Electrical properties and Schottky diodes using N-N′diphenyl-1-4phenylenediamine

Thin films of, N-N′diphenyl 1-4phenylene-diamineane are prepared using vacuum sublimation technique. The electrical conductivity from room temperature down to 127 K is studied. It is found that the conduction of charge carriers obeys T^−1/2 dependence on temperature. The average hopping distance, hopping energy, density of states and their variation due to post-deposition heat treatment are studied. Schottky diodes are fabricated with gold as ohmic contact and aluminium as Schottky contact. From the observed current voltage characteristics the saturation current density, diode ideality factor and the barrier height are determined. Their variation with air annealing is also investigated.     

An Anthracene-Based Metal-Organic Framework for Selective Photo-Reduction of Carbon Dioxide to Formic Acid Coupled with Water Oxidation

A Zr-based metal-organic framework has been synthesized and employed as a catalyst for photochemical carbon dioxide reduction coupled with water oxidation. The catalyst shows significant carbon dioxide reduction property with concomitant water oxidation. The catalyst has broad visible light as well as UV light absorption property, which is further confirmed from electronic absorption spectroscopy. Formic acid was the only reduced product from carbon dioxide with a turn-over frequency (TOF) of 0.69 h⁻¹ in addition to oxygen, which was produced with a TOF of 0.54 h⁻¹. No external photosensitizer is used and the ligand itself acts as the light harvester. The efficient and selective photochemical carbon dioxide reduction to formic acid with concomitant water oxidation using Zr-based MOF as catalyst is thus demonstrated here.     

Synthesis and cytotoxicity evaluation of diastereoisomers and N-terminal analogues of tubulysin-U

Tubulysins are potent anti-mitotic natural compounds and a scalable and efficient synthetic route for generation of its analogues has been developed and extended to the synthesis of diastereoisomers and N-terminal analogues of tubulysin-U. Structure–activity-relationship studies on these synthetic analogues reaffirmed the significance of native stereochemistry of tubulysins for optimal biological activity and cytotoxicity. However, while modification of Tup stereochemistry has only minor effect on the tubulysins cytotoxicity, Tuv stereochemistry is critically important and modification of either Tuv stereocentre produced a dramatic drop in cytotoxicity.     

Enhanced ethanol sensing properties of WO3 modified TiO2 nanorods

Pristine and WO₃ decorated TiO₂ nanorods (NRs) were synthesised to investigate n-n-type heterojunction gas sensing properties. TiO₂ NRs were fabricated via hydrothermal method on fluorine-doped tin oxide coated glass (FTO) substrates. Then, tungsten was sputtered on the TiO₂ NRs and thermally oxidised to obtain WO₃ nanoparticles. The heterostructure was characterised by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive X-ray (EDX) spectroscopy. Fabricated sensor devices were exposed to VOCs such as toluene, xylene, acetone and ethanol, and humidity at different operation temperatures. Experimental results demonstrated that the heterostructure has better sensor response toward ethanol at 200 °C. Enhanced sensing properties are attributed to the heterojunction formation by decorating TiO₂ NRs with WO₃.     

Flowerlike hybrid horseradish peroxidase nanobiocatalyst for the polymerization of guaiacol

In this study, the catalytic activity and stability of flowerlike hybrid horseradish peroxidase (HRP) nanobiocatalyst (HRP-Cu ²⁺ ) obtained from Cu ²⁺ ions and HRP enzyme in the polymerization reaction of guaiacol were analyzed. We demonstrated that HRP-Cu ²⁺ and hydrogen peroxide (H ₂ O ₂ ) initiator showed significantly increased catalytic activity and stability on the polymerization of guaiacol compared to that of free HRP enzyme. Poly(guaiacol) was observed with quite high yields (88%) and molecular weights (38,000 g/mol) under pH 7.4 phosphate-buffered saline (PBS) conditions at 60 °C with 5 weight% of HRP-Cu ²⁺ loading. HRP-Cu ²⁺ also shows very high thermal stability and works even at 70 °C reaction temperature; free HRP enzyme denatures at that temperature. Furthermore, HRP-Cu ²⁺ provided considerable repeated use and showed some degree of catalytic activity, even after the fourth recycle, in the polymerization of guaiacol.     

Chemical composition,antimicrobial, and lipase enzyme activity of essential oil and solvent extracts from Serapias orientalis subsp. orientalis

The volatile components of essential oil (EO), SPME, and SPME of solvent extracts ( n -hexane, methanol, and water) obtained from fresh Serapias orientalis subsp. orientalis ( Soo ) were analyzed by GC-FID/MS. EO of Soo gave 11 compounds in the percentage of 99.97%; capronaldehyde (37.01%), 2-( E )-hexenal (23.19%), and n -nonanal (19.05%) were found to be major constituents. SPME GC-FID/MS analyses of fresh plant and solvent extracts of Soo revealed 7, 12, 7, and 4 compounds within the range of 99.7% to 99.9%. Limonene (76.5%, 41.7%, and 61.3%) was the major compound in SPMEs of the n -hexane and methanol extracts. α -Methoxy- p -cresol (52.9%) was the main component in its water extract. The antimicrobial activity of EO and the solvent extracts of Soo were screened against 9microorganisms. EO showed the best activity against Mycobacterium smegmatis , with 79.5 µg/mL MIC value. The n -hexane, methanol, and water extracts were the most active against the Staphylococcus aureus within the range of 81.25–125.0 µg/mL (MIC). IC ₅₀ values for the lipase enzyme inhibitory activity of EO and solvent extracts ( n -hexane, methanol, and water) were determined to be 59.87 µg/mL, 64.03 µg/mL, 101.91 µg/mL, and 121.24 µg/mL, respectively.     

Low voltage electrodeposition of CNx films and study of the effect of the deposition voltage on bonding configurations

Carbon nitride (CN_x) films were deposited from acetonitrile at low voltage (150-450 V) through electrodeposition. The films were characterized by atomic force microscopy (AFM), Raman spectroscopy and Fourier transform infrared (FT-IR) spectroscopy. AFM investigations revealed that the grain size was ∼200 nm and roughness was ∼10 nm. The films were found to be continuous and close packed. IR spectra revealed existence of strong sp³, sp² type bonding and weak sp type carbon nitrogen bonds and these bonds were found to increase with voltage. The fraction of sp³-bonded species in the sample increased in low voltage range and after reaching maximum at 350 V, decreased for higher voltages. However, the concentration of sp² CN ring structures in the film increased with increasing voltage. Also, the peak width decreased at low voltages reaching a minimum and increased thereafter. It was observed that the voltage dependent increase in the concentration of polymeric type sp² CN (chain) structures was much more pronounced than that of graphitic type sp² CN (ring) structures. Raman spectra showed the presence of both the D and G bands. The shift in the G band indicated the presence of nitrogen in the film. The I_D/I_G ratio was found to increase with the incorporation of nitrogen. Auger electron spectroscopy (AES) showed a clear increase in the nitrogen content with increase in the voltage. The formation of the film could be explained on the basis of dissociation of electrolyte under applied voltage.     

Conformational control in a bipyridine linked π-conjugated oligomer: cation mediated helix unfolding and refolding

A chiral π-conjugated oligomer having alternate bipyridine and carbazole moieties connected through acetylinic bonds undergoes helical folding in chloroform-acetonitrile (40/60, v/v) as evident by fluorescence and circular dichroism changes. In the presence of transition metal cations such as Zn(2+) defolding of the helical conformation occurs. Upon decomplexation of the cation with EDTA, the helical conformation is regained.     

Development of an HPLC method for determination of pentachloronitrobenzene, hexachlorobenzene and their possible metabolites

Background

Pentachloronitrobenzene (PCNB) and hexachlorobenzene (HCB) are highly toxic and widespread in every environmental compartment. Some of metabolic products such as amino/nitro containing chlorinated aromatic compounds can be determined by gas chromatography coupled with electron capture detector (GC-ECD). However, it is difficult to identify some of chlorophenolic and chloroquinolic intermediates produced from PCNB and HCB by the above mentioned technique. Therefore, for analysis of these compounds and their metabolites, we have developed a high performance liquid chromatography (HPLC) based method.

Results

The extraction of PCNB and HCB from soil and minimal salt medium was carried out with ethyl acetate and hexane respectively with good recoveries (98% for PCNB and 97% for HCB). The validation of the proposed extraction and HPLC method was done by analysis of PCNB and HCB biodegradation and their metabolites identification from anaerobic enriched soil samples.

Conclusion

A rapid, sensitive and simple HPLC based analytical method was developed for the analysis of PCNB, HCB and their possible intermediates.     

Surface‐State‐Mediated Charge‐Transfer Dynamics in CdTe/CdSe Core–Shell Quantum Dots

Herein, we report the synthesis of aqueous CdTe/CdSe type‐II core–shell quantum dots (QDs) in which 3‐mercaptopropionic acid is used as the capping agent. The CdTe QDs and CdTe/CdSe core–shell QDs are characterized by X‐ray diffraction (XRD), high‐resolution transmission electron microscopy (HR‐TEM), steady‐state absorption, and emission spectroscopy. A red shift in the steady‐state absorption and emission bands is observed with increasing CdSe shell thickness over CdTe QDs. The XRD pattern indicates that the peaks are shifted to higher angles after growth of the CdSe shell on the CdTe QDs. HR‐TEM images of both CdTe and CdTe/CdSe QDs indicate that the particles are spherical, with a good shape homogeneity, and that the particle size increases by about 2 nm after shell formation. In the time‐resolved emission studies, we observe that the average emission lifetime (τ_av) increases to 23.5 ns for CdTe/CdSe (for the thickest shell) as compared to CdTe QDs (τ_av=12 ns). The twofold increment in the average emission lifetime indicates an efficient charge separation in type‐II CdTe/CdSe core–shell QDs. Transient absorption studies suggest that both the carrier cooling and the charge‐transfer dynamics are affected by the presence of traps in the CdTe QDs and CdTe/CdSe core–shell QDs. Carrier quenching experiments indicate that hole traps strongly affect the carrier cooling dynamics in CdTe/CdSe core–shell QDs.