Nanofibrillated cellulose/carboxymethyl cellulose composite with improved wet strength

In this paper, nanofibrillated cellulose/carboxymethyl cellulose (CMC) composite films were prepared using tape casting. The obtained transparent films showed shear induced partial alignment of fibrils along the casting direction, resulting in birefringence in cross polarized light. The carboxyl groups of CMC could be further utilized to create ionic crosslinking by treatment with glycidyl trimethyl ammonium chloride (GTMA). The GTMA treated composite films had improved mechanical properties both in wet and dry state. The chemical composition and morphologies of composites were analyzed with X-ray photoelectron spectroscopy, elemental analysis, scanning electron microscopy and wide-angle X-ray scattering.     

Thermal and spectroscopic investigation of europium and samarium sulphates hydrates by TG-FTIR and ICP-MS techniques

The investigation of europium(III) sulphate hydrate and samarium(III) sulphate hydrate was performed by thermal analysis (TG-DTG) and simultaneous infrared evolved gas analysis-Fourier transformed infrared (EGA-FTIR) spectroscopy. The TG, DTG and DTA curves were recorded at the 25–1400 °C in the dynamic air atmosphere by TG/DTA analyser. The infrared evolved gas analysis was obtained on the FTIR spectrometer. Eu₂(SO₄)₃·nH₂O (n = 3.97) and Sm₂(SO₄)₃·nH₂O (n = 8.11) were analysed, the dehydration and decomposition steps were investigated and the water content was calculated. The formation of different oxysulphates was studied.

The trace rare earth elements in Eu and Sm sulphates were determined by ICP-MS. The concentration of trace Eu, Sm, La, Gd, Y and Ce ranged from 3.9 × 10⁻⁶ to 1.5 × 10⁻⁴% (m/m).     

H, C NMR spectral and single crystal structural studies of toxaphene congeners. Quantum chemical calculations for preferred conformers of 2,5-endo,6-exo,8,9,9,10,10-octachloro-2-bornene and their DFT/GIAO C chemical shifts

The ¹H and ¹³C NMR chemical shifts for six toxaphene congeners: 2-exo,3-endo,6-exo,8,9,10-hexachloro- (1), 2-exo,3-endo,5-exo,9,9,10,10-heptachloro- (2), 2-exo,3-endo,6-exo,8,9,10,10-heptachloro- (3), 2-exo,3-endo,5-exo,6-endo,8,9,10-heptachloro- (4), 2-exo,3-endo,5-exo,6-endo,8,9,9,10-octachlorobornane (5) and 2,5-endo,6-exo,8,9,9,10,10-octachloro-2-bornene (6) are reported. Their chemical shift assignments have been obtained by means of Pulsed Field Gradient (PFG) Double Quantum Filtered (DQF) ¹H,¹H correlation spectroscopy (COSY), PFG ¹H,¹³C Heteronuclear Multiple Quantum Coherence (HMQC) and PFG ¹H,¹³C Heteronuclear Multiple Bond Correlation (HMBC) experiments. A single crystal X-ray structural analysis was made for compounds 1, 3, 4 and 6. The prevalences of two octachlorobornene rotamers (6a,6b) were elucidated by ab initio MO method and single point DFT/GIAO calculations for ¹³C chemical shifts. Theoretical calculations proved that the single crystal structure of 6 corresponds its most stable conformer in solution.     

Achieving Strong Positive Cooperativity through Activating Weak Non‐Covalent Interactions

Positive cooperativity achieved through activating weak non‐covalent interactions is common in biological assemblies but is rarely observed in synthetic complexes. Two new molecular tubes have been synthesized and the syn isomer binds DABCO‐based organic cations with high orientational selectivity. Surprisingly, the ternary complex with two hosts and one guest shows a high cooperativity factor (α=580), which is the highest reported for synthetic systems without involving ion‐pairing interactions. The X‐ray single‐crystal structure revealed that the strong positive cooperativity likely originates from eight C?H???O hydrogen bonds between the two head‐to‐head‐arranged syn tube molecules. These relatively weak hydrogen bonds were not observed in the free hosts and only emerged in the complex. Furthermore, this complex was used as a basic motif to construct a robust [2+2] cyclic assembly, thus demonstrating its potential in molecular self‐assembly.     

Evaluation and optimization of coherence transfer in high molecular weight systems

For very large proteins in the highest magnetic fields, the large chemical shift anisotropy (CSA) of carbonyl carbon deteriorates coherence transfer efficiency in experiments designed for unambiguous sequential backbone assignment. In this communication, coherence throughput of several TROSY experiments is evaluated. Two new experiments, MP-HNCA and HN(CO)CANH, are also introduced as attractive alternatives for sequential assignment purposes of large proteins with correlation time over 50 ns. Their theoretical coherence transfer efficiencies for the interresidual (13)C(alpha) correlations are significantly better than in recently introduced MP-CT-HNCA and sequential HNCA experiments. The improvement with the new experiments is observed already on 60.8 kDa homodimer of protein Cel6A at 800 (1)H MHz.     

Cationic polymerization of β-pinene,styrene and α-methylstyrene

Molecular weight distributions determined by gel permeation chromatography demonstrate that α-methylstyrene copolymerizes with both β-pinene and styrene, forming both bi- and terpolymers. The composition of precipitated polymer versus crude polymer, as determined by nuclear magnetic resonance, suggests that β-pinene and styrene also copolymerize. Extraction of the latter bipolymer of β-pinene and styrene with acetone gives only a small amount of insoluble β-pinene homopolymer, confirming that β-pinene and styrene copolymerize in m-xylene. GPC analysis shows that each copolymer contains some homopolymer. A comparison of M _n with molecular weight calculated from NMR analysis, assuming chain transfer to solvent, indicates that chain transfer is the predominant method of forming dead polymer. The carbonium ions of the growing chain tend to transfer to solvent with increasing ease in the order β-pinene, styrene, and α-methylstyrene.     

Synthesis, characterization and thermal properties of new aromatic quaternary ammonium bromides: precursors for ionic liquids and complexation studies

Series of new aromatic R₂R′₂N⁺Br⁻ (R=benzyl, 4-methylbenzyl, 2-phenylethyl, 3-phenylpropyl; R′=ethyl, methyl, isopropyl) or RR′₂NH⁺Br⁻-type (R=benzyl, R′=isopropyl) quaternary ammonium bromides were prepared by using novel synthetic route in which a formamide (N,N-diethylformamide, N,N-dimethylformamide, N,N-diisopropylformamide) is treated with aralkyl halide in presence of a weak base. The compounds were characterized by ¹H-NMR and ¹³C-NMR spectroscopy and mass spectrometry. Structures of the crystalline compounds were determined by X-ray single crystal diffraction, and in addition the powder diffraction method was used to study the structural similarities between the single crystal and microcrystalline bulk material. Three of the compounds crystallized in monoclinic, two in orthorhombic and one in triclinic crystal system, showing ion pairs, which are interconnected by weak hydrogen bonds and weak π-π interactions between the phenyl rings. Three of the compounds appeared as viscous oil or waxes. Finally, TG/DTA and DSC methods were used to analyze thermal properties of the prepared compounds. The lowest melting points were obtained for diethyldi-(2-phenylethyl)ammonium bromide (122.2 °C) and for diethyldi-(3-phenylpropyl)-ammonium bromide (109.1 °C). In general, decomposition of the compounds started at 170-190 °C without identifiable cleavages, thus liquid ranges of 30-70 °C were observed for some of the compounds.     

Anion–π Interactions in Salts with Polyhalide Anions: Trapping of I42−

The directionality of interaction of electron‐deficient π systems with spherical anions (e.g,. halides) can be controlled by secondary effects like NH or CH hydrogen bonding. In this study a series of pentafluorophenyl‐substituted salts with polyhalide anions is investigated. The compounds are obtained by aerobic oxidation of the corresponding halide upon crystallization. Solid‐state structures reveal that in bromide 2 , directing NH–anion interactions position the bromide ion in an η¹‐type fashion over but not in the center of the aromatic ring. The same directing forces are effective in corresponding tribromide salt 3 . In the crystal, the bromide ion is paneled by four electron‐deficient aromatic ring systems. In addition, compounds 4 and 6 , which have triiodide and the rare tetraiodide dianion as anions, are described. Computational studies reveal that the latter is highly unstable. In the present case it is stabilized by the crystal lattice, for example, by interaction with electron‐deficient π systems.     

Non-centrosymmetric tetrameric assemblies of tetramethylammonium halides with uranyl salophen complexes in the solid state

Ditopic salophen-UO(2) receptors 1-4 and 7 co-crystallize with tetramethylammonium (TMA) chloride and fluoride salts producing good quality crystals amenable for X-ray diffraction characterization. The arrangement of the receptor and salt units in the crystal lattice is such that tetrameric ball-shaped assemblies are formed, where an inner cluster of four TMA cations are surrounded by an outer shell of four UO(2)-bound anions. These elaborate architectures, which occur in all cases, regardless of a certain degree of structural modification on the receptors, lead to lattices that belong to non-centrosymmetric (NCS) space groups. Interestingly, the tetragonal symmetry of the tetrameric ball-shaped assemblies is either retained (I4?) or lost (R3c and I4?3d) at the lattice level, without compromising the NCS nature of the crystal lattices. The principal X-ray investigation on TMAX (X = Cl/F) co-crystals, that is, 1-(TMA)Cl, 2-(TMA)Cl, 3-(TMA)Cl, 4-(TMA)Cl, 7-(TMA)Cl, and 7-(TMA)F, is accompanied by NMR and electrospray ionization (ESI) mass spectrometry studies to gather additional insight on the modality of formation of the solid state structures observed. The important role of cation-π interactions in the receptor-salt recognition process is renewed and strengthened by comparison with NMR titration data with a novel reference compound, the salophen-UO(2) complex 8. Given the importance of NCS and polar crystalline solids in the development of functional materials, this study shows that this property can be introduced into elaborate host-guest systems, as those which assemble in the architectures described here, thus expanding its field of applicability.