Synthesis and vesicle formation from dimeric pseudoglyceryl lipids with (CH2)(m) spacers: pronounced m-value dependence of thermal properties, vesicle fusion, and cholesterol complexation

Eight new dimeric lipids, in which the two Me2N+ ion headgroups are separated by a variable number of polymethylene units [-(CH2)(m)-], have been synthesized. The electron micrograph (TEM) and dynamic light scattering (DLS) of their aqueous dispersions confirmed the formation of vesicular-type aggregates. The vesicle sizes and morphologies were found to depend strongly on the m value, the method, and thermal history of the vesicle preparation. Information on the thermotropic properties of the resulting vesicles was obtained from microcalorimetry and temperature-dependent fluorescence anisotropy measurements. Interestingly, the T-m values for these vesicles revealed a nonlinear dependence on spacer chain length (m value). These vesicles were able to entrap riboflavin. The rates of permeation of the OH- ion under an imposed transmembrane pH gradient were also found to depend significantly on the m value. X-Ray diffraction of the cast films of the lipid dispersions elucidated the nature and the thickness of these membrane organizations, and it was revealed that these lipids organize in three different ways depending on the m value. The EPR spin-probe method with the doxylstearic acids 5NS, 12NS, and 16NS, spin-labeled at various positions of stearic acid, was used to establish, the chain-flexibility gradient and homogeneity of these bilayer assemblies. The apparent fusogenic propensities of these bipolar tetraether lipids were investigated in the presence of Na2SO4 with fluorescence-resonance energy-transfer fusion assay. Small unilamellar vesicles formed from 1 and three representative biscationic lipids were also studied with fluorescence anisotropy and H-1 NMR spectroscopic techniques in the absence and the presence of varying amounts of cholesterol.

Temperature dependence study of chlorine NQR frequency and spin-lattice relaxation time in 2-amino,-3,5-dichloropyridine

Chlorine-35 NQR frequency and spin-lattice relaxation time measurements as a function of temperature in the range 77-300 K were carried out on 2-amino-3,5-dichloropyridine. Two NQR signals were observed and were assigned to the two chlorines present in the molecule using the additive model for substituent effects. The temperature dependence of the NQR frequency was analysed in terms of the torsional oscillations of the molecule and the torsional frequencies and their temperature dependence were calculated numerically using a two-mode approximation. The temperature dependence of the NQR spin-lattice relaxation time was found to be mainly due to the torsional oscillations of the molecule, with anharmonicity effects showing up at higher temperatures. Copyright (C) 1999 John Wiley & Sons, Ltd.

Theory of coexisting charge and spin-density waves in (TMTTF)(2)Br, (TMTSF)(2)PF6 and alpha-(BEDT-TTF)(2)MHg(SCN)(4)

We discuss a recently formulated microscopic theory of the unusual coexistence of spin density waves (SDWs) and charge density waves (CDWs) that has been seen in recent experiments on (TMTTF)2Br, (TMTSF)2PF6 and α-(BEDT-TTF)2MHg(SCN)4.

Theory of coexisting charge and spin-density waves in (TMTTF)(2)Br, (TMTSF)(2)PF6, and alpha-(BEDT-TTF)(2)MHg(SCN)(4)

Recent experiments indicate that the spin-density waves (SDWs) in (TMTTF)(2)Br, (TMTSF)(2)PF6, and alpha-(BEDT-TTF)(2)MHg(SCN)(4) are highly unconventional and coexist with charge-density waves (CDWs). We present a microscopic theory of this unusual CDW-SDW coexistence. A complete understanding requires the explicit inclusion of strong Coulomb interactions, lattice discreteness, the anisotropic two-dimensional nature of the lattice, and the correct hand filling within the starting Hamiltonian. [S0031-9007(99)08498-7].

Zero-point entropy in 'spin ice'

Common water ice (ice I-h) is an unusual solid-the oxygen atoms form a periodic structure but the hydrogen atoms are highly disordered due to there being two inequivalent O-H bond lengths'. Pauling showed that the presence of these two bond lengths leads to a macroscopic degeneracy of possible ground states(2,3), such that the system has finite entropy as the temperature tends towards zero. The dynamics associated with this degeneracy are experimentally inaccessible, however, as ice melts and the hydrogen dynamics cannot be studied independently of oxygen motion(4). An analogous system(5) in which this degeneracy can be studied is a magnet with the pyrochlore structure-termed 'spin ice'-where spin orientation plays a similar role to that of the hydrogen position in ice I-h. Here we present specific-heat data for one such system, Dy2Ti2O7, from which we infer a total spin entropy of 0.67Rln2. This is similar to the value, 0.71Rln2, determined for ice I-h, SO confirming the validity of the correspondence. We also find, through application of a magnetic field, behaviour not accessible in water ice-restoration of much of the ground-state entropy and new transitions involving transverse spin degrees of freedom.

A C-H center dot center dot center dot O hydrogen bond stabilized polypeptide chain reversal motif at the C terminus of helices in proteins

The serendipitous observation of a C-H...O hydrogen bond mediated polypeptide chain reversal in synthetic peptide helices has led to a search for the occurrence of a similar motif in protein structures. From a dataset of 634 proteins, 1304 helices terminating in a Schellman motif have been examined. The C-H...O interaction between the T - 4 (CH)-H-alpha and T + 1 C=O group (C...O 3.5 Angstrom) becomes possible only when the T + 1 residue adopts an extended beta conformation (T is defined as the helix terminating residue adopting an alpha(L) conformation). In all, 111 examples of this chain reversal motif have been identified and the compositional and conformational. preferences at positions T - 4, T, and T + 1 determined. A marked preference for residues like Set, Glu and Gln is observed at T - 4 position with the motif being further stabilized by the formation of a side-chain-backbone O...H-N hydrogen bond involving the side-chain of residue T - 4 and the N-H group of residue T + 3. In as many as 57 examples, the segment following the helix was extended with three to four successive residues in beta conformation. In a majority of these cases, the succeeding beta strand lies approximately antiparallel with the helix, suggesting that the backbone C-H...O interactions may provide a means of registering helices and strands in an antiparallel orientation. Two examples were identified in which extended registry was detected with two sets of C-H...O hydrogen bonds between (T - 4) (CH)-H-alpha...C=O (T + 1) and (T - 8) (CH)-H-alpha...C=O (T + 3). 0 2002 Published by Elsevier Science Ltd.

Characterization of alkyl chain conformation in an intercalated cationic lipid bilayer by IR spectroscopy

A structural analysis of alkyl chain conformation of an intercalated cationic lipid bilayer is described. Dialkyl dimethylammonium ions (di-C(n)DA) were ion exchanged into the galleries of layered cadmium thiophosphate to give Cd0.83PS3(di-C(n)DA)(0.34). The grafting density and interlayer expansions were identical to those for the intercalated single chain alkyl trimethylammonium (C(n)TA) bilayers. The increased methylene chain density in the galleries, however, forces the intercalated lipid to adopt a more trans ordered structure. Progression bands arising from the coupling of vibrational modes of trans methylene units are used to establish the extent of trans registry. Two types of ordered structures of the intercalated cationic lipid may be distinguished. One in which both alkyl chains adopt an all-trans geometry, and one in which the methylene bond adjacent to the headgroup on one of the alkyl chains is gauche. The latter structure is typically found in the crystalline state of these cationic lipids. The concentrations of the two structures were determined from the ratio of the intensities of the progression bands and were found to remain unchanged with temperature.

Topological phases, Majorana modes and quench dynamics in a spin ladder system

We explore the salient features of the `Kitaev ladder', a two-legged ladder version of the spin-1/2 Kitaev model on a honeycomb lattice, by mapping it to a one-dimensional fermionic p-wave superconducting system. We examine the connections between spin phases and topologically non-trivial phases of non-interacting fermionic systems, demonstrating the equivalence between the spontaneous breaking of global Z(2) symmetry in spin systems and the existence of isolated Majorana modes. In the Kitaev ladder, we investigate topological properties of the system in different sectors characterized by the presence or absence of a vortex in each plaquette of the ladder. We show that vortex patterns can yield a rich parameter space for tuning into topologically non-trivial phases. We introduce and employ a new topological invariant for explicitly determining the presence of zero energy Majorana modes at the boundaries of such phases. Finally, we discuss dynamic quenching between topologically non-trivial phases in the Kitaev ladder and, in particular, the post-quench dynamics governed by tuning through a quantum critical point.

Difference in spin state and covalence between La1-xSrxCoO3 and La2-xSrxLi0.5Co0.5O4

We present a comparative study of the spin states and electronic properties of La1-xSrxCoO3 and La2-xSrxLi0.5Co0.5O4 using X-ray absorption near-edge structure spectroscopy at both the O-K and Co-L-2.3 thresholds. In the La2-xSrxLi0.5Co0.5O4 system the CoO6 octahedra are isolated, the holes induced by Sr doping are trapped in the isolated Co(IV)O-6 octahedra, and a low-spin state is found for the Co ions, which does not change upon Sr doping. In the La1-xSrxCoO3 system, the interconnected CoO6 octahedra, with a 180degrees Co-O-Co bond angle, give rise to a transition from low-spin to intermediate-spin state with a ferromagnetic alignment of the Co spins. The double-exchange, ferromagnetic coupling between Co ions mediated by the 180degrees bond angle is responsible for suppressing the low spin-state. We find that the branching ratio of spectral intensities at the L-2 and L-3 thresholds in the Co-L-2.3 X-ray absorption spectra is sensitive to the spin state of the Co ions allowing its direct spectroscopic determination. (C) 2002 Published by Elsevier Science B.V.

Model exact low-lying states and spin dynamics in ferric wheels: Fe-6 to Fe-12

Using an efficient numerical scheme that exploits spatial symmetries and spin parity, we have obtained the exact low-lying eigenstates of exchange Hamiltonians for ferric wheels up to Fe-12. The largest calculation involves the Fe-12 ring which spans a Hilbert space dimension of about 145x10(6) for the M-S=0 subspace. Our calculated gaps from the singlet ground state to the excited triplet state agree well with the experimentally measured values. Study of the static structure factor shows that the ground state is spontaneously dimerized for ferric wheels. The spin states of ferric wheels can be viewed as quantized states of a rigid rotor with the gap between the ground and first excited states defining the inverse of the moment of inertia. We have studied the quantum dynamics of Fe-10 as a representative of ferric wheels. We use the low-lying states of Fe-10 to solve exactly the time-dependent Schrodinger equation and find the magnetization of the molecule in the presence of an alternating magnetic field at zero temperature. We observe a nontrivial oscillation of the magnetization which is dependent on the amplitude of the ac field. We have also studied the torque response of Fe-12 as a function of a magnetic field, which clearly shows spin-state crossover.

Spin-orbital ordering and mesoscopic phase separation in the double perovskite Ca2FeReO6

Neutron powder diffraction measurements on Ca2FeReO6 reveal that this double perovskite orders ferrimagnetically and shows anomalous lattice parameter behavior below T-C=521 K. Below similar to300 K and similar to160 K we observe that the high-T monoclinic crystal structure separates into two and three monoclinic phases, respectively. A magnetic field suppresses the additional phases at low T in favor of the highest-T phase. These manifestations of the orbital degree of freedom of Re 5d electrons indicate that these electrons are strongly correlated and the title compound is a Mott insulator, with competing spin-orbitally ordered states.

Synthesis, properties, and comparative analyses on the chain flexibility of an ultrastable vinyl polyperoxide

The most stable vinyl polyperoxide, namely, poly(indene peroxide) (PINDP), an alternating copolymer of indene and oxygen, was synthesized by the oxidative polymerization of indene. It was characterized by H-1-NMR and C-13-NMR, Fourier transform infrared, differential scanning calorimetry, direct pyrolysis mass spectrometry, and gas chromatography mass spectrometry studies. The overall activation energy for the degradation and the glass-transition temperature of PINDP were 47 kcal/mol and 327 K respectively, which were very high compared to those of other vinyl polyperoxides. (C) 2002 Wiley Periodicals, Inc.

An infrared spectroscopic study of the low-spin to intermediate-spin state (1A1–3T1) transition in rare earth cobaltates, LnCoO3 (Ln=La, Pr and Nd)

Low-spin (LS) to intermediate-spin (IS) state transitions in crystals of LnCoO3 (Ln=La, Pr and Nd) have been investigated by variable temperature infrared spectroscopy. The spectra reveal the occurrence of the transition around 120, 220 and 275 K, respectively, in LaCoO3,PrCoO3 and NdCoO3, at which temperatures the intensities of the stretching and the bending modes associated with the LS state decrease, accompanied by an increase in the intensities of the bands due to IS state. The characteristic frequencies of both the spin states decrease with increase in temperature, showing anomalies around the transition.

An infrared spectroscopic study of the low-spin to intermediate-spin state ((1)A(1)-T-3(1)) transition in rare earth cobaltates, LnCoO(3) (Ln = La, Pr and Nd)

Low-spin (LS) to intermediate-spin (IS) state transitions in crystals of LnCoO(3) (Ln = La, Pr and Nd) have been investigated by variable temperature infrared spectroscopy. The spectra reveal the occurrence of the transition around 120, 220 and 275 K, respectively, in LaCoO3,PrCoo(3) and NdCoO3, at which temperatures the intensities of the stretching and the bending modes associated with the LS state decrease, accompanied by an increase in the intensities of the bands due to IS state. The characteristic frequencies of both the spin states decrease with increase in temperature, showing anomalies around the transition. (C) 2001 Published by Elsevier Science B.V.

One-dimensional zinc phosphates with linear chain structure

Three one-dimensional zinc phosphates, [C5N2H14][Zn(HPO4)2], I, [C10N4H26][Zn(HPO4)2].2H2O II, and [C4N2H6]2[Zn(HPO4)], III, have been prepared employing hydro/solvothermal methods in the presence of organic amines. While I and II consist of linear chains of corner-shared four-membered rings, III is a polymeric wire where the amine molecule is directly bonded to the metal center. The wire, as well as the chain in these structures, are held together by hydrogen bond interactions involving the amine and the framework oxygens. The polymeric zinc phosphate with wire-like architecture, III, is only the second example of such architecture. Crystal data: I, monoclinic, P21/c (no. 14), a=8.603(2), b=13.529(2), c=10.880(1) Å, β=94.9(1)°, V=1261.6(1) Å3, Z=4, ρcalc.=1.893 gcm−3, μ(MoKα)=2.234 mm−1, R1=0.032, wR2=0.086, [1532 observed reflections with I>2σ(I)], II, orthorhombic, Pbca (no. 61), a=8.393(1), b=15.286(1), c=22.659(1) Å, V=2906.9(2) Å3, Z=8, ρcalc.=1.794 gcm−3, μ(MoKα)=1.957 mm−1, R1=0.055, wR2=0.11, [1565 observed reflections with I>2σ(I) and III, monoclinic, P21/c (no. 14), a=8.241(1), b=13.750(2), c=10.572(1) Å, β=90.9(1)°, V=1197.7(2) Å3, Z=4, ρcalc.=1.805 gcm−3, μ(MoKα)=2.197 mm−1, R1=0.036, wR2=0.10, [1423 observed reflections with I>2σ(I)].