Home About us Contact
|
Home About us Contact | ||
|
|
||
Reaction Vessel (reaction + vessel)
Selected AbstractsSelf-Assembled Molecular Reaction Vessels ReloadedCHEMCATCHEM, Issue 10 2010Prof. Enzyme-like catalysis of Nazarov cyclizations has been achieved by encapsulation of pentadienols into a metallosupramolecular capsule. Constrictive binding of the substrate and functional-group activation give rise to a tremendous rate acceleration of up to a factor of 2.1×106, thus, pushing the efficiency of self-assembled molecular capsules as catalysts to a new level. [source] ChemInform Abstract: Parallel Microwave Synthesis of 2-Styrylquinazolin-4(3H)-ones in a High-Throughput Platform Using HPLC/GC Vials as Reaction Vessels.CHEMINFORM, Issue 50 2009Mostafa Baghbanzadeh Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] Homogeneous, unimolecular gas-phase elimination kinetics of ethyl esters of glyoxylic, 2-oxo-propanoic, and 3-methyl-2-oxo-butanoic acidsINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 5 2007Andreina Reyes The rates of elimination of several ethyl esters of 2-oxo-carboxylic acid were determined in a seasoned static reaction vessel over the temperature range 350,430°C and pressure range 33,240 Torr. The reactions, in the presence of a free-radical inhibitor, are homogeneous, unimolecular, and follow a first-order rate law. The overall and partial rate coefficients are expressed by the Arrhenius equation. Ethyl glyoxalate Ethyl 2-oxo-propionate Ethyl 3-methyl-2-oxo-butyrate The mechanisms of these elimination reactions are described in terms of concerted cyclic transition state structures. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 268,275, 2007 [source] Spectrophotometric variable-concentration kinetic experiments applied to inorganic reactionsINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 10 2003Giuseppe Alibrandi The dependence of the observed rate constant of inorganic substitution reactions on the concentration of nucleophilic reagents was obtained by single variable-parameter kinetic runs. The experiments were carried out spectrophotometrically, varying the concentration of the nucleophile inside the reaction vessel. Software and apparatus were developed for an easy and rapid performance. The method gives accurate results and a saving in time by a factor of up to 100 compared to conventional methods. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 497,502, 2003 [source] The First Example of Saccharin-Lithium Bromide Catalysis: Direct Synthesis of N -Tosylimines from AlcoholsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 10 2010Rajesh Patel Abstract The first procedure to access N -tosylimines directly from alcohols under mild and neutral conditions is reported. The protocol involves saccharin-lithium bromide-catalyzed oxidation of alcohols to aldehydes/ketones with chloramine-T followed by their condensation with the in situ generated oxidation by-product p -toluenesulfonamide in the same reaction vessel to afford N -tosylimines in 40,90% overall yields. The present work opens up a new and efficient synthetic route to N -tosyimines directly from alcohols in a one-pot procedure. [source] Substitution-reduction: an alternative process for the [18F]N -(2-fluoroethylation) of anilinesJOURNAL OF LABELLED COMPOUNDS AND RADIOPHARMACEUTICALS, Issue 4 2004Emmanuelle Briard Abstract Substitution of a halo atom (chloro or bromo) in easily prepared N -haloacetyl-anilines with no-carrier added (NCA) cyclotron-produced [18F]fluoride ion (18F, t1/2= 109.8 min; ,+=96.9%), followed by reduction with borane,tetrahydrofuran (BH3,THF), provides an alternative route to NCA [18F]N -(2-fluoroethyl)-anilines. This two-step and one-pot process is rapid (,50 min) and moderately high yielding (,40% decay-corrected radiochemical yield (RCY) overall). In the nucleophilic substitution reaction, 18-crown-6 is preferred to Kryptofix® 222 as complexing agent for the solubilization of the counter-ion (K+), derived from an added metal salt, in acetonitrile. Weakly basic potassium bicarbonate is preferred as the added metal salt. Inclusion of a small amount of water, equating to 4,5 molar equivalents relative to 18-crown-6, base or precursor (held in equimolar ratio), is beneficial in preventing the adsorption of radioactivity onto the wall of the glass reaction vessel and for achieving high RCY in the nucleophilic substitution reaction. BH3,THF is effective for the rapid reduction of the generated [18F]N -fluoroacetyl-aniline to the [18F]N -(2-fluoroethyl)-aniline. Copyright © 2004 John Wiley & Sons, Ltd. [source] Frontal free-radical copolymerization of urethane,acrylatesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 9 2006Ting Hu Abstract We report the first synthesis of urethane,acrylate copolymers via free-radical frontal polymerization. In a typical run, the appropriate amounts of the reactants (urethane,acrylate macromonomer and 2-hydroxyethyl acrylate) and initiator (ammonium persulfate) were dissolved in dimethyl sulfoxide. Frontal polymerization was initiated by the heating of the wall of the tube with a soldering iron, and the resultant hot fronts were allowed to self-propagate throughout the reaction vessel. Once it was initiated, no further energy was required for the polymerization to occur. The dependence of the front velocity and front temperature on the initiator concentration was investigated. The front temperatures were between 55 and 65 °C, depending on the persulfate concentration. Thermogravimetric analysis indicated that the urethane,acrylate copolymers had higher thermal stability than pure frontally prepared polyurethane. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3018,3024, 2006 [source] Michael Polanyi and the discovery of co-catalysis: Discussion of an autobiographical letter from Michael Polanyi, FRS to Peter H. Plesch of 17 December 1963JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 7 2004P. H. Plesch Abstract The origin of this memoir was a letter from Michael Polanyi (M. P.) to the present writer (P. H. P.) about their researches in the mid-1940s into the mechanism of what are now called cationic polymerizations, at the University of Manchester (England). M. P. analyzes his tactics and the mistakes made in directing this research. When the Manchester-trained researchers made little progress with what was a very recalcitrant problem, M. P. thinking that scientists from a different background might be more sucessful, got P. H. P., from Cambridge, to work with an Oxford-trained chemist. They recognized that the likely cause of the irreproducibility of these polymerizations was the apparatus used which permitted access of atmospheric moisture to the reaction mixtures containing the moisture-sensitive catalytic metal halides. Because the only method for following the very fast polymerizations was by monitoring the accompanying temperature rise, and the reactions had to be done below ambient temperature, the reaction vessel needed to be adiabatic, that is a Dewar (Thermos) flask; hence the problem of how to cool its contents. The solution was P. H. P.'s invention of the pseudo-Dewar vessel, the Dewar space of which, instead of being evacuated permanently, could be filled with air or evacuated. This device permitted the reaction mixture to be made up and cooled, and the reactions to be started without contact with the atmosphere. Thus it was found that isobutene polymerizations, which had stopped unaccountably, could be restarted by water vapor. P. H. P. termed water a "co-catalyst". The consequent "Manchester" theory recognized the monohydrate of TiCl4 as a protonic acid and saw the initiation as due to the protonation of the monomer, with the formation of a tert -carbenium ion, and these ions, formed repetitively, became the propagating species. The Manchester theory was rapidly accepted because it could also explain observations on other related reactions. The involvement of ions established a link with non-aqueous electrochemistry. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1537,1546, 2004 [source] Synthesis and Raman spectroscopic characterisation of hydrotalcite with CO32, and (MoO4)2, anions in the interlayerJOURNAL OF RAMAN SPECTROSCOPY, Issue 3 2008Sara J. Palmer Abstract Raman spectroscopy has been used to characterise synthetic mixed carbonate and molybdate hydrotalcites of formula Mg6Al2(OH)16((CO3)2,,(MoO4)2,)·4H2O. The spectra have been used to assess the molecular assembly of the cations and anions in the hydrotalcite structure. The spectra may be conveniently subdivided into spectral features on the basis of the carbonate anion, the molybdate anion, the hydroxyl units and water units. Bands are assigned to the hydroxyl stretching vibrations of water. Three types of carbonate anions are identified: (1) carbonate hydrogen-bonded to water in the interlayer, (2) carbonate hydrogen-bonded to the hydrotalcite hydroxyl surface, (3) free carbonate anions. It is proposed that the water is highly structured in the hydrotalcite, as it is hydrogen bonded to both the carbonate and the hydroxyl surface. The spectra have been used to assess the contamination of carbonate in an open reaction vessel in the synthesis of a molybdate hydrotalcite of formula Mg6Al2(OH)16((CO3)2,, (MoO4)2,)·4H2O. Bands are assigned to carbonate and molybdate anions in the Raman spectra. Importantly, the synthesis of hydrotalcites from solutions containing molybdate provides a mechanism for the removal of this oxy-anion. Copyright © 2007 John Wiley & Sons, Ltd. [source] The Diplomonad Fish Parasite Spironucleus vortens Produces HydrogenTHE JOURNAL OF EUKARYOTIC MICROBIOLOGY, Issue 5 2010CORALIE O.M. MILLET ABSTRACT. The diplomonad fish parasite Spironucleus vortens causes major problems in aquaculture of ornamental fish, resulting in severe economic losses in the fish farming industry. The strain of S. vortens studied here was isolated from an angelfish and grown in Keister's modified TY-I-S33 medium. A membrane-inlet mass spectrometer was employed to monitor, in a closed system, O2, CO2, and H2. When introduced into air-saturated buffer, S. vortens rapidly consumed O2 at the average rate of 62±4 nmol/min/107 cells and CO2 was produced at 75±11 nmol/min/107 cells. Hydrogen production began under microaerophilic conditions ([O2]=33.±15 ,M) at a rate of 77±7 nmol/min/107 cells. Hydrogen production was inhibited by 62% immediately after adding 150 ,M KCN to the reaction vessel, and by 50% at 0.24 ,M CO, suggesting that an Fe-only hydrogenase is responsible for H2 production. Metronidazole (1 mM) inhibited H2 production by 50%, while CO2 production was not affected. This suggests that metronidazole may be reduced by an enzyme of the H2 pathway, thus competing for electrons with H+. [source] New milliliter-scale stirred tank bioreactors for the cultivation of mycelium forming microorganismsBIOTECHNOLOGY & BIOENGINEERING, Issue 3 2010Ralf Hortsch Abstract A novel milliliter-scale stirred tank bioreactor was developed for the cultivation of mycelium forming microorganisms on a 10 milliliter-scale. A newly designed one-sided paddle impeller is driven magnetically and rotates freely on an axis in an unbaffled reaction vessel made of polystyrene. A rotating lamella is formed which spreads out along the reactor wall. Thus an enhanced surface-to-volume ratio of the liquid phase is generated where oxygen is introduced via surface aeration. Volumetric oxygen transfer coefficients (kLa),>,0.15,s,1 were measured. The fast moving liquid lamella efficiently prevents wall growth and foaming. Mean power consumption and maximum local energy dissipation were measured as function of operating conditions in the milliliter-scale stirred tank bioreactor (V,=,10,mL) and compared to a standard laboratory-scale stirred tank bioreactor with six-bladed Rushton turbines (V,=,2,000,mL). Mean power consumption increases with increasing impeller speed and shows the same characteristics and values on both scales. The maximum local energy dissipation of the milliliter-scale stirred tank bioreactor was reduced compared to the laboratory-scale at the same mean volumetric power input. Hence the milliliter impeller distributes power more uniformly in the reaction medium. Based on these data a reliable and robust scale-up of fermentation processes is possible. This was demonstrated with the cultivation of the actinomycete Streptomyces tendae on both scales. It was shown that the process performances were equivalent with regard to biomass concentration, mannitol consumption and production of the pharmaceutical relevant fungicide nikkomycin Z up to a process time of 120,h. A high parallel reproducibility was observed on the milliliter-scale (standard deviation,<,8%) with up to 48 stirred tank bioreactors operated in a magnetic inductive drive. Rheological behavior of the culture broth was measured and showed a highly viscous shear-thinning non-Newtonian behavior. The newly developed one-sided paddle impellers operated in unbaffled reactors on a 10 milliliter-scale with a magnetic inductive drive for up to 48 parallel bioreactors allows for the first time the parallel bioprocess development with mycelium forming microorganisms. This is especially important since these kinds of cultivations normally exhibit process times of 100,h and more. Thus the operation of parallel stirred tank reactors will have the potential to reduce process development times drastically. Biotechnol. Bioeng. 2010; 106: 443,451. © 2010 Wiley Periodicals, Inc. [source] Template-Directed Synthesis of Multiply Mechanically Interlocked Molecules Under Thermodynamic ControlCHEMISTRY - A EUROPEAN JOURNAL, Issue 16 2005Fabio Aricó Dr. Abstract The template-directed construction of crown-ether-like macrocycles around secondary dialkylammonium ions (R2NH2+) has been utilized for the expedient (one-pot) and high-yielding synthesis of a diverse range of mechanically interlocked molecules. The clipping together of appropriately designed dialdehyde and diamine compounds around R2NH2+ -containing dumbbell-shaped components proceeds through the formation, under thermodynamic control, of imine bonds. The reversible nature of this particular reaction confers the benefits of "error-checking" and "proof-reading", which one usually associates with supramolecular chemistry and strict self-assembly processes, upon these wholly molecular systems. Furthermore, these dynamic covalent syntheses exploit the efficient templating effects that the R2NH2+ ions exert on the macrocyclization of the matched dialdehyde and diamine fragments, resulting not only in rapid rates of reaction, but also affording near-quantitative conversion of starting materials into the desired interlocked products. Once assembled, these "dynamic" interlocked compounds can be "fixed" upon reduction of the reversible imine bonds (by using BH3,THF) to give kinetically stable species, a procedure that can be performed in the same reaction vessel as the inital thermodynamically controlled assembly. Isolation and purification of the mechanically interlocked products formed by using this protocol is relatively facile, as no column chromatography is required. Herein, we present the synthesis and characterization of 1) a [2]rotaxane, 2) a [3]rotaxane, 3) a branched [4]rotaxane, 4) a bis [2]rotaxane, and 5) a novel cyclic [4]rotaxane, demonstrating, in incrementally more complex systems, the efficacy of this one-pot strategy for the construction of interlocked molecules. [source] Encapsulation and Stabilization of Reactive Aromatic Diazonium Ions and the Tropylium Ion Within a Supramolecular HostEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 24 2004Julia L. Brumaghim Abstract Supramolecular assemblies with internal cavities are being developed as nanoscale reaction vessels to protect or modify the reactivity of guest species through encapsulation. Diazonium cations and the tropylium cation were examined for their ability to encapsulate in the tetrahedral [Ga4L6]12, supramolecular assembly. The 4-(diethylamino)benzenediazonium cation 1 readily formed a 1:1 host,guest complex with this assembly, and this encapsulation prevented 1 from reacting with 2,4-pentanedione in D2O. The tropylium cation also formed a 1:1 host,guest complex with the [Ga4L6]12, assembly, greatly slowing its decomposition in D2O. Encapsulation in the protected environment of this host cavity alters the reactivity of these guest molecules, giving them greater stability. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Hydrophobic Chemistry in Aqueous Solution: Stabilization and Stereoselective Encapsulation of Phosphonium Guests in a Supramolecular HostEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 22 2004Julia L. Brumaghim Abstract Encapsulation of guest molecules inside supramolecular host assemblies provides a way to stabilize reactive species in aqueous solution. The stabilization of reactive phosphonium/ketone adducts of the general formula [R1MeC(OH)PR3]+ by encapsulation as guest molecules within a [Ga4L6]12, tetrahedral metal,ligand assembly is reported; although these cations decompose in aqueous solution, encapsulation inside the hydrophobic cavity of the assembly lengthens their lifetimes considerably, in some cases up to weeks. By varying the phosphane (PMe3, PEt3, PPhMe2, and PPh2Me) and ketone (acetone, methyl ethyl ketone, 1,1,1-trifluoroacetone, and fluoroacetone) which form these adducts, as well as the pD of the solutions, it was determined that the pH of the solution as well as the size and shape of the guest cations play an important role in the stability of these host,guest complexes. Encapsulation of chiral guests in the chiral [Ga4L6]12, assembly results in the formation of diastereomers, as characterized by 1H, 19F, and 31P NMR spectroscopy. Although the [Ga4L6]12, assembly is formed from non-chiral ligands, the assembly itself has ,,,, or ,,,, chirality around the metal centers. Due to the chirality of this assembly, diastereomeric selectivity is observed upon initial guest encapsulation (typical diastereomeric excesses are 30,50%). This initial diastereomeric selectivity decreases over time to reach an equilibrium but does not become 1:1, indicating both kinetic and thermodynamic processes promote selective guest encapsulation. These experiments demonstrate further the applications of nanoscale reaction vessels, self-assembled by design from non-chiral ligands, in providing a chiral and hydrophobic environment for guest molecules in aqueous solution. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Growth of Silicon Oxide in Thin Film Block Copolymer Scaffolds,ADVANCED MATERIALS, Issue 8 2004H. Kim Thin films of asymmetric diblock copolymers have been used as scaffolds to define an ordered array of nanometer-scale reaction vessels in which high density arrays of silicon oxide nanostructures (see Figure) are produced by exposure to silicon tetrachloride. Such site-specific silicon oxide nanostructures could have widespread uses for sensory and optoelectronic applications. [source] Highly Efficient Copper-Catalyzed Synthesis of Internal Alkynes via Aerobic Oxidative Arylation of Terminal AlkynesADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 2-3 2010Honghua Rao Abstract We have developed a novel and highly efficient, copper-catalyzed synthesis of internal alkynes via oxidative couplings of aromatic boronic acids with terminal alkynes at room temperature. The protocol uses inexpensive copper(I) oxide [Cu2O] as the catalyst, oxygen in the air as the stoichiometric oxidant; no ligand and sealed reaction vessels are required, and remarkable functional group tolerability is observed with coupling occurring. [source] Assay of gliadin by real-time immunopolymerase chain reactionMOLECULAR NUTRITION & FOOD RESEARCH (FORMERLY NAHRUNG/FOOD), Issue 5 2003Nadine Henterich Abstract Patients with coeliac disease (gluten-sensitive enteropathy) are intolerant against gliadins from wheat and the respective proteins from related cereals and have to keep a lifelong gluten-free diet. For control of gliadin in gluten-free food sensitive assay techniques are necessary. We developed an immunopolymerase chain reaction (iPCR) assay for gliadin. In this technique immunological detection of gliadin by a monoclonal antibody R5 conjugated with an oligonucleotide is amplified by PCR. For quantification, iPCR was performed as real-time PCR (real-time iPCR) in one step. By means of real-time iPCR, the sensitivity of gliadin analysis was increased more than 30-fold above the level reached by enzyme immunoassay. Real time-iPCR using R5 directly conjugated with oligonucleotide was clearly more sensitive than real time-iPCR applying sequentially biotinylated R5, streptavidin, and biotinylated oligonucleotide. With directly conjugated R5 gliadin was detected at a concentration as low as 0.16 ng/mL corresponding to 16 ,g gliadin/100 g food or 0.16 ppm (corresponding to 0.25 g of food extracted in 10 mL of solvent and 25-fold dilution of the extract prior to analysis). This is the first report applying the highly sensitive technique of iPCR for gliadin analysis. Furthermore, this is the first approach to perform real-time iPCR in one step without changing the reaction vessels after enzyme immunoassay for subsequent PCR analysis thus minimizing risks of contamination and loss of sensitivity. [source] Novel Process Windows , Gate to Maximizing Process Intensification via Flow ChemistryCHEMICAL ENGINEERING & TECHNOLOGY (CET), Issue 11 2009V. Hessel Abstract Driven by the economics of scale, the size of reaction vessels as the major processing apparatus of the chemical industry has became bigger and bigger [1, 2]. Consequently, the efforts for ensuring mixing and heat transfer have also increased, as these are scale dependent. This has brought vessel operation to (partly severe) technical limits, especially when controlling harsh conditions, e.g., due to large heat releases. Accordingly, processing at a very large scale has resulted in taming of the chemistry involved in order to slow it down to a technically controllable level. Therefore, reaction paths that already turned out too aggressive at the laboratory scale are automatically excluded for later scale-up, which constitutes a common everyday confinement in exploiting chemical transformations. Organic chemists are barely conscious that even the small-scale laboratory protocols in their textbooks contain many slow, disciplined chemical reactions. Operations such as adding a reactant drop by drop in a large diluted solvent volume have become second nature, but are not intrinsic to the good engineering of chemical reactions. These are intrinsic to the chemical apparatus used in the past. In contrast, today's process intensification [3,12] and the new flow-chemistry reactors on the micro- and milli-scale [13,39] allow such limitations to be overcome, and thus, enable a complete, ab-initio type rethinking of the processes themselves. In this way, space-time yields and the productivity of the reactor can be increased by orders of magnitude and other dramatic performance step changes can be achieved. A hand-in-hand design of the reactors and process re-thinking is required to enable chemistry rather than subduing chemistry around the reactor [40]. This often leads to making use of process conditions far from conventional practice, under harsh environments, a procedure named here as Novel Process Windows. [source] | ||||||||||||||||