Theoretical Studies on Novel Gridspiroarenes: Structures,Noncovalent Interactions and Reorganization Energies

Organic semiconductor materials with low reorganization energy have various applications such as in organic light‐emitting diodes (OLEDs), organic field‐effect transistor (OFETs) and organic solar cells (OSCs). In this work, we have designed a new class of gridspiroarenes (GS‐SFX and GS‐SITF) with #‐shaped structures, which have novel crisscross geometrical structures compared to widely used spirocyclic arenes—SFX and SITF. The structure electronic properties, adiabatic ionization potentials (IP_a), adiabatic electron affinities (EA_a) and reorganization energies (λ) of GS‐SFX and GS‐SITF have been calculated using density functional theory (DFT) method. The calculated HOMO and LUMO spatial distributions suggest that GS‐SFX and GS‐SITF have better transport properties. The noncovalent interaction analysis shows the weak intramolecular interactions between their arms. The results indicate that the reorganization energies of GS‐SFX and GS‐SITF are significantly reduced compared to the dimer structures—DSFX and DSITF. Furthermore, the GS‐SITF1 which is one of the isomers of GS‐SITF exhibits the lowest values for λ(h) (0.067 eV) and λ(e) (0.153 eV). Therefore, we believe the predicted structure, electronic property, and reorganization energy are good indicator for transport materials. This work has systematically studied the effect of gridization, which provides insights to design organic semiconductor materials with excellent charge transport properties.     

Broadband metamaterial absorber on a single-layer ultrathin substrate

In this article, a broadband metamaterial microwave absorber on a low-cost FR-4 Epoxy substrate is proposed. The unit cell of the absorber consists of a staircase shape metallic patch placed on the top of the metal-backed ultrathin dielectric substrate having a thickness of 1.9 mm (0.07 λ₀). The absorption of more than 90% is achieved with this proposed low profile single-layer microwave absorber throughout the operation band from 8.86 to 15.5 GHz. The performance is analyzed for different values of incident angle, polarization angle, substrate height, and dielectric constant. The surface current and the power loss density at the top and bottom planes at the two absorption peaks of 9.46 and 13.90 GHz are also analyzed to elaborate the absorption mechanism of the structure. Experimental result closely follows the simulated one. The broadband characteristics of the design with relative absorption bandwidth (RAB) of 54.51% at both TE and TM polarizations of incident wave for a wide incident angles makes it versatile for applications in the X and Ku bands of microwave frequencies. The proposed work is very compact (unit cell size: 0.22 λ₀) with ultrathin substrate height (0.07 λ₀) and giving RAB performance of 54.51% comparable with that of others. Thus with this single-layer low-cost substrate material a broadband absorber is achieved.     

Viscoelastic properties of dibenzylidene sorbitol (DBS) physical gels at high frequencies

The rheological behavior of Dibenzylidene D-Sorbitol (DBS) gels formed in ethylene glycol, glycerol, mineral oil, ethanol, and chlorobenzene was studied using oscillatory squeezing flow viscometry. The storage (G ^′) and loss (G ^″) moduli were measured as a function of gellant concentration (0.5–2 w/w) and type of solvent. As expected greater values of gel strength (G ^′) were observed for gels containing higher concentrations of DBS. In addition, both storage and loss moduli of 2% systems were mostly frequency independent over the studied range, whereas 0.5% gels did exhibit some degree of dependence. We also found that the solvent plays an important role in the properties of the gels. Among the parameters that affect the viscoelastic properties of DBS gels, the solvent polarity and its ability to form hydrogen bonding may have significant effects on the gel rheology.     

Arsenic trioxide targets Hsp60, triggering degradation of p53 and survivin

The mechanisms of action of arsenic trioxide (ATO), a clinically used drug for the treatment of acute promyelocytic leukemia (APL), have been actively studied mainly through characterization of individual putative protein targets. There appear to be no studies at a system level. Herein, we integrate metalloproteomics through a newly developed organoarsenic probe, As-AC (C₂₀H₁₇AsN₄O₃S₂) with quantitative proteomics, allowing 37 arsenic binding and 250 arsenic regulated proteins to be identified in NB4, a human APL cell line. Bioinformatics analysis reveals that ATO disrupts multiple physiological processes, in particular, chaperone-related protein folding and cellular response to stress. Furthermore, we discover heat shock protein 60 (Hsp60) as a vital target of ATO. Through biophysical and cell-based assays, we demonstrate that ATO binds to Hsp60, leading to abolishment of Hsp60 refolding capability. Significantly, the binding of ATO to Hsp60 disrupts the formation of Hsp60-p53 and Hsp60-survivin complexes, resulting in degradation of p53 and survivin. This study provides significant insights into the mechanism of action of ATO at a systemic perspective, and serves as guidance for the rational design of metal-based anticancer drugs.

A highly selective organoarsenic fluorescent probe As-AC and quantitative proteomics were employed to track arsenic-binding and regulating proteins in live leukemia cells. Hsp60 was validated as a new target of ATO.     

Effect of radiation on conductivity of solid PVA–KOH–PC composite polymer electrolytes

The aim of this work is to enhance the room temperature conductivity of solid alkaline composite polymer electrolytes (ACPEs) based on polyvinyl alcohol/potassium hydroxide/propylene carbonate (PVA–KOH–PC) composites by cross-linking the PVA and bond scission of the PC by γ-radiation. The ACPEs were prepared by solvent-casting technique and irradiated with doses up to 200 kGy at room temperature. The microstructure of the ACPEs was measured using XRD spectrometer, and the results show the structural change from semicrystalline to amorphous, indicating that the cross-linking has been achieved at higher doses. It was found that the PKOH composite at 40 wt% KOH and PPC composite at 60 wt% PC show higher conductivities. The conductivity of the PKPC composites is dominated by dc conductivity at higher frequencies and that PC with 60 wt% has the highest conductivity at a dose of 200 kGy.Paper presented at the International Conference on Functional Materials and Devices 2005, Kuala Lumpur, Malaysia, June 6–8, 2005.     

Sterilization by Low-Pressure Plasma: The Role of Vacuum-Ultraviolet Radiation

Low-pressure plasma is a promising method for destroying microorganisms, an alternative to conventional methods, which have numerous drawbacks. Several plasma-based sterilization technologies are presently under development, even though the exact role of the various plasma constituents, for example ultraviolet radiation, on the sterilization mechanism is still unknown and subject to controversy. In this study, we first report high sporicidal activity of a microwave (MW) plasma compared to its radio-frequency (RF) counterpart, which we believe to be due to the higher concentration of reactive particles in the former plasma. We then report a relatively low sporicidal efficacy of vacuum ultraviolet (VUV) radiation (between 115 and 170 nm) emitted by an hydrogen MW plasma, in spite of the high effectiveness of these photons to break chemical bonds. We discuss these results in terms of etching (ablation), which we have observed for both synthetic polymers and spores, and in terms of other possible mechanisms proposed in the literature. The sporicidal effectiveness of VUV/UV radiation appears to vary markedly with wavelength and intensity, on account of spore structure and molecular absorption.     

Transition metal complexes of a hydrazone–oxime ligand containing the isonicotinoyl moiety: Synthesis,characterization and microbicide activities

Complexes of VO²⁺, Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Ru³⁺ and UO₂²⁺ with (3‐(hydroxyimino)butan‐2‐ylidene)isonicotinohydrazide were synthesized and characterized using physical and spectral methods. Analytical data revealed that the complexes formed in 1:1 or 1:2 metal–ligand ratios. Spectral studies showed that the ligand bonded to the metal ion in neutral tridentate, monobasic tridentate or monobasic bidentate fashion through azomethine nitrogen atom, protonated/deprotonated imine oxime group and/or ketonic/enolic carbonyl group. From the electronic spectral data together with magnetic susceptibility values a square planar, tetrahedral or distorted octahedral structure can be proposed for all complexes. Electron spin resonance spectra for Cu²⁺ complexes ( 2 – 4 ) revealed axial symmetry with g_|| > g_⊥ > g_e, indicating distorted octahedral or square planar structures and the unpaired electron exists in a orbital with marked covalent bond feature. The prepared complexes showed good to excellent biological activity, and the most active complexes against Aspergillus niger were 4 and 9 with zone of inhibition of 25 and 23 mm, respectively. Complexes 10 and 11 showed interesting activity against Escherichia coli with zone of inhibition of 44 and 32 mm, respectively.     

Immune TB Antibody Phage Display Library as a Tool To Study B Cell Immunity in TB Infections

B cells and in particular antibodies has always played second fiddle to cellular immunity in regard to tuberculosis (TB). However, recent studies has helped position humoral immunity especially antibodies back into the foray in relation to TB immunity. Therefore, the ability to correlate the natural antibody responses of infected individuals toward TB antigens would help strengthen this concept. Phage display is an intriguing approach that can be utilized to study antibody-mediated responses against a particular infection via harvesting the B cell repertoire from infected individuals. The development of disease-specific antibody libraries or immune libraries is useful to better understand antibody-mediated immune responses against specific disease antigens. This study describes the generation of an immune single-chain variable fragment (scFv) library derived from TB-infected individuals. The immune library with an estimated diversity of 10⁹ independent clones was then applied for the identification of monoclonal antibodies against Mycobacterium tuberculosis α-crystalline as a model antigen. Biopanning of the library isolated three monoclonal antibodies with unique gene usage. This strengthens the role of antibodies in TB immunity in addition to the role played by cellular immunity. The developed library can be applied against other TB antigens and aid antibody-derived TB immunity studies in the future.     

Synthesis,spectroscopic characterization,crystal structure determination and DFT calculations of [Au(Me<Subscript>2</Subscript>phen)Br<Subscript>2</Subscript>][AuBr<Subscript>2</Subscript>]

New mixed valence gold(III/I) salt containing two complexes [Au(Me₂phen)Br₂][AuBr₂] (1) was prepared from the reaction of AuBr₃ and 5,6-dimethyl-1,10-phenanthroline (Me₂phen) in a mixture of methanol and acetonitrile. Suitable crystals of 1 for X-ray diffraction measurement were obtained by slow evaporation of the resulted red solution at room temperature. This complex was characterized by spectral methods (IR, UV–Vis and ¹H NMR), elemental analysis and single-crystal X-ray diffraction. The X-ray structural analysis indicated that the asymmetric unit of 1 contains one [Au(Me₂phen)Br₂]⁺ cation and two half anions of [AuBr₂]^ˉ. Furthermore, the packing diagram of this complex, 3-D structure stabilized by intermolecular Au…Br and Au…π interactions and intermolecular C–H···Br hydrogen bonds. The experimental investigations on complex have been accompanied computationally by the density functional theory (DFT) and time-dependent DFT calculations. The nature of the Au–N bonds was investigated using quantum theory of atoms in molecules. Moreover, natural bond orbital analysis carried out to obtain hyper-conjugative interactions and electron delocalization on the complex.