Bundle Methods in Stochastic Optimal Power Management: A Disaggregated Approach Using Preconditioners

A specialized variant of bundle methods suitable for large-scale problems with separable objective is presented. The method is applied to the resolution of a stochastic unit-commitment problem solved by Lagrangian relaxation. The model includes hydro- as well as thermal-powered plants. Uncertainties lie in the demand, which evolves in time according to a tree of scenarios. Dual variables are preconditioned by using probabilities associated to nodes in the tree The approach is illustrated by numerical results, obtained on a model of the French production mix over a time horizon of 10 days and 1 month.     

A geometric study of duality gaps, with applications

Lagrangian relaxation is often an efficient tool to solve (large-scale) optimization problems, even nonconvex. However it introduces a duality gap, which should be small for the method to be really efficient. Here we make a geometric study of the duality gap. Given a nonconvex problem, we formulate in a first part a convex problem having the same dual. This formulation involves a convexification in the product of the three spaces containing respectively the variables, the objective and the constraints. We apply our results to several relaxation schemes, especially one called “Lagrangean decomposition” in the combinatorial-optimization community, or “operator splitting” elsewhere. We also study a specific application, highly nonlinear: the unit-commitment problem. Received: June 1997 / Accepted: December 2000?Published online April 12, 2001     

Volatile compounds profiling by using proton transfer reaction‐time of flight‐mass spectrometry (PTR‐ToF‐MS). The case study of dark chocolates organoleptic differences

Direct‐injection mass spectrometry (DIMS) techniques have evolved into powerful methods to analyse volatile organic compounds (VOCs) without the need of chromatographic separation. Combined to chemometrics, they have been used in many domains to solve sample categorization issues based on volatilome determination. In this paper, different DIMS methods that have largely outperformed conventional electronic noses (e‐noses) in classification tasks are briefly reviewed, with an emphasis on food‐related applications. A particular attention is paid to proton transfer reaction mass spectrometry (PTR‐MS), and many results obtained using the powerful PTR‐time of flight‐MS (PTR‐ToF‐MS) instrument are reviewed. Data analysis and feature selection issues are also summarized and discussed. As a case study, a challenging problem of classification of dark chocolates that has been previously assessed by sensory evaluation in four distinct categories is presented. The VOC profiles of a set of 206 chocolate samples classified in the four sensory categories were analysed by PTR‐ToF‐MS. A supervised multivariate data analysis based on partial least squares regression‐discriminant analysis allowed the construction of a classification model that showed excellent prediction capability: 97% of a test set of 62 samples were correctly predicted in the sensory categories. Tentative identification of ions aided characterisation of chocolate classes. Variable selection using dedicated methods pinpointed some volatile compounds important for the discrimination of the chocolates. Among them, the CovSel method was used for the first time on PTR‐MS data resulting in a selection of 10 features that allowed a good prediction to be achieved. Finally, challenges and future needs in the field are discussed.     

Dielectrophoresis‐assisted creation of cell aggregates under flow conditions using planar electrodes

We present a microfluidic platform allowing dielectrophoresis‐assisted formation of cell aggregates of controlled size and composition under flow conditions. When specific experimental conditions are met, negative dielectrophoresis allows efficient concentration of cells towards electric field minima and subsequent aggregation. This bottom‐up assembly strategy offers several advantages with respect to the targeted application: first, dielectrophoresis offers precise control of spatial cell organization, which can be adjusted by optimizing electrode design. Then, it could contribute to accelerate the establishment of cell‐cell interactions by favoring close contact between neighboring cells. The trapping geometry of our chip is composed of eight electrodes arranged in a circle. Several parameters have been tested in simulations to find the best configurations for trapping in flow. Those configurations have been tested experimentally with both polystyrene beads and human embryonic kidney cells. The final design and experimental setup have been optimized to trap cells and release the created aggregates on demand.     

Synthesis and biological activity of PTEN-resistant analogues of phosphatidylinositol 3,4,5-trisphosphate

The activation of phosphatidylinositol 3-kinase (PI 3-K) and subsequent production of PtdIns(3,4,5)P3 launches a signal transduction cascade that impinges on a plethora of downstream effects on cell physiology. Control of PI 3-K and PtdIns(3,4,5)P3 levels is an important therapeutic target in treatments for allergy, inflammation, cardiovascular, and malignant human diseases. We designed metabolically stabilized, that is, phosphatase resistant, analogues of PtdIns(3,4,5)P3 as probes for long-lived potential agonists or potential antagonists for cellular events mediated by PtdIns(3,4,5)P3. In particular, two types of analogues were prepared containing phosphomimetics that would be selectively resistant to the lipid 3-phosphatase PTEN. The total asymmetric synthesis of the 3-phosphorothioate-PtdIns(3,4,5)P3 and 3-methylenephosphonate-PtdIns(3,4,5)P3 analogues is described. These two analogues showed differential binding to PtdIns(3,4,5)P3 binding modules, and both were potential long-lived activators that mimicked insulin action in sodium transport in A6 cells.     

A mild radical procedure for the reduction of B-alkylcatecholboranes to alkanes

A mild radical-mediated reduction of organoboranes is reported. The reducing agent is methanol complexed by the Lewis acidic B-methoxycatecholborane.     

Free-radical hydroxylation reactions of alkylboronates

The radical hydroxylation of B-alkylcatecholboranes, easily prepared by hydroboration of olefins, has been investigated. When molecular oxygen was used as oxidizing agent, the corresponding alcohols were obtained directly without alkaline treatment. The presence of Lewis base additives such as Et3N or DABCO has a benefic effect on the selectivity and yield. Alternatively, 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) reacts cleanly with B-alkylcatecholboranes to afford alkyl radicals that can be trapped by a second equivalent of TEMPO to give alkoxyamines. Reduction of the alkoxyamines with zinc in acetic acid affords the desired alcohols. The whole procedure is particularly mild and does not require any basic condition. The two approaches presented in this paper are valuable and represent mild alternatives to the classical alkaline oxidation of organoboranes to alcohols.     

Perrhenat-katalysierte Umlagerung von Ethinyl-β-ionol

Perrhenate-Catalyzed Rearrangement of Ethinyl-β-ionol The rearrangement of 2-ethinyl-β-ionol ( 1 ) to α,β-unsaturated carbonyl compounds using tetraalkylammonium perrhenate catalysts was studied. It was found that the Rupe-Kambli product, ketone 2 , is the main product (ca. 70%) of this rearrangement. The by-product 4 (ca. 15%) is formed in a ring-closure reaction.     

First enantioselective allylic etherification with phenols catalyzed by chiral ruthenium bisoxazoline complexes

Regio- and enantioselective substitution of cinnamyl chloride by phenols has been achieved with up to 82% enantiomeric excess, using a ruthenium catalyst prepared from [Cp*(CH(3)CN)(3)Ru][PF(6)] and a chiral bisoxazoline ligand.