Stable metal nanoclusters (NCs) with uniform interior nanogaps reproducibly offer a highly robust substrate for surface-enhanced Raman scattering (SERS) because of the presence of abundant hot spots on their surface. The synthesis of such an SERS substrate by a simple route is a challenging task. Here, we have synthesized a highly stable wirelike cluster of silver nanoparticles (Ag-NPs) with an interparticle gap of ~1.7 ± 0.2 nm using deoxyribonucleic acid (DNA) as the template by exploiting an easy and inexpensive chemical route. The red shift in the surface plasmon resonance (SPR) band of Ag-NCs compared to SPR of a single Ag-NP confirms the strong interplasmonic interaction. Methylene Blue (MB) is used as a representative Raman probe to study the SERS effect of the NCs. The SERS measurements reveal that uniform, reproducible, and strong Raman signals were observed up to the single-molecule level. The intensity of the Raman signal is not highly dependent on the polarization of the excitation laser. The DNA-based Ag-NCs as a substrate show better isotropic behavior for their SERS intensity compared to the dimer, as confirmed from both the experimental and theoretical simulation results. We believe that in the future the DNA-based Ag-NCs might be useful as a potential SERS substrate for ultrasensitive trace detection, biomolecular assays, NP-based photothermal therapeutics, and a few other technologically important fields.

The coupling of structural fluctuation and the dynamics of associated water molecules of biological macromolecules is vital for various biological activities. Although a number of molecular dynamics (MD) studies on proteins/DNA predicted the importance of such coupling, experimental evidence of variation of hydration dynamics with controlled structural fluctuation even in model macromolecule is sparse and raised controversies in the contemporary literature. Here, we have investigated dynamics of hydration at the surfaces of two similar anionic micelles sodium dodecyl sulfate (SDS) and sodium dodecylbenzenesulfonate (SDBS) as model macromolecules using coumarin 500 (C500) as spectroscopic probe with femtosecond to picosecond time resolution up to 20 ns time window. The constituting surfactants SDS and SDBS are structurally similar except one benzene moiety in the SDBS may offer additional rigidity to the SDBS micelles through π-stacking and added bulkiness. The structural integrity of the micelles in the aqueous medium is confirmed in dynamic light scattering (DLS) studies. A variety of studies including polarization gated fluorescence spectroscopy and quasielastic neutron scattering (QENS) have been used to confirm differential structural fluctuation of SDS and SDBS micelles. We have also employed femtosecond-resolved Förster resonance energy transfer (FRET) in order to study binding of a cationic organic ligand ethidium bromide (EtBr) salt at the micellar surfaces. The distance distribution of the donor (C500)-acceptor (EtBr) in the micellar media reveals the manifestation of the structural flexibility of the micelles. Our studies on dynamical coupling of the structural flexibility with surface hydration in the nanoscopic micellar media may find the relevance in the "master-slave" type water dynamics in biologically relevant macromolecules.

The pathways of molecular recognition, which is a central event in all biological processes, belong to the most important subjects of contemporary research in biomolecular science. By using fluorescence spectroscopy in a microfluidics channel, it can be determined that molecular recognition of α-chymotrypsin in hydrous surroundings at two different pH values (3.6 and 6.3) follows two distinctly different pathways. Whereas one corroborates an induced-fit model (pH 3.6), the other one (pH 6.3) is consistent with the selected-fit model of biomolecular recognition. The role of massive structural perturbations of differential recognition pathways could be ruled out by earlier XRD studies, rather was consistent with the femtosecond-resolved observation of dynamic flexibility of the protein at different pH values. At low concentrations of ligands, the selected-fit model dominates, whereas increasing the ligand concentration leads to the induced-fit model. From molecular modelling and experimental results, the timescale associated with the conformational flexibility of the protein plays a key role in the selection of a pathway in biomolecular recognition.

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An active volumetric device for active detection and measurement of drop nucleation of superheated emulsions is described. The drop nucleation is detected by an optical arrangement using a pair of a laser and a light-dependent resistor (LDR). The electric pulses from LDR are converted into binary pulses for counting. The device senses a volume change as low as 0.55 µL, and provides a fast data acquisition facility.