Enantioselective solvent-free Robinson annulation reactions

The enantioselective cyclization of the prochiral cyclic substrates1 to7 and26, can be carried out in theneat using S-proline as catalyst. The substrates18 to22 and27 could not be cyclized with S-proline but could be cyclized with a mixture of S-phenylalanine and d-camphorsulphonic acid. The enantioselective cyclization of prochiral acyclic triones45 and47 and also the racemic tricarbonyl compounds54 to57 could also be carried out in theneat using S-proline as catalyst. The optically active enediones obtained in the above cyclizations could also be obtained directly from 1,3-diones or 2-hydroxymethylene cycloalkanones in a one-pot reaction with methyl vinyl ketone (MVK) and S-proline in the absence of solvents.¹³C NMR studies of the one-pot synthesis ofS-11 andS-14 reveal that the annulations involve initial formation of an acid-base complex followed by a Michael reaction and then an enantioselective cyclization. Such enantioselective cyclizations probably occur on the surface of S-proline crystals.     

An improved turbidimetric procedure for the determination of sulphate in plants and soils

A rapid turbidimetric procedure for the determination of sulphate in soils and plants has been developed with sorbitol as stabilizing agent. When used in a concentration of 20% in the final volume, the sorbitol regulates the size of the BaSO(4) particles formed and stabilizes them against sedimentation, growth and aggregation for long periods of time. The conditions of precipitation are not rigorous, as they are in similar procedures. Linearity of the calibration curve up to 50 ppm of sulphate and good reproducibility are special attributes of the procedure.     

Base catalyzed rearrangement of some bicyclic ketol acetates.

The ketol $\text{3a}$ and its acetate $\text{3b}$ when refluxed in methanolic potassium hydroxide (5%) were found to rearrange to 4-methyl-8-acetyl-5,6,7,8-tetrahydro-1-naphthol $\text{4}$. The epimeric acetate $\text{3c}$ also behaved likewise. A mechanism is suggested for the rearrangement.     

Black Hole Hawking Radiation May Never Be Observed!

Thermal Hawking emission from black holes is a remarkable consequence of the unification of quantum physics and gravitation. Black holes of a few solar masses are the only ones which can form in the present universe. However, having temperatures million times smaller than the ambient cosmic background radiation they cannot evaporate. Primordial black holes of M 10¹⁴g would evaporate over a Hubble age and considerable ongoing effort is on to detect such explosions. I point out, however, that at the early universe epochs when such black holes form, the ambient radiation temperature considerably exceeds their corresponding Hawking temperature. This results in rapid continual accretion (absorption) of ambient radiation by these holes. Consequently by the end of the radiation era their masses grow much greater so that their lifetimes (scaling as M³) would now be enormously greater than the Hubble age implying undetectably small emission.     

Fifth force as a manifestation of torsion

A deviation from the Newtonian inverse square law can arise from torsion coupling.     

Kaluza-Klein space and strong gravity

A study of strong gravity theory is carried out in five-dimensional Kaluza-Klein space-time. A relation between the cosmological constant and the radius parameter of the fifth dimension is obtained. The effect of the extra dimension is seen through the generation of masses simulating a Regge-like mass spectrum. It is found that the confinement mechanism is built into the strong gravity formalism. We also discuss the trapping of quarks in the 5D background.     

Study of MILD combustion using LES and advanced analysis tools

A cylindrical confined combustor operating under MILD condition is investigated using LES. The combustion and its interaction with turbulence are modeled using two reactor based models, PaSR and EDC. Results show that the Partially Stirred Reactor (PaSR) model yields improved estimation for mean temperature and species mole fractions compared to Eddy Dissipation Concept (EDC). LES data are analysed using advanced post-processing methods such as the chemical Tangential Stretching Rate (TSR), balance analysis and local Principle Component (PCA) analysis. TSR can identify chemical explosive (ignition-like) and contractive (burnt) regions. With the balance analysis of the convective, diffusive and reactive terms in temperature equation, regions with substantial heat release coming from ignition or flame are identified. The local PCA analysis classifies the whole domain into clusters (regions with specific features) and provides the leading species in each cluster. The three analyses correlate well with one another and it is observed that the most chemically active region locates upstream (in the near-field). Also, both autoignition and flame-like structures play equally important roles in MILD combustion.     

Validation of Sun Exposure Reported Annually Against Interim Self‐report and Daily Sun Diaries

Data on personal sun exposure over a period exceeding the immediate past days or weeks are typically self‐reported in brief questionnaire items. The validity of such self‐reporting of longer term personal sun exposure, for example over a year, including detail on variation across seasons, has not previously been investigated. In a volunteer sample (n = 331) of Australian adults aged 18 years and over, we assessed the 12‐month reliability of sun exposure reported separately for each season, and its accuracy compared to a daily sun diary in the same season. Seasonal time outdoors displayed fair‐to‐good reliability between baseline and end of study (12 months), with responses showing higher agreement at lower levels of time outdoors. There was good agreement for ranking of individuals' time outdoors with the daily sun diary data, although the actual diary time outdoors was typically considerably lower than the self‐reported questionnaire data. Place of residence, education, being a smoker, day of the week (i.e. working day vs nonworking day) and working mainly outdoors were significant predictors of agreement. While participants overestimated their actual time outdoors, the self‐report questionnaire provided a valid ranking of long‐term sun exposure against others in the study that was reliable over time.     

Uncertainty principle limits on the cosmological constant

The identification of the cosmological constant term with the energy density of the vacuum enables lower and upper limits to be placed on its value. The upper limit arises from the constraint that the total zero-point energy, which also gravitates, should not dominate cosmological dynamics, while the lower limit can result from the operational requirement that the vacuum-energy shifts over atomic or nuclear scales be at least measurable over Hubble time scales.