Engineered inorganic core/shell nanoparticles

It has been for a long time recognized that nanoparticles are of great scientific interest as they are effectively a bridge between bulk materials and atomic structures. At first, size effects occurring in single elements have been studied. More recently, progress in chemical and physical synthesis routes permitted the preparation of more complex structures. Such structures take advantages of new adjustable parameters including stoichiometry, chemical ordering, shape and segregation opening new fields with tailored materials for biology, mechanics, optics magnetism, chemistry catalysis, solar cells and microelectronics. Among them, core/shell structures are a particular class of nanoparticles made with an inorganic core and one or several inorganic shell layer(s). In earlier work, the shell was merely used as a protective coating for the core. More recently, it has been shown that it is possible to tune the physical properties in a larger range than that of each material taken separately. The goal of the present review is to discuss the basic properties of the different types of core/shell nanoparticles including a large variety of heterostructures. We restrict ourselves on all inorganic (on inorganic/inorganic) core/shell structures. In the light of recent developments, the applications of inorganic core/shell particles are found in many fields including biology, chemistry, physics and engineering. In addition to a representative overview of the properties, general concepts based on solid state physics are considered for material selection and for identifying criteria linking the core/shell structure and its resulting properties. Chemical and physical routes for the synthesis and specific methods for the study of core/shell nanoparticle are briefly discussed.     

N-Boc and N-CBz Ethyl Oxamates: New Gabriel Reagents

N-Boc and N-CBz ethyl oxamates can be directly coupled with various halides under Gabriel conditions which afford the corresponding N-protected amines after mild deprotection with LiOH.     

The enhanced cyan fluorescent protein: a sensitive pH sensor for fluorescence lifetime imaging

pH is an important parameter that affects many functions of live cells, from protein structure or function to several crucial steps of their metabolism. Genetically encoded pH sensors based on pH-sensitive fluorescent proteins have been developed and used to monitor the pH of intracellular compartments. The quantitative analysis of pH variations can be performed either by ratiometric or fluorescence lifetime detection. However, most available genetically encoded pH sensors are based on green and yellow fluorescent proteins and are not compatible with multicolor approaches. Taking advantage of the strong pH sensitivity of enhanced cyan fluorescent protein (ECFP), we demonstrate here its suitability as a sensitive pH sensor using fluorescence lifetime imaging. The intracellular ECFP lifetime undergoes large changes (32 %) in the pH 5 to pH 7 range, which allows accurate pH measurements to better than 0.2 pH units. By fusion of ECFP with the granular chromogranin A, we successfully measured the pH in secretory granules of PC12 cells, and we performed a kinetic analysis of intragranular pH variations in living cells exposed to ammonium chloride.     

Nonparametric estimation for i.i.d. Gaussian continuous time moving average models

Statistical Inference for Stochastic Processes - We consider a Gaussian continuous time moving average model $$X(t)=\int _0^t a(t-s)dW(s)$$ where W is a standard Brownian motion and a(.) a...     

Testing “microscopic” theories of glass-forming liquids

We assess the validity of “microscopic” approaches of glass-forming liquids based on the sole knowledge of the static pair density correlations. To do so, we apply them to a benchmark provided by two liquid models that share very similar static pair density correlation functions while displaying distinct temperature evolutions of their relaxation times. We find that the approaches are unsuccessful in describing the difference in the dynamical behavior of the two models. Our study is not exhaustive, and we have not tested the effect of adding corrections by including, for instance, three-body density correlations. Yet, our results appear strong enough to challenge the claim that the slowdown of relaxation in glass-forming liquids, for which it is well established that the changes of the static structure factor with temperature are small, can be explained by “microscopic” approaches only requiring the static pair density correlations as nontrivial input.     

Adiabatic versus nonadiabatic photoisomerization in photochromic ruthenium sulfoxide complexes: a mechanistic picture from density functional theory calculations

Polypyridine ruthenium sulfoxide complexes are intriguing compounds which can display both photochromic and electrochromic properties. These properties are based on the Ru-S → Ru-O linkage isomerization capability of the sulfoxide group. The photoisomerization mechanism is of particular importance in order to understand the photophysical properties of such molecules. Density functional theory calculations demonstrate that the main photoisomerization mechanism is nonadiabatic for the system under study in agreement with the experimental observations. Indeed, funnels for efficient radiationless decay back to the ground state are shown to be easily accessible compared to transition states on the adiabatic triplet potential energy surface. However, we highlight for the first time that triplet metal-centered states play a central role in the photoisomerization mechanism of these compounds.     

Response functions of 58Ni, 116Sn AND 208Pb to the excitation of intermediate-energy α-particles

Inelastic scattering of 340 MeV and 480 MeV α-particles has been measured on ⁵⁸Ni, ¹¹⁶Sn and ²⁰⁸Pb up to 60 MeV excitation energy. Consistent background subtraction and multipole analysis has provided the repartition of multipole strength for all three nuclei. The so-obtained response functions show the already known low-energy giant resonances in a detailed way, as well as new giant resonances at high energy.     

Role of nanomechanical properties in the tribological performance of phospholipid biomimetic surfaces

The role of phospholipid bilayers in controlling and reducing frictional forces between biological surfaces is investigated by three complementary experiments: friction forces are measured using a homemade tribometer, mechanical resistance to indentation is measured by AFM, and lipid bilayer degradation is controlled in situ during friction testing using fluorescence microscopy. DPPC lipid bilayers in the solid phase generate friction coefficients as low as 0.002 (comparable to that found for cartilage) that are stable through time. DOPC bilayers formed by the vesicle fusion method or the adsorption of mixed micelles generate higher friction coefficients. These coefficients increased through time, during which the bilayers degraded. The friction coefficient is correlated with the force needed to penetrate the bilayer with the AFM tip. With only one bilayer in the contact region, the friction increased to a similar value of about 0.08 for the DPPC and DOPC. Our study therefore shows that good mechanical stability of the bilayers is essential and suggests that the low friction coefficient is ensured by the hydration layers between adjacent lipid bilayers.