Classical electrodynamic systems interacting with classical electromagnetic random radiation

In the past, a few researchers have presented arguments indicating that a statistical equilibrium state of classical charged particles necessarily demands the existence of a temperature-independent, incident classical electromagnetic random radiation. Indeed, when classical electromagnetic zero-point radiation is included in the analysis of problems with macroscopic boundaries, or in the analysis of charged particles in linear force fields, then good agreement with nature is obtained. In general, however, this agreement has not been found to hold for charged particles bound in nonlinear force fields. The point is raised here that this disagreement arising for nonlinear force fields may be a premature conclusion on this classical theory for describing atomic systems, because past calculations have not directed strict attention to electromagnetic interactions between charges. This point is illustrated here by examining the classical hydrogen atom and showing that this problem has still not been adequately solved.     

Intermediate mass fragments in the reaction6Li+46Ti atE/A=26 MeV

Intermediate mass fragment cross-sectionsσ(E, θ, 4≤Z≤11) have been measured in the reaction⁶Li+⁴⁶Ti at 156 MeV incident energy. A simple sequential binary decay model describes most of theZ>8 data as evaporation from the compound nucleus. The complete fusion cross-section is also well reproduced. An intermediate velocity source model (β=2β _CN, T=7 MeV) has been used in order to explain the small angle and Z≤8 data which indicate aZ ^?4.1 dependence.     

Characterization of an exception to the ‘even‐electron rule’ upon low‐energy collision induced decomposition in negative ion electrospray tandem mass spectrometry

Electrospray‐generated precursor ions usually follow the ‘even‐electron rule’ and yield ‘closed shell’ fragment ions. We characterize an exception to the ‘even‐electron rule.’ In negative ion electrospray mass spectrometry (ES‐MS), 2‐(ethoxymethoxy)‐3‐hydroxyphenol (2‐hydroxyl protected pyrogallol) easily formed a deprotonated molecular ion (M‐H)^? at m/z 183. Upon low‐energy collision induced decomposition (CID), the m/z 183 precursor yielded a radical ion at m/z 124 as the base peak. The radical anion at m/z 124 was still the major fragment at all tested collision energies between 0 and 50 eV (E_lab). Supported by computational studies, the appearance of the radical anion at m/z 124 as the major product ion can be attributed to the combination of a low reverse activation barrier and resonance stabilization of the product ions. Furthermore, our data lead to the proposal of a novel alternative radical formation pathway in the protection group removal of pyrogallol. Copyright © 2009 John Wiley & Sons, Ltd.     

A facile synthesis of novel 2-amino-6-arylmethyl-7-carboxamido-7,8-dihydropyrimido[5,4-f][1,4]thiazepin-5-ones

A facile synthesis of novel 2-amino-6-arylmethyl-7-carboxamido-7,8-dihydropyrimido[5,4-f][1,4]thiazepin-5-ones is described. The synthesis was developed on solid phase and was applied to provide a series of analogs in good yield. The key reactions are acylation of a cysteine derivative with 2,4-dichloropyrimidine-5-carbonyl chloride followed by cyclization to generate a 6-arylmethyl-7-carboxamido-2-chloro-7,8-dihydropyrimido[5,4-f][1,4]thiazepin-5-one, which is further derivatized with an amine to give the desired 2-amino-6-arylmethyl-7-carboxamido-7,8-dihydropyrimido[5,4-f][1,4]thiazepin-5-one.     

Evaluation of thiol‐ene click chemistry in functionalized polysiloxanes

Polysiloxanes are commonly used in a myriad of applications, and the “click” nature of the thiol‐ene reaction is well suited for introducing alternative functionalities or for crosslinking these ubiquitous polymers. As such, understanding of the thiol‐ene reaction in the presence of silicones is valuable and would lead to enhanced methodologies for modification and crosslinking. Here, the thiol‐ene reaction kinetics were investigated in functionalized oligosiloxanes having varying degrees of thiol functionalization (SH), π–π interactions (from diphenyls, DP), and ene types (C?C). In the ene‐functionalized oligomers, π–π interactions were controlled through the use of dioctyl repeats (DO). The polymerization rate and rate‐limiting steps were determined for all systems containing an allyl‐functionalized oligomer, and rates ranging from 0.10 to 0.54 mol L^?1 min^?1 were seen. The rate‐limiting step varied with the oligomer composition; examples of rate‐limited propagation (5:3:2 C?C:DP:DO/1:1 SH:DP) or chain transfer (5:3:2 C?C:DP:DO/3:1 SH:DP) were found in addition to cases with similar reaction rate constants (5:2:3 C?C:DP:DO/1:1 SH:DP). None of the siloxanes were found to exhibit autoacceleration despite their relatively high viscosities. Instead, the allyl‐, vinyl‐, and acrylate‐functionalized siloxanes were all found to undergo unimolecular termination based on their high α scaling values (0.98, 0.95, and 0.82, respectively) in the relation R_p ∝ R_i^α. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

The structures of trimethylene oxide and trimethylene sulphide as studied by proton magnetic resonance of the solutions in a nematic liquid crystal

The structures of trimethylene oxide and sulphide have been studied by the nematic liquid crystal N.M.R. method. Corrections for the ring puckering motion have been applied and structures determined in conjunction with data from microwave spectroscopic studies. Improved results are obtained if a third motional constant is included in the analysis.     

Rhodium nitrosyl catalysts for CO2 hydrogenation to formic acid under mild conditions

A new synthetic protocol for catalysing CO₂ hydrogenation to formic acid under mild conditions is reported, and the CO₂ hydrogenation is efficiently achieved by dcpe‐rhodium‐nitrosyl catalyst precursors, Rh(NO)(dcpe) (1) (dcpe = 1,2‐dicyclohexylphosphinoethane) and Rh(III)(NO)(dcpe)Cl₂ (2). The catalytic activity of 1 is noteworthy for being able to proceed in the absence of protic conditions. Compound 2 is characterized by NMR, IR and X‐ray crystallography. In particular, 2 is observed to bear a bent NO ligand with a Rh–N–O angle of 115.7(3)°, representing one of the smallest M–N–O angles known. Copyright © 2012 John Wiley & Sons, Ltd.     

Transonic Hodograph Design Problems

The hodograph method is used to formulate several design problems in transonic flow using small-disturbance theory. Analytical and numerical methods give solutions to several optimum critical airfoil designs with different constraints on the tail angle. Special airfoil shapes flying at free-stream Mach number one are designed. The problem of constructing a shock-free body of revolution at subsonic speed but having a supersonic zone is formulated in the hodograph and solved numerically. Received 10 January 1997 and accepted 14 April 1997