Vibrational spectroscopy of 3,4-difluorocyclobutenes: cis-d0, trans-d0 and trans-d4 species

Infrared and Raman spectra were recorded for cis-3,4-difluorocyclobutene (cDFCB) and trans-3,4-difluorocyclobutene-d4. Unscaled density functional theory (DFT) calculations of frequencies and intensities at the B3LYP/6-311++G(d,p) level supported the complete assignment of the vibrational fundamentals. The previous assignment of fundamentals of trans-3,4-difluorocyclobutene was revised. An unusual blue shift occurs for the methylenic CH-stretching frequencies of cis-3,4-difluorocyclobutene in going from the gas phase to the liquid phase. This hydrogen bond effect is related to similar observations recently reported and interpreted. The blue shift does not occur for the vinylic CH bonds of the cis isomer and does not occur for either type of CH bond in the trans isomer.     

Cocrystal Formation through Mechanochemistry: from Neat and Liquid‐Assisted Grinding to Polymer‐Assisted Grinding

Mechanochemistry is an effective method for the preparation of multicomponent crystal systems. In the present work, we propose an alternative to the established liquid‐assisted grinding (LAG) approach. Polymer‐assisted grinding (POLAG) is demonstrated to provide a new class of catalysts for improving reaction rate and increasing product diversity during mechanochemical cocrystallization reactions. We demonstrate that POLAG provides advantages comparable to the conventional liquid‐assisted process, whilst eliminating the risk of unwanted solvate formation as well as enabling control of resulting particle size. It represents a new approach for the development of functional materials through mechanochemistry, and possibly opens new routes toward the understanding of the mechanisms and pathways of mechanochemical cocrystal formation.     

The modeling of coalition for environmental protection within co-utility framework

The game theoretic modelling of coalition for environmental protection within the framework of a new concept of co-utility is discussed. The co-utility concept contains mainly two elements. Firstly, agents can increase their payoffs by collaborating with each-other. Secondly, the outcome of collaboration is robust towards internal and external disturbances. The advantages of using of co-utility are two-fold. Primarily, the co-utility concept is broad and can serve as an umbrella concept in all applications where agents have a space for simultaneous improvement of payoffs. Secondly the co-utility concept can be associated with different stability concept such as myopic or farsighted stability. The myopic and farsighted co-utile sets are defined and their element-co-utile outcomes are found.     

Crystallographic analysis of metal-ion binding to human ubiquitin

The metal-binding ability of human ubiquitin (hUb) towards a selection of biologically relevant metal ions and complexes has been probed. Different techniques have been used to obtain crystals suitable for crystallographic analysis. In the first type of experiments, crystals of hUb have been soaked in solutions containing copper(II) acetate and two metallodrugs, Zeise salt (K[PtCl(3)(η(2)-C(2)H(4))]·H(2)O) and cisplatin (cis-[PtCl(2)(NH(3))(2)]). The Zeise salt is used in a test for hepatitis, whereas cisplatin is one of the most powerful anticancer drugs in clinical use. The Zeise salt readily reacts with hUb crystals to afford an adduct with three platinum residues per protein molecule, Pt(3)-hUb. In contrast, copper(II) acetate and cisplatin were found to be unreactive for contact times up to one hour and to cause degradation of the hUb crystals for longer times. In the second type of experiments, hUb was cocrystallized with a solution of copper(II) or zinc(II) acetate or cisplatin. Zinc(II) acetate gives, at low metal-to-protein molar ratios (8:1), crystals containing one metal ion per three molecules of protein, Zn-hUb(3) (already reported in previous work), whereas at high metal-to-protein ratios (70:1) gives crystals containing three Zn(II) ions per protein molecule, Zn(3)-hUb. In contrast, once again, copper(II) acetate and cisplatin, even at low metal-to-protein ratios, do not give crystalline material. In the soaking experiment, the Zeise anion leads to simultaneous platination of His68, Met1, and Lys6. Present and previous results of cocrystallization experiments performed with Zn(II) and other Group 12 metal ions allow a comprehensive understanding of the metal-ion binding properties of hUb with His68 as the main anchoring site, followed by Met1 and carboxylic groups of Glu16, Glu18, Glu64, Asp21, and Asp32, to be reached. In the case of platinum, Lys6 can also be a binding site. The amount of bound metal ion, with respect to that of the protein, appears to be a relevant parameter influencing crystal packing.     

A multiscale analysis of the mechanical behavior of a thermo-oxidized c/epoxy lamina

The mechanical behavior of carbon-fiber-reinforced polymer matrix composites having undergone a thermo-oxidation process is studied. The purpose is to perform a multiscale analysis of the consequences of oxidation on the intrinsic mechanical properties of the external composite ply and on the internal mechanical states experienced by the structure under mechanical loads. The effective mechanical properties of oxidized composite plies are determined according to the Eshelby–Kr?ner self-consistent homogenization procedure, depending on evolution of the oxidation process. The results obtained are compared with estimates found by the finite-element method. The macroscopic mechanical states are calculated for a unidirectional composite and laminates. The macroscopic stresses in each ply of the structure are determined by the classical lamination theory and the finite-element method, whereas the local stresses in the carbon fiber and epoxy matrix are calculated by using an analytical stress concentration relation.     

A Multi-Period Renewal equipment problem

This paper looks at a Multi-Period Renewal equipment problem (MPR). It is inspired by a specific real-life situation where a set of hardware items is to be managed and their replacement dates determined, given a budget over a time horizon comprising a set of periods. The particular characteristic of this problem is the possibility of carrying forward any unused budget from one period to the next, which corresponds to the multi-periodicity aspect in the model. We begin with the industrial context and deduce the corresponding knapsack model that is the subject of this paper. Links to certain variants of the knapsack problem are next examined. We provide a study of complexity of the problem, for some of its special cases, and for its continuous relaxation. In particular, it is established that its continuous relaxation and a special case can be solved in (strongly) polynomial time, that three other special cases can be solved in pseudo-polynomial time, while the problem itself is strongly NP-hard when the number of periods is unbounded. Next, two heuristics are proposed for solving the MPR problem. Experimental results and comparisons with the Martello&Toth and Dantzig heuristics, adapted to our problem, are provided.     

A robust approach to the chance-constrained knapsack problem

In this paper, the chance-constrained knapsack problem (CKP) is addressed. Relying on robust optimization, a tractable combinatorial algorithm is proposed to solve approximately CKP. For two specific classes of uncertain knapsack problems, it is proved to solve CKP at optimality.     

The robust binomial approach to chance-constrained optimization problems with application to stochastic partitioning of large process networks

In this paper, we study an interpretation of the sample-based approach to chance-constrained programming problems grounded in statistical testing theory. On top of being simple and pragmatic, this approach is theoretically well founded, non parametric and leads to a general method for leveraging existing heuristic algorithms for the deterministic case to their chance-constrained counterparts. Throughout this paper, this algorithm design approach is illustrated on a real world graph partitioning problem which crops up in the field of compilation for parallel systems. Extensive computational results illustrate the practical relevance of the approach, as well as the robustness of the obtained solutions.     

Timetabling of sorting slots in a logistic warehouse

We study a problem that occurs at the end of a logistic stream in a warehouse and which concerns the timetabling of the sorting slots that are used to accommodate the prepared orders before they are dispatched. We consider a set of orders to be prepared in a certain number of preparation shops over a given time horizon. Each order is associated with the truck that will transport it to the customer. A sorting slot is an accumulation area where processed orders wait to be loaded onto a truck. For a given truck a known number of sorting slots is needed from the time the first order for this truck begins to be prepared, right up until the truck’s scheduled departure time. Since several orders destined for different trucks are processed simultaneously, and since the number of sorting slots is limited, the timetabling of these resources is necessary to ensure that all orders can be processed over the considered time horizon. In this paper we describe the general industrial context of the problem and we formalize it. We state that some particular cases of the problem are polynomially solvable while the general problem is NP-complete. We then propose optimization methods for solving the problem.     

Mechanochemical reactivity inhibited,prohibited and reversed by liquid additives: examples from crystal-form screens

We demonstrate that liquid additives can exert inhibitive or prohibitive effects on the mechanochemical formation of multi-component molecular crystals, and report that certain additives unexpectedly prompt the dismantling of such solids into physical mixtures of their constituents. Computational methods were employed in an attempt to identify possible reasons for these previously unrecognised effects of liquid additives on mechanochemical transformations.

Liquid additives can exert catalytic, inhibitive or prohibitive effects on the mechanochemical formation of multi-component molecular crystals.