Photochemistry of Far Red Responsive Tetrahydroquinoxaline-Based Squaraine Dyes

The photochemical and redox properties of two newly synthesized tetrahydroquinoxaline-based squaraine dyes (SQ) are investigated Using femto- and nanosecond laser flash photolysis, pulse radiolysis, and cyclic voltammetry. In acetonitrile and dichloromethane, these squaraines exist its monomers in the zwitterionic form (lambda(max) approximate to 715 nm, epsilon(max) approximate to 1.66 x 10(5) M-1 cm(-1) in acetonitrile). Their excited sin-let states ((1)SQ*) exhibit a broad absorption hand at 480 nm, with singlet lifetimes of 44 and 123 ps for the two dyes. Both squaraines exhibit poor intersystem crossing efficiency (Phi(ISC) < 0.001). Their excited triplet states ((3)SQ*), however, Ire efficiently generated by triplet-triplet energy transfer Using triplet excited 9,10-dibromoanthracene. The excited triplet states of the squaraines dyes exhibit it broad absorption hand at ca. 560 nm (epsilon(triplet) approximate to 4.2 x 10(4) M-1 cm(-1)) and undergo deactivation via triplet-triplet annihilation and ground-state quenching processes. The oxidized forms of the investigated squaraines (SQ(center dot+)) exhibit absorption maxima at 510 and 610 nm.

Peptide mimics for structural features in proteins. Crystal structures of three heptapeptide helices with a C-terminal 6-->1 hydrogen bond.

The crystal structure determination of three heptapeptides containing alpha-aminoisobutyryl (Aib) residues as a means of helix stabilization provides a high-resolution characterization of 6-->1 hydrogen-bonded conformations, reminiscent of helix-terminating structural features in proteins. The crystal parameters for the three peptides, Boc-Val-Aib-X-Aib-Ala-Aib-Y-OMe, where X and Y are Phe, Leu (I), Leu, Phe (II) and Leu, Leu (III) are: (I) space group P1, Z = 1, a = 9.903 A, b = 10.709 A, c = 11.969 A, alpha = 102.94 degrees, beta = 103.41 degrees, gamma = 92.72 degrees, R = 4.55%; (II) space group P21, Z = 2, a = 10.052 A, b = 17.653 A, c = 13.510 A, beta = 108.45 degrees, R = 4.49%; (III) space group P1, Z = 2 (two independent molecules IIIa and IIIb in the asymmetric unit), a = 10.833 A, b = 13.850 A, c = 16.928 A, alpha = 99.77 degrees, beta = 105.90 degrees, gamma = 90.64 degrees, R = 8.54%. In all cases the helices form 3(10)/alpha-helical (or 3(10)helical) structures, with helical columns formed by head-to-tail hydrogen bonding. The helices assemble in an all-parallel motif in crystals I and III and in an antiparallel motif in II. In the four crystallographically characterized molecules, I, II, IIIa and IIIb, Aib(6) adopts a left-handed helical (hL) conformation with positive phi, psi values, resulting in 6-->1 hydrogen-bond formation between Aib(2) CO and Leu(7)/Phe(7) NH groups. In addition a 4-->1 hydrogen bond is seen between Aib(3) CO and Aib(6) NH groups. This pattern of hydrogen bonding is often observed at the C-terminus of helices proteins, with the terminal pi-type turn being formed by four residues adopting the hRhRhRhL conformation.

Biosynthesis of valine and isoleucine in plants I. Formation of α-acetolactate in Phaseolus radiatus

1. 1. The presence of an enzyme system in plants catalyzing the formation of α-acetolactate from pyruvate has been demonstrated; the system in green gram (Phaseolus radiatus) has been partially purified and its characteristics have been studied.2. Free acetaldehyde is formed as a product of the reaction and so the reaction is mainly diverted towards the formation of acetoin. 3. The system requires thiamine pyrophosphate and a divalent metal ion (Mn2+ or Mg2+) for maximum activity. The optimum pH is around 6.0 and the optimum temperature is 60°. 4. The system is very labile in absence of pyruvate, Mn2+ and DPT. 5. The Km values for pyruvate, Mn2+, Mg2+ and DPT are 3·10−2 M. 5·10−5 M, 2·10−5 M, and e·10−6 M respectively. The activation energy is 3540 cal/mole. 6. The enzyme is strongly inhibited by p-chloromercuribenzoate and the inhibition can be reversed partially by 2-mercaptoethanol, BAL or cysteine. Heavy metals, such as Hg2+ and Ag+, are inhibitory but l-valine does not inhibit the reaction.

Porphyrin synthesis in drug induced hepatic porphyria

Liver δ-aminolaevulate (ALA) synthetase and ALA dehydratase are induced to a greater extent in 3,5-diethoxy carbonyl-1,4-dihydrocollidine (DDC) injected mice as compared to the allyl isopropyl acetamide (AIA) injected rats. DDC treated mice do not show an increase in porphobilinogen (PEG) levels commensurate with the increase in ALA levels and the two enzyme activities, but accumulate enormous quantities of protoporphyrin in the liver. Normal mouse liver has an inherent greater capacity to convert PBG to porphyrins as compared to that of the rat. This together with the inhibition of iron incorporation into protoporphyrin in vivo at later stages of DDC administration can account for the large accumulation of protoporphyrin in these animals.

Studies on the brookite-rutile transformation

Brookite, the orthorhombic modification of titanium dioxide, transforms to the tetragonal modification, rutile, on heating. The kinetics and energetics of the transformation have been studied. Below 715±10°C, the rate of transformation is extremely slow. There appears to be little or no induction time. The kinetic data can be fitted reasonably well by the first-order equation. The energy of activation is about 60 kcal/mole and the frequency factor is of the order of 1013 h-1. The entropy of activation from Eyring's theory is about -18 cal/mole deg. at 800°C. The heat of this transformation is -100±75 cal/mole. The kinetic results may be explained qualitatively in terms of various analogies but more clearly by the application of the order-disorder theory to diffusionless transformation in solids. It has been shown that the ratio of propagation rate constant to the nucleation rate constant is small and that there is little or negligible phase aggregation.

Studies on induction of delta-aminolevulinic acid synthetase in mouse liver

Administration of 3,5-diethoxy carbonyl-1,4-dihydrocollidine (DDC) to mice resulted in a striking increase in the level of δ-aminolevulinic acid (ALA) synthetase in liver. Although the enzyme activity was primarily localized in mitochondria and postmicrosomal supernatant fluid, a significant level of activity was also detected in purified nuclei. The time course of induction showed a close parallelism between the bound and free enzyme activities with the former always accounting for a higher percentage of the total activity as compared to the latter. Studies with cycloheximide indicated a half-life of around 3 hr for both the bound and free ALA synthetase. Actinomycin D and hemin prevented enzyme induction when administered along with DDC, but when administered 12 hr after DDC treatment Actinomycin D did not lead to a decay of either the bound or free enzyme activity and hemin inhibited the bound enzyme activity but not the free enzyme level. The molecular sizes of the mitochondrial and cytosolic ALA synthetase(s) were found to be similar on sephadex columns.

Transfer of F- in the reaction of SF6- with SOF4: Implications for SOF4 production in corona discharges

The temperature (T) and electric field-to-gas pressure (E/P) dependences of the rate coefficientk for the reaction SF 6 � +SOF4rarrSOF 5 � +SF5 have been measured. ForT<270>k approaches a constant of 2.1×10�9 cm3/s, and for 433>T>270 K,k decreases withT according tok (cm3/s)=0.124 exp [�3.3 lnT(K)]. ForE/Pk has a constant value of about 2.5×10�10 cm3/s, and for 130 V/cm·torr>E/P>60 V/cm·torr, the rate is approximately given byk (cm3/s)sim7.0×10�10 exp (�0.022E/P). The measured rate coefficient is used to estimate the influence of this reaction on SOF4 production from negative, point-plane, glow-type corona discharges in gas mixtures containing SF6 and at least trace amounts of O2 and H2O. A chemical kinetics model of the ion-drift region in the discharge gap is used to fit experimental data on SOF4 yields assuming that the SF 6 � +SOF4 reaction is the predominant SOF4 loss mechanism. It is found that the contribution of this reaction to SOF4 destruction falls considerably below the estimated maximum effect assuming that SF 6 � is the predominant charge carrier which reacts only with SOF4. The results of this analysis suggest that SF 6 � is efficiently deactivated by other reactions, and the influence of SF 6 � +SOF4 on SOF4 production is not necessarily more significant than that of other slower secondary processes such as gas-phase hydrolysis

Dispersion of resistivity anomalies in critical binary liquid systems

The critical resistivity in the binary liquid systems n-C7H16 + CH3OH and CS2 + CH3NO2 is measured from 10 Hz to 100 kHz. There is no noticeable effect of the frequency on the resistivity singularities. Thus any contribution from dielectric dispersion is not appreciable.

Studies of cryotreatment on the performance of integral diaphragm pressure transducers for space application

The integral diaphragm pressure transducers machined out of precipitation hardened martensite stainless steel (APX4) are widely used for propellant pressure measurements in space applications. These transducers are expected to exhibit dimensional stability and linearity for their entire useful life. These vital factors are very critical for the reliable performance and dependability of the pressure transducers. However, these transducers invariably develop internal stresses during various stages of machining. These stresses have an adverse effect on the performance of the transducers causing deviation from linearity. In order to eliminate these possibilities, it was planned to cryotreat the machined transducers to improve both the long-term linearity and dimensional stability. To study these effects, an experimental cryotreatment unit was designed and developed based on the concept of indirect cooling using the concept of cold nitrogen gas forced closed loop convection currents. The system has the capability of cryotreating large number of samples for varied rates of cooling, soaking and warm-up. After obtaining the initial levels of residual stress and retained austenite using X-ray diffraction techniques, the pressure transducers were cryotreated at 98 K for 36 h. Immediately after cryotreatment, the transducers were tempered at 510 degrees C for 3 h in vacuum furnace. Results after cryo treatment clearly indicated significant reduction in residual stress levels and conversion of retained austenite to martensite. These changes have brought in improvements in long term zero drift and dimensional stability. The cryotreated pressure transducers have been incorporated for actual space applications. (c) 2010 Published by Elsevier Ltd.

An assessment of the current Indian scene in biotechnology

Biotechnology holds great promise, and is sure to make an impact in India in the nineties. The role of the government's Department of Biotechnology in focusing attention and resources on crucial problems and in supporting basic research is laudable.

Photoconductivity in β-AgI

Excitation spectra and transient and steady-state photoconductivity have been studied in undoped and 0.8-mole% Cu-doped single-crystal β-AgI between 150 and 260°K. A single peak in the spectral response was found to occur in each case, at 2.88 eV for undoped and at 2.81 eV for copper-doped specimens at 260 K, the difference being due to a decrease in band gap. The anisotropy due to polarization of incident radiation parallel or perpendicular to the c direction, which is a measure of the energy difference between the Γ9 and Γ7 levels in the valence band, was found to be 0.010 eV. Transient-photoconductivity experiments showed that the hole lifetime was 6 μ sec at 300°K, an order of magnitude larger than the electron lifetime. The hole drift mobility was found to be 12±2 cm2/ V sec at 300°K and limited by traps at a depth of 0.51±0.01 eV with concentration (3-5)×109/cm3 and capture cross section 10-11 cm2. The study of photoconductivity decay versus temperature revealed the presence of shallow hole traps at 0.14±0.02 eV with concentration greater than 1016/cm3 and capture cross section 10-19 cm2. The steady-state photoconductivity was determined by the deep hole traps at 0.51 eV, and showed the presence of shallow electron traps at a depth of 0.28 eV. The trap distribution was found to be substantially the same in pure and copper-doped specimens, indicating the monovalent substitutional role of copper. The effects of iodine annealing, cadmium doping, and heating above the transition temperature were also studied. The possible nature of the traps is discussed.

Jahn-Teller effect induced phase transitions in CsCuCl3

Occurence of the three Jahn-Teller effect induced phase transitions of CsCuCl3 at 423, 510 and 535 K has been established and the nature of the transitions examined by X-ray crystallography, far infrared spectroscopy and other techniques.

Jahn-Teller effect induced phase transitions in CsCuCl3

Occurence of the three Jahn-Teller effect induced phase transitions of CsCuCl3 at 423, 510 and 535 K has been established and the nature of the transitions examined by X-ray crystallography, far infrared spectroscopy and other techniques.

Synthesis and catalytic properties of cobalt- and molybdenum-containing mesoporous MCM-41 molecular sieves

Mesoporous MCM-41 type silicas containing molybdenum and cobalt have been prepared with pore sizes in the range 30-38 Angstrom and 54-59 Angstrom. Catalytic properties of these materials have been examined with respect to the oxidation of cyclooctene and aniline.

Identification of a core promoter and a novel isoform of the human TSCI gene transcript and structural comparison with mouse homolog

Tuberous sclerosis complex (TSC) is an autosomal dominant disorder with loci on chromosome 9q34.12 (TSC1) and chromosome 16p13.3 (TSC2). Genes for both loci have been isolated and characterized. The promoters of both genes have not been characterized so far and little is known about the regulation of these genes. This study reports the characterization of the human TSC1 promoter region for the first time. We have identified a novel alternative isoform in the 5' untranslated region (UTR) of the TSC1 gene transcript involving exon 1. Alternative isoforms in the 5' UTR of the mouse Tsc1 gene transcript involving exon I and exon 2 have also been identified. We have identified three upstream open reading frames (uORFs) in the 5' UTR of the TSC1/Tsc1 gene. A comparative study of the 5' UTR of TSC1/Tsc1 gene has revealed that there is a high degree of similarity not only in the sequence but also in the splicing pattern of both human and mouse TSC1 genes. We have used PCR methodology to isolate approximately 1.6 kb genomic DNA 5' to the TSC1 cDNA. This sequence has directed a high level of expression of luciferase activity in both HeLa and HepG2 cells. Successive 5' and 3' deletion analysis has suggested that a -587 bp region, from position +77 to -510 from the transcription start site (TSS), contains the promoter activity. Interestingly, this region contains no consensus TATA box or CAAT box. However, a 521-bp fragment surrounding the TSS exhibits the characteristics of a CpG island which overlaps with the promoter region. The identification of the TSC1 promoter region will help in designing a suitable strategy to identify mutations in this region in patients who do not show any mutations in the coding regions. It will also help to study the regulation of the TSC1 gene and its role in tumorigenesis. (C) 2003 Elsevier B.V. All rights reserved.