Hybrid organo-inorganic clay with nonionic interlayers. mid- and near-IR spectroscopic studies

The intercalation of organic polymers molecules (i.e., PEGs and BRIJ) into a standard Ca-montmorillonite has been studied by XRD, TG, and IR spectroscopy. The polymer intercalation is confirmed by the increasing of the d(001) in XRD spectra as well as by the complex multisteps thermal decomposition behavior of the organo-clay materials. Mid-IR and diffuse reflectance near-IR spectra of the intercalated materials show the polymer diagnostic bands (CH stretching and deformation mode), shifted or changed in shape by the interaction with the clay matrix. Both PEG 1500 and PEG 4000 based materials are likely intercalated in an extended configuration, similar to the amorphous polymer form. BRIJ intercalated polymer spectra suggest the disordered conformation of the alkilic chain in a prevailing "gauche", poorly packed, conformation. Host montmorillonite IR bands, mainly OH and water stretching and deformation fundamentals, combination, and overtone bands, are reduced in intensity by polymer intercalation, pointing out an interaction, likely through H-bonding and/or a possible substitution of cations hydration water molecules.     

Structural determination of ruthenium-porphyrin complexes relevant to catalytic epoxidation of olefins

A reproducible synthesis of a competent epoxidation catalyst, [Ru(VI)(TPP)(O)2)] (TPP = tetraphenylporphyrin dianion), starting from [Ru(II)(TPP)(CO)L] (L = none or CH3OH), is described. The molecular structure of the complex was determined by using ab initio X-ray powder diffraction (XRPD) methods, and its solution behavior was in detail investigated by NMR techniques such as PGSE (pulsed field gradient spin-echo) measurements. [Ru(IV)(TPP)(OH)]2O, a reported byproduct in the synthesis of [Ru(VI)(TPP)(O)2], was synthesized in a pure form by oxidation of [Ru(II)(TPP)(CO)L] or by a coproportionation reaction of [Ru(VI)(TPP)(O)2] and [Ru(II)(TPP)(CO)L], and its molecular structure was then determined by XRPD analysis. [Ru(VI)(TPP)(O)2] can be reduced by dimethyl sulfoxide or by carbon monoxide to yield [Ru(II)(TPP)(S-DMSO)2] or [Ru(II)(TPP)(CO)(H2O)], respectively. These two species were characterized by conventional single-crystal X-ray diffraction analysis.     

On the decay of KCl:Cu+ fluorescence

Summary The fluorescence of Cu⁺ in KCl was investigated in the range 19–300 K, in particular by performing accurate measurements of lifetime and quantum yield. The data were found irrespective of the doping method. It was evidenced that, among the models proposed in the literature, the Pedrini model gives the most reasonable explanation for the Cu⁺ de-excitation mechanism: two excited states in thermal equilibrium are involved in the emission process, one of which is metastable and lying just below the emitting level.     

Network models for vehicle and crew scheduling

Network models and methods have proven to be rather successful in many application fields. In this survey their use in the solution of Vehicle Scheduling and Crew Scheduling problems in Mass Transit settings is reviewed. An attempt is made to encompass in a unified framework some of the most relevant models on the subject to be found in the literature.     

Single DNA molecule stretching in sudden mixed shear and elongational microflows

High-throughput stretching and monitoring of single DNA molecules in continuous elongational flow offers compelling advantages for biotechnology applications such as DNA mapping. However, the polymer dynamics in common microfluidic implementations are typically complicated by shear interactions. These effects were investigated by observation of fluorescently labeled 185 kb bacterial artificial chromosomes in sudden mixed shear and elongational microflows generated in funneled microfluidic channels. The extension of individual free DNA molecules was studied as a function of accumulated fluid strain and strain rate. Under constant or gradually changing strain rate conditions, stretching by the sudden elongational component proceeded as previously described for an ideal elongational flow (T. T. Perkins, D. E. Smith and S. Chu, Science, 1997, 276, 2016): first, increased accumulated fluid strain and increased strain rate produced higher stretching efficiencies, despite the complications of shear interactions; and second, the results were consistent with unstretched molecules predominantly in hairpin conformations. More abrupt strain rate profiles did not deliver a uniform population of highly extended molecules, highlighting the importance of balance between shear and elongational components in the microfluidic environment for DNA stretching applications. DNA sizing with up to 10% resolution was demonstrated. Overall, the device delivered 1000 stretched DNA molecules per minute in a method compatible with diffraction-limited optical sequence motif mapping and without requiring laborious chemical modifications of the DNA or the chip surface. Thus, the method is especially well suited for genetic characterization of DNA mixtures such as in pathogen fingerprinting amidst high levels of background DNA.     

Dynamic uniqueness for stochastic chains with unbounded memory

We say that a probability kernel exhibits dynamic uniqueness (DU) if all the stochastic chains starting from a fixed past coincide on the future tail $\sigma$-algebra. Our first theorem is a set of properties that are pairwise equivalent to DU which allow us to understand how it compares to other more classical concepts. In particular, we prove that DU is equivalent to a weak-${?}^2$ summability condition on the kernel. As a corollary to this theorem, we prove that the Bramson–Kalikow and the long-range Ising models both exhibit DU if and only if their kernels are ${?}^2$ summable. Finally, if we weaken the condition for DU, asking for coincidence on the future $\sigma$-algebra for almost every pair of pasts, we obtain a condition that is equivalent to $\beta$-mixing (weak-Bernoullicity) of the compatible stationary chain. As a consequence, we show that a modification of the weak-${?}^2$ summability condition on the kernel is equivalent to the $\beta$-mixing of the compatible stationary chain.     

Finite Time Extinction by Nonlinear Damping for the Schrödinger Equation

We consider the Schrödinger equation on a compact manifold, in the presence of a nonlinear damping term, which is homogeneous and sublinear. For initial data in the energy space, we construct a weak solution, defined for all positive time, which is shown to be unique. In the one-dimensional case, we show that it becomes zero in finite time. In the two and three-dimensional cases, we prove the same result under the assumption of extra regularity on the initial datum.     

Sub‐ and Supramolecular X‐Ray Characterization of Engineered Tissues from Equine Tendon,Bovine Dermis,and Fish Skin Type‐I Collagen

Collagen represents one of the most widely used biomaterial for scaffolds fabrication in tissue engineering as it represents the mechanical support of natural tissues. It also provides physical scaffolding for cells and it influences their attachment, growth, and tissue regeneration. Among all fibrillary collagens, type I is considered one of the gold standard for scaffolds fabrication, thanks to its high biocompatibility, biodegradability, and hemostatic properties. It can be extracted by chemical and enzymatic protocols from several collagen‐rich tissues, such as tendon and skin, of different animal species. Both the extraction processes and the manufacturing protocols for scaffolds fabrication provide structural and mechanical changes that can be tuned in order to deeply impact the properties of the final biomaterial. The aim of this review is to discuss the role of X‐rays to study structural changes of type I collagen from fresh collagen‐rich tissues (bovine, equine, fish) to the final scaffolds, with the aim to screen across available collagen sources and scaffolds fabrication protocols to be used in tissue regeneration.