Supramolecular chirality: a caveat in assigning the handedness of chiral aggregates.

The handedness of a supramolecular chiral aggregate is often assigned based on the sign of circular dichroism spectra, adopting the exciton chirality method. However, the method does not properly account for the nature of intermolecular interactions. We introduce a generalized picture on the use of the sign of chiral signals in determining the helicity of chiral aggregates, rooted in the exciton model, supported by TD-DFT results.

Cost-Effective Plasmonic Platforms: Glass Capillaries Decorated with Ag@SiO2 Nanoparticles on Inner Walls as SERS Substrates.

A cost-effective method for the fabrication of a glass capillary based plasmonic platform for the selective detection and identification of analytes of importance in health, environment, and safety is demonstrated. This was achieved by coating Ag@SiO2 nanoparticles (Ag ∼ 60 nm) having silica shell of varying thickness (∼2 and ∼25 nm) on the inside walls of glass capillaries, over 2 cm in length, with uniform coverage. It was found that the particle density on the surface plays a decisive role on the enhancement of Raman signals. Multiple hot spots, which are essentially junctions of amplified electric field, were generated when ∼30 Ag@SiO2 particles/µm2 were bound onto the walls of glass capillaries. The pores of the silica shell allow the localization of analyte molecules to the vicinity of hot spots resulting in signal enhancements of the order of 1010 (using pyrene as analyte; excitation wavelength, 632.8 nm). The applicability of Ag@SiO2 coated capillaries for the detection of a wide range of molecules has been explored, by taking representative examples of polyaromatic hydrocarbons (pyrene), amino acids (tryptophan), proteins (bovine serum albumin), and explosives (trinitrotoluene). By increasing the thickness of the silica shell of Ag@SiO2 nanoparticles, an effective filtration cum detection method has been developed for the selective identification of small molecules such as amino acids, without the interference of large proteins.

CuInS2-Sensitized Quantum Dot Solar Cell. Electrophoretic Deposition, Excited-State Dynamics, and Photovoltaic Performance.

Ternary metal chalcogenides such as CuInS2 offer new opportunities to design quantum dot solar cells (QDSC). Chemically synthesized CuInS2 quantum dots (particle diameter, 2.6 nm) have been successfully deposited within the mesoscopic TiO2 film using electrophoretic deposition (150 V cm(-1) dc field). The primary photoinduced process of electron injection from excited CuInS2 into TiO2 occurs with a rate constant of 5.75 × 10(11) s(-1). The TiO2/CuInS2 films are photoactive and produce anodic photocurrent with a power conversion efficiency of 1.14%. Capping the TiO2/CuInS2 film with a CdS layer decreases the interfacial charge recombination and thus offers further improvement in the power conversion efficiency (3.91%). The synergy of using CdS as a passivation layer in the composite film is also evident from the increased external quantum efficiency of the electrode in the red region where only CuInS2 absorbs the incident light.

Ag@SiO2 Core-Shell Nanostructures: Distance-Dependent Plasmon Coupling and SERS Investigation.

Enhancement of Raman signals of pyrene due to the enhanced electric fields on the surface of silver nanoparticles has been investigated by controlling the thickness of the silica shell. Dimeric nanostructures having well-defined gaps between two silver nanoparticles were prepared, and the gap size (d) was varied from 1.5 to 40 nm. The molecules trapped at the dimeric junctions showed higher Raman signal enhancements when the gap was less than 15 nm due to the presence of amplified electric field, in agreement with our theoretical studies. The experimental Raman enhancement factors at the hot spots follow a 1/d(n) dependence, with n = 1.5, in agreement with the recent theoretical studies by Schatz and co-workers. Experimental results presented here on the distance dependence of surface enhanced Raman spectroscopy (SERS) enhancement at the hot spots can provide insight on the design of newer plasmonic nanostructures with optimal nanogaps.