trans-Dichloro-bis-(arylazoimidazole)palladium(II): Synthesis, Structure, Photoisomerization, and DFT Calculation

Reaction between PdCl2 and 1-alkyl-2-(arylazo)imidazole (RaaiR') or 1-alkyl-2-(naphthyl-alpha/beta-azo)imidazole (alpha/beta-NaiR') under reflux in ethanol has isolated complexes of compositions Pd(RaaiR')(2)Cl-2 (5, 6) and Pd(alpha/beta-NaiR')(2)Cl-2 (7, 8). The X-ray structure determination of one of the molecules, Pd(alpha-NaiBz)(2)Cl-2 (7c), has reported a trans-PdCl2 configuration, and alpha-NaiBz acts as monodentate N(imidazole) donor ligand. The spectral (IR, UV-vis, H-1 NMR) data support the structure. UV light irradiation (light source: Perkin-Elmer LS 55 spectrofluorimeter, Xenon discharge lamp, lambda = 360-396 nm) in a MeCN solution of the complexes shows E-to-Z isomerization of the coordinated azoimidazole unit. The reverse transformation, Z-to-E, is very slow with visible light irradiation. Quantum yields (phi(E-Z)) of E-to-Z isomerization are calculated, and phi is lower than that of the free ligand but comparable with those of Cd(II) and Hg(II) complexes of the same ligand. The Z-to-E isomerization is a thermally induced process. The activation energy (E-a) of Z-to-E isomerization is calculated by controlled-temperature experimentation. cis-Pd(azoimidazole)Cl-2 complexes (azomidazole acts as N(imidazole) and N(azo) Chelating ligand) do not respond upon light irradiation, which supports the idea that the presence of noncoordinated azo-N to make free azo (-N=N-) function is important to reveal photochromic activity. DFT calculation of Pd(alpha-NaiBz)(2)Cl-2 (7c) has suggested that the HOMO of the molecule is constituted of Pd (32%) and Cl (66%), and hence photo excitation may use the energy of Pd and Cl instead of that of the photofunctional -N=N-Ar motif; thus, the rate of photoisomerization and quantum yield decrease versus the free ligand values.

Synthesis, crystal structures and protease activity of amino acid Schiff base iron(III) complexes

Iron(III) complexes, (NHEt3)[Fe(III)(sal-met)(2)] and (NHEt3)[Fe(III)(sal-phe)(2)], of amino acid Schiffbase ligands, viz., N-salicylidene-L-methionine and N-salicylidene L-phenylalanine, have been prepared and their binding to bovine serum albumin (BSA) and photo-induced BSA cleavage activity have been investigated. The complexes are structurally characterized by single crystal X-ray crystallography. The crystal Structures of the discrete mononuclear rnonoanionic complexes show FeN2O4 octahedral coordination geometry in which the tridentate dianionic amino acid Schiff base ligand binds through phenolate and carboxylate oxygen and imine nitrogen atoms. The imine nitrogen atoms are trans to each other. The Fe-O and Fe-N bond distances range between 1.9 and 2.1 angstrom. The sal-met complex has two pendant thiomethyl groups. The high-spin iron(III) complexes (mu(eff) similar to 5.9 mu(B)) exhibit quasi-reversible Fe(III)/Fe(II) redox process near -0.6 V vs. SCE in water. These complexes display a visible electronic hand near 480 nm in tris-HCl buffer assignable to the phenolate-to-iron(III) charge transfer transition. The water soluble complexes bind to BSA giving binding constant values of similar to 10(5) M-1. The Complexes show non-specific oxidative cleavage of BSA protein on photo-irradiation with UV-A light of 365 nm.

Novel ultrahigh resolution silverless photothermal imaging in obliquely deposited amorphous Se-Ge films

A new photothermal imaging process which utilizes no silver has been demonstrated in obliquely deposited Se-Ge films. Band-gap irradiation of Se-Ge films has been found to give rise to phases of the type SeOx, GeO, and Se as borne by x-ray initiated Auger electron spectroscopy and x-ray photoelectron spectroscopy. Annealing of SeOx leads to the formation of SeO2. The large (several orders of magnitude) difference in vapor pressures of SeO2 and Se-Ge films results in differential evaporation of the films when annealed around 200 °C, thereby leading to imaging. Such a large contrast in evaporation rates between the exposed and unexposed regions has great potential applications in high resolution image storage and phase holography. Applied Physics Letters is copyrighted by The American Institute of Physics.

Laser surface cladding of MRI 153M magnesium alloy with (Al+Al2O3)

Laser surface cladding was carried out on a creep-resistant MRI 153M magnesium alloy with a mixture of Al and Al2O3 powders using a pulsed Nd:YAG laser at scan speeds of 21, 42, 63 and 84 mm/s. The Al2O3 particles partially or completely melted during laser irradiation and re-solidified with irregular shapes in the size range of 5–60 µm along with a few islands as large as 500 µm, within the grain-refined Mg-rich dendritic matrix. More than an order of magnitude improvement in wear resistance after cladding was attributed to the presence of ultra-hard Al2O3 particles, increased solid solubility of Al and other alloying elements, and a very fine dendritic microstructure as a result of rapid solidification in the cladded layer. However, corrosion resistance of the laser cladded alloy was reduced by almost an order of magnitude compared to that of the as-cast alloy mainly due to the presence of cracks and pores in the cladded layer.

Structure-reactivity correlation in inclusion complexes: deoxycholic acid di-tert-butyl thioketone

Ultraviolet irradiation of crystalline molecular inclusion complexes of deoxycholic acid with di-tert-butyl thioketone results in no reaction. The structure of the above complex has been determined via X-ray diffraction. The absence of expected photoreactions. namely, photoreduction and photooxidation, is rationalized on the basis of the X-ray structure analysis of the complex.

Dynamics of the ammonium ion in the ferroelectric transition in sodium ammonium selenate, NaNH4SeO4·2H2O-an E.S.R. study

E.S.R. investigations of γ-irradiated ferroelectric Sodium ammonium selenate, NaNH4SeO4•2H2O and its deuteriated analogue in powder and single crystal forms have led to a deeper understanding of the nature of the ferroelectric transition of 180 K. A number of paramagnetic species formed due to γ-irradiation have been identified on the basis of their g-factors and hyperfine features from 77Se. The radical SeO4 has been used as a microprobe in studying the phase transition.

Effect of microwave radiation on seed mortality of rubber vine (Cryptostegia grandiflora R.Br.), parthenium (Parthenium hysterophorous L.) and bellyache bush (Jatropha gossypiifolia L.)

A trial was undertaken to evaluate the effect of microwaves on seed mortality of three weed species. Seeds of rubber vine (Cryptostegia grandiflora R.Br.), parthenium (Parthenium hysterophorous L.) and bellyache bush (Jatropha gossypiifolia L.) were buried at six depths (0, 2.5, 5, 10, 20 and 40 cm) in coarse sand maintained at one of two moisture levels, oven dry or wet (field capacity), and then subjected to one of five microwave radiation durations of (0, 2, 4, 8 and 16 min). Significant interactions between soil moisture level, microwave radiation duration, seed burial depth and species were detected for mortality of seeds of all three species. Maximum seed mortality of rubber vine (88%), parthenium (67%) and bellyache bush (94%) occurred in wet soil irradiated for 16 min. Maximum seed mortality of rubber vine and bellyache bush seeds occurred in seeds buried at 2.5 cm depth whereas that of parthenium occurred in seeds buried at 10 cm depth. Maximum soil temperatures of 114.1 and 87.5°C in dry and wet soil respectively occurred at 2.5 cm depth following 16 min irradiation. Irrespective of the greater soil temperatures recorded in dry soil, irradiating seeds in wet soil generally increased seed mortality 2.9-fold compared with dry soil. Moisture content of wet soil averaged 5.7% compared with 0.1% for dry soil. Results suggest that microwave radiation has the potential to kill seeds located in the soil seed bank. However, many factors, including weed species susceptibility, determine the effectiveness of microwave radiation on buried seeds. Microwave radiation may be an alternative to conventional methods at rapidly depleting soil seed banks in the field, particularly in relatively wet soils that contain long lived weed seeds.

The impact of inter-fraction set-up errors on the probability of pulmonary and cardiac complication in left-sided breast cancer patients

Purpose This study evaluated the impact of patient set-up errors on the probability of pulmonary and cardiac complications in the irradiation of left-sided breast cancer. Methods and Materials Using the CMS XiO Version 4.6 (CMS Inc., St Louis, MO) radiotherapy planning system's NTCP algorithm and the Lyman -Kutcher-Burman (LKB) model, we calculated the DVH indices for the ipsilateral lung and heart and the resultant normal tissue complication probabilities (NTCP) for radiation-induced pneumonitis and excess cardiac mortality in 12 left-sided breast cancer patients. Results Isocenter shifts in the posterior direction had the greatest effect on the lung V20, heart V25, mean and maximum doses to the lung and the heart. Dose volume histograms (DVH) results show that the ipsilateral lung V20 tolerance was exceeded in 58% of the patients after 1cm posterior shifts. Similarly, the heart V25 tolerance was exceeded after 1cm antero-posterior and left-right isocentric shifts in 70% of the patients. The baseline NTCPs for radiation-induced pneumonitis ranged from 0.73% - 3.4% with a mean value of 1.7%. The maximum reported NTCP for radiation-induced pneumonitis was 5.8% (mean 2.6%) after 1cm posterior isocentric shift. The NTCP for excess cardiac mortality were 0 % in 100% of the patients (n=12) before and after setup error simulations. Conclusions Set-up errors in left sided breast cancer patients have a statistically significant impact on the Lung NTCPs and DVH indices. However, with a central lung distance of 3cm or less (CLD <3cm), and a maximum heart distance of 1.5cm or less (MHD<1.5cm), the treatment plans could tolerate set-up errors of up to 1cm without any change in the NTCP to the heart.

Synthesis, Characterization, and Photocatalytic Properties of ZrMo2O8

ZrMo2O8 was synthesized via two routes, namely, the traditional solid-state method and the solution combustion method. The compounds were characterized by powder X-ray diffraction, UV−visible spectroscopy, scanning electron microscopy, and transmission electron microscopy. The crystals belong to a trigonal crystal system, space group P 1c (No. 163) with a = 10.1391(6) Å, c = 11.7084(8) Å, and Z = 6. The band gap of the compounds was around 2.7 eV, and DFT calculations suggest the indirect nature of the band gap. The irregular MoO4 tetrahedra create a dipole and inhibit the process of electron−hole recombination, thereby making the material photoactive. The photocatalytic activity of the compounds prepared by both routes has been investigated for the degradation of various dyes under UV irradiation, and this showed the specificity of the compounds towards the degradation of non-anthraquinonic dyes.

Ultrafine powders of SrTiO3 from the hydrothermal preparation and their catalytic activity in the photolysis of water

Ultrafine powders of SrTiO3 are prepared at 100–150°C by the hydrothermal method, starting from TiO2·xH2O gel and Sr(OH)2 and H2O-isopropanol mixed solvent as the medium, The X-ray diffractograms of the powder show line broadening. The minimum crystallite size obtained ranges from 5 to 20nm with 20% H2O-80% C3H7OH as the reaction medium, as estimated from X-ray half-peak widths and TEM studies. The electron diffraction results indicate high concentration of lattice defects in these crystallites. The optical spectra of the particle suspensions in water show that the absorption around the band gap is considerably broadened, together with the appearance of maxima in the far ultraviolet. Aqueous suspensions of SrTiO3 powders, as such, do not produce H2 or O2 on UV irradiation. After coating with rhodium, H2 and O2 are evolved on illumination. However, the turn over number of O2 is lower than the stoichiometrically expected values from the corresponding values of H2. No correlation of the photocatalytic activity with surface area is observed. The activity of Rh-SrTiO3 slowly deteriorates with extended period of irradiation.

EPR study of trap-centres produced on TiO2 particles during water photolysis

The results of an EPR investigation are presented on the paramagnetic trap-centres produced on hydrothermally prepared TiO2 particles during water photolysis at room temperature under band-gap irradiation. The trapped holes correspond to O− species adjacent to cation vacancies that are formed to compensate the hydroxyl ions in the subsurface layers. The trapped electrons are accounted for as Ti3+ in the conduction band or Ti3+ - adjoining oxygen vacancy to form shallow donor states. Although hole-centres are normally stabler than electron-centres, strongly adsorbed donor molecules reverse the stability. Concentration of hole-centres is increased by the presence of platinum on TiO2 surface and electron-centres are not detected on Pt/TiO2 during water photolysis.

Origin of anomalous photoinduced transformations in amorphous Ge-based chalcogenide thin films

Anomalous photoinduced transformations in amorphous Ge-based chalcogenide thin films are established as being due to photochemical modification of the surfaces, by photoemission studies. Mass measurements indicate that the giant thickness reduction on irradiation is predominantly due to the loss of material as a result of photogenerated volatile high vapor pressure oxide fractions on the surface. This extrinsic contribution contradicts the models of the phenomenon proposed so far, which are based purely on intrinsic structural transformations.

Room temperature gas sensing properties of ultrathin carbon nanotubes by surfactant-free dip coating

Large-scale production of reliable carbon nanotubes (CNTs) based gas sensors involves the development of scalable and reliable processes for the fabrication of films with controlled morphology. Here, we report for the first time on highly scalable, ultrathin CNT films, to be employed as conductometric sensors for NO2 and NH3 detection at room temperature. The sensing films are produced by dip coating using dissolved CNTs in chlorosulfonic acid as a working solution. This surfactant-free approach does not require any post-treatment for the removal of dispersants or any CNTs functionalization, thus promising high quality CNTs for better sensitivity and low production costs. The effect of CNT film thickness and defect density on the gas sensing properties has been investigated. Detection limits of 1 ppm for NO2 and 7 ppm for NH3 have been achieved at room temperature. The experimental results reveal that defect density and film thickness can be controlled to optimize the sensing response. Gas desorption has been accelerated by continuous in-situ UV irradiation.

An Electron-Microscopic Investigation Of Oxides Related To Beta-Alumina

High resolution electron microscopic (HREM) investigation of potassiumbeta-alumina and the related gallate and ferrite has revealed that whereas the aluminate and gallate are highly disordered, consisting of random sequence ofbeta andbetaPrime units, the ferrite is more ordered. The aluminate and gallate are sensitive to electron beam irradiation exhibiting beam-induced damage similar to sodiumbetaPrime-alumina. Significantly, the ferrite is beamstable, the difference in behaviour amongst these related oxides arising from the different mechanisms by which alkali metal nonstoichiometry is accommodated. Barium hexaaluminate and hexaferrite are both highly ordered; specimens prepared by the barium borate flux method exhibit a new radic3a×radic3a superstructure of the hexagonal magnetoplumbite cell.

Switching Process in Ferroelectric Triglycine Selenate

Triglycine selenate (TGSe) is isomorphous with Triglycine sulphate and is ferroelectric below 22°C. It is interesting to study the switching process in TGSe in the ferro-state with a view to comparing the results with TSG. The switching process was studied by applying electrical square pulses to produce fields up to 5 kV/cm on the sample, and measuring the parameters characterizing the transient current flowing in the sample, according to the Merz method. The temperature range in which the process was studied was 15°C to -20°C. The results were analysed by applying the Pulvari-Kuebler theory and the parameters α the activation field and µ the mobility of the domains were evaluated. It is found that µ varies with temperature in TGSe in a manner similar to TGS. µ is lesser for TGSe than for TGS for the same shift of temperature from Tc. The switching behaviour of γ-irradiated TGSe is qualitatively similar to that of unirradiated crystal eventhougth the process gets slowed down as a result of irradiation.