A spectroscope study of some semiquinone radical ions

The effect of substituents on the value of the oxidation potential of quinones is reviewed and attempts to prepare substituted diphenoquinones with high oxidation potentials are reported. Attempts to characterise the mechanism of addition and substitution in diphenoquinones by identifying the products of the Thiele acetylation of diphenoquinone are reported. The reaction proved most efficient when the incoming acetylinium ion is directed by substituents in the diphenoquinone. A 1,8-addition to diphenoquinone is reported and characterised by isolating the products of the reaction between acetyl chloride and diphenoquinone, with perchloric acid as catalyst. The alternating linewidth effects observed in e.s.r.spectra are discussed and applied to account for such effects observed in the e.s.r.spectra of diphenosemiquinone anion and cation radicals. The spectra are analysed and the intramolecular processes producing these effects are discussed. A dianion diradical where intramolecular rotation about the 1 - 1' bond is restricted is produced by the oxidation of 2,2' ,4,4' -tetra hydroxybiphenyl. Previous studies of diphenosemiquinone anions are reviewed and alkylated diphenosemiquinone anion are produced by the reduction of the parent quinone with potassium hydroxide solution, the resulting radical being stabilised by the presence of pyridine. A qualitative interpretation of the solvent-ion effect in alkylated diphenosemiquinone anions is given. Diphanosemiquinone cation radicals are reviewed and previous studies are re-examined.

Dielectric relaxation of polysiloxanes and kerr effect of p-phenylene vinylene oligomers

The dielectric relaxation behaviour of a series of cyclic and linear poly(dimethylsiloxanes) with overline nn in the range 28 to 99 has been studied, as a function of temperature (142.0K-157.5K) and frequency (12-105Hz). Activation energies for the -relaxation process, Davidson-Cole empirical distribution factors, , and mean-square dipole moments per repeat unit, < 2> , have been calculated. Differences in values of H_act reflected restricted dipolar rotation for the cyclic structures, compared to the linear structures, over the range of molecular weights studied. The dielectric relaxation behaviour of a series of linear oligomers of methyl phenyl siloxane, with n in the range 4 to 10, a series of linear fractions of poly(methyl phenyl siloxane), with overline n_n in the range 31 to 1370, and a cyclic oligomer of mehyl phenyl siloxane, with n = 10, has been studied as a function of temperature (155.5K-264.0K) and frequency (12-105Hz). Activation energies for the -relaxation process, Davidson-Cole and Cole-Cole empirical distribution factors, and , respectively, and mean-square dipole moments per repeat unit have been calculated. The reduced flexibility of short methyl phenyl siloxane chains, compared to dimethyl siloxane chains, was apparent from a comparison of dipole moment ratios. The dilectric relaxation behaviour of poly(methyl hydrogen siloxane) and poly(n-hexyl methyl siloxane) has been studied as a function of temperature and frequency. A polysiloxane liquid crystal has been synthesised and its dielectric relaxation behaviour has been studied, as a function of temperature and frequency, in the liquid crystalline phase and below T_g. Poly(p-phenylene vinylene) and related oligomers have been synthesised and characterised by a variety of experimental techniques. The Kerr effect of two oligomeric fractions, in solution in PPG 2025, has been measured. The electrical conductivities of the undoped and I_2-doped polymer and oligomers have been measured.

Conformational Evaluation of Indol-3-yl-N-alkyl-glyoxalylamides and Indol-3-yl-N,N-dialkyl-glyoxalylamides

Restricted rotation in indol-3-yl-N-alkyl- and indol-3-yl-N,N-dialkyl-glyoxalylamides can in principle give the syn-periplanar and anti-periplanar rotamers. In asymmetrically disubstituted glyoxalylamides, steric effects lead to the occurrence of both rotamers, as observed by NMR spectroscopy. The predominant peak corresponds with the anti rotamer, in which the bulkier alkyl group is orientated trans to the amide carbonyl group. In monoalkylated glyoxalylamides, only one set of peaks is observed, consistent with the presence of only one rotamer. Crystal structures of 5-methoxyindole-3-yl-N-tert-butylglyoxalylamide, indole-3-yl-N-tert-butylglyoxalylamide, and indole-3-yl-N-isopropylglyoxalylamide reported here reveal a syn conformation held by an intramolecular N-HO hydrogen bond.

Dynamics of learning with restricted training sets

The dynamics of supervised learning in layered neural networks were studied in the regime where the size of the training set is proportional to the number of inputs. The evolution of macroscopic observables, including the two relevant performance measures can be predicted by using the dynamical replica theory. Three approximation schemes aimed at eliminating the need to solve a functional saddle-point equation at each time step have been derived.

Noise, regularizers, and unrealizable scenarios in online learning from restricted training sets

We study the dynamics of on-line learning in multilayer neural networks where training examples are sampled with repetition and where the number of examples scales with the number of network weights. The analysis is carried out using the dynamical replica method aimed at obtaining a closed set of coupled equations for a set of macroscopic variables from which both training and generalization errors can be calculated. We focus on scenarios whereby training examples are corrupted by additive Gaussian output noise and regularizers are introduced to improve the network performance. The dependence of the dynamics on the noise level, with and without regularizers, is examined, as well as that of the asymptotic values obtained for both training and generalization errors. We also demonstrate the ability of the method to approximate the learning dynamics in structurally unrealizable scenarios. The theoretical results show good agreement with those obtained by computer simulations.

Objective analysis of toric intraocular lens rotation and centration

PURPOSE: To assess the repeatability of an objective image analysis technique to determine intraocular lens (IOL) rotation and centration. SETTING: Six ophthalmology clinics across Europe. METHODS: One-hundred seven patients implanted with Akreos AO aspheric IOLs with orientation marks were imaged. Image quality was rated by a masked observer. The axis of rotation was determined from a line bisecting the IOL orientation marks. This was normalized for rotation of the eye between visits using the axis bisecting 2 consistent conjunctival vessels or iris features. The center of ovals overlaid to circumscribe the IOL optic edge and the pupil or limbus were compared to determine IOL centration. Intrasession repeatability was assessed in 40 eyes and the variability of repeated analysis examined. RESULTS: Intrasession rotational stability of the IOL was ±0.79 degrees (SD) and centration was ±0.10 mm horizontally and ±0.10 mm vertically. Repeated analysis variability of the same image was ±0.70 degrees for rotation and ±0.20 mm horizontally and ±0.31 mm vertically for centration. Eye rotation (absolute) between visits was 2.23 ± 1.84 degrees (10%>5 degrees rotation) using one set of consistent conjunctival vessels or iris features and 2.03 ± 1.66 degrees (7%>5 degrees rotation) using the average of 2 sets (P =.13). Poorer image quality resulted in larger apparent absolute IOL rotation (r =-0.45,P<.001). CONCLUSIONS: Objective analysis of digital retroillumination images allows sensitive assessment of IOL rotation and centration stability. Eye rotation between images can lead to significant errors if not taken into account. Image quality is important to analysis accuracy.

Independent detectors for expansion and rotation, and for orthogonal components of deformation

It is well known that optic flow - the smooth transformation of the retinal image experienced by a moving observer - contains valuable information about the three-dimensional layout of the environment. From psychophysical and neurophysiological experiments, specialised mechanisms responsive to components of optic flow (sometimes called complex motion) such as expansion and rotation have been inferred. However, it remains unclear (a) whether the visual system has mechanisms for processing the component of deformation and (b) whether there are multiple mechanisms that function independently from each other. Here, we investigate these issues using random-dot patterns and a forced-choice subthreshold summation technique. In experiment 1, we manipulated the size of a test region that was permitted to contain signal and found substantial spatial summation for signal components of translation, expansion, rotation, and deformation embedded in noise. In experiment 2, little or no summation was found for the superposition of orthogonal pairs of complex motion patterns (eg expansion and rotation), consistent with probability summation between pairs of independent detectors. Our results suggest that optic-flow components are detected by mechanisms that are specialised for particular patterns of complex motion.

Evaluation of the sonically induced narrowing of nuclear magnetic resonance spectra of solids

The Nuclear Magnetic Resonance (NMR) spectra of liquids contain a wealth of quantitative information that may be derived, for instance, from chemical shifts and spin-spin couplings. The available information depends on the incoherent rapid molecular motion that causes complicating effects present in the solid state to average to zero. Whereas liquid state NMR spectra show narrow lines, the corresponding NMR spectra from the solid state are normally composed of exceedingly broad resonance lines due to highly restricted molecular motion. It is, therefore, difficult to obtain directly as detailed information from the spectra of solids as from those derived from the liquid state. Studies on a new technique (SINNMR, the sonically induced narrowing of the NMR spectra of solids) to remove line broadening effects in the NMR spectra of the solid state are reported within this thesis. SINNMR involves narrowing the NMR absorptions from solid particles by irradiating them with ultrasound when they are suspended in a support liquid. It is proposed that ultrasound induces incoherent motion of the suspended particles, producing motional characteristics of the particles similar to those of rather large molecules. The first report of apparently successful experiments involving SINNMR[1] emphasised both the irreproducibility of the technique and the uncertainty regarding its true origin. If SINNMR can be made reproducible and the effect definitively attributed to the sonically induced incoherent motional averaging of particles, the technique could offer a simple alternative to the now classical magic-angle spinning (MAS) NMR[2] and the recently reported dynamic angle spinning (DAS)[3] and double rotation (DOR)[4] techniques. Evidence is presented in this thesis to support the proposal that ultrasound may be used to narrow the NMR spectral resonances from solids by inducing incoherent motion of particles suspended in support liquids and, additionally, for some solids, by inducing rotational motion of molecular constituents in the lattices of solids. Successful SINNMR line narrowing using 20 kHz ultrasound is reported for a variety of samples: including trisodium orthophosphate, polytetrafluoroethylene and aluminium alloys. Investigations of SINNMR line narrowing in trisodium phosphate have revealed the relationship between ultrasonic power, particle size and support liquid density for the production of optimum SINNMR conditions. It is also proposed that the incoherent motion of particles induced by 20 kHz ultrasound can originate from interactions between acoustically induced cavitation microjets and particles.

The beta effect in alkylsilanes

It was suggested to us that compounds of the type XCH2SiR2CH2CH2Y might show interesting chemical and biological activity due to them possessing both an alpha group and a beta group. The aim of this research was to discover whether or not the alpha and beta effects interact with each other, and if so whether interaction is via steric or electronic effects. A series of compounds were made with a constant chloromethyl alpha function and varying beta functions (hydroxy, methoxy and chloro groups); plus a second series of trimethylsilyl substituted silanes with the same variety of beta functions were synthesised. The stereochemistry of the products was investigated by analysis of NMR spectra and of dipole moment data. It was found that the β-chloro-substituted compounds possessed restricted rotation. The methoxy- and hydroxy-substituted compounds which displayed more or less simple triplets, appear to possess free rotation; the smaller sized hydroxy and methoxy groups seemingly no great barrier to rotation. Similarly, compounds possessing larger alpha alkyl groups appeared also to possess restricted rotation, it was concluded that for the compounds possessing large alpha or a large beta function steric effects dominate. The kinetics of the solvolysis reaction were studied. β-functional alkylsilanes commonly undergo solvolysis by unimolecular elimination at remarkably enhanced rates. The β-hydroxy- and β-methoxy-substituted chloroethyl derivatives reacted substantially slower that their trimethylsilyl analogues, due to the electronegative chlorine pulling electrons into the Si-C bond. For compounds possessing an electronegative substituent alpha to silicon it seems it is the electronic effects that act to inhibit the beta effect. 2-Chloroethylchloromethyldimethylsilane initially appeared not to react solvolytically, however NMR analysis of the solvolysis products indicated that a reaction did occur but by an as yet unknown mechanism. For compounds with an a α-electronegative substituent in conjunction with a large β-function it was concluded both steric and electronic effects are important.

From detection of complex motion to descriptions of moving surfaces in human vision

A preliminary study by Freeman et al (1996b) has suggested that when complex patterns of motion elicit impressions of 2-dimensionality, odd-item-out detection improves given targets can be differentiated on the basis of surface properties. Their results can be accounted for, it if is supposed that observers are permitted efficient access to 3-D surface descriptions but access to 2-D motion descriptions is restricted. To test the hypothesis, a standard search technique was employed, in which targets could be discussed on the basis of slant sign. In one experiment, slant impressions were induced through the summing of deformation and translation components. In a second theory were induced through the summing of shear and translation components. Neither showed any evidence of efficient access. A third experiment explored the possibility that access to these representations may have been hindered by a lack of grouping between the stimuli. Attempts to improve grouping failed to produce convincing evidence in support of life. An alternative explanation is that complex patterns of motion are simply not processed simultaneously. Psychophysical and physiological studies have, however, suggested that multiple mechanisms selective for complex motion do exist. Using a subthreshold summation technique I found evidence supporting the notion that complex motions are processed in parallel. Furthermore, in a spatial summation experiment, coherence thresholds were measured for displays containing different numbers of complex motion patches. Consistent with the idea that complex motion processing proceeds in parallel, increases in the number of motion patches were seen to decrease thresholds, both for expansion and rotation. Moreover, the rates of decrease were higher than those typically expected from probability summation, thus implying mechanisms are available, which can pool signals from spatially distinct complex motion flows.

Oxidized phospholipid inhibition of toll-like receptor (TLR) signaling is restricted to TLR2 and TLR4 roles for cd14, lps-binding protein, and md2 as targets for specificity of inhibition

The generation of reactive oxygen species is a central feature of inflammation that results in the oxidation of host phospholipids. Oxidized phospholipids, such as 1-palmitoyl-2-arachidonyl-sn-glycero-3-phosphorylcholine (OxPAPC), have been shown to inhibit signaling induced by bacterial lipopeptide or lipopolysac-charide (LPS), yet the mechanisms responsible for the inhibition of Toll-like receptor (TLR) signaling by OxPAPC remain incompletely understood. Here, we examined the mechanisms by which OxPAPC inhibits TLR signaling induced by diverse ligands in macrophages, smooth muscle cells, and epithelial cells. OxPAPC inhibited tumor necrosis factor- production, IB degradation, p38 MAPK phosphorylation, and NF-B-dependent reporter activation induced by stimulants of TLR2 and TLR4 (Pam3CSK4 and LPS) but not by stimulants of other TLRs (poly(I·C), flagellin, loxoribine, single-stranded RNA, or CpG DNA) in macrophages and HEK-293 cells transfected with respective TLRs and significantly reduced inflammatory responses in mice injected subcutaneously or intraperitoneally with Pam3CSK4. Serum proteins, including CD14 and LPS-binding protein, were identified as key targets for the specificity of TLR inhibition as supplementation with excess serum or recombinant CD14 or LBP reversed TLR2 inhibition by OxPAPC, whereas serum accessory proteins or expression of membrane CD14 potentiated signaling via TLR2 and TLR4 but not other TLRs. Binding experiments and functional assays identified MD2 as a novel additional target of OxPAPC inhibition of LPS signaling. Synthetic phospholipid oxidation products 1-palmitoyl-2-(5-oxovaleryl)-sn-glycero-3-phosphocholine and 1-palmitoyl-2-glutaryl-sn-glycero-3-phosphocholine inhibited TLR2 signaling from 30 µM. Taken together, these results suggest that oxidized phospholipid-mediated inhibition of TLR signaling occurs mainly by competitive interaction with accessory proteins that interact directly with bacterial lipids to promote signaling via TLR2 or TLR4.

Multiwavelength fiber laser with fine adjustment, based on nonlinear polarization rotation and birefringence fiber filter

We have proposed and demonstrated a multiwavelength fiber laser based on nonlinear polarization rotation (NPR). The mechanism for stable room-temperature multiwavelength operation contributes to the ability of the intensity-dependent loss in NPR to effectively alleviate mode competition. In addition, through tuning the birefringence fiber filter, the lasing wavelength can be accurately tuned in the free spectrum range of the in-line periodic filter.

Biomass production in short rotation effluent-irrigated plantations in North-West India

This study estimates above-ground biomass in high density plantations of six important semi-arid tree species at Palwal (70 km from Delhi) irrigated with secondary treated sewage water at the rate of 0, 25, 50 and 100% of daily net evaporation potential (EP). In 2.5 y old plantations (plant spacing, 2 m x 2 m for single stem species and 2 m x 1 m for multi-stem species), Melia azedarach showed fairly high biomass production (38.4 t/ha) followed by Ailanthus excelsa (27.2 t/ha). Order of biomass production (kg / tree) was: Eucalyptus tereticornis (24.1) > A. excelsa (21.8) > M. azedarach (12.6) > Populus deltoides clone G 48 (8.3) > Alstonia scholaris (6.6)> Pongamia pinnata (3.7). Survival of plants after 2.5 y ranged from 25.2% in P. deltoides to 71.7% in P. pinnata, and had a significant effect on biomass production per unit area. ANOVA shows that levels of irrigation (0 - 100%) did not have statistically significant effect on plant growth. Correlation between diameter and biomass was found highly significant (p< 0.01) with R2 nearing to 1.