Growth, structure, and temperature dependent emission processes in emerging metal hexachloride scintillators Cs2HfCl6 and Cs2ZrCl6.

Crystals of metal hexachlorides Cs2MCl6 (M = Hf or Zr) have recently emerged as promising materials for scintillation applications due to their excellent energy resolution. In this work, we investigated the crystal structure and scintillation properties of Cs2HfCl6 and Cs2ZrCl6 crystals in the broad temperature range from 9 to 300 K. X-ray diffraction data confirmed the same cubic structure (space group Fm3m) for Cs2HfCl6 and Cs2ZrCl6 over the entire examined temperature range. The room temperature scintillation light yield of Cs2HfCl6 excited with a 137Cs γ-source is measured to be 24 800 photons per MeV, while Cs2ZrCl6 exhibits 33 900 photons per MeV resulting in energy resolutions of 5.3% and 4.5%, respectively. The alpha-to-beta ratio determined at room temperature for 5.5 MeV α-particles from an 241Am source is equal to 0.39 for Cs2HfCl6 and 0.35 for Cs2ZrCl6. The measurements of scintillation decay curves revealed complex kinetics due to delayed recombination processes. A tangible enhancement of the scintillation yield with heating is observed in the 125-150 K range. This effect is a manifestation of negative thermal quenching explained by thermal activation of trapped carriers. A model of the emission centre is proposed that consistently explains the observed changes of emission intensity with temperature in the crystals under study.

Ultrasound delivery of Surface Enhanced InfraRed Absorption active gold-nanoprobes into fibroblast cells: a biological study via Synchrotron-based InfraRed microanalysis at single cell level.

Ultrasound (US) induced transient membrane permeabilisation has emerged as a hugely promising tool for the delivery of exogenous vectors through the cytoplasmic membrane, paving the way to the design of novel anticancer strategies by targeting functional nanomaterials to specific biological sites. An essential step towards this end is the detailed recognition of suitably marked nanoparticles in sonoporated cells and the investigation of the potential related biological effects. By taking advantage of Synchrotron Radiation Fourier Transform Infrared micro-spectroscopy (SR-microFTIR) in providing highly sensitive analysis at the single cell level, we studied the internalisation of a nanoprobe within fibroblasts (NIH-3T3) promoted by low-intensity US. To this aim we employed 20 nm gold nanoparticles conjugated with the IR marker 4-aminothiophenol. The significant Surface Enhanced Infrared Absorption provided by the nanoprobes, with an absorbance increase up to two orders of magnitude, allowed us to efficiently recognise their inclusion within cells. Notably, the selective and stable SR-microFTIR detection from single cells that have internalised the nanoprobe exhibited clear changes in both shape and intensity of the spectral profile, highlighting the occurrence of biological effects. Flow cytometry, immunofluorescence and murine cytokinesis-block micronucleus assays confirmed the presence of slight but significant cytotoxic and genotoxic events associated with the US-nanoprobe combined treatments. Our results can provide novel hints towards US and nanomedicine combined strategies for cell spectral imaging as well as drug delivery-based therapies.

Generating single metalloprotein crystals in well-defined redox states: electrochemical control combined with infrared imaging of a NiFe hydrogenase crystal.

We describe an approach to generating and verifying well-defined redox states in metalloprotein single crystals by combining electrochemical control with synchrotron infrared microspectroscopic imaging. For NiFe hydrogenase 1 from Escherichia coli we demonstrate fully reversible and uniform electrochemical reduction from the oxidised inactive to the fully reduced state, and temporally resolve steps during this reduction.

Towards microfluidic reactors for in situ synchrotron infrared studies.

Anodically bonded etched silicon microfluidic devices that allow infrared spectroscopic measurement of solutions are reported. These extend spatially well-resolved in situ infrared measurement to higher temperatures and pressures than previously reported, making them useful for effectively time-resolved measurement of realistic catalytic processes. A data processing technique necessary for the mitigation of interference fringes caused by multiple reflections of the probe beam is also described.

Amine-terminated nanoparticle films: pattern deposition by a simple nanostencilling technique and stability studies under X-ray irradiation.

Thin films made up of arrays of amine-terminated silicon nanoparticles (NH2-SiNPs) synthesized by a new evaporation technique have been formed by employing TEM grids as nanostencils. FTIR imaging illustrates the feasibility of the method in nanoscale device fabrication applications. Micro-mapping over areas of the nanoparticle material allows the surface chemistry to be examined. FTIR imaging shows trace amounts of oxide confined to the NP surfaces. Thicker films formed by dropcasting allowed the nanoparticle behaviour to be studied under conditions of extended exposure to 150 eV photons radiation by X-ray photoelectron spectroscopy (XPS). The XPS spectrum was monitored over the Si2p region and the initial peak at 100.53 eV was observed to shift to higher binding energies as irradiation progressed which is indicative of charge trapping within the film. This result has potential consequences for applications where NH2-SiNPs are used in X-ray environments such as in bioimaging where the increasing charge buildup is related to enhanced cytotoxicity.

ac Stark splitting and quantum interference with intersubband transitions in quantum wells.

Resonant optical coupling experiments have demonstrated coherent quantum interference between the Stark-split "dressed states" of a synthesized 3-level electronic system in a semiconductor quantum well. Analysis of the dephasing mechanisms reveals dipole selection rules closely analogous to those seen in atomic spectroscopy experiments. In this respect, these systems behave as "artificial atoms" for the purposes of observing a range of nonclassical coherent optical effects. The prospects for exploiting them for scalable quantum information processing applications are more promising than previous dephasing models would have predicted.

Mechanical alignment of quasi-one-dimensional nanoparticles.

Randomly oriented rod or rope-like nanoparticles on the surface of an elastomeric substrate are aligned along one direction simply by stretching the substrate. The technique is demonstrated here using single-walled carbon nanotube ropes, and the degree of alignment is assessed by polarized Raman spectroscopy. The alignment is preserved after the particles are removed from the substrate surface, showing that the aligned nanoparticles can be stamped in patterns onto another surface.