Manifestation of diamagnetic chemical shifts of proton NMR signals by an anisotropic shielding effect of nitrate anions

A remarkable upfield shift of the py_α protons of complexed 2,2′-bipyridine in [cis-Pd(bpy)(NO₃)₂] is observed which is considered to originate from the anisotropic influence of suitably positioned coordinated nitrate anions around the Pd(II) centre of the molecule. A typical complexation-induced downfield shift is observed for the NH₂ protons in [cis-Pd(en)(NO₃)₂] where ‘en’ stands for ethylenediamine.     

Doubling Förster Resonance Energy Transfer Efficiency in Proteins with Extrinsic Thioamide Probes: Implications for Thiomodified Nucleobases

Designing a potential protein–ligand pair is pivotal, not only to track the protein structure dynamics, but also to assist in an atomistic understanding of drug delivery. Herein, the potential of a small model thioamide probe being used to study albumin proteins is reported. By monitoring the Förster resonance energy transfer (FRET) dynamics with the help of fluorescence spectroscopic techniques, a twofold enhancement in the FRET efficiency of 2-thiopyridone (2TPY), relative to that of its amide analogue, is observed. Molecular dynamics simulations depict the relative position of the free energy minimum to be quite stable in the case of 2TPY through noncovalent interactions with sulfur, which help to enhance the FRET efficiency. Finally, its application is shown by pairing thiouracils with protein. It is found that the site-selective sulfur atom substitution approach and noncovalent interactions with sulfur can substantially enhance the FRET efficiency, which could be a potential avenue to explore in the design of FRET probes to study the structure and dynamics of biomolecules.     

Convergence properties of high-Reynolds-number separated flow calculations

The convergence properties of an iterative solution technique for the Reduced Navier–Stokes equations are examined for two-dimensional steady subsonic flow over bump and trough geometries. Techniques for decreasing the sensitivity to the initial pressure approximation, for fine meshes in particular, are investigated. They are shown to improve the robustness of the relaxation process and to decrease the computational work required to obtain a converged solution. A semi-coarsening multigrid technique that has previously been found to be particularly advantageous for high-Reynolds-number (Re) flows with flow separation and with highly stretched surface-normal grids is applied herein to further accelerate convergence. Solutions are obtained for the laminar flow over a trough that is more severe than has been considered to date. Sufficient axial grid refinement in this case leads to a shock-like reattachment and, for sufficiently large Re, to a local ‘divergence’ of the numerical computations. This ‘laminar flow breakdown’ appears to be related to an instability associated with high-frequency fine-grid modes that are not resolvable with the present modelling. This behaviour may be indicative of dynamic stall or of incipient transition. The breakdown or instability is shown to be controllable by suitable introduction of transition turbulence models or by laminar flow control, i.e. small amounts of wall suction. This lends further support to the hypothesis that the instability is of a physical rather than numerical character and suggests that full three-dimensional analysis is required to properly capture the flow behaviour. Another inference drawn from this investigation is that there is a need for careful grid refinement studies in high-Re flow computations, since coarser grids may yield oscillation-free solutions that cannot be obtained on finer grids.     

Lifetime measurements of SO2 below the Clement's A-band

High resolution laser induced fluorescence spectrum of jet-cooled SO(2) is recorded toward the blue side of the Clement's A-Band in the region of 314-319 nm. Time resolved fluorescence measurements have been carried out for all the prominent peaks in this region. Most of the peaks exhibited double exponential decay profiles. Some of the rovibronic bands exhibited quantum beats with strong quantum beats observed at 315.261 and 315.271 nm. This is the first observation of quantum beats in SO(2) in the absence of any external magnetic or electric fields. The decay profiles of the beating rovibronic bands were fitted using a four-level model by least-squares fitting method. The fitting shows that all the measured bands were double exponential with a similar first lifetime of approximately 3 mus and a varying second lifetime of the order of 1 micros-100 ns with a beating frequency of approximately 1 MHz. These quantum beats, in the absence of any external field, indicate rotational level mixing between the A (1)A(2) and the B (1)B(1) vibronic states which are near resonant due to the high density of states of these two states.     

Kinetics of aquation of pentaammine(substituted salicylato)cobalt(III) complexes by ferric ion

Summary The aquation of pentaammine (substituted salicylato) cobalt(III) complexes [(NH₃)₅CoO₂CC₆H₃(X)OH]²⁺,X = 5-SO₃, 5-Br, 5-NO₂, and 3-NO₂ in the presence of ferric ion was studied spectrophotometrically in the 65°–80° range. Ferric ion catalyses the aquation of the substratesvia formation of a reactive binuclear species.Reprints of this article are not available.     

OH···X (X = O, S) hydrogen bonding in thetrahydrofuran and tetrahydrothiophene

In this article, hydrogen bonding interaction between p-cresol (p-CR) and cyclic ether, tetrahydrofuran (THF) and thioether, tetrahydrothiophene (THT) has been investigated. Two-color resonantly enhanced two-photon ionization in conjunction with the fluorescence detected IR (FDIR) spectroscopy was used to record the changes in the OH stretching frequency in these complexes. The FDIR spectra showed existence of a single conformer of the p-CR·THF and two conformers of the p-CR·THT complex. With the help of computed IR spectra and atoms-in-molecules analysis, the two conformers of p-CR·THT were assigned as the complex of p-CR with THT (C(2))/THT (C(S)). The redshift of OH stretching frequency for the p-CR·THF complex was greater compared to those for the conformers of the p-CR·THT complex. The binding energies of the p-CR·THF and p-CR·THT complexes were computed to be 7.42 and 6.15 kcal/mole. These were of the same order as those for the acyclic analogs, diethylether (DEE), and diethylsulfide (DES), of the solvent molecules under investigation. Although the DEE and THF consist of same number of carbon atoms, the dispersion energy contribution was much higher (43%) for DEE than that for THF (30%). In the case of sulfur analogs, however, it was similar (~50%) in the case of both DES well as THT complexes. All the computed H-bond indicators for these two complexes nicely correlate with the observed redshift of the O-H stretch.     

Molecular‐Level Understanding of Ground‐ and Excited‐State O?H⋅⋅⋅O Hydrogen Bonding Involving the Tyrosine Side Chain: A Combined High‐Resolution Laser Spectroscopy and Quantum Chemistry Study

The present study combines both laser spectroscopy and ab initio calculations to investigate the intermolecular O? H???O hydrogen bonding of complexes of the tyrosine side chain model chromophore compounds phenol (PH) and para‐cresol (pCR) with H₂O, MeOH, PH and pCR in the ground (S₀) state as well as in the electronic excited (S₁) state. All the experimental and computational findings suggest that the H‐bond strength increases in the S₁ state and irrespective of the hydrogen bond acceptor used, the dispersion energy contribution to the total interaction energy is about 10–15 % higher in the S₁ state compared to that in the S₀ state. The alkyl‐substituted (methyl; +I effect) H‐bond acceptor forms a significantly stronger H bond both in the S₀ and the S₁ state compared to H₂O, whereas the aryl‐substituted (phenyl; ?R effect) H‐bond donor shows a minute change in energy compared to H₂O. The theoretical study emphasizes the significant role of the dispersive interactions in the case of the pCR and PH dimers, in particular the C? H???O and the C? H???π interactions between the donor and acceptor subunits in controlling the structure and the energetics of the aromatic dimers. The aromatic dimers do not follow the acid–base formalism, which states that the stronger the base, the more red‐shifted is the X? H stretching frequency, and consequently the stronger is the H‐bond strength. This is due to the significant contribution of the dispersion interaction to the total binding energy of these compounds.     

GRAFT COPOLYMERIZATION OF CELLULOSE,CELLULOSE DERIVATIVES,AND LIGNOCELLULOSE

Abstract

The growth of polymer science has led to the development of new materials in direct competition with natural materials, many of which have been in use since earliest times. This has caused researchers to look more critically at both natural and synthetic macromolecules in order to learn more about their underlying structures and their relation to the properties exhibited by the macromolecules. In this regard, chemical modifications have been devised to impart certain desirable properties of both natural and synthetic macromolecules, and their applications have become an integral part of such chemical modifications. Various chemical modifications (e.g., change of functionality, oxidative degradation, inter- and intramolecular gelation, graft copolymerization), have been practiced to add improved properties to the base polymers. However, among all these methods, modification of polymers via graft copolymerization has been the subject of much interest and has made paramount contribution toward improved industrial and biomedical applications.     

Non-conventional Hydrogen Bonding and Aromaticity: A Systematic Study on Model Nucleobases and Their Solvated Clusters

The conceptual development of aromaticity is essential to rationalize and understand the structure and behavior of aromatic heterocycles. This work addresses for the first time, the interconnection between aromaticity and sulfur/selenium centered hydrogen bonds (S/SeCHBs) involved in representative heterocycle models of canonical nucleobases (2-Pyridone; 2PY) and its sulfur (2-Thiopyridone; 2TPY) and selenium (2-Selenopyridone; 2SePY) analogs. The nucleus-independent chemical shift (NICS) and gauge induced magnetic current density (GIMIC) values suggested significant reduction of aromaticity upon replacement of exocyclic carbonyl oxygen with sulfur and selenium. However, we observed two-fold (57 %) and three-fold (80 %) enhancement in the aromaticity for 2TPY dimer, and 2SePY dimer, respectively which are connected through S/SeCHBs. Aromaticity enhancement was also noticed in 1 : 1 H-bonded complexes (heterodimers), micro hydrated clusters and for bulk hydration. It is expected that exocyclic S and Se incorporation into heterocycles without compromising aromatic loss would definitely reinforce to design new supramolecular building blocks via S/SeCH-bonded complexes.