Synthetic Organic Design for Solar Fuel Systems

From the understanding of biological processes and metalloenzymes to the development of inorganic catalysts, electro‐ and photocatalytic systems for fuel generation have evolved considerably during the last decades. Recently, organic and hybrid organic systems have emerged to challenge the classical inorganic structures through their enormous chemical diversity and modularity that led earlier to their success in organic (opto)electronics. This Minireview describes recent advances in the design of synthetic organic architectures and promising strategies toward (solar) fuel synthesis, highlighting progress on materials from organic ligands and chromophores to conjugated polymers and covalent organic frameworks.     

Gelatin‐Alginate Gels and Their Enzymatic Modifications: Controlling the Delivery of Small Molecules

The release of molecules entrapped within biogels is dictated by diffusion laws. Innovative biogel architectures are conceived and tested to control small molecule delivery from gelatin gels. The ionic interactions modulate the release of small molecules. Alginate is then added to gelatin gels and further hydrolyzed; the influence of viscosity is discussed. Next, various mixed gels are compared, such as a gelatin‐alginate IPN and the original architecture of an alginate gel entrapped in a gelatin gel with or without a polysaccharidase. The relative influence of ionic interactions and diffusional constraints on the delivery of small charged molecules is explored, and a solution for controlling diffusion is proposed for any situation.

     

Organic solvent extraction as a versatile procedure to identify hydrophobic chloroplast membrane proteins

As a complementary approach to genome projects, proteomic analyses have been set up to identify new gene products. One of the major challenges in proteomics concerns membrane proteins, especially the minor ones. A procedure based on the differential extraction of membrane proteins in chloroform/methanol mixtures, was tested on the two different chloroplast membrane systems: envolope and thylakoid membranes. Combining the use of classical sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) and mass spectrometry analyses, this procedure enabled identification of hydrophobic proteins. The propensity of hydrophobic proteins to partition in chloroform/methanol mixtures was directly correlated with the number of amino acid residues/number of putative transmembrane regions (Res/TM ratio). Regardless of the particular case of some lipid-interacting proteins, chloroform/methanol extractions allowed enrichment of hydrophobic proteins and exclusion of hydrophilic proteins from both membrane systems, thus demonstrating the versatility of the procedure.     

Optimization of Hydrogen‐Evolving Photochemical Molecular Devices

A molecular photocatalyst consisting of a Ru^II photocenter, a tetrapyridophenazine bridging ligand, and a PtX₂ (X=Cl or I) moiety as the catalytic center functions as a stable system for light‐driven hydrogen production. The catalytic activity of this photochemical molecular device (PMD) is significantly enhanced by exchanging the terminal chlorides at the Pt center for iodide ligands. Ultrafast transient absorption spectroscopy shows that the intramolecular photophysics are not affected by this change. Additionally, the general catalytic behavior, that is, instant hydrogen formation, a constant turnover frequency, and stability are maintained. Unlike as observed for the Pd analogue, the presence of excess halide does not affect the hydrogen generation capacity of the PMD. The highly improved catalytic efficiency is explained by an increased electron density at the Pt catalytic center, this is confirmed by DFT studies.     

Computing the conditioning of the components of a linear least‐squares solution

In this paper, we address the accuracy of the results for the overdetermined full rank linear least‐squares problem. We recall theoretical results obtained in (SIAM J. Matrix Anal. Appl. 2007; 29 (2):413–433) on conditioning of the least‐squares solution and the components of the solution when the matrix perturbations are measured in Frobenius or spectral norms. Then we define computable estimates for these condition numbers and we interpret them in terms of statistical quantities when the regression matrix and the right‐hand side are perturbed. In particular, we show that in the classical linear statistical model, the ratio of the variance of one component of the solution by the variance of the right‐hand side is exactly the condition number of this solution component when only perturbations on the right‐hand side are considered. We explain how to compute the variance–covariance matrix and the least‐squares conditioning using the libraries LAPACK (LAPACK Users' Guide (3rd edn). SIAM: Philadelphia, 1999) and ScaLAPACK (ScaLAPACK Users' Guide. SIAM: Philadelphia, 1997) and we give the corresponding computational cost. Finally we present a small historical numerical example that was used by Laplace (Théorie Analytique des Probabilités. Mme Ve Courcier, 1820; 497–530) for computing the mass of Jupiter and a physical application if the area of space geodesy. Copyright © 2008 John Wiley & Sons, Ltd.     

A minimal amount of acrylonitrile turns the nitroxide‐mediated polymerization of methyl methacrylate into an almost ideal controlled/living system

Nitroxide‐mediated controlled/living free‐radical polymerization of methyl methacrylate initiated by the SG1‐based alkoxyamine BlocBuilder was successfully performed in bulk at 80–99 °C with the help of a very small amount of acrylonitrile (AN, 2.2–8.8 mol %) as a comonomer. Well‐defined PMMA‐rich P(MMA‐co‐AN) copolymers were prepared with the number‐average molar mass, M_n, in the 6.1–32 kg mol^?1 range and polydispersity indexes as low as 1.24. Incorporation of AN in the copolymers was demonstrated by ¹H and ¹³C NMR spectroscopy, and its effect on the chain thermal properties was evaluated by DSC and TGA analyses. Investigation of chain‐end functionalization by an alkoxyamine group was performed by means of ³¹P NMR spectroscopy and chain extensions from a P(MMA‐co‐AN)‐SG1 macroinitiator. It demonstrated the very high proportion of SG1‐terminated polymer chains, which opened the door to block copolymer synthesis with a high quality of control. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 34–47, 2010     

Modular approach for modeling a multi-energy district boiler

The present paper deals with the modeling of a district boiler (city of La Rochelle, west coast of France), as part of the OptiEnR research project. This “multi-energy” boiler supplies domestic hot water and heats residential and public buildings, using mainly wood and sometimes fuel or gas if necessary. The OptiEnR research project focuses on optimizing the performance of the boiler. Its main objective is to minimize the use of fossil energy, stocking renewable energy during low-demand periods and using it when peak-demand is high. Because of both the complexity of the plant as a whole and the strong interactions between the sub-systems (the wood boiler, the gas-fuel oil boiler, the breaking pressure bottle, the cogeneration plant, the hot water distribution network), a modular approach has been proposed. According to what information is available, a combination of white, grey and black boxes (Hammerstein–Wiener models) has been used to carry out the modeling task. To answer for the lack of information, additional parameters were proposed and identified. The model has been first used in simulation during heating periods, with the aim of optimizing both the parameters of the boilers control systems and the use of wood, gas and fuel oil. Next, it will be used, when adding to the plant a thermal storage unit and implementing a model predictive controller, to improve its functioning, especially reducing the coverage rate of the fossil energy boiler.     

A two-mass expanding exact space-time solution

In order to understand how locally static configurations around gravitationally bound bodies can be embedded in an expanding universe, we investigate the solutions of general relativity describing a space–time whose spatial sections have the topology of a 3-sphere with two identical masses at the poles. We show that Israel junction conditions imply that two spherically symmetric static regions around the masses cannot be glued together. If one is interested in an exterior solution, this prevents the geometry around the masses to be of the Schwarzschild type and leads to the introduction of a cosmological constant. The study of the extension of the Kottler space–time shows that there exists a non-static solution consisting of two static regions surrounding the masses that match a Kantowski–Sachs expanding region on the cosmological horizon. The comparison with a Swiss-Cheese construction is also discussed.