Macrocyclic Bridgehead Fluorophores, Pyrrolyl-diazabicyclo[8.3.1]tetradecadienones, with Giant Stokes Shifts.

A previously unknown class of fluorophores was discovered, which represents 14-membered bridgehead heterocycles, pyrrolyl-diazabicyclo[8.3.1]tetradecadienones, herein referred to as PY-14-ONEs.

Gladstone-Dale compatibility, electronic polarizability and vibrational spectroscopy of minerals and inorganic compounds with VO and VO vanadyl groups.

VO and VO vanadyl groups with short (typically 1.57-1.68 Å), essentially covalent, V-O bonds are common for V-bearing oxysalts with [5]- and [6]-coordinated vanadium.

Encapsulation of Paraffin Phase-Change Materials within Monolithic MTMS-Based Silica Aerogels.

To address the leakage issue of paraffin phase-change materials in thermal management, a monolithic MTMS-based silica aerogel (MSA) is employed to encapsulate paraffin through a facile impregnation process. We find that the paraffin and MSA form a physical combination, with little interaction occurring between them. The prepared no-leakage paraffin/MSA composites have a density of 0.

Crystal Chemistry of the Copper Oxalate Biomineral Moolooite: The First Single-Crystal X-ray Diffraction Studies and Thermal Behavior.

Moolooite, Cu(CO)·HO, is a typical biomineral which forms due to Cu-bearing minerals coming into contact with oxalic acid sources such as bird guano deposits or lichens, and no single crystals of moolooite of either natural or synthetic origin have been found yet. This paper reports, for the first time, on the preparation of single crystals of a synthetic analog of the copper-oxalate biomineral moolooite, and on the refinement of its crystal structure from the single-crystal X-ray diffraction (SCXRD) data. Along with the structural model, the SCXRD experiment showed the significant contribution of diffuse scattering to the overall diffraction data, which comes from the nanostructural disorder caused by stacking faults of Cu oxalate chains as they lengthen.

Temperature-Dependent Circularly Polarized Luminescence of a Cholesteric Copolymer Doped with a Europium Complex.

The design of new materials for non-contact temperature sensors is an important task for scientists working in the fields of chemistry, physics, and materials science. In the present paper, a novel cholesteric mixture based on a copolymer doped with a highly luminescent europium complex was prepared and studied. It was found that the spectral position of the selective reflection peak strongly depends on temperature and a shift towards shorter wavelengths is observed upon heating with an amplitude of more than 70 nm, from the red to green spectral range.

H multiple quantum NMR in alternating quasi-one-dimensional spin chains of hambergite.

Multiple quantum (MQ) dynamics was investigated in quasi-one-dimensional H zigzag spin chains in hambergite (BeBOOH) single crystals. Due to the non-linear arrangement of the spins, dipolar coupling strengths alternate along the chain. To solve the problem of MQ NMR experiments taking too much time due to extremely long H spin-lattice relaxation times, the samples were exposed to gamma irradiation to produce the defects accelerating the relaxation.

Thermal and Bulk Properties of Triblock Terpolymers and Modified Derivatives towards Novel Polymer Brushes.

We report the synthesis of three (3) linear triblock terpolymers, two (2) of the ABC type and one (1) of the BAC type, where A, B and C correspond to three chemically incompatible blocks such as polystyrene (PS), poly(butadiene) of exclusively (~100% vinyl-type) -1,2 microstructure (PB) and poly(dimethylsiloxane) (PDMS) respectively. Living anionic polymerization enabled the synthesis of narrowly dispersed terpolymers with low average molecular weights and different composition ratios, as verified by multiple molecular characterization techniques. To evaluate their self-assembly behavior, transmission electron microscopy and small-angle X-ray scattering experiments were conducted, indicating the effect of asymmetric compositions and interactions as well as inversed segment sequence on the adopted morphologies.

Magnetic field and nuclear spin influence on the DNA synthesis rate.

The rate of a chemical reaction can be sensitive to the isotope composition of the reactants, which provides also for the sensitivity of such "spin-sensitive" reactions to the external magnetic field. Here we demonstrate the effect of the external magnetic field on the enzymatic DNA synthesis together with the effect of the spin-bearing magnesium ions ([Formula: see text]Mg). The rate of DNA synthesis monotonously decreased with the external magnetic field induction increasing in presence of zero-spin magnesium ions ([Formula: see text]Mg).

Characteristic of Ultrastructure of Mice B16 Melanoma Cells under the Influence of Different Lighting Regimes.

Circadian rhythms of physiological processes, constantly being in a state of dynamic equilibrium and plastically associated with changes in environmental conditions, are the basis of homeostasis of an organism of human and other mammals. Violation of circadian rhythms due to significant disturbances in parameters of main environmental effectors (desynchronosis) leads to the development of pathological conditions and a more severe course of preexisting pathologies. We conducted the study of the ultrastructure of cells of mice transplantable malignant melanoma B16 under the condition of normal (fixed) lighting regime and under the influence of constant lighting.

Anomalously field-susceptible spin clusters emerging in the electric-dipole liquid candidate κ-(ET)Hg(SCN)Br.

Mutual interactions in many-body systems bring about various exotic phases, among which liquid-like states failing to order due to frustration are of keen interest. The organic system with an anisotropic triangular lattice of molecular dimers, κ-(ET)Hg(SCN)Br, has been suggested to host a dipole liquid arising from intradimer charge-imbalance instability, possibly offering an unprecedented stage for the spin degrees of freedom. Here, we show that an extraordinary unordered/unfrozen spin state having soft matter-like spatiotemporal characteristics emerges in this system.

Pentagonal-bipyramidal 4d and 5d complexes with unquenched orbital angular momentum as a unique platform for advanced single-molecule magnets: current state and perspectives.

This article overviews the current state and prospects of the concept of advanced single-molecule magnets (SMMs) based on low-spin ( = 1/2) pentagonal-bipyramidal (PBP) 4d and 5d complexes with unquenched orbital angular momentum. This approach is based on the unique property of PBP 4d and 5d complexes to cause highly anisotropic spin coupling of perfect uniaxial symmetry, -zizj - (xixj + yiyj), regardless of the local geometric symmetry. The M(4d/5d)-M(3d) exchange-coupled pairs in the apical positions of the PBP complexes produce Ising-type exchange interactions (|| > ||), which serve as a powerful source of uniaxial magnetic anisotropy of a SMM cluster.

Synthesis and Characterization of Hybrid Materials Derived from Conjugated Copolymers and Reduced Graphene Oxide.

In this study the preparation of hybrid materials based on reduced graphene oxide (rGO) and conjugated copolymers is reported. By tuning the number and arrangement of thiophenes in the main chain (indacenothiophene or indacenothienothiophene) and the nature of the polymer acceptor (difluoro benzothiadiazole or diketopyrrolopyrrole) semiconducting copolymers were synthesized through Stille aromatic coupling and characterized to determine their molecular characteristics. The graphene oxide was synthesized using the Staudenmaier method and was further modified to reduced graphene oxide prior to structural characterization.

[M(Hdapsc)]-[Cr(CN)] (M = Mn, Co) Chain and Trimer Complexes: Synthesis, Crystal Structure, Non-Covalent Interactions and Magnetic Properties.

Four new heterometallic complexes combining [M(Hdapsc)] cations with the chelating Hdapsc {2,6-diacetylpyridine-bis(semicarbazone)} Schiff base ligand and [Cr(CN)] anion were synthesized: {[M(Hdapsc)]Cr(CN)K(HO)(EtOH)}·1.2(HO), M = Mn () and Co (), {[Mn(Hdapsc)]Cr(CN)(HO)}Cl·HO () and {[Co(Hdapsc)]Cr(CN)(HO)}Cl·2EtOH·3HO (). In all the compounds, M(II) centers are seven-coordinated by NO atoms of Hdapsc in the equatorial plane and N or O atoms of two apical -CN/water ligands.

Preparation of FeCo/C-N and FeNi/C-N Nanocomposites from Acrylamide Co-Crystallizates and Their Use as Lubricant Additives.

FeCo and FeNi nanoalloy particles encapsulated in a nitrogen-doped carbonized shell (FeCo/C-N and FeNi/C-N) were synthesized by thermolysis at 400 °C of polyacrylamide complexes after frontal polymerization of co-crystallizate of Fe and Co or Ni nitrates and acrylamide. During the thermolysis of polyacrylamide complexes in a self-generated atmosphere, Co(II) or Ni(II) and Fe(III) cations are reduced to form FeCo and FeNi nanoalloy particles, while polyacrylamide simultaneously forms a nitrogen-doped carbon shell layer. This unique architecture provides high chemical and thermal stability of the resulting nanocomposites.

Current Distribution in the Discharge Unit of a 10-Cell Vanadium Redox Flow Battery: Comparison of the Computational Model with Experiment.

Shunting currents are among the main problems of all-vanadium redox flow battery stacks since, in addition to capacity losses, they cause negative effects associated with the local destruction of electrodes and bipolar plates. The values of both the shunting currents and their destructive effects on materials can be reduced at the battery development stage by adjusting the resistance of the electrolyte supply channels. The solution to this problem can be found using a calculation model for current distribution based on the current balance in the nodes as well as voltage drops and electromotive force in internal circuits according to Kirchhoff's laws.

Infrared spectroscopy as a tool for the analysis of framework topology and extra-framework components in microporous cancrinite- and sodalite-related aluminosilicates.

The identification of the framework type in multilayer cancrinite- and sodalite-group minerals and synthetic compounds is predominantly based on the unit-cell dimensions determined from powder or single-crystal X-ray diffraction data, by analogy with previously characterized samples with known crystal structures. However, topological type of the framework cannot be reliably determined in this way because of the different possible ABC staking sequences and different sets of cages with the same number of layers in the repeat unit. To solve this problem, additional criteria are required.

Crystalline paramagnetic supramolecular 2D-polymer of the tetra(4-pyridyl)porphyrin and terbium(III) complex.

A new promising method for the preparation of crystalline 2D polymers based on tetra(4-pyridyl)porphyrin has been developed. Radical anion {HT(4-Py)P˙} species are used as the starting material. A new solid-state supramolecular array [{HT(4-Py)P}·{Tb(TMHD)}]·2.

Aramid Pulp Reinforced Clay Aerogel Composites: Mechanical, Thermal and Combustion Behavior.

In this work, we reported that aramid pulps (AP) reinforced clay aerogel composites with improved mechanical strength, good thermal insulation and fire resistance based on the combination of AP, Poly(vinyl alcohol) (PVA) and sodium montmorillonite (MMT), which present a promising prospect in the thermal insulation application. The PVA-MMT-AP (x: denotes the mass content of AP) aerogel composites present an isotropic "lamella-honeycomb" porous structure, which endows them with excellent comprehensive performance. With the AP content increasing, the extremely low density is kept, ranging between 67-73 mg/cm, and the low thermal conductivity is maintained within 40.

Magnetically bistable cobalt-dioxolene complexes with a tetradentate N-donor base.

Synthesis and magnetic characterization of a family of cobalt-dioxolene complexes [(MeTPA)Co(36-DBCat)] (1), [(MeTPA)Co(36-DBCat)](PF) (2) and [(MeTPA)Co(diox-(OMe))](BPh) (3) (MeTPA = bis(6-methyl-2-pyridyl)methyl-(2-pyridylmethyl)amine; 36-DBCat = dianion of 3,6-di--butylcatechol; diox-(OMe) - 2,5-di--butyl-3,3,4-trimethoxy-6-oxocyclohexa-1,4-dienolate) is reported. The neutral complex 1 is found to form hexa- (CoON, 1a) and pentacoordinated (CoON, 1b) isomers. Variable temperature single crystal X-ray diffraction analysis of 1a and 1b clearly indicates the presence of the high-spin divalent metal ion and the dianionic catecholate form of the dioxolene ligand.

[2+2] Photocycloaddition in a bichromophoric dyad: photochemical concerted forward reaction following Woodward-Hoffmann rules and photoinduced stepwise reverse reaction of the ring opening predissociation.

A novel biphotochromic dyad with styrylbenzo[]quinoline photochromes was designed and synthesized to study the [2+2] photocycloaddition (PCA) reaction leading to cyclobutane with two benzo[]quinoline (BQ) substituents and the reverse four-membered ring opening reaction. In the dyad, PCA occurs in a concerted manner according to the Woodward-Hoffmann rules in the ππ* excited state after excitation of the whole conjugated π-system comprising the ethylene group. Nanosecond time-resolved emission spectroscopy indicated formation of an excimer as a possible intermediate of the PCA reaction.

Cellulose from Annual Plants and Its Use for the Production of the Films Hydrophobized with Tetrafluoroethylene Telomers.

Cellulose was produced by the modified traditional method with 35% yield from the stem of Sosnovsky hogweed and was characterized by elemental analysis, infrared (IR) spectroscopy, powder X-ray diffractometry, differential scanning calorimetry (DSC) and X-ray photoelectron spectroscopy (XPS). For , the degree of crystallinity (approximately 70%) and the glass transition temperature (105-108 °C) were determined. It was found that the whiteness characteristic in the case of was 92% and this significate was obtained without a bleaching procedure using chlorine-containing reagents.

Polymer Electrolytes Based on Na-Nafion Plasticized by Binary Mixture of Ethylene Carbonate and Sulfolane.

The development of post-lithium current sources, such as sodium-ion batteries with improved energy characteristics and an increased level of safety, is one of the key issues of modern energy. It requires the search and study of materials (including electrolytes) for these devices. Polyelectrolytes with unipolar cationic conductivity based on Nafion membranes are promising.

Analysis of the Composition of Bromide Anion Oxidation Products in Aqueous Solutions with Different pH via Rotating Ring-Disk Electrode Method.

We measured the ring collection coefficient of bromide anion oxidation products in a neutral and slightly alkaline medium on a rotating ring-disk electrode (glassy carbon disk, platinum ring) varying the following parameters: disk electrode rotation velocity, sodium bromide concentration, pH of the medium (in the range of 6−12), anode current on the disk, and the electroreduction potential of the bromide anion oxidation products on the ring. The data obtained are presented via dependences of the cathode ring current on the disk current ratio vs. the ring electrode potential.

In-Situ Synthesis of Layered Double Hydroxide/Silica Aerogel Composite and Its Thermal Safety Characteristics.

To adjust the thermal safety of hydrophobic silica aerogel, layered double hydroxide (LDH)/silica aerogel (SA) composites were prepared by an in-situ sol-gel process at ambient pressure. This study found the physical combination of SA and MgAl-LDH based on the FTIR spectra and phase composition of LDH/SA. The N sorption analysis confirms that the introduction of MgAl-LDH does not change the mesoporous attribution of LDH/SA significantly.