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Reaction Cycles (reaction + cycle)
Selected AbstractsSpontaneous Emergence of Homochirality via Coherently Coupled Antagonistic and Reversible Reaction CyclesCHEMPHYSCHEM, Issue 16 2008Michael Mauksch Dr. Abstract Asymmetric synthesis aims at obtaining enantio-enriched products in stereoselective reactions under a chiral influence. We demonstrate both mathematically and numerically that, even under nominally achiral conditions, fully homochiral steady states can be obtained in open reactive systems by spontaneous mirror-symmetry breaking in the homogenous solution phase when the autocatalytic reaction network is closed in the form of coherently coupled antagonistic reversible reaction cycles which, paradoxically, allow for complete recycling of the reactant. We show that the fully reversible Frank mechanism for spontaneous mirror-symmetry breaking is closely related to the Lotka,Volterra system, which models predator,prey relations in ecosystems. Amplification of total enantiomeric excess and the principle of microscopic reversibility are not in conflict for all conceivable reactions. A viable and widely applicable reaction protocol is introduced and discussed, and it permits the theoretical implications to be applied to practical laboratory examples. Implications for the possible origin of biological homochirality on early earth are discussed. [source] Covalently crosslinked complexes of bovine adrenodoxin with adrenodoxin reductase and cytochrome P450sccFEBS JOURNAL, Issue 6 2001Edman degradation of complexes of the steroidogenic hydroxylase system, Mass spectrometry NADPH-dependent adrenodoxin reductase, adrenodoxin and several diverse cytochromes P450 constitute the mitochondrial steroid hydroxylase system of vertebrates. During the reaction cycle, adrenodoxin transfers electrons from the FAD of adrenodoxin reductase to the heme iron of the catalytically active cytochrome P450 (P450scc). A shuttle model for adrenodoxin or an organized cluster model of all three components has been discussed to explain electron transfer from adrenodoxin reductase to P450. Here, we characterize new covalent, zero-length crosslinks mediated by 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide between bovine adrenodoxin and adrenodoxin reductase, and between adrenodoxin and P450scc, respectively, which allow to discriminate between the electron transfer models. Using Edman degradation, mass spectrometry and X-ray crystallography a crosslink between adrenodoxin reductase Lys27 and adrenodoxin Asp39 was detected, establishing a secondary polar interaction site between both molecules. No crosslink exists in the primary polar interaction site around the acidic residues Asp76 to Asp79 of adrenodoxin. However, in a covalent complex of adrenodoxin and P450scc, adrenodoxin Asp79 is involved in a crosslink to Lys403 of P450scc. No steroidogenic hydroxylase activity could be detected in an adrenodoxin ,P450scc complex/adrenodoxin reductase test system. Because the acidic residues Asp76 and Asp79 belong to the binding site of adrenodoxin to adrenodoxin reductase, as well as to the P450scc, the covalent bond within the adrenodoxin,P450scc complex prevents electron transfer by a putative shuttle mechanism. Thus, chemical crosslinking provides evidence favoring the shuttle model over the cluster model for the steroid hydroxylase system. [source] The unfolding story of the Escherichia coli Hsp70 DnaK: is DnaK a holdase or an unfoldase?MOLECULAR MICROBIOLOGY, Issue 5 2002Sergey V. Slepenkov Summary We discuss recent experiments that have illuminated individual steps in the reaction cycle of the Escherichia coli Hsp70 molecular chaperone DnaK. Using this new information, we comparetwo distinctly different global mechanisms of action , holding versus unfolding , and argue that the available evidencesuggests that DnaK is an unfoldase. [source] Pd on Porous Glass: A Versatile and Easily Recyclable Catalyst for Suzuki and Heck ReactionsCHEMSUSCHEM CHEMISTRY AND SUSTAINABILITY, ENERGY & MATERIALS, Issue 4 2008Christine Schmöger Abstract The catalytic activity of Pd supported on porous glass was studied for both Suzuki and Heck reactions under aerobic conditions, with particular focus on the Suzuki coupling. The reactions were carried out in water under microwave irradiation. The effects of the catalyst preparation process (calcination time and temperature), as well as the base, substrate, and boron compound used on the coupling reaction were investigated in relation to the reusability of the catalyst. Various bases promote the Suzuki coupling of phenylboronic acid with bromophenol very effectively resulting in quantitative conversion and excellent selectivity for the coupling product. However, most bases lead to deactivation of the catalyst after the first reaction cycle and the catalyst must be reactivated before reuse. Therefore, excellent conversions and selectivities for individual reactions are not sufficient to conclude if the chosen conditions are suitable for a given reaction, but results from recycling studies have to be considered also. [source] Simple Preparation of Dimeric Cinchona Alkaloid Derivatives on Polystyrene Supports and a Highly Enantioselective Catalytic Heterogeneous Dimerization of KetenesADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 9 2010Ravindra Abstract A convenient route for the covalent immobilization of quinidine and hydroquinidine pyridazine ethers on insoluble polystyrene supports is described, which avoids the need of chromatographic purifications at any stage. The use of the heterogeneized alkaloid derivatives in the asymmetric organocatalytic dimerization of ketenes afforded high enantioselectivity values (90,97% ee) in the course of 20 reaction cycles. [source] The normal and cancerous living cellINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 14 2006Janos Ladik Abstract We do not have a definition of the living and cancerous states; we can give only their main characteristics at the different levels of organization: cell, organ, and organism. A simple model is proposed for a normal eukaryotic cell based on Prigogine's equation of chemical kinetics with diffusion. In this model, possibly only a few hundred key biochemical reactions should be selected together with their rate and diffusion constants. To solve these coupled nonlinear partial differential equation systems, it is proposed that the model cell be subdivided into compartments and that the problem be worked out always for one compartment (finite element method). This is possible, since the most important biochemical reactions and reaction cycles occur in different parts of the cell. The solutions (concentrations) obtained in one compartment can be used as input to the other compartments (together with the components entering from the environment). As an example, the problem of 10 reactions and 3 compartments has been solved by discretizing the space coordinates and choosing time steps. The solutions obtained by solving the 10 differential equations directly and by the compartmentalization agree very well. The main obstacles to further progress lie in the right choice of reactions and compartments, as well as in the correct estimation of the rate and diffusion constants, which were measured in only a few cases. If such a model cell can be obtained, the solutions should be investigated to determine (i) for their stability (homeostasis); (ii) whether changing the input concentrations to a larger degree one would obtain a new stationary state showing the characteristics of a precancerous state; and (iii) a method of extracting those input concentrations, or functions of them, which are the most important regulatory parameters. If successful, this would provide a scientific definition of the living state in the normal and cancerous states, respectively, at least at the cell level. Finally, outline is provided showing how the model might be extended to multicellular cases, as well as the main difficulties of such a process. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2006 [source] 3,5-Bis(n -perfluorooctyl)benzyltriethylammonium Bromide (F-TEBA): An Efficient, Easily Recoverable Fluorous Catalyst for Solid-Liquid PTC ReactionsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 18 2009Gianluca Pozzi Abstract A readily available 3,5-bis(perfluorooctyl)benzyl bromide and triethylamine were reacted under mild conditions to give 3,5-bis(n -perfluorooctyl)benzyltriethylammonium bromide (F-TEBA), an analogue of the versatile phase-transfer catalyst, benzyltriethylammonium chloride (TEBA), containing two fluorous ponytails. This perfluoroalkylated quaternary ammonium salt was successfully employed as a catalyst in a variety of reactions run under solid-liquid phase-transfer catalysis (SL-PTC) conditions. Thus, being both hydrophobic and lipophobic, F-TEBA could be quickly recovered in quantitative yields, and reused without loss of activity over several reaction cycles. [source] Comparison of different methods of bacterial detection in blood componentsISBT SCIENCE SERIES: THE INTERNATIONAL JOURNAL OF INTRACELLULAR TRANSPORT, Issue 1 2009M. Schmidt Background, Over the last two decades, the residual risk of acquiring a transfusion-transmitted viral infection has been reduced to less than 1 : 1 000 000 via improvements in different techniques (e.g. donor selection, leuco-depletion, introduction of 3rd or 4th generation enzyme-linked immunosorbent assays and mini-pool nucleic acid testing (MP-NAT). In contrast, the risk for transfusion-associated bacterial infections has remained fairly stable, and is estimated to be in a range between 1 : 2000 and 1 : 3000. Platelets are at an especially higher risk for bacterial contamination, because they are stored at room temperature, which provides good culture conditions for a broad range of bacterial strains. To improve bacterial safety of blood products, different detection systems have been developed that can be divided into culture systems like BacT/ALERT or Pall eBDS, rapid detection systems like NAT systems, immunoassays and systems based on the FACS technique. Culture systems are used for routine bacterial screening of platelets in many countries, whereas rapid detection systems so far are mainly used in experimental spiking studies. Nevertheless, pathogen-reduction systems are currently available for platelet concentrates and plasma, and are under investigation for erythrocytes. Methods, In this review, the functional principles of the different assays are described and discussed with regard to their analytical sensitivity, analytical specificity, diagnostic sensitivity, diagnostic specificity and clinical efficiency. The detection methods were clustered into three groups: (i) detection systems currently used for routine screening of blood products, (ii) experimental detection systems ready to use for routine screening of blood products, and (iii) new experimental detection systems that need to be investigated in additional spiking studies and clinical trials. Results, A recent International Society of Blood Transfusion international forum reported on bacterial detection methods in 12 countries. Eight countries have implemented BacT/ALERT into blood donor screening, whereas in three countries only quality controls were done by culture methods. In one country, shelf-life was reduced to 3 days, so no bacterial screening was implemented. Screening data with culture methods can be used to investigate the prevalence of bacterial contamination in platelets. Differing results between the countries could be explained by different test definitions and different test strategies. Nevertheless, false-negative results causing severe transfusion-related septic reactions have been reported all over the world due to a residual risk of sample errors. Rapid screening systems NAT and FACS assays have improved over the last few years and are now ready to be implemented in routine screening. Non-specific amplification in NAT can be prevented by pre-treatment with Sau3AI, filtration of NAT reagents, or reduction of the number of polymerase chain reaction cycles. FACS systems offer easy fully automated handling and a handling time of only 5 min, which could be an option for re-testing day-5 platelets. New screening approaches like immunoassays, detection of bacterial adenosine triphosphate, or detection of esterase activity need to be investigated in additional studies. Conclusion, Bacterial screening of blood products, especially platelets, can be done with a broad range of technologies. The ideal system should be able to detect one colony-forming unit per blood bag without a delay in the release process. Currently, we are far away from such an ideal screening system. Nevertheless, pathogen-inactivation systems are available, but a system for all blood components will not be expected in the next few years. Therefore, existing culture systems should be complemented by rapid systems like NAT or FACS especially for day-5 platelets. [source] Photooxidation of Benzyl Alcohols with Immobilized FlavinsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 1-2 2009Harald Schmaderer Abstract Benzyl alcohols are oxidized cleanly and efficiently to the corresponding aldehydes under irradiation using flavin photocatalysts and aerial oxygen as the terminal oxidant in homogeneous aqueous solution. Turnover frequencies (TOF) of more than 800,h,1 and turnover numbers (TON) of up to 68 were obtained. Several flavin photocatalysts with fluorinated or hydrophobic aliphatic chains were immobilized on solid supports like fluorous silica gel, reversed phase silica gel or entrapped in polyethylene pellets. The catalytic efficiency of the heterogeneous photocatalysts was studied for the oxidation of different benzyl alcohols in water and compared to the analogous homogeneous reactions. Removal of the heterogeneous photocatalyst stops the reaction conversion immediately, which shows that the immobilized flavin is the catalytically active species. The immobilized catalysts are stable, retain their reactivity if compared to the corresponding homogeneous systems and are easily removed from the reaction mixture and reused. TOF of up to 26,h,1, TON of 280 and up to 3 reaction cycles without loss of activity are possible with the heterogeneous flavin photocatalysts. [source] Hybrid Inorganic-Organic Materials Carrying Tertiary Amine and Thiourea Residues Tethered on Mesoporous Silica Nanoparticles: Synthesis, Characterization, and Co-Operative CatalysisADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 1-2 2009Alessandra Puglisi Abstract Mesoporous silica nanoparticles carrying different loadings of tertiary amine and thiourea residues (residues ratios 53/47, 68/32, and 22/78, respectively) were synthesized by the co-condensation method and fully characterized by CP MAS NMR, powder XRD, SEM, BET, BJH and FT-IR techniques. These materials were tested as bifunctional catalysts in the conjugate addition of acetylacetone to 2-nitrostyrene, a reaction that under solvent-free conditions occurred in quantitative yield. By carrying out several experiments with the bifunctional catalysts featuring different molar ratios of active sites, and with different combinations of monofunctional supported and non-supported catalyst, the co-operativity of the tertiary amine and thiourea residues in catalyzing the reaction was demonstrated. The use of the bifunctional catalyst was extended to the addition of acetylacetone to an activated imine. Catalyst recycling for a total of three reaction cycles was demonstrated without significant erosion of activity. [source] Stille Reactions with Tetraalkylstannanes and Phenyltrialkylstannanes in Low Melting Sugar-Urea-Salt MixturesADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 15 2006Giovanni Imperato Abstract The transfer of simple alkyl groups in Stille reactions usually requires special solvents (HMPA) or certain organotin reagents (stannatranes, monoorganotin halides) to be efficient. Using low-melting mixtures of sugar, urea and inorganic salt as solvent, a fast and efficient palladium-catalyzed alkyl transfer with tetraalkyltin reagents was observed. The high polarity and nucleophilic character of the solvent melt promotes the reaction. Stille biaryl synthesis using electron-poor and electron-rich aryl bromides proceeds with quantitative yields in the sugar-urea-salt melt. Catalyst loading may be reduced to 0.001 mol,% and the catalyst melt mixture remains active in several reaction cycles. Showing the same or improved performance for Stille reactions than organic solvents and allowing a very simple work up, sugar-urea-salt melts are a non-toxic and cheap alternative reaction medium available in bulk quantities for the catalytic process. [source] Second Generation Sol-Gel Encapsulated Lipases: Robust Heterogeneous BiocatalystsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 6-7 2003Manfred Abstract The original procedure for the encapsulation of lipases in sol-gel materials produced by the fluoride-catalyzed hydrolysis of mixtures of RSi(OCH3)3 and Si(OCH3)4 has been improved considerably. This involves higher enzyme loading, variation of the alkylsilane precursor, and the use of additives such as isopropyl alcohol, 18-crown-6, Tween,80®, methyl-,-cyclodextrin and/or KCl. A dramatic increase in enzyme activity is observed. The sol-gel lipase immobilizates are also excellent catalysts in the kinetic resolution of chiral alcohols and amines, recycling without any substantial loss in enantioselectivity and a residual activity of 70% being possible even after 20 reaction cycles. [source] Application of immobilized bovine enterokinase in repetitive fusion protein cleavage for the production of mucin 1BIOTECHNOLOGY JOURNAL, Issue 11 2009Tina Kubitzki Abstract Bovine enterokinase is a serine protease that catalyzes the hydrolysis of peptide bonds and plays a key role in mammalian metabolism. Because of its high specificity towards the amino acid sequence (Asp)4 -Lys, enterokinase is a potential tool for the cleavage of fusion proteins, which are gaining more importance in biopharmaceutical production. A candidate for adaptive cancer immunotherapy is mucin 1, which is produced recombinantly as a fusion protein in CHO cells. Here, we present the first repetitive application of immobilized enterokinase for the cleavage of the mucin fusion protein. The immobilization enables a facile biocatalytic process due to simplified separation of the biocatalyst and the target protein. Immobilized enterokinase was applied in a maximum of 18 repetitive reactions. The enzyme utilization (total turnover number) was increased significantly 419-fold compared to unbound enzyme by both immobilization and optimization of process conditions. Slight enzyme inactivation throughout the reaction cycles was observed, but was compensated by adjusting the process time accordingly. Thus, complete fusion protein cleavage was achieved. Furthermore, we obtained isolated mucin 1 with a purity of more than 90% by applying a simple and efficient purification process. The presented results demonstrate enterokinase to be an attractive tool for fusion protein cleavage. [source] Enhancement of Activity of Lipase-Displaying Yeast Cells and Their Application to Optical Resolution of (R,S)-1-Benzyloxy-3-Chloro-2-Propyl MonosuccinateBIOTECHNOLOGY PROGRESS, Issue 4 2006Yurie Nakamura Rhizopus oryzae lipase (ROL) was displayed on the cell surface of Saccharomyces cerevisiae via the Flo1 N-terminal region (1100 amino acids), which corresponds to a flocculation functional domain. The activity of lipase-displaying yeast whole-cell biocatalysts was enhanced 7.3-fold by incubation of the yeast cells at 20 °C in distilled water for 8 days after 8 day cultivation. The amount of lipase molecules present in cell wall and intracellular fractions was found to be increased 4.5- and 1.8-fold, respectively, by incubation, which proves that ROL molecules are expressed during incubation. The ROL-displaying yeast whole-cell biocatalyst with enhanced activity was successfully catalyzed by optical resolution of the pharmaceutical precursor (R,S)-1-benzyloxy-3-chloro-2-propyl monosuccinate. Moreover, it showed stable activity through at least eight reaction cycles. These results demonstrate that ROL-displaying yeast cells with enhanced activity by incubation in distilled water are very effective in industrial bioconversion processes. [source] Spontaneous Emergence of Homochirality via Coherently Coupled Antagonistic and Reversible Reaction CyclesCHEMPHYSCHEM, Issue 16 2008Michael Mauksch Dr. Abstract Asymmetric synthesis aims at obtaining enantio-enriched products in stereoselective reactions under a chiral influence. We demonstrate both mathematically and numerically that, even under nominally achiral conditions, fully homochiral steady states can be obtained in open reactive systems by spontaneous mirror-symmetry breaking in the homogenous solution phase when the autocatalytic reaction network is closed in the form of coherently coupled antagonistic reversible reaction cycles which, paradoxically, allow for complete recycling of the reactant. We show that the fully reversible Frank mechanism for spontaneous mirror-symmetry breaking is closely related to the Lotka,Volterra system, which models predator,prey relations in ecosystems. Amplification of total enantiomeric excess and the principle of microscopic reversibility are not in conflict for all conceivable reactions. A viable and widely applicable reaction protocol is introduced and discussed, and it permits the theoretical implications to be applied to practical laboratory examples. Implications for the possible origin of biological homochirality on early earth are discussed. [source] Supercritical Carbon Dioxide-Induced Phase Changes in (Ionic Liquid, Water and Ethanol Mixture) Solutions: Application to Biphasic Catalysis.CHEMPHYSCHEM, Issue 5 2003Vesna Najdanovic-Visak The best of both worlds: Phase changes in ionic liquid + water systems, induced by addition of ethanol and supercritical carbon dioxide, allow reaction cycles to proceed as depicted, combining the high rates of one-phase conditions with easy separation of products; characteristic of biphasic catalysis. The (usually slow) epoxidation of isophorone by hydrogen peroxide, catalysed by sodium hydroxide, was rapidly carried out in these conditions, with complete recovery of the reaction product by supercritical CO2 decompression. [source] | |||||||||||||