Mechanistic pathway for controlled extraction of guest molecule bound to herring sperm DNA using α-cyclodextrin

trans-2-[4-(Dimethylamino)styryl]benzothiazole (DMASBT) is known to have dual emitting states where the locally excited (LE) state is responsible for fluorescence in less polar environment and in polar milieu fluorescence is from the twisted intramolecular charge transfer (TICT) state. This compound also undergoes minor groove binding to herring sperm DNA (hsDNA) evidenced by the absorption spectra before and after the binding process and an effect on DMASBT fluorescence by an anionic quencher. The binding occurs efficiently in a 1:1 manner, i.e. one guest molecule binds to one site on the hsDNA. Instead of following the DNA twist, the aromatic part seems to project outward. Thus, the bound molecule can be successfully extracted out from the DNA in a controlled way by the hydrophobic cavity of α-cyclodextrin (α-CD). The extraction starts even with a low concentration of α-CD and increases as the concentration is increased. Absorption, steady-state and time resolved fluorescence spectroscopic methods have been employed to explore the mechanistic pathway of binding of DMASBT to hsDNA. The mechanistic approach toward controlled extraction of the guest molecules from hsDNA by α-CD is reported and is expected to serve a significant purpose in treatment of drug overdose.     

An investigation into the mechanisms of DNA strand breakage by direct ionization of variably hydrated plasmid DNA

The mechanisms by which ionizing radiation directly causes strand breaks in DNA were investigated by comparing the chemical yield of DNA-trapped free radicals to the chemical yield of DNA single strand break (ssb) and double strand break (dsb), as a function of hydration (Gamma). Solid-state films of plasmid pUC18, hydrated to 2.5 < Gamma < 22.5 mol, were X-irradiated at 4 K, warmed to room temperature, and dissolved in water. Free radical yields were determined by EPR at 4 K. With use of the same samples, Gel electrophoresis was used to measure the chemical yield of total strand breaks, which includes prompt plus heat labile ssb; G'total(ssb) decreased from 0.092 +/- 0.016 micromol/J at Gamma= 2.5 to 0.066 +/- 0.008 micromol/J at Gamma= 22.5. Most provocative is that at Gamma= 2.5 the yield of total ssb exceeds the yield of trapped deoxyribose radicals: G'total(ssb) - G'sugar(fr) = 0.06 +/- 0.02 micromol/J. Nearly 2/3 of the strand breaks are derived from precursors other than radicals trapped on the deoxyribose moiety. To account for these nonradical precursors, we hypothesize that strand breaks are produced by two one-electron oxidations at a single deoxyribose residue within an ionization cluster.     

Synthesis of Silver Nanoparticles Using a Novel Graft Copolymer and Enhanced Particle Stability via a “Polymer Brush Effect”

Polymer‐encapsulated silver nanoparticles were synthesized and sterically stabilized by a new core‐shell type system consisting of poly(S‐alt‐MA)‐graft‐PMMA copolymer that acts as a scaffold for the synthesis of size confined nanoparticles. The graft copolymer is synthesized via ambient temperature ATRP using the CuBr/PMDETA catalytic system at ambient temperature. The graft copolymer is hypothesized to function as a scaffold with the anhydride part interacting strongly with the silver ions, while the PMMA graft functions as a polymer brush that stabilizes the dispersion and prevents the particle aggregation due to a ‘polymer brush effect’. UV absorption and TEM studies confirm that the synthesized silver composite particles have a core‐shell structure.

     

Effect of thermodiffusion on pH‐regulated surface charge properties of nanoparticle

Surface properties of nanoparticle are of high importance in the field of biotechnology, drug delivery and micro/nanofabrication. In this article, we developed a comprehensive theoretical model and subsequently solved that numerically to study the effect of thermodiffusion of ions on surface charge properties of nanoparticle. The theoretical study has been done considering silica nanoparticle for two aqueous solutions NaCl and KCl. The effect of solution pH in conjunction with nanoparticle temperature on surface charge density has been obtained for different salt concentrations (1, 10 and 100 mM) and nanoparticle size (diameter of 2 and 100 nm). It is observed from the results that with increasing temperature of the nanoparticle, the negative surface charge density gets higher due to increasing thermodiffusion effect. It is also found out that the magnitude of surface charge density is higher for KCl solution than NaCl solution under same condition which is attributed mostly due to less thermodiffusion of counterions for KCl than NaCl. Present study also shows that magnitude of surface charge density decreases with increasing nanoparticle size until it reaches a limiting value (called critical size) above which the effect of nanoparticle size on surface charge density is insignificant.     

Nano‐Graphene Oxide Based Multichannel Sensor Arrays towards Sensing of Protein Mixtures

Optical array‐based sensors are attractive candidates for the detection of various bio‐analytes due to their convenient fabrication and measurements. For array‐based sensors, multichannel arrays are more advantageous and used frequently in many electronic sensors. But most reported optically array based sensors are constructed on a single channel array. This difficulty is mainly instigated from the overlap in optical responses. In this report we have used nano‐graphene oxide (nGO) and suitable fluorophores as sensor elements to construct a multichannel sensor array for the detection of protein analytes. By using the optimized multichannel array we are able to detect different proteins and mixtures of proteins with 100 % classification accuracy at sub‐nanomolar concentration. This modified method expedites the sensing analysis as well as minimizes the use of both analyte and sensor elements in array‐based protein sensing. We have also used this system for the single channel array‐based sensing to compare the sensitivity and the efficacy of these two systems for other applications. This work demonstrated an intrinsic trade‐off associated with these two methods which may be necessary to balance for array‐based analyte detections.     

Physicochemical perspective of cyclodextrin nano and microaggregates

'Chemistry beyond the molecule' is the nickname for supramolecular chemistry. This branch of study is based on molecular recognition that is host-guest chemistry. A number of potential hosts have been defined and applied in scores of studies. Among all potential hosts, cyclodextrins occupy a high position due to their characteristic solubilisation capability and biocompatibility. In the present article we are revisiting the host-guest aspects of cyclodextrins from a physicochemical perspective. We present details of formation and applications of cyclodextrin nanoaggregates induced by guest molecules, the concerned thermodynamics behind the process and also the effect of concentration of the guest molecules on the morphology of the aggregates. This article reviews the topic mainly from the spectroscopic point of view.     

Peptidoglycan as Nod1 ligand; fragment structures in the environment, chemical synthesis, and their innate immunostimulation

Covering: up to 2011. This review focuses on the recent revealing of the immunostimulatory bacterial cell wall peptidoglycan (PGN) fragments as Nod1 ligands, especially a newly developed chemical synthesis of the partial structures, fragment structures in the environment and bacterial supernatant, and the immunostimulatory activities of the Nod1 ligands.     

Photoluminescence of 2-(2′-hydroxy-5′-methylbenzoyl)-1,5-diphenylpyrrole in aqueous and β-cyclodextrin environments: manifestation of open and closed conformers

Steady-state fluorometric studies have been performed on 2-(2′-hydroxy-5′-methylbenzoyl)-1,5-diphenylpyrrole (HMBDPP) in aqueous and aqueous β-cyclodextrin (β-CD) environments at ambient temperature. The fluorophore mostly shows a single emission in aqueous solution. Addition of β-CD to the aqueous solution of the fluorophore results in the development of another emission band at higher energy. The difference in the fluorometric behaviour is assigned to a remarkable change in the polarity of the microenvironment within the supramolecular structural environment compared to that of the bulk aqueous phase. Semi-empirical calculation (AM1-SCI) rules out the possibility of intramolecular proton transfer reaction in any of the S₀, S₁ and T₁ states of the fluorophore. It is proposed that HMBDPP exists mostly in the intermolecularly hydrogen-bonded form (open conformer) in aqueous solution while within β-CD environment, it is the intramolecularly hydrogen-bonded form (closed conformer) that predominates.     

New formulas and predictions for running masses at higher scales in MSSM

The effects of the scale dependent vacuum expectation values (VEVs) on the running masses of quarks and leptons in non-SUSY gauge theories have been considered by a number of authors. Here we use RGEs of the VEVs, and the gauge and Yukawa couplings in the MSSM to analytically derive new one loop formulas for the running masses above the SUSY breaking scale. Some of the masses exhibit a substantially different behaviour with respect to their dependence on the gauge and Yukawa couplings when compared with earlier formulas in the MSSM derived ignoring RGEs of VEVs. In particular, the masses of the first two generations are found to be independent of the Yukawa couplings of the third generation in the small mixing limit. New numerical estimates at the two loop level are also presented. Received: 30 July 1999 / Published online: 6 April 2000