Tip-enhanced Raman spectroscopy (TERS) is capable of amplifying the extremely weak Raman response of azobenzene self-assembled monolayers (SAMs), thus allowing for the chemical characterization of ...the sample surface at the nanoscale. Recently, we introduced a physical model describing the TERS intensity of azobenzene SAMs probed in a scanning tunneling mode configuration (STM-TERS) that takes into account the molecular bending induced by the high electric field inside the tunneling junction. The model predicts quite well the experimental variation in the TERS intensity of a hexyl azobenzene SAM (AzoC6) on gold polycrystalline film (111) by changing the electric field in the gap between the tip and the substrate. Nevertheless, a disagreement between the model and the experiment has been observed while studying, in the same conditions, the TERS intensity of undecyl azobenzene (AzoC11) SAM formed by molecules featuring an alkyl chain that is nearly two times longer with respect to the previous case. In this work, we extend the molecular bending model by considering an additional bending mechanism due to the mechanical interaction between the tip and the SAM, occurring when the tip-to-sample distance is shorter than the molecular length. The extended model is able to describe well the TERS intensity behavior by changing either the bias voltage or the tip-to-sample distance for both AzoC6 and AzoC11. Eventually, we determine quantitatively the difference in the elastic properties of the two molecules physically accounting for the difference in the TERS intensity behavior of the two SAMs.
Abstract
Cosmic dust plays a dominant role in the universe, especially in the formation of stars and planetary systems. Furthermore, the surface of cosmic dust grains is the benchwork where molecular ...hydrogen and simple organic compounds are formed. We manipulate individual dust particles in a water solution by contactless and noninvasive techniques such as standard optical and Raman tweezers, to characterize their response to mechanical effects of light (optical forces and torques) and to determine their mineral compositions. Moreover, we show accurate optical force calculations in the T-matrix formalism highlighting the key role of composition and complex morphology in the optical trapping of cosmic dust particles. This opens perspectives for future applications of optical tweezers in curation facilities for sample-return missions or in extraterrestrial environments.
In recent years, considerable effort has been devoted to the synthesis and characterization of two-dimensional materials. Liquid phase exfoliation (LPE) represents a simple, large-scale method to ...exfoliate layered materials down to mono- and few-layer flakes. In this context, the contactless trapping, characterization, and manipulation of individual nanosheets hold perspectives for increased accuracy in flake metrology and the assembly of novel functional materials. Here, we use optical forces for high-resolution structural characterization and precise mechanical positioning of nanosheets of hexagonal boron nitride, molybdenum disulfide, and tungsten disulfide obtained by LPE. Weakly optically absorbing nanosheets of boron nitride are trapped in optical tweezers. The analysis of the thermal fluctuations allows a direct measurement of optical forces and the mean flake size in a liquid environment. Measured optical trapping constants are compared with T-matrix light scattering calculations to show a quadratic size scaling for small size, as expected for a bidimensional system. In contrast, strongly absorbing nanosheets of molybdenum disulfide and tungsten disulfide are not stably trapped due to the dominance of radiation pressure over the optical trapping force. Thus, optical forces are used to pattern a substrate by selectively depositing nanosheets in short times (minutes) and without any preparation of the surface. This study will be useful for improving ink-jet printing and for a better engineering of optoelectronic devices based on two-dimensional materials.
An innovative technique to access the nuclear matrix elements entering the expression of the life time of the double beta decay by relevant cross sections of double charge exchange reactions is ...proposed. The basic point is the coincidence of the initial and final state wave-functions in the two classes of processes and the similarity of the transition operators, which in both cases present a superposition of Fermi, Gamow-Teller and rank-two tensor components with a relevant implicit momentum transfer. First pioneering experimental results obtained at the INFN-LNS laboratory for the 40Ca(18O,18Ne)40Ar reaction at 270 MeV, give encouraging indication on the capability of the proposed technique to access relevant quantitative information. A key aspect of the project is the use of the K800 Superconducting Cyclotron (CS) for the acceleration of the required high resolution and low emittance heavy- ion beams and of the MAGNEX large acceptance magnetic spectrometer for the detection of the ejectiles. The use of the high-order trajectory reconstruction technique, implemented in MAGNEX, allows to reach the high mass, angular and energy resolution required even at very low cross section. The LNS set-up is today an ideal one for this research even in a worldwide perspective. However a main limitation on the beam current delivered by the accelerator and the maximum rate accepted by the MAGNEX focal plane detector must be sensibly overcome in order to systematically provide accurate numbers to the neutrino physics community in all the studied cases. The upgrade of the LNS facilities in this view is part of this project.
Aldehyde oxidase (AOX1) is an enzyme with broad substrate specificity, catalyzing the oxidation of a wide range of endogenous and exogenous aldehydes as well as N-heterocyclic aromatic compounds. In ...humans, the enzyme's role in phase I drug metabolism has been established and its importance is now emerging. However, the true physiologic function of AOX1 in mammals is still unknown. Further, numerous single-nucleotide polymorphisms (SNPs) have been identified in human AOX1. SNPs are a major source of interindividual variability in the human population, and SNP-based amino acid exchanges in AOX1 reportedly modulate the catalytic function of the enzyme in either a positive or negative fashion. For the reliable analysis of the effect of amino acid exchanges in human proteins, the existence of reproducible expression systems for the production of active protein in ample amounts for kinetic, spectroscopic, and crystallographic studies is required. In our study we report an optimized expression system for hAOX1 in Escherichia coli using a codon-optimized construct. The codon-optimization resulted in an up to 15-fold increase of protein production and a simplified purification procedure. The optimized expression system was used to study three SNPs that result in amino acid changes C44W, G1269R, and S1271L. In addition, the crystal structure of the S1271L SNP was solved. We demonstrate that the recombinant enzyme can be used for future studies to exploit the role of AOX in drug metabolism, and for the identification and synthesis of new drugs targeting AOX when combined with crystallographic and modeling studies.
Transport efficiency in large acceptance spectrometers Cavallaro, M.; Cappuzzello, F.; Carbone, D. ...
Nuclear instruments & methods in physics research. Section A, Accelerators, spectrometers, detectors and associated equipment,
05/2011, Letnik:
637, Številka:
1
Journal Article
Recenzirano
A general technique to study the transmission efficiency of charged particles through a large acceptance magnetic device is presented. This basically involves the measurement of the impact positions ...and angles of the particles in any plane normal to the optical axis and the use of a powerful algorithm for the reconstruction of the trajectories. This latter is designed to perform the calculations of highly non-linear transport functions and is essential when high-order aberrations are not negligible. The technique is applied to study the transport efficiency of the heavy ions produced in different nuclear reactions and analyzed by the MAGNEX large acceptance spectrometer. Both the angular integral and differential efficiency have been deduced with overall accuracy of about ±1.5% and ±5%, respectively.
Atopic dermatitis (AD) is a chronic inflammatory disease that may involve any cutaneous site; involvement of the genital area may greatly impair patients’ quality of life but, as the inspection of ...genitals is not usually conducted during the routine physical examination of patients with AD, the genital presentation of AD is frequently neglected and under‐reported. We decided to evaluate the incidence of genital AD in patients with moderate–severe AD and the relative response to anti‐interleukin (IL)‐4/IL‐13 dupilumab. In our study, a high incidence of genital AD emerged but the use of dupilumab allowed a generalized improvement.