A family of ordered mesoporous carbons derived from mesophase pitch using ordered mesoporous silicas as templates

A variety of ordered mesoporous carbons (OMCs) were synthesized using ordered mesoporous silicas (OMSs) as hard templates and the mesophase pitch (MP) as a carbon precursor. The synthesis included the mixing of OMS with MP, the infiltration of OMS with MP at 450–550?°C and the carbonization of MP in OMS/MP composite followed by the dissolution of the OMS template. OMCs with structures of two-dimensional hexagonal arrays of nanorods and three-dimensional arrays of nanospheres were obtained through the replication of silica templates, including large-pore SBA-15, KIT-6, large-pore FDU-12 and SBA-16. In particular, 2-D hexagonal array of carbon nanorods (CMK-3 carbon) with (100) interplanar spacing of ～13 nm as well as an array of carbon nanospheres arranged in the face-centered cubic structure with the unit-cell parameter of 33 nm were successfully prepared. The specific surface areas of the resulting carbons were up to 400 m²/g, and the total pore volumes were up to 0.43 cm³/g, with the highest values achieved when the MP infiltration temperature was 500?°C. The OMCs exhibited narrow mesopore size distributions. As inferred from XRD, the frameworks of OMCs featured semi-graphitic structures even though moderate carbonization temperature (850?°C) was employed.     

Theoretical Studies on the Intermolecular Interactions of Potentially Primordial Base‐Pair Analogues

Recent experimental studies on the Watson–Crick type base pairing of triazine and aminopyrimidine derivatives suggest that acid/base properties of the constituent bases might be related to the duplex stabilities measured in solution. Herein we use high‐level quantum chemical calculations and molecular dynamics simulations to evaluate the base pairing and stacking interactions of seven selected base pairs, which are common in that they are stabilized by two N? H???O hydrogen bonds separated by one N? H???N hydrogen bond. We show that neither the base pairing nor the base stacking interaction energies correlate with the reported pK_a data of the bases and the melting points of the duplexes. This suggests that the experimentally observed correlation between the melting point data of the duplexes and the pK_a values of the constituent bases is not rooted in the intrinsic base pairing and stacking properties. The physical chemistry origin of the observed experimental correlation thus remains unexplained and requires further investigations. In addition, since our calculations are carried out with extrapolation to the complete basis set of atomic orbitals and with inclusion of higher electron correlation effects, they provide reference data for stacking and base pairing energies of non‐natural bases.     

Spontaneous Hierarchical Assembly of Crown Ether‐like Macrocycles into Nanofibers and Microfibers Induced by Alkali‐Metal and Ammonium Salts

Schiff base macrocycle 1 , which has a crown ether like central pore, was combined with different alkali‐metal and ammonium salts in chloroform, resulting in one‐dimensional supramolecular aggregates. The ion‐induced self‐assembly was studied with solid‐state NMR spectroscopy, transmission electron microscopy (TEM), scanning electron microscopy (SEM), and atomic force microscopy (AFM). It was found that the lengths and widths of the superstructures depend on the cation and counteranion of the salts. Among the salts being used, Na⁺ and NH₄⁺ ions with BF₄^? ions showed the most impressive fibrous structures that can grow up to 1 μm in diameter and hundreds of microns in length. In addition, the size of the fibers can be controlled by the evaporation rate of the solvent. A new macrocycle with bulky triptycenyl substituents that prevent supramolecular assembly was prepared and did not display any nanofibers with alkali‐metal ions in chloroform when studied with TEM.     

Star-shaped azomethines based on tris(2-aminoethyl)amine. Characterization,thermal and optical study

The synthesis and detailed (physico)-chemical (¹H/¹³C NMR, FTIR, UV–vis and elemental analysis) characterizations of new star-shaped compounds based on tris(2-aminoethyl)amine, including in their structure an azomethine function (HCN–) and alkoxysemiperfluorinated (–O–(CH₂)₃–(CF₂)₇–CF₃), octadecyloxy aliphatic (–O–(CH₂)₁₇–CH₃) chain or two phenyl rings (–Ph–Ph–) as a terminal group, were reported. The mesomorphic behavior was investigated by means of differential scanning calorimetry (DSC), polarized optical microscopy (POM) and additionally by FTIR(T) and UV–vis(T) spectroscopy. Wide-angle X-ray diffraction (WAXD) technique was used to probe the structural properties of the azomethines. Moreover, the azomethine A1 was electro-spun to prepare fibers with poly(methyl methacrylate) (PMMA) and investigated by DSC and POM. Additionally, a film of the A1 with PMMA was cast from chloroform and the thermal properties of the film were compared with the thermal properties of the fiber and powder. It was showed that terminal groups dramatically influence the thermal and optical properties of the star-shaped azomethines.     

Crystal Chemistry and Physical Properties of the Nonmagnetic Kondo Compound HfAs1.7Se0.2

Single crystals of HfAs_1.7Se_0.2 are grown by chemical transport reaction and their chemical composition characterized in detail by various analytical methods. Chemical analyses and crystal structure investigations by single‐crystal X‐ray diffraction as well as powder diffraction with synchrotron radiation reveal a tetragonal PbFCl structure type with strong disorder caused by a significant arsenic deficiency (As_0.9) on the 2a site and mixed occupancy of the 2c site (As_0.8Se_0.2). HfAs_1.7Se_0.2 is a diamagnetic metal which transforms into a superconducting state at T_c=0.52 K. Similar to other PbFCl‐type arsenide selenides, the title compound displays a magnetic‐field‐independent ?AT^1/2 term in the low‐temperature electrical resistivity. This unusual term presumably originates from the electron scattering of structural two‐level systems. According to the experimental results, HfAs1.7Se0.2 appears to be a rare example of a nonmagnetic Kondo material.     

Absence of 633-nm laser irradiation-induced effects on glucose phosphorylation by hexokinase

In a paper by Amat et al. (Modification of the intrinsic fluorescence and biochemical behavior of adenosine triphosphate ATP after irradiation with visible and near-infrared laser light, J. Photochem. Photobiol. B 81 (2005) 26–32) it was shown that the conversion of glucose to glucose-6-phosphate by hexokinase in vitro was accelerated when ATP, which supplies the reaction with energy, was priorly irradiated at non-resonant optical frequencies (NROF, i.e., 655 and 830 nm). Correspondingly, the authors postulated that NROF may lower the energy barrier for the dephosphorylation of ATP’s terminal phosphate and thus accelerate the reaction rate through a more expeditious energy delivery. Next to the established photobiostimulatory influence of visible light on cells, which is mediated by cytochrome c oxidase through resonant effects of light, Amat et al. posited an interesting theory with which the same processes could be induced through non-resonant effects. To investigate the effects of NROF with respect to the hexokinase reaction in greater detail, the reaction rates were measured spectrofluorometrically after 633-nm laser irradiation of ATP, the ATP-Mg complex, hexokinase, and the entire reaction mixture at room temperature (22 °C) and at the optimal reaction temperature (30 °C). No differences in reaction rates between the NROF-irradiated and control groups were found at either temperature. The hypothesis that NROF enhances in vitro hexokinase activity by lowering the activation energy for the dephosphorylation of ATP’s terminal phosphate by hexokinase was therefore disproven. Consequently, it is questionable, albeit not unequivocal, that NROF exerts an effect on other ATP-driven reactions in cell metabolic pathways through a direct impact on ATP.     

Electric-field-induced steering in soliton direction of propagation in chiral nematic liquid crystals

In this work we demonstrate the properties of spatial solitary waves in chiral nematic liquid crystals with an external electric field. Such self-trapped beams, called nematicons, were created due to the optical reorientation nonlinearity for a light power of a few tens of milliwatts. We show that the direction of propagation of such nematicons can be changed by applying an external electric field. Additionally, this effect can be modified by changing the input polarization of the light beam. The experimental results were obtained in four independent guiding layers created by a chiral nematic structure.     

Scaled MP3 Non‐Covalent Interaction Energies Agree Closely with Accurate CCSD(T) Benchmark Data

Scaled MP3 interaction energies calculated as a sum of MP2/CBS (complete basis set limit) interaction energies and scaled third‐order energy contributions obtained in small or medium size basis sets agree very closely with the estimated CCSD(T)/CBS interaction energies for the 22 H‐bonded, dispersion‐controlled and mixed non‐covalent complexes from the S22 data set. Performance of this so‐called MP2.5 (third‐order scaling factor of 0.5) method has also been tested for 33 nucleic acid base pairs and two stacked conformers of porphine dimer. In all the test cases, performance of the MP2.5 method was shown to be superior to the scaled spin‐component MP2 based methods, e.g. SCS–MP2, SCSN–MP2 and SCS(MI)–MP2. In particular, a very balanced treatment of hydrogen‐bonded compared to stacked complexes is achieved with MP2.5. The main advantage of the approach is that it employs only a single empirical parameter and is thus biased by two rigorously defined, asymptotically correct ab‐initio methods, MP2 and MP3. The method is proposed as an accurate but computationally feasible alternative to CCSD(T) for the computation of the properties of various kinds of non‐covalently bound systems.