Automatic off/on-line preconcentration for ICP-OES: Powerful instrumentation for water analysis

Automated preconcentration techniques for off/on-line determination with ICP-OES have been developed for various metal ions of environmental interest. Preconcentration studies were performed on two different types of chemically bonded chelating ion-exchangers, namely EDTrA-cellulose (iminoacetate groups) and HSO₃ · oxine-cellulose. Enrichment studies were carried out at various preconcentration factors and also at different loadings.Presented in part at the 1989 European Winter Conference on Plasma Spectrochemistry, Reutte, Austria     

Optical pumping and coherence effects in fluorescence from a four level system

An effective four-level system around the D2 line of ⁸⁵Rb at room temperature, is experimentally investigated by fluorescent studies under the action of two driving fields L1 and L2. This system exhibits unique features in fluorescence as a function of frequency separation between L1 and L2. In particular, at two-photon resonance, when the Rabi frequency of L1 exceeds that of L2, signatures of Electromagnetically Induced Transperancy effect (EIT) arising from the three-level Λ sub-system is present as a sub-natural dip in fluorescence from the fourth level. At comparable strengths of L1 and L2 the fluorescence features indicate a regime, where the effects arising from optical pumping and EIT effect due to ground hyperfine level coherence coexist. We see in the coexistence regime, saturation effects arising from difference frequency crossing (DFC) resonances and optical pumping around the EIT window. At low strengths of L1, all signs of coherence vanishes from the system and the fluorescent features result from incoherent optical pumping through the Autler-Townes split states of the excited state hyperfine levels, which are split due to the stronger L2 laser. The dominant role of the L1 laser in creating a robust transparency signal even in the presence of an off-resonant excitation is brought out. The results are supported by density matrix calculations.     

An Ethenoadenine FAD Analog Accelerates UV Dimer Repair by DNA Photolyase

Reduced anionic flavin adenine dinucleotide (FADH^?) is the critical cofactor in DNA photolyase (PL) for the repair of cyclobutane pyrimidine dimers (CPD) in UV‐damaged DNA. The initial step involves photoinduced electron transfer from *FADH^? to the CPD. The adenine (Ade) moiety is nearly stacked with the flavin ring, an unusual conformation compared to other FAD‐dependent proteins. The role of this proximity has not been unequivocally elucidated. Some studies suggest that Ade is a radical intermediate, but others conclude that Ade modulates the electron transfer rate constant (k_ET) through superexchange. No study has succeeded in removing or modifying this Ade to test these hypotheses. Here, FAD analogs containing either an ethano‐ or etheno‐bridged Ade between the AN1 and AN6 atoms (e‐FAD and ε‐FAD, respectively) were used to reconstitute apo‐PL, giving e‐PL and ε‐PL respectively. The reconstitution yield of e‐PL was very poor, suggesting that the hydrophobicity of the ethano group prevented its uptake, while ε‐PL showed 50% reconstitution yield. The substrate binding constants for ε‐PL and rPL were identical. ε‐PL showed a 15% higher steady‐state repair yield compared to FAD‐reconstituted photolyase (rPL). The acceleration of repair in ε‐PL is discussed in terms of an ε‐Ade radical intermediate vs superexchange mechanism.     

Integral equation formulation for buoyancy-driven convection problems

An integral equation formulation for buoyancy-driven convection problems is developed and illustrated. Buoyancy-driven convection in a bounded cylindrical geometry with a free surface is studied for a range of aspect ratios and Nusselt numbers. The critical Rayleigh number, the nature of the cellular motion, and the heat transfer enhancement are computed using linear theory. Green's functions are used to convert the linear problem into linear Fredholm integral equations. Theorems are proved which establish the properties of the eigenvalues and eigenfunctions of the linear integral operator which appears in these equations.     

Water-promoted unprecedented chemoselective nucleophilic substitution reactions of 1,4-quinones with oxygen nucleophiles in aqueous micelles

Unique nucleophilic substitution and addition reactions of nitrogen and sulfur nucleophiles with 1,4-quinones in aqueous suspension with amines and thiols have recently been demonstrated by us.² However, the reactivity of oxygen nucleophiles toward nucleophilic substitution compared to nitrogen and sulfur nucleophiles ‘on water’ is not facile. An unprecedented economical, green methodology approach using ordinary laundry detergent (LD; washing powder, 0.5 mol %, reusable)/SDS as surfactant ‘in water’ for nucleophilic substitution by oxygen nucleophiles in 1,4-quinones in excellent yields has been demonstrated.     

Acoustic characteristics of chamfered Hartmann whistles

Experimental studies are conducted to investigate the effect of internal chamfer at the mouth of Hartmann resonators. Studies involve a range of nozzle pressure ratios from 4 to 6, and chamfer angles 15°, 30°, and 45°. Further, the effects of cavity length and stand-off distance are also considered. The spectra, directivity, and acoustic power characteristics are studied in detail. Detailed numerical simulations are carried out to capture the flow oscillations inside as well as at the outside of the mouth of the chamfered cavities. Computations show flow diversion in chamfered cavities and explain the shift in the directivity observed experimentally. The fundamental frequency of cavities with 15° and 30° chamfers is observed to be higher than that of regular cavities. Resonance is intensified by the presence of chamfer resulting in higher overall sound pressure levels of chamfered whistles. Thus, chamfered Hartmann whistles are found to emit more than twice the acoustic power of a regular cylindrical whistle. The tonal quality of sound is analyzed using a new metric termed as “resonance index”.     

Heteronuclear dipolar decoupling in solid-state nuclear magnetic resonance under ultra-high magic-angle spinning

We compare in this communication several heteronuclear dipolar decoupling sequences in solid-state nuclear magnetic resonance experiments under a magic-angle spinning frequency of 60 kHz. The decoupling radiofrequency field amplitudes considered are 190 and 10 kHz. No substantial difference was found among the sequences considered here in performance barring the difference in the optimisation protocol of the various schemes, an aspect that favours the use of swept-frequency two pulse phase modulation (SW(f)-TPPM).