Challenges in thermal noise for 3rd generation of gravitational wave detectors

Various noise sources limit the sensitivity of current interferometric gravitational wave detectors, including seismic noise, thermal noise of the optical components and suspension elements and photon shot noise. Plans are in place for a suite of hardware upgrades which should increase the sensitivity of these detectors by reducing the various noise sources. With these designs for 2nd generation detectors mature, techniques for further improvement of detector sensitivity by a factor of approximately 10 are under study. A particular challenge is the reduction of the thermal noise associated with the interferometer mirrors and their suspensions. We review the current status of research on thermal noise in interferometric gravitational wave detectors. Aspects of possible techniques for use in future ‘3rd generation detectors’ such as cryogenics and diffractive optics are discussed.     

Retention prediction of a set of amino acids under gradient elution conditions in hydrophilic interaction liquid chromatography

The analysis of amino acids presents significant challenges to contemporary analytical separations. The present paper investigates the possibility of retention prediction in hydrophilic interaction chromatography (HILIC) gradient elution based on the analytical solution of the fundamental equation of the multilinear gradient elution derived for reversed‐phase systems. A simple linear dependence of the logarithm of the solute retention (ln k) upon the volume fraction of organic modifier (φ) in a binary aqueous‐organic mobile is adopted. Utility of the developed methodology was tested on the separation of a mixture of 21 amino acids carried out with 14 different gradient elution programs (from simple linear to multilinear and curved shaped) using ternary eluents in which a mixture of methanol and water (1:1, v/v) was the strong eluting member and acetonitrile was the weak solvent. Starting from at least two gradient runs, the prediction of solute retention obtained under all the rest gradients was excellent, even when curved gradient profiles were used. Development of such methodologies can be of great interest for a wide range of applications.     

D-optimal design of an untargeted HS-SPME-GC-TOF metabolite profiling method

In recent times we have seen the development of many "-omics" technologies. One of the youngest is undoubtedly metabolomics, which aims to define the whole chemical fingerprint unique to each specific organism. The development and optimisation of an untargeted high-throughput method capable of investigating the volatile fraction of a biological system represents a crucial step for the success of such holistic approaches, and specific optimisation criteria must be developed in connection with suitable experimental designs. In this paper experimental designs (D-optimal) were applied for the first time as an automatic optimisation tool to an untargeted HS-SPME-GC-TOF method. In this case, optimal conditions correspond to a maximal number of detected features, in order to provide a fingerprint that is as complete as possible. The system under study is the grape berry. Four variables were considered: the type of fibre, extraction time, equilibration time and temperature. The results show that the D-optimal design methodology provides an easily interpretable assessment of experimental settings. This and other specific properties of the D-optimal design, such as the possibility to explicitly exclude certain experimental conditions, make it an extremely suitable strategy for method optimisation in untargeted metabolomics.     

Hydrophilic interaction ultra performance liquid chromatography retention prediction under gradient elution

The development and application of new separation mechanisms such as hydrophilic interaction chromatography (HILIC) is of high importance for the simultaneous analysis of polar molecules such as primary metabolites. However the retention mechanism in HILIC is not fully understood and as a result retention prediction tools are not at hand for this chromatographic approach. In the present report we study the utility of a simple algorithm, based on a simple linear and/or a simple logarithmic retention model, for retention prediction in HILIC gradient separation of a mixture of 23 selected compounds including (poly)amines, amino acids, saccharides, and other molecules. Utilizing two types of gradient elution programs with or without an isocratic part, retention data were collected in order to build prediction models. Starting from at least three gradient runs the prediction of analyte retention was very satisfactory for all gradient programs tested, providing useful evidence of the value of such retention time prediction methodologies.     

Population branching in the conical intersection of the retinal chromophore revealed by multipulse ultrafast optical spectroscopy

The branching ratio of the excited-state population at the conical intersection between the S(1) and S(0) energy surfaces (Φ(CI)) of a protonated Schiff base of all-trans retinal in protic and aprotic solvents was studied by multipulse ultrafast transient absorption spectroscopy. In particular, pump-dump-probe experiments allowed to isolate the S(1) reactive state and to measure the photoisomerization time constant with unprecedented precision. Starting from these results, we demonstrate that the polarity of the solvent is the key factor influencing the Φ(CI) and the photoisomerization yield.     

Mechanisms responsible for chemical shifts of core-level binding energies and their relationship to chemical bonding

A comprehensive review of different mechanisms which contribute to the chemical shifts of core-level binding energies, BEs, is made. A principle focus is on showing how the mechanisms can be used to relate the BE shifts to features of the chemical bonding and chemical interactions in the studied system. Several initial state mechanisms are identified; while some are well known, the importance of others has been only recognized fairly recently. A theoretical framework is presented which places the analysis and interpretation of these BE shifts on a firm foundation. A rigorous definition and distinction of initial and final state effects is presented. This definition is applied to show that initial state effects are often the dominant factors for the chemical BE shifts. It is also shown that, in many cases, theoretical approaches involving the use of constrained variations can permit a clear and definitive separation of the contributions of the different mechanisms. Several representative applications to the analysis and interpretation of core-level BE shifts are described which show how the theoretical methods of analysis can be used to identify the mechanisms important for the BE shifts. Often more than one mechanism makes an important contribution to the shifts and it is common that the contributions will be canceling. When all of the relevant mechanisms are taken into account in the analysis of the BE shifts, these shifts do provide valuable information about the chemical bonding and electronic structure of the materials being studied. The mechanisms presented and the theoretical frameworks described provide a unified view of BE chemical shifts.