Zn2+‐Regulated Self‐Sorting and Mixing of Phosphates and Carboxylates on the Surface of Functionalized Gold Nanoparticles

Herein, we describe the self‐sorting of phosphate‐ and carboxylate‐containing molecules on the surface of monolayer‐protected gold nanoparticles. Self‐sorting is driven by selective interactions between the phosphate probe and Zn²⁺ complexes in one monolayer; these interactions force the carboxylate probe to move to a second type of nanoparticle. This process effectively separates the probes and causes their localization in well‐defined spaces surrounding the nanoparticles. The removal/addition of Zn²⁺ metal ions from the system is used to convert the system from an ordered to a disordered state and vice versa. The possibility to control the location and transport of populations of molecules in a complex mixture creates new perspectives for the development of innovative complex catalytic systems that mimic nature.     

Elasticity and structure of chemically crosslinked polyurethanes

A combination of electron-microscopy, light-scattering, and stress-birefringence studies on chemically crosslinked polyurethanes point toward the existence of rodlike regions (“bundles”), approximately 3000–8000 Å in length and involving about 5% of the volume, in which molecular orientations are correlated. The elastic behavior of these networks—as indeed that of most rubberlike networks—deviates substantially from the Gaussian behavior. The empirical representation of the data in Mooney-Rivlin plots yields C₁ and C₂ constants which depend on the type of imposed strain. It is thus impossible to identify C₁ with the Gaussian behavior and C₂ with the deviation there-from. Instead, it is found that the elastic behavior can be adequately described if it is assumed that, as a result of the bundle structure, about 5% of the segments of each chain are not free to assume the normal random-walk configurations. The determination of the number of chains in the network from the elastic behavior remains ambiguous, however, and the behavior upon swelling is not (yet) adequately reproduced by the theory. It is conceivable that in many cases deviations from Gaussian elasticity behavior may be caused by an intermolecular structuring effect, rather than by various minor deficiencies in the Gaussian model for the single chain statistics or by anisotropic excluded volume effects, as has been proposed in the past. In the present case, the amount of bundle structure, as well as the C₂/C₁ values, increase with the number of urethane couplings per chain, and this suggests that the interaction of the highly polar urethane couplings is responsible for the structuring. In other networks one often finds a dependence of C₂/C₁ on the previous history of the sample, which suggests that an accidentally trapped order may be responsible for the elastic behavior.     

The rotating particles probe: A new technique to measure interactions between particles and a substrate

We demonstrate a new probing technique to measure physicochemical interactions between particles and a substrate in a fluid. The technique is based on the measurement of field-induced rotation of individual magnetic particles in contact with the substrate. The parallel measurement of many particles with single-particle resolution gives reliable statistics in a short time. Using this technique, the interaction between streptavidin-coated magnetic particles and a glass substrate is measured for various buffer conditions. Increased binding is quantified for increasing ionic strength and decreasing pH. The results are found to be in agreement with calculations of electrostatic interactions. We also apply the technique to study how binding is reduced by blocking the substrate with albumin.     

A memetic algorithm with dynamic population management for an integrated production–distribution problem

This paper studies an NP-hard multi-period production–distribution problem to minimize the sum of three costs: production setups, inventories and distribution. This problem is solved by a very recent form of metaheuristic called memetic algorithm with population management (MA∣PM). Contrary to classical two-phase methods (production planning, then distribution planning), the algorithm simultaneously tackles production and distribution decisions. Several versions with different population management strategies are evaluated and compared with a two-phase heuristic and a Greedy Randomized Adaptive Search Procedure (GRASP), on 90 randomly generated instances with 20 periods and 50, 100 or 200 customers. The significant savings obtained compared to the two other methods confirm both the interest of integrating production and distribution decisions and of using the MA∣PM template.     

Implicit depot assignments and rotations in vehicle routing heuristics

Vehicle routing variants with multiple depots and mixed fleet present intricate combinatorial aspects related to sequencing choices, vehicle type choices, depot choices, and depots positioning. This paper introduces a dynamic programming methodology for efficiently evaluating compound neighborhoods combining sequence-based moves with an optimal choice of vehicle and depot, and an optimal determination of the first customer to be visited in the route, called rotation. The assignment choices, making the richness of the problem, are thus no more addressed in the solution structure, but implicitly determined during each move evaluation. Two meta-heuristics relying on these concepts, an iterated local search and a hybrid genetic algorithm, are presented. Extensive computational experiments demonstrate the remarkable performance of these methods on classic benchmark instances for multi-depot vehicle routing problems with and without fleet mix, as well as the notable contribution of the implicit depot choice and positioning methods to the search performance. New state-of-the-art results are obtained for multi-depot vehicle routing problems (MDVRP), and multi-depot vehicle fleet mix problems (MDVFMP) with unconstrained fleet size. The proposed concepts are fairly general, and widely applicable to many other vehicle routing variants.