Thermal Stability of Amorphous Solid Dispersions

Amorphous solid dispersion drug delivery systems (ASD DDS) were proved to be efficient for the enhancement of solubility and bioavailability of poorly water-soluble drugs. One of the major keys for successful preparation of ASD is the selection of appropriate excipients, mostly polymers, which have a crucial role in improving drug solubility and its physical stability. Even though, excipients should be chemically inert, there is some evidence that polymers can affect the thermal stability of active pharmaceutical ingredients (API). The thermal stability of a drug is closely related to the shelf-life of pharmaceutical products and therefore it is a matter of high pharmaceutical relevance. An overview of thermal stability of amorphous solids is provided in this paper. Evaluation of thermal stability of amorphous solid dispersion is perceived from the physicochemical perspective, from a kinetic (motions) and thermodynamic (energy) point of view, focusing on activation energy and fragility, as well all other relevant parameters for ASD design, with a glance on computational kinetic analysis of solid-state decomposition.     

Finite-stretching corrections to the Milner-Witten-Cates theory for polymer brushes

This paper investigates finite-stretching corrections to the classical Milner-Witten-Cates theory for semi-dilute polymer brushes in a good solvent. The dominant correction to the free energy originates from an entropic repulsion caused by the impenetrability of the grafting surface, which produces a depletion of segments extending a distance μ∝L^-1 from the substrate, where L is the classical brush height. The next most important correction is associated with the translational entropy of the chain ends, which creates the well-known tail where a small population of chains extend beyond the classical brush height by a distance ξ∝L^-1/3. The validity of these corrections is confirmed by quantitative comparison with numerical self-consistent field theory.     

A PBC‐DFT study of electronic properties of substituted polythiophenes

The electronic properties of polythiophenes substituted with various electron‐withdrawing and electron‐donating groups are investigated by employing periodic density functional calculations. The polymer is modeled as infinite one‐dimensional system with periodic boundary condition along the molecular direction. The effect of substitution on bandgaps is studied with various substituents like alkyls, halogens, aromatic and alkoxy groups in different regioregular forms. The alkoxy groups are found to substantially lower the bandgap of unsubstituted polythiophene, and aromatic groups in head–head/tail–tail forms are found to increase the bandgap. Irrespective of the type of substituents, groups that show deviations in planarity in oligomeric forms have shown an increase in bandgap in contrast to the general perception that head–head linkage always results in an increase in bandgap. Our study also confirms the previous findings that scaling from the oligomer bandgaps poses serious limitation to the prediction of polymeric bandgaps and that it should be evaluated with the infinite polymer system employing periodic boundary condition. Copyright © 2015 John Wiley & Sons, Ltd.     

Solid-phase Pd-catalysed cross-coupling methods for the construction of π-conjugated peptide nanomaterials

We describe the development of two procedures for the synthesis of peptides that are embedded with a variety of π-conjugated semi-conducting oligomers. These procedures utilise solid-phase variants of classical palladium-catalysed cross-couplings commonly used to prepare π-conjugated oligomers. The resulting peptide–π–electron hybrids are soluble in aqueous media and self-assemble to produce 1D nanostructures, simultaneously forming networks of π-stacked conduits. The procedures have allowed for the inclusion of complex chromophores including mixed aryl units, ethynylene linkers and sexithiophenes where the latter peptide's nanostructures demonstrated substantial conductivity when employed as an active layer in a field-effect transistor.     

Manganese‐Corrole Complexes as Versatile Catalysts for the Ring‐Opening Homo‐ and Co‐Polymerization of Epoxide

Manganese‐corrole complexes in combination with a co‐catalyst [PPN]X ([PPN]⁺=bis(triphenylphosphoranylidene)iminium) were found to be new versatile catalysts for the polymerization of epoxides, copolymerization of epoxides with CO₂, and copolymerization of epoxides with cyclic anhydrides affording a wide range of polymeric materials. This work should allow the synthesis of new types of improved innovative (co)polymers with original properties and would clearly increase the number of applications for polyesters, polycarbonates, and polyethers.     

Highly Tin‐Selective Stille Coupling: Synthesis of a Polymer Containing a Stannole in the Main Chain

The incorporation of heavier Group 14 element heteroles into semiconducting polymers leads to unusual optoelectronic properties. However, polymers containing stannoles have not been accessible to date. We report a synthetic route to a well‐defined, stannole‐containing polymer, the first example of this class of π‐conjugated polymers. This route was made possible by developing difunctionalized stannole monomers and highly tin‐selective Stille coupling reactions that leave the tin in the stannole untouched. Compared to poly(3‐n‐hexylthiophene), the resulting polymer displays a remarkable bathochromic shift in its absorption.     

A Novel 3D Heterobimetallic Cyano-bridged Coor- dination Polymer {（NH4）2[Cd（H20）Fe（CN）6]}n： Synthesis and Crystal Structure①

A novel heterobimetaUic coordination polymer, {（NH4）2[Cd（H20）Fe（CN）6]}n 1, has been synthesized by using the slow diffusion method and structurally characterized by elemental analysis, 1R spectroscopy and single-crystal X-ray diffraction. The crystal crystallizes in the monoclinic system, space group P21/n, a = 7.4202（16）, b = 14.939（3）, c = 10.868（2） A and ,8 = 91.660（3）°. For 1, five CN groups of Fe（CN）6]4- are involved in bridging. The polymer displays a 3D open microporous framework with 5-connected uninodal （46.64） topology.     

Elongation method with intermediate mechanical and electrostatic embedding for geometry optimizations of polymers

The elongation method with intermediate mechanical and electrostatic embedding (ELG-IMEE) is proposed. The electrostatic embedding uses atomic charges generated by a charge sensitivity analysis (CSA) method and parameterized for three different population analyses, namely, the Merz–Singh–Kollman scheme, the charge model 5, and the atomic polar tensor. The obtained CSA models were tested on two model systems. Test calculations show that the electrostatic embedding provides several times of decrease in the difference of energies of testing and reference calculations in comparison with the conventional elongation approach (ELG). The mechanical embedding is implemented in a combination of the conventional elongation method and the ONIOM approach. Moreover, it was demonstrated that the geometry optimization with the ELG-IMEE reduces the errors in the optimized structures by about one order in root-mean-square deviation, when compared to ELG.     

On the strength of hydrogen bonding within water clusters on the coordination limit

Hydrogen bonds (HB) are arguably the most important noncovalent interactions in chemistry. We study herein how differences in connectivity alter the strength of HBs within water clusters of different sizes. We used for this purpose the interacting quantum atoms energy partition, which allows for the quantification of HB formation energies within a molecular cluster. We could expand our previously reported hierarchy of HB strength in these systems (Phys. Chem. Chem. Phys., 2016, 18 , 19557) to include tetracoordinated monomers. Surprisingly, the HBs between tetracoordinated water molecules are not the strongest HBs despite the widespread occurrence of these motifs (e.g., in ice I_h). The strongest HBs within H₂O clusters involve tricoordinated monomers. Nonetheless, HB tetracoordination is preferred in large water clusters because (a) it reduces HB anticooperativity associated with double HB donors and acceptors and (b) it results in a larger number of favorable interactions in the system. Finally, we also discuss (a) the importance of exchange-correlation to discriminate among the different examined types of HBs within H₂O clusters, (b) the use of the above-mentioned scale to quickly assess the relative stability of different isomers of a given water cluster, and (c) how the findings of this research can be exploited to indagate about the formation of polymorphs in crystallography. Overall, we expect that this investigation will provide valuable insights into the subtle interplay of tri- and tetracoordination in HB donors and acceptors as well as the ensuing interaction energies within H₂O clusters.     

Helical Coordination Polymers Based on Keggin-type POMs and N-donor Ligand

Two new 1D helical coordination polymers based on polyoxometalate were synthesized by self-assembly of Keggin-type POMs and copper salts in the presence of triangular N-heterocyclic derivatives or long-chain N-containing carboxylate ligand, that are, (H₃O)[{Cu(H₂tpim)₂}{SiMo₁₂O₄₀}] · 0.5H₂O [Htpim = 2,4,5-tri(4-pyridyl)-imidazole] ( 1 ) and [Cu₂(Hcpp)₃(cpp)(H₂O)][PMo₁₂O₄₀] · 2H₂O [Hcpp = 1-(4-cyanobenzyl)-3–2-yl)pyrazole] ( 2 ). Their structures were determined by single-crystal X-ray diffraction and further characterized by elemental analyses and TG analyses. Compounds 1 and 2 exhibit (1D→2D) interdigitated architectures assembled from 1D helical chains. In compound 1 , the achiral 2D interdigitated nets containing left- and right-handed helixes are further interdigitated with each other to form a 3D supramolecular framework. In compound 2 , adjacent 2D interdigitated layers with opposite chirality are further extended by supramolecular interactions into a 3D supramolecular network, in which non-coordinating Keggin-type POMs as guests are encapsulated.