Elastic strain at the interface in Ge clusters on Si substrate—a Raman spectroscopic measurement

Ge clusters are grown on Si substrate at room temperature (Ge-RT) and also at liquid nitrogen temperature (Ge-LNT) by cluster evaporation technique. These clusters show blue luminescence. Raman measurement demonstrates the increase in strain with annealing in diffused disordered Si at the interface between Ge-LNT clusters and Si substrate. This manifests in strain-relaxation in the clusters as observed by Photoluminescence (PL) measurements. The decrease in PL intensity for Ge-RT with annealing has been attributed to reduction in surface oxide species, which is supported by Raman spectroscopic measurements. The objective of the paper is to understand the effect of thermal annealing on both interfacial strain and interdiffusion of elemental Si at the interface, together with luminescence characteristics of the clusters.     

Site directed maleimide bifunctional chelators for the M(CO)3+ core (M =(99m)Tc, Re)

A series of bifunctional chelates containing a tridentate donor set for complexation of the M(CO)3+ core and a maleimide group for site-specific coupling to peptides and proteins containing free thiol groups has been prepared and their Re(CO)3+ complexes and glutathione conjugates structurally characterized. The flexibility of design allows preparation of ligands suitable for both fluorescence imaging, radioimaging and radiotherapeutic studies of proteins and peptides as well as other biopolymers using site specific conjugation.     

Synthesis and biological activities of 2-methyl-4-N-2′-cyanoethyl-N-substituted benzaldehydes and their derivatives

Synthesis and antiAIDS, anticancer, antitubercular, fungicidal and antibacterial activities of 2-methyl-4-N-2′-cyanoethyl-N-methane/benzenesulphonylaminobenzaldehyde and their hydrazones are reported.     

ssDNA binding reveals the atomic structure of graphene

We used AFM to investigate the interaction of polyelectrolytes such as ssDNA and dsDNA molecules with graphene as a substrate. Graphene is an appropriate substrate due to its planarity, relatively large surfaces that are detectable via an optical microscope, and straightforward identification of the number of layers. We observe that in the absence of the screening ions deposited ssDNA will bind only to the graphene and not to the SiO(2) substrate, confirming that the binding energy is mainly due to the π-π stacking interaction. Furthermore, deposited ssDNA will map the graphene underlying structure. We also quantify the π-π stacking interaction by correlating the amount of deposited DNA with the graphene layer thickness. Our findings agree with reported electrostatic force microscopy (EFM) measurements. Finally, we inspected the suitability of using a graphene as a substrate for DNA origami-based nanostructures.     

Development of a reversed-phase high-performance liquid chromatography method for the analysis of components from a closed-loop insulin delivery system

A reversed-phase HPLC method has been developed which enables separation of the three components of a closed-loop insulin delivery system, namely concanavalin A methacrylamide (Con A-MA), dextran methacrylate (Dex-MA) and bovine insulin. The analysis of Con A-MA represents a significant challenge due to the formation of multiple conformations on contact with the chromatographic surface and the mobile phase. The extent of conformational change is shown to be dependent on a number of parameters: column temperature, mobile phase pH, contact time with the chromatographic surface, salt type and concentration and the organic modifier. By manipulation of these variables, protein denaturation can be minimised and recovery improved.     

Design and synthesis of site directed maleimide bifunctional chelators for technetium and rhenium

A new family of heterobifunctional linkers (L1-L9) containing a terminus consisting of a tridentate donor set for coordination of the {M(CO)(3)}(+) core (M = Tc, Re), and a thiol reactive maleimide group has been prepared conveniently and in high yield under Mitsunobu reaction conditions by the coupling of an appropriate alcohol derivative with maleimide. The rhenium complexes [Re(CO)(3)(Lx)]Br (x= 1-9) were prepared in good yields from the reactions of the ligands and (NEt(4))(2)[Re(CO)(3)Br(3)] in refluxing methanol. The ligands and their Re complexes were characterized by (1)H and (13)C NMR, IR, and ESI-MS. Ligand L4 and [Re(CO)(3)(L5)]Br have been structurally characterized by X-ray crystallography. Photoexcitation of solutions of the complexes [Re(CO)(3)(Lx)]Br (x= 4-6) gives rise to intense and prolonged luminescence at room temperature (fluorescence lifetimes of ca. 16 micros). The ligands and their Re complexes react smoothly at the maleimide linker with sulfhydryl groups of peptides and proteins at room temperature in phosphate-buffered saline (PBS, pH 7.4) to form stable thioether bioconjugates. The photoluminescence properties of the labeled conjugates are similar to those of the parent complexes, but with even longer lifetimes. The ligands can also be labeled at room temperature with (99m)Tc to give chemically robust complexes. The corresponding hydrazinonicotinamide derivative N-[5-(6'-hydrazinopyridine-3'-carbonyl)aminopentyl]maleimide (L10) was also prepared. While coupling of L10 to cysteine ethylester and synthesis of the rhenium derivative [ReCl(3)(HYNIC-maleimide)(2)] were successfully accomplished, attempts to couple [ReCl(3)(HYNIC-maleimide)(2)] to glutathione or BSA yielded intractable mixtures.     

Fluorescence resonance energy transfer (FRET) in chemistry and biology: Non-F?rster distance dependence of the FRET rate

Fluorescence resonance energy transfer (FRET) is a popular tool to study equilibrium and dynamical properties of polymers and biopolymers in condensed phases and is now widely used in conjunction with single molecule spectroscopy. In the data analysis, one usually employs the F?rster expression which predicts (l/R ⁶) distance dependence of the energy transfer rate. However, critical analysis shows that this e_xpression can be of rather limited validity in many cases. We demonstrate this by explicitly considering a donor-acceptor system, polyfluorene (PF₆)-tetraphenylporphyrin (TPP), where the size of both donor and acceptor is comparable to the distance separating them. In such cases, one may expect much weaker distance (as l/R ² or even weaker) dependence. We have also considered the case of energy transfer from a dye to a nanoparticle. Here we find l/R ⁴ distance dependence at large separations, completely different from F?rster. We also discuss recent application of FRET to study polymer conformational dynamics. Dedicated to Prof J Gopalakrishnan on his 62nd birthday.     

Cloaking and imaging effects in plasmonic checkerboards of negative and and dielectric photonic crystal checkerboards

Negative refractive index materials are known to be able to support a host of surface plasmon states for both polarizations of light. This makes possible unique effects such as a perfect lens. Checkerboards consisting of alternating cells of positive and negative refractive index represent a very singular situation in which the density of modes diverges at the corners. This raises the question as to whether such effects will still be observed in a real dissipative system of finite size. We have considered several aspects of such structures including these and symmetry aspects (rectangular against triangular checkerboards). We have also studied silver checkerboards whose transverse extent is finite. Negative refractive index checkerboards bring new electromagnetic paradigms both through the intriguing possibilities they appear to offer, and the challenges they present to our understanding of the diffraction process. Most intriguing of all is the possibility of a triangular checkerboard lens whose resolution is limited not by wavelength, but only by the losses in the constituent materials, while a ray picture suggests it behaves as a perfect mirror. The resolution of this lens increases without limit as the losses tend to zero as shown by the generalized lens theorem. We finally show that light confinement can be achieved to certain extent using dielectric triangular photonic crystal (PC) checkerboards displaying the all-angle-negative-refraction (AANR) within the Bragg regime in p polarization. Effectively even a single rectangular or triangular PC can act as an open resonator that confines light in its neighborhood. This cloaking effect has been previously observed in PC slabs displaying the AANR effect. We show that the cloaking is enhanced for three triangular PC wedges sharing a vertex and further improved for 12 triangular PC wedges arranged in a checkerboard fashion.