Synthesis,Characterization, Covalent Binding,and Degree of Unwinding of Platinum(II) Bipyridine Complexes

The complexes [Pt(3′′‐clpbpy)Cl₂] ( 1 ) [3′′‐clpbpy = 4‐(3′′‐chlorophenyl)‐6‐phenyl‐2, 2′‐bipyridine], [Pt(4′′‐clpbpy)Cl₂] ( 2 ) [4′′‐clpbpy = 4‐(4′′‐chlorophenyl)‐6‐phenyl‐2, 2′‐bipyridine], [Pt(3′′‐brpbpy)Cl₂] ( 3 ) [3′′‐brpbpy = 4‐(3′′‐bromophenyl)‐6‐phenyl‐2, 2′‐bipyridine], and [Pt(4′′‐brpbpy)Cl₂] ( 4 ) [4′′‐brpbpy = 4‐(4′′‐bromophenyl)‐6‐phenyl‐2, 2′‐bipyridine] were synthesized and characterized. The binding of the complexes with herring sperm DNA (HS DNA) was investigated by absorption titration and viscosity measurements. It was found that the complexes have ability of interaction with DNA by covalent mode. The intrinsic binding constant K_b of the complexes with HS DNA is 8.76 × 10⁴ ( 1 ), 9.89 ×10⁴ ( 2 ), 1.52 × 10⁵ ( 3 ), and 2.31 × 10⁵ ( 4 ) M^–1. The slight depression in relative specific viscosity was observed, which also attributes to covalent binding of complexes with DNA bases. Gel electrophoresis assay demonstrated the ability of the complexes to unwind negatively supercoiled pUC19 plasmid by 14° ( 1 ), 13° ( 2 ), 13° ( 3 ), and 11° ( 4 ). The in vitro cytotoxic property of the synthesized metal complexes was also carried out against brine shrimp bioassay.     

Voltammetric studies of polyoxometalate microparticles in contact with the reactive distillable ionic liquid DIMCARB

The voltammetry of the polyoxometalate salts [Bu₄N]₄[SiW₁₂O₄₀] (α, β, γ* isomers), [Bu₄N]₄[S₂W₁₈O₆₂] (α, γ* isomers) and [Bu₄N]₄[S₂Mo₁₈O₆₂] (α isomer) has been studied in the “distillable ionic liquid” DIMCARB (a mixture of adducts, both ionic and neutral, of dimethylamine and carbon dioxide). Dissolution of these salts tended to be slow and the anions, except [α-SiW₁₂O₄₀]⁴⁻, reacted with DIMCARB. However, high quality voltammograms were obtained from microparticles of the salts adhered to a glassy carbon electrode in contact with DIMCARB. Rapid dissolution of the reduced forms of each of the polyoxometalate anions provided reversible potential data. The higher basicity of the more highly reduced anions promoted interactions with the acidic solvent component of this medium. Comparison of reversible potentials indicated that the polarity of DIMCARB is similar to CH₃CN, but smaller than that of conventional non-volatile ionic liquids and water.     

Site-selective glycosylation of hemoglobin with variable molecular weight oligosaccharides: potential alternative to PEGylation

Poly(ethylene glycol) (PEG) conjugation (i.e., PEGylation) is a commonly used strategy to increase the circulatory half-life of therapeutic proteins and colloids; however, few viable alternatives exist to replicate its functions. Herein, we report a method for the rapid site-selective glycosylation of proteins with variously sized carbohydrates, up to a molecular weight (MW) of 10,000, thus serving as a potential alternative for PEGylation. More importantly, the method developed has two unique features. First, traditional protecting group strategies that typically accompany the modification of the carbohydrate fragments are circumvented, allowing for the facile site-selective glycosylation of a desired protein with variously sized glycans. Second, the methodology employed is not limited by oligosaccharide size; consequently, glycans of MW similar to that of PEG, used in the PEGylation of therapeutic proteins, can be employed. To demonstrate the usefulness of this technology, hemoglobin (Hb) was site-selectively glycosylated with a series of carbohydrates of increasing MW (from 504 to ～10,000). Hb was selected on the basis of the vast wealth of biochemical and biophysical knowledge present in the literature and because of its use as a precursor in the synthesis/formulation of artificial red blood cell substitutes. Following the successful site-selective glycosylation of Hb, the impact of increasing the glycan MW on Hb's biophysical properties was investigated in vitro.     

Improvement of polarization extinction in silicon waveguide devices

The SOI based waveguide devices are found to be highly polarization sensitive. Unwanted polarization excitations can be attenuated by integrating a TE- or TM-pass polarizer. A large attenuation of TM-polarized light has been observed when a thin film of metal is coated on the top of silicon rib waveguide, while TE-polarized light remains almost unaffected. The attenuation of TM-polarized light is attributed to the plasmonic absorption of the evanescent field in the metal cladding. Typically, with an Al cladding of thickness ～ 100 nm and a length of 1 mm on top of a single-mode (λ ～ 1550 nm) SOI rib waveguide structure, TE vs TM extinction ratio of ～ 15 dB has been obtained. Integrating such waveguide polarizers in a directional coupler and MZI based DWDM channel interleaver, we have also achieved an improvement in polarization extinction by ～ 15 dB.     

Thorium free antireflection coating in MWIR region on Silicon optics

Most infrared transmitting optics have high refractive indices which in turn have high per surface reflection loss. So antireflection coating has very important role in increasing the transmission in the desired wavelength region. In this paper a study has been carried out on the design and fabrication of Thorium free antireflection coating effective for Silicon substrate in MWIR (3.6–4.9 μm) region. The wave band 3.6–4.9 μm is chosen for the reported work because the detected system used in MWIR region has a band selection filter effective in the same wavelength region. Comprehensive search method was used to design the multilayer stack on Silicon substrate. The coating materials used in the design were Germanium (Ge) and Silicon dioxide (SiO₂). The fabrication of coating was made in a coating plant fitted with Cryo pump system and Residual Gas Analyzer. The evaporation was carried out at high vacuum (2–6 × 10–6 mbar) using Electron Beam Gun and layer thicknesses were measured with crystal monitor. The result achieved for the antireflection coating was 96% average transmission in 3.6–4.9 μm band which withstood MIL-F-48616 environmental testing. This work provides an alternate antireflection coating on Silicon by replacing radioactive Thorium Fluoride, used as a coating material in most IR antireflection coating designs.     

Electronic structure of thin film iron-tetracyanoethylene: Fe(TCNE)<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>

Thin film iron-tetracyanoethylene Fe(TCNE) _x , x∼2, as determined by photoelectron spectroscopy, was grown in situ under ultra-high vacuum conditions using a recently developed physical vapor deposition-based technique for fabrication of oxygen- and precursor-free organic-based molecular magnets. Photoelectron spectroscopy results show no spurious trace elements in the films, and the iron is of Fe²⁺ valency. The highest occupied molecular orbital of Fe(TCNE) _x is located at ∼1.7 eV vs. Fermi level and is derived mainly from the TCNE⁻ singly occupied molecular orbital according to photoelectron spectroscopy and resonant photoelectron spectroscopy results. The Fe(3d)-derived states appear at higher binding energy, ∼4.5 eV, which is in contrast to V(TCNE)₂ where the highest occupied molecular orbital is mainly derived from V(3d) states. Fitting ligand field multiplet and charge transfer multiplet calculations to the Fe L-edge near edge X-ray absorption fine structure spectrum yields a high-spin Fe²⁺ (3d⁶) configuration with a crystal field parameter 10Dq∼0.6 eV for the Fe(TCNE) _x system. We propose that the significantly weaker Fe-TCNE ligand interaction as compared to the room temperature magnet V(TCNE)₂ (10Dq∼2.3 eV) is a strongly contributing factor to the substantially lower magnetic ordering temperature (T _C ) seen for Fe(TCNE) _x -type magnets.     

Interaction of Li ions with ethylene carbonate (EC): Density functional theory calculations

Electronic structures of Li⁺ ion-ethylene carbonate (EC) complexes were studied by density functional theory. The structural, electronic and dynamical properties of Li⁺-EC complexes were studied for both an isolated EC molecule and clusters including Li⁺ ion. Our structural analysis showed only one type of Li⁺ coordination with EC through Li⁺?OC which was supported by the vibration spectral analysis for interaction between Li⁺ ion and a solvent (EC) molecule. It was analyzed that the solvation energy and Mulliken charge of Li+ ion solvated by EC molecule decrease with increase in number of EC molecule. However, electron affinity shows the opposite change. This analysis with solvation energy, electron affinity and Mulliken charge supported the stabilization of 4-coordinated solvation shell among [Li⁺(EC)_n]_n=1-5 complexes.     

Trichloroisocyanuric acid mediated one-pot synthesis of 3,5-diarylisoxazoles from α,β-unsaturated ketones

A facile one-pot synthesis of 3,5-diarylisoxazoles from α,β-unsaturated ketones and hydroxylamine hydrochloride is reported. The reaction is efficiently promoted by trichloroisocyanuric acid (TCCA) to afford the desired products, mostly in high yields and in relatively short time. The mild nature of the synthesis and short reaction time are notable advantages of the developed protocol. This protocol is effective towards various substrates having different functionalities.     

Chaos in a non-autonomous nonlinear system describing asymmetric water wheels

We derive a water wheel model from first principles under the assumption of an asymmetric water wheel for which the water inflow rate is in general unsteady (modeled by an arbitrary function of time). Our model allows one to recover the asymmetric water wheel with steady flow rate, as well as the symmetric water wheel, as special cases. Under physically reasonable assumptions, we then reduce the underlying model into a non-autonomous nonlinear system. In order to determine parameter regimes giving chaotic dynamics in this non-autonomous nonlinear system, we consider an application of competitive modes analysis. In order to apply this method to a non-autonomous system, we are required to generalize the competitive modes analysis so that it is applicable to non-autonomous systems. The non-autonomous nonlinear water wheel model is shown to satisfy competitive modes conditions for chaos in certain parameter regimes, and we employ the obtained parameter regimes to construct the chaotic attractors. As anticipated, the asymmetric unsteady water wheel exhibits more disorder than does the asymmetric steady water wheel, which in turn is less regular than the symmetric steady state water wheel. Our results suggest that chaos should be fairly ubiquitous in the asymmetric water wheel model with unsteady inflow of water.