Vacuum ultraviolet circular dichroism spectrum of β-turn in solution

The vacuum ultraviolet circular dichroism spectrum of an isolated 4 → 1 hydrogen bonded β-turn is reported. The observed spectrum of N-acetyl-Pro-Gly-Leu-OH at − 40°C in trifluoroethanol is in good agreement with the theoretically calculated CD spectrum of the β-turn conformation. This spectrum, particularly the presence of a strong negative band around 180 nm and a large ratio [θ]201/[θ]225, can be taken as a characteristic feature of the isolated β-turn conformation. These CD spectral features can thus be used to distinguish the β-turn conformation from the β-structure in solution.

Synthetic studies in aromatic hemiterpenes of natural origin, Part 5: Synthesis of 6-acetyl-2,2-dimethyl-8-methoxychromene via benzylic oxidation route

The synthesis of 6-acetyl-2,2-dimethyl-8-methoxychromene (lc), a naturally occurring isomer of encecalin (la)h~s been described startilag from 2,2,6- trimethyl-8-methoxyclaromene (2e) which was obtained from creosol (4) in two steps involving condensation of the phenol with malic acid to the coumarin (3), followed by Grignard reaction with CHaMgI. The transformation of (2e) to the natural product (lc) was effeeted by oxidative dehydrogenation by DDQ of the 6-meth~r function to the formyl group (2f), Grignard reaction to the carbinol (2g) and finally its oxidation to the acetyl moiety (lc), the sequence of the essential steps schematically summarised as : Ar-CHs --* Ar-CHO --* Ar-CH (OH) CHs --* Ar---COCHs.

A model for antiferromagnetic to superconductor transition

A model system capable of exhibiting both superconductivity of conduction electrons and “antiferromagnetic” order of site localised electrons is studied. Coexistence of both types of order seems a possibility and the model predicts a re-entrant behaviour of the transition temperature.

Oestrogen-induced synthesis of thiamin-binding protein in immature chicks. Kinetics of induction, hormonal specificity and modulation

A specific radioimmunoassay procedure was developed to monitor the plasma concentrations of thiamin-binding protein, a minor yolk constituent of the chicken egg. By using this sensitive assay, the kinetics of oestrogen-induced elaboration of this specific protein in immature chicks was investigated. After a single injection of the steroid hormone, with an initial lag period of 4–5h the thiamin-binding protein rapidly accumulated in the plasma, attaining peak concentrations around 75h and declining thereafter. A 4-fold amplification of the response was noticed during the secondary stimulation, and this increased to 9-fold during the tertiary stimulation with the steroid hormone. The magnitude of the response was dependent on the hormone dose, and the initial latent period and the duration of the ascending phase of induction were unchanged for the hormonal doses tested during both the primary and secondary stimulations. The circulatory half-life of the protein was 6h as calculated from the measurement of the rate of disappearance of the exogenously administered 125I-labelled protein. Simultaneous administration of progesterone, dihydrotestosterone or corticosterone did not alter the pattern of induction. On the other hand, hyperthyroidism markedly decreased the oestrogenic response, whereas propylthiouracil-induced hypothyroidism had the opposite effect. The anti-oestrogen E- and Z-clomiphene citrates, administered 30min before oestrogen, effectively blocked the hormonal induction. a-Amanitin and cycloheximide administered along with or shortly after the sex steroid severely curtailed the protein elaboration. A comparison of the kinetics of induction of thiamin- and riboflavin-binding proteins by oestrogen revealed that, beneath an apparent similarity, a clear-cut difference exists between the two vitamin-binding proteins, particularly with regard to hormonal dose-dependent sensitivity of induction and the half-life in circulation. The steroid-mediated elaboration of the two yolk proteins thus appears to be not strictly co-ordinated, despite several common regulatory features underlying their induction.

Infrared divergences and confinement in massive (2+1)-dimensional QED

In (2+1)-dimensional quantum electrodynamics with massless photons and massive matter fields, it is shown that the mass renormalization of the latter is infrared divergent at one loop. This result remains unchanged at two loops. A simple argument based on a similar divergence of the Coulomb potential leads us to conjecture that charged states are not observable in this model. This argument holds in 1+1 dimensions also.

Sensitivity of wetland methane emissions to model assumptions: application and model testing against site observations

Abstract. Methane emissions from natural wetlands and rice paddies constitute a large proportion of atmospheric methane, but the magnitude and year-to-year variation of these methane sources is still unpredictable. Here we describe and evaluate the integration of a methane biogeochemical model (CLM4Me; Riley et al., 2011) into the Community Land Model 4.0 (CLM4CN) in order to better explain spatial and temporal variations in methane emissions. We test new functions for soil pH and redox potential that impact microbial methane production in soils. We also constrain aerenchyma in plants in always-inundated areas in order to better represent wetland vegetation. Satellite inundated fraction is explicitly prescribed in the model because there are large differences between simulated fractional inundation and satellite observations. A rice paddy module is also incorporated into the model, where the fraction of land used for rice production is explicitly prescribed. The model is evaluated at the site level with vegetation cover and water table prescribed from measurements. Explicit site level evaluations of simulated methane emissions are quite different than evaluating the grid cell averaged emissions against available measurements. Using a baseline set of parameter values, our model-estimated average global wetland emissions for the period 1993–2004 were 256 Tg CH4 yr−1, and rice paddy emissions in the year 2000 were 42 Tg CH4 yr−1. Tropical wetlands contributed 201 Tg CH4 yr−1, or 78 % of the global wetland flux. Northern latitude (>50 N) systems contributed 12 Tg CH4 yr−1. We expect this latter number may be an underestimate due to the low high-latitude inundated area captured by satellites and unrealistically low high-latitude productivity and soil carbon predicted by CLM4. Sensitivity analysis showed a large range (150–346 Tg CH4 yr−1) in predicted global methane emissions. The large range was sensitive to: (1) the amount of methane transported through aerenchyma, (2) soil pH (± 100 Tg CH4 yr−1), and (3) redox inhibition (± 45 Tg CH4 yr−1).

Structure of a steriod fungal metabolite

3a,7a, 14a-Trihydroxypregn-16-en-20-one, C21H3204, M r = 348.48, orthorhombic, P212121, a = 9.211 (1), b = 13.201 (1), c = 16.031 (1),~, V = 1949.28 (29)/~3, Z = 4, Dx = 1.187 g cm -3, A(Cu Ka), = 1.5418 ,~,/z = 6.07 cm-l, F(000) = 760, T= 293 K, R = 0.061 for 1337 observations. The A, B and C rings adopt normal chair conformations with the D ring in a 14a-envelope conformation. The molecules are held together by two hydrogen bonds [0(3)..'0(20) = 2.879 and O(7).--O(14)= 2.612 A,].

A simplified kinetic model for oxidative dehydrogenation of ethylbenzene over Pd-NaBr/Al2O3 catalyst

The oxidative dehydrogenation of ethylbenzene is gaining considerable importance in recent years as a promising alternative for styrene production. This vapour phase reaction has been studied over Pd-NaBr/Al2O3 catalyst in the temperature range 623-793 K in a fixed bed reactor. Kinetic analysis of this reaction has been done using a recursion procedure developed in this work from first principles. The advantage of this method is the absence of any restriction on the conversion level as it uses an integrated rate equation. The rate of styrene formation was found to follow a linear relationship with concentration of ethylbenzene and shows a Langmuir type dependence on the concentration of oxygen.

Primary structure of sesbania mosaic virus coat protein: its implications to the assembly and architecture of the virus

Sesbania mosaic virus (SMV) is a plant virus that infects Sesbania grandiflora plants in Andhra Pradesh, India. The amino acid sequence of the coat protein of SMV was determined using purified peptides generated by cleavage with trypsin, chymotrypsin, V8 protease and clostripain. The 230 residues so far determined were compared to the corresponding residues of southern bean mosaic virus (SBMV), the type member of sobemoviruses. The overall identity between the sequences is 61.7%. The amino terminal 64 residues, which constitute an independent domain (R-domain) known to interact with RNA, are conserved to a lower extent (52.5%). Comparison of the positively charged residues in this domain suggests that the RNA-protein interactions are considerably weaker in SMV. The residues that constitute the major domain of the coat protein, the surface domain (S-domain, residues 65-260), are better conserved (66.5%). The positively charged residues of this domain that face the nucleic acid are well conserved. The longest conserved stretch of residues (131-142) corresponds to the loop involved in intersubunit interactions between subunits related by the quasi 3-fold symmetry. A unique cation binding site located on the quasi 3-fold axis contributes to the stability of SMV. These differences are reflected in the increased stability of the SMV coat protein and its ability to be reconstituted with RNA at pH 7.5. A major epitope was identified using monoclonal antibodies to SMV in the segment 201-223 which contains an exposed helix in the capsid structure. This region is highly conserved between SMV and SBMV (70%) suggesting that it could represent the site of an important function such as vector recognition.

Modification of photochemical reactivity on formation of inclusion complexes: photorearrangement of benzyl phenyl ethers and methyl phenoxyacetates

The photorearrangement of benzyl phenyl ethers and methyl phenoxyacetates was investigated in methanol and in complexes with cyclodextrin in both the solid state and aqueous solutions. Irradiation in cyclodextrin media leads to a large change in product distribution with a very significant ortho selectivity different from that found in methanol where the reaction is non-selective. For meta-substituted ethers and phenoxyacetates, an impressive regioselectivity between the two ortho-rearranged isomers is observed and this is significantly enhanced by increasing the substituent chain length which acts as a spacer to induce a tight fit between the host and the guest. The observed results are rationalized on the basis of specific orientations of the unsubstituted and meta-substituted ethers and phenoxyacetates in the cyclodextrin cavity.

Thermodynamic modelling of absorption-resorption heating cycles with some new working pairs

This paper presents the results of a thermodynamic cycle analysis of single stage resorption heat pump (RHP) and resorption heat transformer (RHT) cycles with the new working pairs R22-NMP and R22-DMA. The coefficients of performance (COP) are correlated with the low grade source temperature, temperature at which useful heat is obtained and ambient temperature. The COPs are in the range 1.20–1.60 for the RHP mode and 0.25–0.45 for the RHT mode. Absorber temperatures (useful temperatures) as high as 50°C in the RHP mode and 87°C in the RHT mode have been obtained. It is observed that absorption-resorption systems are inflexible in their range of operating temperature and necessitate a higher pump work as compared with simple single-stage absorption heating systems. However, single stage RHTs show higher temperature boosts than simple absorption heat transformers.

Phonons and fractons in sol-gel alumina: Raman study

We report Raman scattering from the boehmite, gamma-, delta- and alpha-phases of the alumina gel. Samples are characterized by transmission and scanning electron microscopy, X-ray diffraction and density measurements. The main Raman line in the boehmite phase is red-shifted as well as asymmetrically broadened with respect to that in the crystalline boehmite, signifying the nanocrystalline nature of the gel. Raman signatures are absent in the gamma- and delta-phases due to the disorder in cation vacancies. We also show that low frequency Raman scattering from the boehmite phase resembles that from a fractal network, characterized in terms of fraction dimension ($) over tilde d. Taking Hausdorff dimension D of the boehmite gel to be 2.5 (or 3.0), the value of ($) over tilde d is 1.33 +/- 0.02 (or 1.44 +/- 0.02), which is close to the theoretically predicted value of 4/3.