Reaction-controlled phase transfer catalysis for styrene epoxidation to styrene oxide with aqueous hydrogen peroxide

The epoxidation of styrene catalyzed by a reaction-controlled phase transfer catalyst [(C18H37(30%)+C16H33(70%))N(CH3)(3))(3)](3)-[PW4O16] with H2O2 in a biphasic medium was investigated. Under certain conditions, the selectivity for styrene oxide was 95%, the conversion of styrene based on H2O2 was 85%, and the reaction time was less than 1 h. During the reaction, this catalyst powder formed soluble active species by the action of H2O2, was recovered as a precipitate, and was reused after H2O2 was used up. After two times recycling, the catalyst kept almost the same activity.

Reaction path for oxidation of ethylene to acetic acid over Pd/WO3-ZrO2 in the presence of water

Pd-supported on WO3-ZrO2 (W/Zr atomic ratio=0.2) calcined at 1073 K was found to be highly active and selective for gas-phase oxidation of ethylene to acetic acid in the presence of water at 423 K and 0.6 MPa. Contact time dependence demonstrated that acetic acid is formed via acetaldehyde formed by a Wacker-type reaction, not through ethanol by hydration of ethylene.

Capillary array electrophoresis for the research of asymmetric transformation reaction of L-proline to D-proline

One asymmetric transformation reaction Of L-proline (L-Pro) to D-proline was studied by a home-made capillary array electrophoresis (CAE) for the first time. The aldehyde catalysts and the organic acid solvents for the asymmetric transformation reaction were rapidly screened and the enantiomeric excess values of the asymmetric product Of L-Pro were directly obtained from the electrophoretogram of CAE.

Reaction time and replenishment time of SP and CGRP after incision in rat skin

Background. the skin neurogenic inflammation is mainly related to Substance P (SP) and Calcitonin Gene-related Peptide (CGRP). There is no data on their availability in the dynamics of skin nerve endings, concerning their release and replenishment after a nociceptive stimulus, so this was investigated. Materials and methods. 25 rats were randomly distributed in 5 groups. the animals of the control group (CG) determined the baseline levels of neuropeptides in the skin. the groups S0 and S30 did not receive any cutaneous stimulus at 30 and 60 minutes, respectively. in the group S1, an incision stimulus was made at 30 minutes. in the group S31, a nociceptive stimulus was performed by subdermal scratching at 30 minutes and, at 60 minutes, the incision stimulus was carried out in the same location (nociceptive hyperstimulation). the skin samples of the other animals were harvested from the back 1 minute after their death. SP, pro-CGRP and CGRP were quantified by Western Blotting. Results. the incision stimulus released SP, S1 compared to S0 (p < 0.05) detected in the first minute, and the replenishment time was more than 30 minutes. Also, it cleaved pro-CGRP, S1 compared to S31 (p < 0.05) in the first minute, and its replenishment time less than 30 minutes. Release of CGRP was not detected. Conclusion. the incision released SP already detected in the first minute; its replenishment time is more than 30 minutes. the incision decreased pro-CGRP, also detected in the first minute; and its replenishment time is less than 30 minutes.

Microwave-Assisted Biginelli Reaction

Excellent laboratory procedure for a small focused library of dihydropyrimidinones. Good example of a multicomponent reaction performed using microwave irradiation.

Reductive Amination Reaction

A simple, solventless procedure for reductive amination that results in an impressive color change. Reaction proceeds in three stages: imine formation, reduction, and acetylation and purification is done by crystallization.

Grignard Reaction - Synthesis of Substituted Benzoic Acids

A convenient preparation of substituted benzoic acids from Grignard additions to solid carbon dioxide. Students create a library of carboxylic acids by using differentially substituted, commercially available aryl bromides, which can be used as the starting materials for a multistep synthesis. This is a modification and improvement of a very popular undergraduate organic chemistry experiment.

Ab initio calculations of group 4 metallocene reaction mechanisms: atomic layer deposition and bond activation catalysis

Thin film dielectrics based on titanium, zirconium or hafnium oxides are being introduced to increase the permittivity of insulating layers in transistors for micro/nanoelectronics and memory devices. Atomic layer deposition (ALD) is the process of choice for fabricating these films, as it allows for high control of composition and thickness in thin, conformal films which can be deposited on substrates with high aspect-ratio features. The success of this method depends crucially on the chemical properties of the precursor molecules. A successful ALD precursor should be volatile, stable in the gas-phase, but reactive on the substrate and growing surface, leading to inert by-products. In recent years, many different ALD precursors for metal oxides have been developed, but many of them suffer from low thermal stability. Much promise is shown by group 4 metal precursors that contain cyclopentadienyl (Cp = C5H5-xRx) ligands. One of the main advantages of Cp precursors is their thermal stability. In this work ab initio calculations were carried out at the level of density functional theory (DFT) on a range of heteroleptic metallocenes [M(Cp)4-n(L)n], M = Hf/Zr/Ti, L = Me and OMe, in order to find mechanistic reasons for their observed behaviour during ALD. Based on optimized monomer structures, reactivity is analyzed with respect to ligand elimination. The order in which different ligands are eliminated during ALD follows their energetics which was in agreement with experimental measurements. Titanocene-derived precursors, TiCp*(OMe)3, do not yield TiO2 films in atomic layer deposition (ALD) with water, while Ti(OMe)4 does. DFT was used to model the ALD reaction sequence and find the reason for the difference in growth behaviour. Both precursors adsorb initially via hydrogen-bonding. The simulations reveal that the Cp* ligand of TiCp*(OMe)3 lowers the Lewis acidity of the Ti centre and prevents its coordination to surface O (densification) during both of the ALD pulses. Blocking this step hindered further ALD reactions and for that reason no ALD growth is observed from TiCp*(OMe)3 and water. The thermal stability in the gas phase of Ti, Zr and Hf precursors that contain cyclopentadienyl ligands was also considered. The reaction that was found using DFT is an intramolecular α-H transfer that produces an alkylidene complex. The analysis shows that thermal stabilities of complexes of the type MCp2(CH3)2 increase down group 4 (M = Ti, Zr and Hf) due to an increase in the HOMO-LUMO band gap of the reactants, which itself increases with the electrophilicity of the metal. The reverse reaction of α-hydrogen abstraction in ZrCp2Me2 is 1,2-addition reaction of a C-H bond to a Zr=C bond. The same mechanism is investigated to determine if it operates for 1,2 addition of the tBu C-H across Hf=N in a corresponding Hf dimer complex. The aim of this work is to understand orbital interactions, how bonds break and how new bonds form, and in what state hydrogen is transferred during the reaction. Calculations reveal two synchronous and concerted electron transfers within a four-membered cyclic transition state in the plane between the cyclopentadienyl rings, one π(M=X)-to-σ(M-C) involving metal d orbitals and the other σ(C-H)-to-σ(X-H) mediating the transfer of neutral H, where X = C or N. The reaction of the hafnium dimer complex with CO that was studied for the purpose of understanding C-H bond activation has another interesting application, namely the cleavage of an N-N bond and resulting N-C bond formation. Analysis of the orbital plots reveals repulsion between the occupied orbitals on CO and the N-N unit where CO approaches along the N-N axis. The repulsions along the N-N axis are minimized by instead forming an asymmetrical intermediate in which CO first coordinates to one Hf and then to N. This breaks the symmetry of the N-N unit and the resultant mixing of MOs allows σ(NN) to be polarized, localizing electrons on the more distant N. This allowed σ(CO) and π(CO) donation to N and back-donation of π*(Hf2N2) to CO. Improved understanding of the chemistry of metal complexes can be gained from atomic-scale modelling and this provides valuable information for the design of new ALD precursors. The information gained from the model decomposition pathway can be additionally used to understand the chemistry of molecules in the ALD process as well as in catalytic systems.

Measurement of the differential cross section for the reaction gamman-->pi- p from deuterium.

We report a measurement of the differential cross section for the gamman-->pi- p process from the CLAS detector at Jefferson Laboratory in Hall B for photon energies between 1.0 and 3.5 GeV and pion center-of-mass (c.m.) angles (thetac.m.) between 50 degrees and 115 degrees. We confirm a previous indication of a broad enhancement around a c.m. energy ([sqrt]s) of 2.1 GeV at thetac.m.=90 degrees in the scaled differential cross section s7dsigma/dt and a rapid falloff in a center-of-mass energy region of about 400 MeV following the enhancement. Our data show an angular dependence of this enhancement as the suggested scaling region is approached for thetac.m. from 70 degrees to 105 degrees.

Using ground reaction force to predict knee kinetic asymmetry following anterior cruciate ligament reconstruction.

Asymmetries in sagittal plane knee kinetics have been identified as a risk factor for anterior cruciate ligament (ACL) re-injury. Clinical tools are needed to identify the asymmetries. This study examined the relationships between knee kinetic asymmetries and ground reaction force (GRF) asymmetries during athletic tasks in adolescent patients following ACL reconstruction (ACL-R). Kinematic and GRF data were collected during a stop-jump task and a side-cutting task for 23 patients. Asymmetry indices between the surgical and non-surgical limbs were calculated for GRF and knee kinetic variables. For the stop-jump task, knee kinetics asymmetry indices were correlated with all GRF asymmetry indices (P < 0.05), except for loading rate. Vertical GRF impulse asymmetry index predicted peak knee moment, average knee moment, and knee work (R(2)  ≥ 0.78, P < 0.01) asymmetry indices. For the side-cutting tasks, knee kinetic asymmetry indices were correlated with the peak propulsion vertical GRF and vertical GRF impulse asymmetry indices (P < 0.05). Vertical GRF impulse asymmetry index predicted peak knee moment, average knee moment, and knee work (R(2)  ≥ 0.55, P < 0.01) asymmetry indices. The vertical GRF asymmetries may be a viable surrogate for knee kinetic asymmetries and therefore may assist in optimizing rehabilitation outcomes and minimizing re-injury rates.