X-ray photoelectron spectroscopy of nitroanilines and their derivatives

N 1s core-electron spectra have been studied for nitroanilines and related compounds. The spectral data are qualitatively interpreted by means of the molecules-in-molecule method, which describes the interaction between the aromatic amine part (donor moiety) and the nitro group (acceptor moiety) in terms of a composite system consisting of a donor and an acceptor. It was found that the nitro-N 1s spectra and the separation between the nitro-N 1s and the amino-N 1s ionization energies depend upon the magnitude of the intramolecular charge-transfer interaction in the ground state. A similarity between the relaxation effect in the nitro-N 1s or nitro-O 1s core-hole ion and a nitration reaction of the donor moiety is demonstrated.     

High-resolution inverse Raman spectroscopy of the ν1 band of 28SiH4

A near-Doppler-limited isotropic Raman spectrum of the symmetric stretching fundamental ν₁ of ²⁸SiH₄ has been recorded between 2182.8 and 2187.0 cm^?1 using high-sensitivity “quasi-cw” inverse Raman spectroscopy. The band exhibits compact, nonoverlapping J manifolds, which were measured from Q(0) through Q(13), plus a portion of Q(14). Since ν₁ is in resonance with the nearby infrared-active stretch ν₃, these two bands were analyzed simultaneously using the infrared frequencies of ν₃ reported by Cabana, Gray, Robiette, and Pierre. The results confirm their analysis, in which several perturbation-allowed ν₁ transitions were identified in the infrared, but the molecular constants for the v₁ = 1 state are much better determined with the inclusion of the Raman data. At higher J, ν₁ exhibits significant intensity perturbations due to a breakdown of the selection rule ΔN = 0; these have been quantitatively accounted for.     

Assignment of the doublet states arising from ionization of chlorine lone-pairs in molecules possessing C2υ symmetry

The He(I) photoelectron spectra of Cl₂CCH₂, Cl₂CCF₂, Cl₂CF₂ and Cl₂CBr₂ have been recorded. Detailed assignments of the     

Theoretical studies of ion neutralization: Two-dimensional tight binding models

The neutralization of ions impinging on a substrate is modeled by treating the substrate as both a two-dimensional, tight-binding, semi-infinite sheet and a two-dimensional, tight-binding, infinite sheet. In both cases the equations of motion are set up in a generalized Langevin format. Results are presented for a model interaction and compared with previous computations using a semi-infinite chain model and an infinite chain model.     

Torsional splitting and l-doubling in the ν9 R Q 0 infrared band of ethane

A high resolution diode laser absorption spectrum of the ν₉ ^R Q ₀ branch of C₂H₆ at 822 cm^-1 reveals a rotational progression with anomalous spacing and intensity, which is shown to be a result of both l-doubling and torsional splitting of rotational levels, both of which give rise to a J(J+1) energy dependence. From a contour analysis of the spectrum we estimate values for the l-doubling and torsional splitting parameters.     

Peptides-XXXXVI: Studies in the synthesis of an analogue of hen egg white lysozyme

The previously synthesised (1–37), (38–75), (76–93), (94–104), (105–117) and (118–129) fragments of the analogue were combined making extensive use of the DCCI/HONSu method. The final coupling involved the (1–75) and (76–129) sub-fragments. Aggregation of the latter fragment caused problems in purification by routine gel filtration methods employing Enzacryl K2 or Sephadex LH60. The fully protected (1–129) product was partially purified by washing, then deprotectcd and purified by gel filtration and ion exchange chromatography. Satisfactory removal of the acetamidomethyl group used for cysteine protection could not be achieved.     

The change of the proton magnetic shielding in red- and blue-shifted linear hydrogen-bonded complexes

The change in the proton magnetic shielding constant of FH and FArH on the formation of the vibrationally red-shifted FH... Rg and blue-shifted FArH... Rg (Rg = Ne, Ar). complexes was determined by GIAO ab initio computations at various levels of theory. The blue-shifted FArH... N₂ and red-shifted FArH... P₂ complexes were also studied. The characteristic downfield shift of the isotropic proton magnetic resonance in red-shifted hydrogen-bonded complexes is smaller in the blue-shifted complexes. In FArH... Ne and FArH... N₂ the proton NMR actually shifts to higher fields on complexation. These results are rationalized by considering the changes in the magnetic and electric contributions to the proton shielding in FH and FArH.     

Atmospheric pressure plasma induced grafting of poly(ethylene glycol) onto silicone elastomers for controlling biological response

This study investigates the role that surface functionalisation of silicone elastomer (SE) by atmospheric pressure plasma induced graft immobilisation of poly(ethylene glycol) methyl ether methacrylate (PEGMA) plays in the attendant biological response. SE is used in modern ophthalmic medical devices and samples of the material were initially plasma treated using a dielectric barrier discharge reactor (DBD) to introduce reactive oxygen functionalities, prior to in situ grafting of two molecular weights of PEGMA (MW 1000 Da: PEGMA(1000), MW 2000 Da: PEGMA(2000)). The variously processed surfaces were characterised by water contact angle analysis, X-ray photoelectron spectroscopy, time-of-flight secondary ion mass spectrometry and atomic force microscopy. Lens epithelial cells were then cultured on the PEGMA grafted SE surfaces. It was found that cells on the pristine surface were not well spread and had shrunken morphology. On the DBD pre-treated surfaces, the cells were well spread. On the PEGMA(1000) surface, the cells displayed evidence of shrinkage and were on the verge of detaching. Remarkably, on the PEGMA(2000) surface, no cell adhesion was detection. Bacterial adhesion to the surfaces was studied using Staphylococcus aureus NTC8325. There was no difference in the number of bacteria adhering to any of the surfaces studied.     

A new single-center perturbation theory for the treatment of simple hydrides

The perturbation expansion of Hartree-Fock potential energy surfaces of simple hydrides in a single-center scale 1/Z-expansion is carried out using diagrammatic methods. Diagrams having the topological structure of third-order diagrams are summed to all orders using an integral equation technique. The resulting one-electron wavefunction is used to generate a resummed perturbation series correct through fourth order.