(z) = z up> n up> with n ≥ 1. Finally, some applications of our results to the theory of Toeplitz operators are discussed.     

ABS-Modified Epoxy Resins – Curing Kinetics,Polymerization Induced Phase Separation,and Resulting Morphologies

Summary : A commercial diglycidylether of bisphenol A (DGEBA) was modified with an acrylonitrile-butadiene-styrene-copolymer (ABS) and cured with the diamine hardener 4,4′-diaminodiphenylsulfone (DDS). The curing kinetics was followed by DSC- and PVT-measurements. The polymerization induced phase separation (PIPS) was studied using light microscopy and electron microscopy. While the cloud point analyzed by light microscopy is independent of the ABS content, the curing is accelerated by the presence of ABS. The non-linear dependency of the curing rate on the ABS content must have its origin in the different morphologies developed due to PIPS.     

Janus Gold Nanostars–Mesoporous Silica Nanoparticles for NIR-Light-Triggered Drug Delivery

Janus gold nanostar–mesoporous silica nanoparticle ( AuNSt–MSNP ) nanodevices able to release an entrapped payload upon irradiation with near infrared (NIR) light were prepared and characterized. The AuNSt surface was functionalized with a thiolated photolabile molecule ( 5 ), whereas the mesoporous silica face was loaded with a model drug (doxorubicin) and capped with proton-responsive benzimidazole-β-cyclodextrin supramolecular gatekeepers ( N 1 ). Upon irradiation with NIR-light, the photolabile compound 5 photodissociated, resulting in the formation of succinic acid, which induced the opening of the gatekeeper and cargo delivery. In the overall mechanism, the gold surface acts as a photochemical transducer capable of transforming the NIR-light input into a chemical messenger (succinic acid) that opens the supramolecular nanovalve. The prepared hybrid nanoparticles were non-cytotoxic to HeLa cells, until they were irradiated with a NIR laser, which led to intracellular doxorubicin release and hyperthermia. This induced a remarkable reduction in HeLa cells viability.