Thermodynamic transferability of coarse-grained potentials for polymer-additive systems

In this work we study the transferability of systematically coarse-grained (CG) potentials for polymer-additive systems. The CG nonbonded potentials between the polymer (atactic polystyrene) and three different additives (ethylbenzene, methane and neopentane) are derived using the Conditional Reversible Work (CRW) method, recently proposed by us [Brini et al., Phys. Chem. Chem. Phys., 2011, 13, 10468-10474]. A CRW-based effective pair potential corresponds to the interaction free energy between the two atom groups of an atomistic parent model that represent the coarse-grained interaction sites. Since the CRW coarse-graining procedure does not involve any form of parameterisation, thermodynamic and structural properties of the condensed phase are predictions of the model. We show in this work that CRW-based CG models of polymer-additive systems are capable of predicting the correct structural correlations in the mixture. Furthermore, the excess chemical potentials of the additives obtained with the CRW-based CG models and the united-atom parent models are in satisfactory agreement and the CRW-based CG models show a good temperature transferability. The temperature transferability of the model is discussed by analysing the entropic and enthalpic contributions to the excess chemical potentials. We find that CRW-based CG models provide good predictions of the excess entropies, while discrepancies are observed in the excess enthalpies. Overall, we show that the CRW CG potentials are suitable to model structural and thermodynamic properties of polymer-penetrant systems.     

Exploring the Palladium? and Platinum?Bis(pyridine) Complex Motif by NMR Spectroscopy,X‐ray Crystallography, (Tandem) Mass Spectrometry,and Isothermal Titration Calorimetry: Do Substituent Effects Follow Chemical Intuition?

A series of ten palladium? bis(pyridine) complexes, as well as their corresponding platinum complexes, have been synthesized. The pyridine ligands in each series carried different σ‐donor and/or π‐acceptor/donor substituents at the para‐position of their pyridine rings. These complexes were analysed by NMR spectroscopy, X‐ray crystallography, (tandem) MS, and isothermal titration calorimetry (ITC) to validate whether these methods allowed us to obtain a concise and systematic picture of the relative and absolute thermodynamic stabilities of the complexes, as determined by the electronic effects of the substituents. Interestingly, the NMR spectroscopic data hardly correlated with the expected substituent effects but the heteronuclear platinum? phosphorus coupling constants did. Crystallographic data were found to be blurred by packing effects. Instead, tandem MS and ITC data were in line with each other and followed the expected trends.     

Probiotic and prebiotic applications for vaginal health

Infections of the urogenital tract in women are extremely common, and there is no evidence of a reduction in incidence. Treatment and preventive strategies have been relatively unchanged for 50 years. The concept of using probiotic lactobacilli or prebiotics that stimulate the growth of protective organisms emerged in the mid-1980s and has led to several strains being tested successfully in women. With the advent of genomic profiling of the healthy vaginal microbiota, an improved understanding of metabolic systems within lactobacilli, and the ability to deliver products in food and supplement forms, the future should see new ways for women to restore and maintain their vaginal health, without the side effects of pharmaceutical agents. Indeed, studies indicate that probiotics can be taken in conjunction with the antibiotics and antifungal agents used to eradicate infections. In the future, probiotics and prebiotics will represent an important adjunct to pharmaceutical and other approaches used to care for feminine health.     

Nilpotent algebras and affinely homogeneous surfaces

To every nilpotent commutative algebra N{\mathcal{N}} of finite dimension over an arbitrary base field of characteristic zero a smooth algebraic subvariety S ì N{S\subset\mathcal{N}} can be associated in a canonical way whose degree is the nil-index and whose codimension is the dimension of the annihilator A{\mathcal{A}} of N{\mathcal{N}}. In case N{\mathcal{N}} admits a grading, the surface S is affinely homogeneous. More can be said if A{\mathcal{A}} has dimension 1, that is, if N{\mathcal{N}} is the maximal ideal of a Gorenstein algebra. In this case two such algebras N{\mathcal{N}}, [(N)\tilde]{\tilde{\mathcal{N}}} are isomorphic if and only if the associated hypersurfaces S, [(S)\tilde]{\tilde S} are affinely equivalent. If one of S, [(S)\tilde]{\tilde S} even is affinely homogeneous, ‘affinely equivalent’ can be replaced by ‘linearly equivalent’. In case the nil-index of N{\mathcal{N}} does not exceed 4 the hypersurface S is always affinely homogeneous. Contrary to the expectation, in case nil-index 5 there exists an example (in dimension 23) where S is not affinely homogeneous.     

Facile routes to alkyl-BIAN ligands

The Alkyl-BIAN ligands tert-Butyl-BIAN and 1-Adamantyl-BIAN have been synthesized and their structures have been determined by single-crystal X-ray diffraction along with that of the ZnCl2 complex of tert-Butyl-BIAN.     

Optical force field mapping in microdevices

We present a method for characterizing microscopic optical force fields. Two dimensional vector force maps are generated by measuring the optical force applied to a probe particle for a grid of particle positions. The method is used to map out the force field created by the beam from a lensed fiber inside a liquid filled microdevice. We find transverse gradient forces and axial scattering forces on the order of 2 pN per 10 mW laser power which are constant over a considerable axial range (>35 microm). These findings suggest future useful applications of lensed fibers for particle guiding/sorting. The propulsion of a small particle at a constant velocity of 200 microm s(-1) is shown.     

A single-bonded cationic terminal borylene complex

The cationic terminal borylene complex [(eta5-C5H5)(CO)2FeB(eta5-C5Me5)][AlCl4] has been isolated from the reaction of [(eta5-C5H5)(CO)2FeB(Cl)(eta1-C5Me5)] with AlCl3 and on the basis of X-ray crystallographic data, spectroscopic data and a DFT calculation it is concluded that the B-->Fe bond order is one.     

Kerr effect as a tool for the investigation of dynamic heterogeneities

We propose a dynamic Kerr effect experiment for the distinction between dynamic heterogeneous and homogeneous relaxations in glassy systems. The possibility of this distinction is due to the inherent nonlinearity of the Kerr effect signal. We model the slow reorientational molecular motion in supercooled liquids in terms of noninertial rotational diffusion. The Kerr effect response, consisting of two terms, is calculated for heterogeneous and for homogeneous variants of the stochastic model. It turns out that the experiment is able to distinguish between the two scenarios. We furthermore show that exchange between relatively "slow" and "fast" environments does not affect the possibility of frequency-selective modifications. It is demonstrated how information about changes in the width of the relaxation-time distribution can be obtained from experimental results.