Pushkar Singh

Spatially resolved spectroscopic differentiation of hydrophilic and hydrophobic domains on individual insulin amyloid fibrils

The formation of insoluble β-sheet-rich protein structures known as amyloid fibrils is associated with numerous neurodegenerative diseases, such as Alzheimer’s and Parkinson’s disease. A detailed understanding of the molecular structure of the fibril surface is of interest as the first contact with the physiological environment in vivo and plays a decisive role in biological activity and associated toxicity. Recent studies reveal that the inherent sensitivity and specificity of tip-enhanced Raman scattering (TERS) renders this technique a compelling method for fibril surface analysis at the single-particle level. Here, the reproducibility of TERS is demonstrated, indicating its relevance for detecting molecular variations. Consequently, individual fibrils are systematically investigated at nanometer spatial resolution. Spectral parameters were obtained by band-fitting, particularly focusing on the identification of the secondary structure via the amide III band and the differentiation of hydrophobic and hydrophilic domains on the surface. In addition multivariate data analysis, specifically the N-FINDR procedure, was employed to generate structure-specific maps. The ability of TERS to localize specific structural domains on fibril surfaces shows promise to the development of new fibril dissection strategies and can be generally applied to any (bio)chemical surface when structural variations at the nanometer level are of interest.

Characterization of 700 μJ T rays generated during high-power laser solid interaction

Laser-produced solid density plasmas are well-known as table-top sources of electromagnetic radiation. Recent studies have shown that energetic broadband terahertz pulses (T rays) can also be generated from laser-driven compact ion accelerators. Here we report the measurement of record-breaking T-Ray pulses with energies no less than 0.7 mJ. The terahertz spectrum has been characterized for frequencies ranging from 0.1-133 THz. The dependence of T-Ray yield on incident laser energy is linear and shows no tendencies of saturation. The noncollinear emission pattern and the high yield reveal that the T rays are generated by the transient field at the rear surface of the solid target.

Surface enhanced Raman scattering investigation of two novel piperazine carbodithioic acids adsorbed on Ag and ZnO nanoparticles

In this work piperazine-1-carbodithioic acid (PZCDT) and piperazine-1,4-dicarbodithioic acid (PZbCDT) were synthesized. These analytes PZCDT and PZbCDT have chair conformations, which is expected to give specific surface-enhanced Raman scattering (SERS) effects on individual bands. SERS, UV-Visible, TEM and DFT methods have proved that the dithiocarbamate moiety is a potential and suitable functional group for silver and ZnO nanoparticles (AgNPs and ZnONPs). The enhancement mechanism and enhancement factors in both SERS@AgNPs and SERS@ZnONPs are also discussed. Two new strong bands appear at 1630, 1286 cm−1 with very large intensity in SERS@AgNPs, which signifies the conversion of the C–N bond of the dithiocarbamate moiety into CN bonds. The SERS signatures that are observed are quite different in SERS@AgNPs and SERS@ZnONPs.

Surface enhanced Raman scattering based reaction monitoring of in vitro decyclization of creatinine → creatine

Creatinine → creatine decyclization is an important reaction wherein we obtain a beneficial compound from a toxic substance. Decyclization of creatinine at basic pH has been monitored in vitro by time series surface enhanced Raman scattering (SERS) using a silver island film. NH2 scissoring, CN and CO stretching modes of creatinine serve as Raman markers for monitoring the decyclization reaction. Transition state calculations using DFT have revealed the path of the formation of creatine by the cleavage of the endocyclic CN bond of creatinine. The Raman signatures of ring opening are clearly observed after 120 min at pH 8, and further increasing the pH increases the reaction rate even more, as the signatures are observed after 60 and 30 min at pH 10 and 12, respectively; however, the reversibility of the reaction is more prominent at higher pH. Therefore, pH 8 is the most favorable among the three pH values for the decyclization reaction to be stable at room temperature. The proper understanding of this reaction where a toxic substance is converted to a beneficial compound is expected to open the scope for further extensive research.

FD 177 - Introductory Lecture

This article is intended to set the scope of the meeting, in particular for the high spatial resolution section

Ultra-energetic THz pulses from a laser-driven particle accelerator

Summary form only given. High peak-power THz sources find many applications in material science, non-linear optics and next generation particle accelerators. We report the experimental realization of a gigawatt (GW) class T-rays from a laser-driven particle accelerator. Laser-driven particle accelerators are one of the well studied and promising methods for the generation of energetic particle beams and radiation extending the whole electromagnetic spectrum. Recent studies have shown that powerful T-rays can also be generated during such an interaction [1]. A conversion efficiency of higher than 10-3 and a peak power above a GW makes our source the most efficient and powerful THz source known today.

700μJ THz pulses from a laser-driven particle accelerator

Here we report a laser plasma-driven source of T-rays with the highest pulse energy ever recorded in a laboratory. T-rays are emitted from the rear surface of a solid target in the non-collinear direction at incident laser intensities ~ 1019 W/cm2. Pulse energy measurements reported T-ray pulses with peak energies no less than 700 μJ. Temporal measurements using a single-shot electro-optic method showed the presence of sub-picosecond T-ray pulses with 570 fs duration, thus rendering the peak-power of the source higher even than that of state-of-the-art synchrotrons. A conversion efficiency of higher than 10−3 and an average power of 7 mW makes it the most efficient compact and powerful THz source known today. Spectral analysis revealed the presences of frequencies ranging from 0.1 − 133 THz, while most of the energy is localised in the low frequency region. The dependence of T-ray yield on incident laser energy is linear and shows no signs of saturation. The spatial distribution of the recorded T-rays indicates that most of the T-rays are emitted in the non-collinear direction from the rear-surface of a solid target and the contribution in the forward direction is very small. 2D particle-in-cell simulations show the presence of transient current at the target rear surface.