Bridging the Ruddlesden–Popper and the Dion–Jacobson series of layered perovskites: synthesis of layered oxides, A2–xLa2Ti3–xNbxO10(A = K, Rb), exhibiting ion exchange

Solid solutions of the formula, A2–xLa2Ti3–xNbxO10(A = K, Rb), exist for the range 0[less-than-or-eq]x[less-than-or-eq]1.0, bridging n= 3 members of the Ruddlesden–Popper series (A2La2Ti3O10) and the Dion–Jacobson series (ALa2Ti2NbO10). For 0[less-than-or-eq]x[less-than-or-eq]0.75, the phases possess body-centred structures characteristic of the Ruddlesden–Popper phases, while the x= 1 members are isostructural with KCa2Nb3O10(A = K) and CsCa2Nb3O10(A = Rb). Protonated derivatives, H2–xLa2Ti3–xNbxO10, which are prepared by ion exchange, retain the structural difference of the parent phases. A difference in the Brønsted acidity of the protonated derivatives revealed by intercalation experiments with organic bases seems to be related to this structural difference.

Direct versus kinetic exchange in multiband models for organic ferromagnetism

Multiband Hubbard and Pariser-Parr-Pople calculations have been carried out on mixed donor-acceptor (DA) stacks with doubly degenerate acceptor orbitals and nondegenerate donor orbitals at two-thirds filling. Model exact results for 2, 3, and 4 DA units show that McConnell's prediction of high-spin ground states in these systems is, in general, incorrect. The larger phase space available for the low-spin states leads to their kinetic stabilization in preference to high-spin states. However, for large electron-correlation strengths, the direct exchange dominates over the kinetic exchange resulting in a high-spin ground state

The Exchange Processes in Zinc-Complexes of o-Vanillin Salicyloylhydrazone as studied by 2-Dimensional NMR

Zinc forms two types of complexes with o-vanillin salicyloylhydrazone. The H-1 and C-13 nmr studies suggest that it coordinates with azomethine nitrogen, the carbonyl oxygen and with one or both of the phenolic oxygens. The H-1-H-1 and H-1 decoupled C-13-C-13 two-dimensional nuclear Overhauser and exchange spectra show that there is an exchange between the two types of complexes.

DNA Binding, Coprotease, and Strand Exchange Activities of Mycobacterial RecA Proteins: Implications for Functional Diversity among RecA Nucleoprotein Filaments

One of the fundamental questions concerning homologous recombination is how RecA or its homologues recognize several DNA sequences with high affinity and catalyze all the diverse biological activities. In this study, we show that the extent of single-stranded DNA binding and strand exchange (SE) promoted by mycobacterial RecA proteins with DNA substrates having various degrees of GC content was comparable with that observed for Escherichia coli RecA. However, the rate and extent of SE promoted by these recombinases showed a strong negative correlation with increasing amounts of sequence divergence embedded at random across the length of the donor strand. Conversely, a positive correlation was seen between SE efficiency and the degree of sequence divergence in the recipient duplex DNA. The extent of heteroduplex formation was not significantly affected when both the pairing partners contained various degrees of sequence divergence, although there was a moderate decrease in the case of mycobacterial RecA proteins with substrates containing larger amounts of sequence divergence. Whereas a high GC content had no discernible effect on E. coli RecA coprotease activity, a negative correlation was apparent between mycobacterial RecA proteins and GC content. We further show clear differences in the extent of SE promoted by E. coli and mycobacterial RecA proteins in the presence of a wide range of ATP:ADP ratios. Taken together, our findings disclose the existence of functional diversity among E. coli and mycobacterial RecA nucleoprotein filaments, and the milieu of sequence divergence (i.e., in the donor or recipient) exerts differential effects on heteroduplex formation, which has implications for the emergence of new genetic variants.

Magnetism, exchange and crystal field parameters in the orbitally unquenched Ising antiferromagnet FePS3

FePS3 is a layered antiferromagnet (T N=123 K) with a marked Ising anisotropy in magnetic properties. The anisotropy arises from the combined effect of the trigonal distortion from octahedral symmetry and spin-orbit coupling on the orbitally degenerate5 T 2g ground state of the Fe2+ ion. The anisotropic paramagnetic susceptibilities are interpreted in terms of the zero field Hamiltonian, ?=?i [?(L iz 2 ?2)+|?|L i .S i ]?? ij J ij S i .S j . The crystal field trigonal distortion parameter ?, the spin-orbit coupling ? and the isotropic Heisenberg exchange,J ij, were evaluated from an analysis of the high temperature paramagnetic susceptibility data using the Correlated Effective Field (CEF) theory for many-body magnetism developed by Lines. Good agreement with experiment were obtained for ?/k=215.5 K; ?/k=166.5 K;J nn k=27.7 K; andJ nnn k=?2.3 K. Using these values of the crystal field and exchange parameters the CEF predicts aT N=122 K for FePS3, which is remarkably close to the observed value of theT N. The accuracy of the CEF approximation was also ascertained by comparing the calculated susceptibilities in the CEF with the experimental susceptibility for the isotropic Heisenberg layered antiferromagnet MnPS3, for which the high temperature series expansion susceptibility is available.

Investigation of exchange of energy between zeeman and dipolar reservoirs in the rotating frame in solids

Exchange of energy between Zeeman and dipolar reservoirs in the rotating frame during spin-lock has important implications for the understanding of the Hartmann-Hahn cross polarisation process and is examined here with experiments on ammonium dihydrogen phosphate. It is observed that energy exchange between the two reservoirs takes place indicating that the relative magnitude of the dipolar coupling in relation to the applied r.f. field may have a role to play in determining the rate of exchange of energy between the two reservoirs.

Oxygen-Exchange Reactions Accompanying Oxidation of Vanadyl Sulfate by Diperoxovanadate

The absorption spectrum in the visible range and the, ESR spectrum of vanadyl sulfate were lost on addition of diperoxovanadate. The V-51-NMR spectra revealed that diperoxovanadate was reduced to vanadate and its oligomers. With excess vanadyl, tetrameric vanadate was found to be the major product, During this reaction oxygen was released into the medium. The oxygen-release reaction was inhibited by a variety of organic ligands-imidazole, benzoate, formate, mannitol, ethanol, Tris, DMPO, malate, and asparagine. An oxygen-consuming reaction emerged at high concentrations of some of these compounds, e.g. benzoate and ethanol. Using DMPO as the spin-trap, an oxygen-radical species with a 1:2:2:1 type of ESR spectrum was detected in the reaction mixtures resulting from vanadyl oxidation by diperoxovanadate which was unaffected by addition of catalase or ethanol. The results showed that secondary oxygen-exchange reactions occur which depend on and utilize the intermediates in the primary reaction during diperoxovanadate-dependent oxidation of vanadyl sulfate.

Thiol-ene Clickable Hyperscaffolds Bearing Peripheral Allyl Groups

Radical catalyzed thiol-ene reaction has become a useful alternative to the Huisgen-type click reaction as it helps to expand the variability in reaction conditions as well as the range of clickable entities. Thus, direct generation of hyper-branched polymers bearing peripheral allyl groups that could be clicked using a variety of functional thiols would be of immense value. A specifically designed AB(2) type monomer, that carries two allyl benzyl ethers groups and one alcohol functionality, was shown to undergo self-condensation under acid-catalyzed melt-transetherification to yield a hyperbranched polyether that carries numerous allyl end-groups. Importantly, it was shown that the kinetics of polymerization is not dramatically affected by the change of the ether unit from previously studied methyl benzyl ether to an allyl benzyl ether. The peripheral allyl groups were readily clicked quantitatively, using a variety of thiols, to generate an hydrocarbon-soluble octadecyl-derivative, amphiphilic systems using 2-mercaptoethanol and chiral amino acid (N-benzoyl cystine) derivatized hyperbranched structures; thus demonstrating the versatility of this novel class of clickable hyperscaffolds. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49:1735-1744, 2011

ChemInform Abstract: Synthesis of Anion-Deficient Layered Perovskites, ACa2Nb3-xMxO10-x (A: Rb, Cs; M: Al, Fe), Exhibiting Ion-Exchange and Intercalation. Evidence for the Formation of Layered Brownmillerites, ACa2Nb2AlO9 (A: Cs, H)

Anion-deficient layered perovskite oxides of the formula, ACa2Nb3-xMxO10-x (A = Rb, Cs; M = Al, Fe) for 0 < x less-than-or-equal-to 1.0, possessing tetragonal structures similar to the parent ACa2Nb3O10, have been synthesized. The interlayer A cations in these materials are readily exchanged with protons in aqueous HNO3 to give the protonated derivatives, HCa2Nb3-xMxO10-x; the latter are solid Bronsted acids intercalating a number of organic amines including aniline (pK(a) = 4.63). The distribution of acid sites in the interlayer region of HCa2Nb2MO9 inferred from n-alkylamine intercalation suggests that oxygen vacancies and Nb/M atoms are disordered in the ACa2Nb2MO9 samples prepared at 1100-1200-degrees-C. Annealing a disordered sample of CsCa2Nb2AlO9 for a long time at lower temperatures tends to order the Nb/Al atoms and oxygen vacancies to produce octahedral (NbO6/2)-tetrahedral (AlO4/2)-octahedral (NbO6/2) layer sequence reminiscent of the brownmillerite structure.

The exchange processes in o-vanillin salicyloylhydrazone as studied by two-dimensional NMR

Multidimensional NMR studies of o-vanillin salicyloylhydrazone at various temperatures have been undertaken in deuterated dimethyl sulfoxide and its cryoprotective mixture in H2O and D2O, acetone and acetonitrile. The molecule is found to exist in two conformers in dimethyl sulfoxide and the cryoprotective mixture. The exchange between the two conformers has been detected from the two-dimensional experiments - information which is not easily obtainable from the normal one-dimensional spectra. Results in the different solvents are interpreted in terms of solvent-solute interactions.

Fast algorithm for data exchange in reconfigurable tree structures

This paper presents a fast algorithm for data exchange in a network of processors organized as a reconfigurable tree structure. For a given data exchange table, the algorithm generates a sequence of tree configurations in which the data exchanges are to be executed. A significant feature of the algorithm is that each exchange is executed in a tree configuration in which the source and destination nodes are adjacent to each other. It has been proved in a theorem that for every pair of nodes in the reconfigurable tree structure, there always exists two and only two configurations in which these two nodes are adjacent to each other. The algorithm utilizes this fact and determines the solution so as to optimize both the number of configurations required and the time to perform the data exchanges. Analysis of the algorithm shows that it has linear time complexity, and provides a large reduction in run-time as compared to a previously proposed algorithm. This is well-confirmed from the experimental results obtained by executing a large number of randomly-generated data exchange tables. Another significant feature of the algorithm is that the bit-size of the routing information code is always two bits, irrespective of the number of nodes in the tree. This not only increases the speed of the algorithm but also results in simpler hardware inside each node.

Non-linear optical response of rutile-related oxides, LiM(V)M(VI)O(6), and their derivatives obtained by ion-exchange and intercalation

Polycrystalline samples of oxides of the general formula LiM(V)M(VI)O(6) (M(V) = Nb, Ta; M(VI) = Mo, W), crystallizing in a non-centrosymmetric (space group P (4) over bar 2(1)m) trirutile structure, exhibit second harmonic generation (SHG) of 1064 nm radiation with efficiencies 15-45 times that of alpha-quartz; interestingly, the SHG response is retained by the protonated derivatives HM(V)M(VI)O(6) . xH(2)O, and their n-alkylamine intercalates as well.

Role of free valences and spin densities on the migrating atom in location of saddle points in radical-exchange reactions

The principle of the conservation of bond orders during radical-exchange reactions is examined using Mayer's definition of bond orders. This simple intuitive approximation is not valid in a quantitative sense. Ab initio results reveal that free valences (or spin densities) develop on the migrating atom during reactions. For several examples of hydrogen-transfer reactions, the sum of the reaction coordinate bond orders in the transition state was found to be 0.92 +/- 0.04 instead of the theoretical 1.00 because free valences (or spin densities) develop on the migrating atom during reactions. It is shown that free valence is almost equal to the square of the spin density on the migrating hydrogen atom and the maxima in the free valence (or spin density) profiles coincide (or nearly coincide) with the saddle points in the corresponding energy profiles.

Purification and partial characterization of acyl carrier proteins from developing oil seeds of pisa (Actinodaphne hookeri) and ground nut (Arachis hypogaea)

Acyl carrier proteins (ACP) were purified to homogeneity in the active form from developing seeds of pisa (Actinodaphne hookeri) which synthesizes exclusively trilaurin and from ground nut (Arachis hypogaea) which synthesizes triacylglycerols containing long chain fatty acids. Two major isoforms of ACPs were purified from developing pisa seeds using DEAE-cellulose, Superose-6 FPLC and C-4 reversed phase HPLC chromatographic methods. In contrast, only a single form of ACP was present in ground nut seeds which was purified by anion-exchange and activated thiol-Sepharose 4B affinity chromatography. The two isoforms of ACPs from pisa showed nearly the same specific activity of 6,706 and 7,175 pmol per min per mg protein while ground nut ACP showed a specific activity of 3,893 pmol per min per mg protein when assayed using E. coli acyl-ACP synthetase and [1-C-14]palmitic acid. When compared with E. coli ACP, the purified ACPs from both the seeds showed considerable difference in their mobility in native PAGE, but showed similar mobility in SDS-PAGE under reducing conditions. In the absence of reducing agents formation of dimers was quite prominent. The ACPs from both the seed sources were acid- and heat-stable. The major isoform of pisa seed ACP and the ground nut ACP contain 91 amino acids with M(r) 11,616 and 1,228 respectively. However, there is significant variation in their amino acid composition. A comparision of the amino acid sequence in the N-terminal region of pisa and ground nut seed ACPs showed considerable homology between themselves and with other plant ACPs but not with E. coli ACP.

Spin state and exchange in the quasi-one-dimensional antiferromagnet KFeS2

We report the optical spectra and single crystal magnetic susceptibility of the one-dimensional antiferromagnet KFeS2. Measurements have been carried out to ascertain the spin state of Fe3+ and the nature of the magnetic interactions in this compound. The optical spectra and magnetic susceptibility could be consistently interpreted using a S = 1/2 spin ground state for the Fe3+ ion. The features in the optical spectra have been assigned to transitions within the d-electron manifold of the Fe3+ ion, and analysed in the strong field limit of the ligand field theory. The high temperature isotropic magnetic susceptibility is typical of a low-dimensional system and exhibits a broad maximum at similar to 565 K. The susceptibility shows a well defined transition to a three dimensionally ordered antiferromagnetic state at T-N = 250 K. The intra and interchain exchange constants, J and J', have been evaluated from the experimental susceptibilities using the relationship between these quantities, and chi(max), T-max, and T-N for a spin 1/2 one-dimensional chain. The values are J = -440.71 K, and J' = 53.94 K. Using these values of J and J', the susceptibility of a spin 1/2 Heisenberg chain was calculated. A non-interacting spin wave model was used below T-N. The susceptibility in the paramagnetic region was calculated from the theoretical curves for an infinite S = 1/2 chain. The calculated susceptibility compares well with the experimental data of KFeS2. Further support for a one-dimensional spin 1/2 model comes from the fact that the calculated perpendicular susceptibility at 0K (2.75 x 10(-4) emu/mol) evaluated considering the zero point reduction in magnetization from spin wave theory is close to the projected value (2.7 x 10(-4) emu/mol) obtained from the experimental data.