Recycling of homogeneous hydrogenation catalysts by dialysis coupled catalysis

Although transition-metal complexes are very attractive as homogeneous catalysts in fine chemistry, their high prices often limit their applications. A means to recycle those catalysts would solve this problem and would simultaneously facilitate the downstream purification of the product. This is now realized in a new concept in which homogeneous catalysis is coupled to dialysis. The advantages of homogeneous catalysis (off-the-shelf catalysts, high activities and selectivities) are thus combined with those of heterogeneous catalysis (easy catalyst separation from product solution, reuse of catalyst, and possibility for continuous operation). Since the heart of the process is the membrane, self-prepared membranes were preferred as they allow a better control and understanding of the separation characteristics. Rhodamine B was used as a probe molecule to define the working conditions of the membrane. The concept is proven to work for two relevant chiral reactions: a hydrogenation with Ru-BINAP and a hydrogen transfer reaction with Ru-TsDPEN [BINAP=(1,1'-binaphthalene)-2,2'-diylbis(diphenylphosphine); TsDPEN= tosyl-N,N'-diphenyl-1,2-ethanediamine].     

A model reaction assesses contribution of h-tunneling and coupled motions to enzyme catalysis

To assess the contribution of physical features to enzyme catalysis, the enzymatic reaction has to be compared to a relevant uncatalyzed reaction. While such comparisons have been conducted for some hydrolytic and radical reactions, it is most challenging for biological hydride transfer and redox reactions in general. Here, the same experimental tools used to study the H-tunneling and coupled motions for enzymatic hydride transfer between two carbons were used in the study of an uncatalyzed model reaction. The enzymatic oxidations of benzyl alcohol and its substituted analogues mediated by alcohol dehydrogenases were compared to the oxidations by 9-phenylxanthylium cation (PhXn(+)). The PhXn(+)serves as an NAD(+) model, while the solvent, acetonitrile, models the protein environment. Experimental comparisons included linear free energy relations with Hammett reaction constant (ρ) of zero versus -2.7; temperature-independent versus temperature-dependent primary KIEs; deflated secondary KIEs with deuteride transfer (i.e., primary-secondary coupled motion) versus no coupling between secondary KIEs and H- or D-transfer; and large versus small secondary KIEs for the enzymatic versus uncatalyzed alcohol oxidation. Some of the differences may come from differences in the order of microscopic steps between the catalyzed versus uncatalyzed reactions. However, several of these comparative experiments indicate that in contrast to the uncatalyzed reaction the transition state of the enzymatic reaction is better reorganized for H-tunneling and its H-donor is better rehybridized prior to the C-H→C transfer. These findings suggest an important role for these physical features in enzyme catalysis.     

Polarographic immunoassay coupled with catalysis of non-radioactive multiple iodine label

A now polarographic immunoassay was developed In this assay,human serum albumin (HSA) as the model antigen was covalently labeled with organic compound erythrosin B(EB) containing four non-radioactive iodides through Ⅰ step chemical reaction The labeling procedure is simple and the conditions needed are moderate.The molar labeling ratio of KB HSA was 12 Ⅰ The content of iodine in the conjugate obtained by the proposed procedure is ninth higher than that by the other existing methods.A heterogeneous competitive immunoassay was established by compling the catalysis of the conjugate to substrate As(Ⅲ)-Ce(Ⅳ) reaction with the linear-sweep polarographic detec-tion of As(Ⅲ) amount HSA can be determined in the HSA concentration range from 1 to 200μg/mL,with the de-tection hum of 0 66μg/ml.     

Rattle-type microspheres as a support of tiny gold nanoparticles for highly efficient catalysis

SiO(2)/poly(ethyleneglycol dimethacrylate) (PEGDMA) rattle-type microspheres loaded with tiny sized gold nanoparticles (~2 nm) were prepared through a facile and novel method. Catalyzed reduction of 4-nitrophenol with NaBH(4) demonstrated that this rattle-type microsphere possessed high catalytic efficiency.     

Evidence for environmentally coupled hydrogen tunneling during dihydrofolate reductase catalysis

Hydride transfer during catalysis by dihydrofolate reductase from Thermotoga maritima has been studied by stopped flow spectroscopy. The reduction of dihydrofolate by NADPH showed a biphasic temperature dependence of the deuterium kinetic isotope effect. At temperatures above 25 degrees C the KIE was temperature independent, while the reaction rates were strongly temperature dependent. Below 25 degrees C the KIE becomes dependent on temperature, and the ratio of the preexponential factors is inverse, suggesting a greater role for active dynamics that modulate the tunneling distance.     

Solvent effects on environmentally coupled hydrogen tunnelling during catalysis by dihydrofolate reductase from Thermotoga maritima

Protein motions may be perturbed by altering the properties of the reaction medium. Here we show that dielectric constant, but not viscosity, affects the rate of the hydride-transfer reaction catalysed by dihydrofolate reductase from Thermotoga maritima (TmDHFR), in which quantum-mechanical tunnelling has previously been shown to be driven by protein motions. Neither dielectric constant nor viscosity directly alters the kinetic isotope effect of the reaction or the mechanism of coupling of protein motions to tunnelling. Glycerol and sucrose cause a significant increase in the rate of hydride transfer, but lead to a reduction in the magnitude of the kinetic isotope effect as well as an extension of the temperature range over which "passive" protein dynamics (rather than "active" gating motions) dominate the reaction. Our results are in agreement with the proposal that non-equilibrium dynamical processes (promoting motions) drive the hydride-transfer reaction in TmDHFR.     

Tunneling and coupled motion in the Escherichia coli dihydrofolate reductase catalysis

H-transfer was studied in the complex kinetic cascade of dihydrofolate reductase. Intrinsic kinetic isotope effects, their temperature dependence, and other temperature-dependent parameters indicated H-tunneling, but no 1 degrees to 2 degrees coupled motion. The data also suggested environmentally coupled tunneling and commitment to catalysis on pre-steady-state isotope effects.     

Fluorocarbon-bonded magnetic mesoporous microspheres for the analysis of perfluorinated compounds in human serum by high-performance liquid chromatography coupled to tandem mass spectrometry

We report herein an extraction method for the analysis of perfluorinated compounds in human serum based on magnetic core–mesoporous shell microspheres with decyl-perfluorinated interior pore-walls (Fe₃O₄@mSiO₂-F₁₇). Thanks to the unique properties of the Fe₃O₄@mSiO₂-F₁₇ microspheres, macromolecules like proteins could be easily excluded from the mesoporous channels due to size exclusion effect, and perfluorinated compounds (PFCs) in protein-rich biosamples such as serum could thus be directly extracted with the fluorocarbon modified on the channel wall without any other pretreatment procedure. The PFCs adsorbed Fe₃O₄@mSiO₂-F₁₇ microspheres could then be simply and rapidly isolated by using a magnet, followed by being identified and quantified by LC–MS/MS (high-performance liquid chromatography coupled to tandem mass spectrometry). Five perfluorinatedcarboxylic acids (C6, C8–C11) and perfluorooctane sulfonate (PFOS) were selected as model analytes. In order to achieve the best extraction efficiency, some important factors including the amount of Fe₃O₄@mSiO₂-F₁₇ microspheres added, adsorption time, type of elution solvent, eluting solvent volume and elution time were investigated. The ranges of the LOD were 0.02–0.05 ng mL⁻¹ for the six PFCs. The recovery of the optimized method varies from 83.13% to 92.42% for human serum samples.     

Controllable synthesis of VSB-5 microspheres and microrods: growth mechanism and selective hydrogenation catalysis

Nanoporous VSB-5 nickel phosphate molecular sieves with relatively well controllable sizes and morphology of microspheres assembled from nanorods were synthesized at 140 degrees C over a short time in the presence of hexamethylenetetramine (HMT) by a facile hydrothermal method. The pH value, reaction time, and ratio of HMT to NaHPO2.H2O crucially influence the morphology and quality of the final products. By adjusting the pH value of the initial reaction solution, the morphology changes from disperse rods to microspheres assembled from rods and finally to a large quantity of fibers, and the diameters of the VSB-5 rods can be varied. The catalytic activity of VSB-5 in selective hydrogenation of several unsaturated organic compounds was tested. Nickel(II) in VSB-5 can selectively catalyze hydrogenation of C=C in trans-cinnamaldehyde and 3-methylcrotonaldehyde. In addition, since nitrobenzene (NB) and 2-chloronitrobenzene could be reduced to aniline (AN) and 2-chloroaniline with high selectivity, VSB-5 could have potential applications in synthesizing dyes, agrochemicals, and pharmaceuticals.     

Multi-detection method for five common microalgal toxins based on the use of microspheres coupled to a flow-cytometry system

Freshwater and brackish microalgal toxins, such as microcystins, cylindrospermopsins, paralytic toxins, anatoxins or other neurotoxins are produced during the overgrowth of certain phytoplankton and benthic cyanobacteria, which includes either prokaryotic or eukaryotic microalgae. Although, further studies are necessary to define the biological role of these toxins, at least some of them are known to be poisonous to humans and wildlife due to their occurrence in these aquatic systems. The World Health Organization (WHO) has established as provisional recommended limit 1 μg of microcystin-LR per liter of drinking water. In this work we present a microsphere-based multi-detection method for five classes of freshwater and brackish toxins: microcystin-LR (MC-LR), cylindrospermopsin (CYN), anatoxin-a (ANA-a), saxitoxin (STX) and domoic acid (DA). Five inhibition assays were developed using different binding proteins and microsphere classes coupled to a flow-cytometry Luminex system. Then, assays were combined in one method for the simultaneous detection of the toxins. The IC₅₀'s using this method were 1.9 ± 0.1 μg L⁻¹ MC-LR, 1.3 ± 0.1 μg L⁻¹ CYN, 61 ± 4 μg L⁻¹ ANA-a, 5.4 ± 0.4 μg L⁻¹ STX and 4.9 ± 0.9 μg L⁻¹ DA. Lyophilized cyanobacterial culture samples were extracted using a simple procedure and analyzed by the Luminex method and by UPLC–IT-TOF-MS. Similar quantification was obtained by both methods for all toxins except for ANA-a, whereby the estimated content was lower when using UPLC–IT-TOF-MS. Therefore, this newly developed multiplexed detection method provides a rapid, simple, semi-quantitative screening tool for the simultaneous detection of five environmentally important freshwater and brackish toxins, in buffer and cyanobacterial extracts.     

Fe-Nx sites coupled with core-shell FeS@C nanoparticles to boost the oxygen catalysis for rechargeable Zn-air batteries

The development of efficient single-atom catalysts(SACs) for the oxygen reduction reaction(ORR)remains a formidable challenge,primarily due to the symmetric charge distribution of metal singleatom sites(M-N₄).To address such issue,herein,Fe-N_x sites coupled synergistic catalysts fabrication strategy is presented to break the uniform electronic distribution,thus enhancing the intrinsic catalytic activity.Precisely,atomically dispersed Fe-N_x sites supported on N/S-...     

Determination of chloroplatinates by CE coupled to inductively coupled plasma sector field MS

In the present work the degradation of chloroplatinates emitted into the aquatic environment has been investigated in model studies. CE coupled to inductively coupled plasma sector field MS (ICP-SFMS) was employed as an analytical method of measurement. The CE-ICP-MS interface utilized the functional make-up flow design with a microconcentric nebulizer. [Pt(Cl(4))](2-) and [Pt(Cl(6))](2-) were separated within 5 min. During a measurement period of 6 h an excellent reproducibility of migration times (RSD 2.3%) could be achieved. The high sensitivity of ICP-SFMS resulted in an LOD of 80 ng/L platinum for the two compounds. External calibration using rhenium as internal standard was linear over three orders of magnitude. However, with external calibration a long-term drift of signal intensity was observed. In order to reduce the uncertainty of the obtained results, quantification of [PtCl(6)](2-) was performed for the first time by species-specific on-line isotope dilution MS using (194)[PtCl(6)](2-) as spike. The two different quantification strategies were compared in terms of their total combined uncertainty of measurement according to the EURACHEM guideline. The method was employed for monitoring the time-dependent degradation of [Pt(Cl(4))](2-) and [Pt(Cl(6))](2-) in water containing 0 and 2.8 mmol/L Cl(-) and river water. [Pt(Cl(6))](2-) was stable whereas [Pt(Cl(4))](2-) showed rapid degradation following pseudo first-order kinetics.     

Chiral amplification by polypeptides and its relevance to prebiotic catalysis

Polyleucine prepared from scalemic Leu-NCA monomers, shows high chiral amplification in the Julia-Colonna epoxidation of chalcone.     

Successful application of Marcus Theory to catalysis by labile metal ions

The successful applications of Marcus theory to catalysis by labile metal ions in the base-catalyzed enolization and decarboxylation of oxalacetate and in the ketonization and condensation of enolpyruvate are described. Illustrations are presented describing the prediction of rate constants and the use of the theory in original and expanded versions to gain insight into possible features of a reaction mechanism.     

Two-dimensional solvent-mediated phase transformation in lipid membranes induced by sphingomyelinase

The spatial pattern changes in model raft membranes during sphingomyelinase (SMase)-induced solvent-mediated phase transformation are characterized in terms of a model that combines three major kinetic processes suggested by experimental observations: the release of sphingomyelin (SM) by the dissolution of SM-enriched domains within the raft membrane, the diffusion of SM from the dissolution sites to the reaction site in a solvent-like fluid lipid phase, and the consumption of SM by the enzymatic reaction at this reaction site, termed an SMase feature. Such processes may be responsible for the control of morphological changes in cell membrane organization, which are suggested to influence the signal transduction through the cell membrane walls. The model predictions are shown to be consistent with our previously reported experimental results. We numerically evaluated the range of possible scenarios of spatial pattern change and provide analytical expressions for SM-domain-area change rates and total dissolution times for several limiting cases. The model results suggest that it may be possible to tune the pattern changes by adjusting the relative importance of each of the three kinetic processes, which can be discriminated through experimentally measurable time-dependent SM concentration distributions or SM-domain-area variations with time.     

Signal amplification by allosteric catalysis

In this article we unify a series of recent studies on bio- and chemosensors under a single signaling strategy: signal amplification by allosteric catalysis (SAAC). The SAAC strategy mimics biological signal transduction processes, where molecular recognition between an external signal and a protein receptor is allosterically transduced into catalytically amplified chemical information (usually second messengers). Several recent biosensing and chemosensing studies apply this nature-inspired strategy by using engineered allosteric enzymes, ribozymes, or regulatable organic catalysts. The factors pertinent to achieving high sensitivity and specificity in SAAC strategies are analyzed. The authors believe that these early studies from a variety of research groups have opened up a new venue for the development of sensing technologies where molecular recognition and catalysis can be coupled for practical purposes.     

Telomerization kinetics by redox catalysis

A new formula for redox catalyzed telomerization kinetics was set up: 1/DP _n = C_Me(Me)/(M) + C_XY(XY)/(M), where C_Me is the transfer constant for the metallic ion Me, C_XY is the transfer constant for the telogen XY, M the monomer, and DP _n is the degree of polymerization. This study has shown that classic transfer and termination reactions can be neglected because of their slow rates and that the metal transfer constant (C_Me) is the predominant factor influencing telomer molecular weight. This formula was verified by telomerizations of three monomers [chlorotrifluoroethylene (CTFE), acrylic acid, and ethyl acrylate] with CCl₄, catalyzed with ferric chloride-benzoin. In this last case the initiation rate constant (fK_i), the initiation and termination rates, and the radical concentration were measured.     

Methylation of cyclodextrins by phase-transfer catalysis

A new, simple method has been developed for the methylation of cyclodextrins. The reaction proceeds in the heterogeneous phase with dimethyl sulphate, using a solvent in which the original cyclodextrins and the bases used are poorly soluble or insoluble. However, in the presence of phase transfer catalysts, methylation proceeds with good yields. The products are mixtures of randomly methylated cyclodextrins (RAMEB), containing 60–70% of heptakis(2,6-di-O-methyl)--cyclodextrin (DIMEB), 10–15% of heptakis(2,3,6-tri-O-methyl)--cyclodextrin (TRIMEB) and some monomethylated isomers. These methylated products have proved to be excellent detergents; e.g., they are able to significantly increase the water solubility of hydrocortisone, methyltesterone, etc. On repeating methylation twice, the amount of TRIMEB increases, and a pure product (28% yield) can be obtained by crystallisation.Proceedings of the Fourth International Symposium on Cyclodextrins (Ed. O. Huber and J. Szejtli), Munich 1988, p. 113. Kluwer Academic Publishers.Dedicated to Professor Szejtli.     

Micellar catalysis by perfluorooctanoic acid

Rates of acidic hydrolysis of hexano-, octano-, and decanohydroxamic acids and of 4-bromophenylaceto- and phenylacetohydroxamic acids have been determined in aqueous perfluorooctanoic acid—a reactive counterion surfactant system. Typical micellar catalysis was observed for the hydrolyses of the n-alkyl hydroxamic acids but not for the arylacetohydroxamic acids. The Arrhenius activation energy for hydrolysis of octano-hydroxamic acid is smaller above the cmc of the surfactant than it is below the cmc.