Anisotropy of spin relaxation of water protons in cartilage and tendon

Transverse spin relaxation rates of water protons in articular cartilage and tendon depend on the orientation of the tissue relative to the applied static magnetic field. This complicates the interpretation of magnetic resonance images of these tissues. At the same time, relaxation data can provide information about their organisation and microstructure. We present a theoretical analysis of the anisotropy of spin relaxation of water protons observed in fully hydrated cartilage. We demonstrate that the anisotropy of transverse relaxation is due almost entirely to intramolecular dipolar coupling modulated by a specific mode of slow molecular motion: the diffusion of water molecules in the hydration shell of a collagen fibre around the fibre, such that the molecular director remains perpendicular to the fibre. The theoretical anisotropy arising from this mechanism follows the “magic-angle” dependence observed in magnetic-resonance measurements of cartilage and tendon and is in good agreement with the available experimental results. We discuss the implications of the theoretical findings for MRI of ordered collagenous tissues.

Raman spectroscopic study of the mixed anion mineral Yecoraite Bi5Fe3O9(Te4+O3)(Te6+O4)2•9H2O

Tellurates are rare minerals as the tellurate anion is readily reduced to the tellurite ion. Often minerals with both tellurate and tellurite anions in the mineral are found. An example of such a mineral containing tellurate and tellurite is yecoraite. Raman spectroscopy has been used to study this mineral, the exact structure of which is unknown. Two Raman bands at 796 and 808 cm-1 are assigned to the ν1 (TeO4)2- symmetric and ν3 (TeO3)2- antisymmetric stretching modes and Raman bands at 699 cm-1 are attributed to the the ν3 (TeO4)2- antisymmetric stretching mode and the band at 690 cm-1 to the ν1 (TeO3)2- symmetric stretching mode. The intense band at 465 cm-1 with a shoulder at 470 cm-1 is assigned the (TeO4)2- and (TeO3)2- bending modes. Prominent Raman bands are observed at 2878, 2936, 3180 and 3400 cm-1. The band at 3936 cm-1 appears quite distinct and the observation of multiple bands indicates the water molecules in the yecoraite structure are not equivalent. The values for the OH stretching vibrations listed provide hydrogen bond distances of 2.625 Å (2878 cm-1), 2.636 Å (2936 cm-1), 2.697 Å (3180 cm-1) and 2.798 Å (3400 cm-1). This range of hydrogen bonding contributes to the stability of the mineral. A comparison of the Raman spectra of yecoraite with that of tellurate containing minerals kuranakhite, tlapallite and xocomecatlite is made.

Sodium 2-nitrocinnamate dihydrate: a one-dimensional hydrogen-bonded coordination polymer

The title compound catena-poly[aqua-mu3-2-nitrocinnamato], [Na(C9H6NO4)(H2O)2]n, the sodium salt of trans-2-nitrocinnamic acid, is a one-dimensional coordination polymer based on six-coordinate octahedral NaO6 centres comprising three facially-related monodentate carboxylate O-atom donors from separate ligands (all bridging)[Na-O, 2.4370(13)-2.5046(13)A] and three water molecules (two bridging, one monodentate) [Na-O, 2.3782(13)-2.4404(17)A]. The structure is also stabilized by intra-chain water-O-H...O(carboxylate) and O-H...O(nitro) hydrogen bonds.

An Improved Synthetic Route to the Potent Angiogenesis Inhibitor Benzyl Manα(1→3)-Manα(1→3)-Manα(1→3)-Manα(1→2)-Man Hexadecasulfate

An improved synthetic route to α(1→3)/α(1→2)-linked mannooligosaccharides has been developed and applied to a more efficient preparation of the potent anti-angiogenic sulfated pentasaccharide, benzyl Manα(1→3)-Manα(1→3)-Manα(1→3)-Manα(1→2)-Man hexadecasulfate, using only two monosaccharide building blocks. Of particular note are improvements in the preparation of both building blocks and a simpler, final deprotection strategy. The route also provides common intermediates for the introduction of aglycones other than benzyl, either at the building block stage or after oligosaccharide assembly. The anti-angiogenic activity of the synthesized target compound was confirmed via the rat aortic assay.

Ceramic membranes for separation of proteins and DNA by in situ growth of alumina nanofibres with a nanomesh of metal oxide nanofibres

Ceramic membranes were fabricated by in situ synthesis of alumina nanofibres in the pores of an alumina support as a separation layer, and exhibited a high permeation selectivity for bovine serum albumin relative to bovine hemoglobin (over 60 times) and can effectively retain DNA molecules at high fluxes.

Unusual hydrate stabilization in the two-dimensional layered structure of quinacrinium bis(2-carboxy-4,5-dichlorobenzoate) tetrahydrate, a proton-transfer compound of the drug quinacrine

The crystal structure of the hydrated proton-transfer compound of the drug quinacrine [rac-N'-(6-chloro-2-methoxyacridin-9-yl)-N,N-diethylpentane-1,4-diamine] with 4,5-dichlorophthalic acid, C23H32ClN3O2+ . 2(C8H3Cl2O4-).4H2O (I), has been determined at 200 K. The four labile water molecules of solvation form discrete ...O--H...O--H... hydrogen-bonded chains parallel to the quinacrine side chain, the two N--H groups of which act as hydrogen-bond donors for two of the water acceptor molecules. The other water molecules, as well as the acridinium H atom, also form hydrogen bonds with the two anion species and extend the structure into two-dimensional sheets. Between these sheets there are also weak cation--anion and anion--anion pi-pi aromatic ring interactions. This structure represents only the third example of a simple quinacrine derivative for which structural data are available but differs from the other two in that it is unstable in the X-ray beam due to efflorescence, probably associated with the destruction of the unusual four-membered water chain structures.

Proton-transfer versus nontransfer in compounds of the diazo-dye precursor 4-(phenyldiazenyl) aniline (aniline yellow) with strong organic acids: the 5-sulfosalicylate and the dichroic benzenesulfonate salts, and the 1:2 adduct with 3,5-dinitrobenzoic

The structures of two 1:1 proton-transfer red-black dye compounds formed by reaction of aniline yellow [4-(phenyldiazenyl)aniline] with 5-sulfosalicylic acid and benzenesulfonic acid, and a 1:2 nontransfer adduct compound with 3,5-dinitrobenzoic acid have been determined at either 130 or 200 K. The compounds are 2-(4-aminophenyl)-1-phenylhydrazin-1-ium 3-carboxy-4-hydroxybenzenesulfonate methanol solvate, C12H12N3+.C7H5O6S-.CH3OH (I), 2-(4-aminophenyl)-1-hydrazin-1-ium 4-(phenydiazinyl)anilinium bis(benzenesulfonate), 2C12H12N3+.2C6H5O3S-, (II) and 4-(phenyldiazenyl)aniline-3,5-dinitrobenzoic acid (1/2) C12H11N3.2C~7~H~4~N~2~O~6~, (III). In compound (I) the diaxenyl rather than the aniline group of aniline yellow is protonated and this group subsequently akes part in a primary hydrogen-bonding interaction with a sulfonate O-atom acceptor, producing overall a three-dimensional framework structure. A feature of the hydrogen bonding in (I) is a peripheral edge-on cation-anion association involving aromatic C--H...O hydrogen bonds, giving a conjoint R1/2(6)R1/2(7)R2/1(4)motif. In the dichroic crystals of (II), one of the two aniline yellow species in the asymmetric unit is diazenyl-group protonated while in the other the aniline group is protonated. Both of these groups form hydrogen bonds with sulfonate O-atom acceptors and thee, together with other associations give a one-dimensional chain structure. In compound (III), rather than proton-transfer, there is a preferential formation of a classic R2/2(8) cyclic head-to-head hydrogen-bonded carboxylic acid homodimer between the two 3,5-dinitrobenzoic acid molecules, which in association with the aniline yellow molecule that is disordered across a crystallographic inversion centre, result in an overall two-dimensional ribbon structure. This work has shown the correlation between structure and observed colour in crystalline aniline yellow compounds, illustrated graphically in the dichroic benzenesulfonate compound.

Enhanced human bone marrow stromal cell affinity for modified poly(L-lactide) surfaces by the upregulation of adhesion molecular genes

To enhance and regulate cell affinity for poly (l-lactic acid) (PLLA) based materials, two hydrophilic ligands, poly (ethylene glycol) (PEG) and poly (l-lysine) (PLL), were used to develop triblock copolymers: methoxy-terminated poly (ethylene glycol)-block-poly (l-lactide)-block-poly (l-lysine) (MPEG-b-PLLA-b-PLL) in order to regulate protein absorption and cell adhesion. Bone marrow stromal cells (BMSCs) were cultured on different composition of MPEG-b-PLLA-b-PLL copolymer films to determine the effect of modified polymer surfaces on BMSC attachment. To understand the molecular mechanism governing the initial cell adhesion on difference polymer surfaces, the mRNA expression of 84 human extracellular matrix (ECM) and adhesion molecules was analysed using quantitative reverse transcriptase polymerase chain reaction (qRT-PCR). It was found that down regulation of adhesion molecules was responsible for the impaired BMSC attachment on PLLA surface. MPEG-b-PLLA-b-PLL copolymer films improved significantly the cell adhesion and cytoskeleton expression by upregulation of relevant molecule genes significantly. Six adhesion genes (CDH1, ITGL, NCAM1, SGCE, COL16A1, and LAMA3) were most significantly influenced by the modified PLLA surfaces. In summary, polymer surfaces altered adhesion molecule gene expression of BMSCs, which consequently regulated cell initial attachment on modified PLLA surfaces.

Raman spectroscopic study of the uranyl mineral natrouranospinite (Na2,Ca)[(UO2)(AsO4)]2•5H2O

Raman spectra of natrouranospinite complemented with infrared spectra were studied and related to the structure of the mineral. Observed bands were assigned to the stretching and bending vibrations of (UO2)2+ and (AsO4)3- units and of water molecules. U-O bond lengths in uranyl and O-H…O hydrogen bond lengths were calculated from the Raman and infrared spectra.

Raman spectroscopic study of the uranyl sulphate mineral jáchymovite (UO2)8(SO4)(OH)14•13H2O

Raman spectra of jáchymovite, (UO2)8(SO4)(OH)14•13H2O, were studied, complemented with infrared spectra, and compared with published Raman and infrared spectra of uranopilite, [(UO2)6(SO4)O2(OH)6(H2O)6] •6H2O. Bands related to the stretching and bending vibrations of (UO2)2+, (SO4)2-, (OH)- and water molecules were assigned. U-O bond lengths in uranyl and O-H…O hydrogen bond lengths were calculated from the Raman and infrared spectra.

EPR, UV-visible and near infrared spectroscopic characterization of dolomite

Dolomite mineral samples having white and light green colours of Indian origin have been characterized by EPR, optical and NIR spectroscopy. The optical spectrum exhibits a number of electronic bands due to presence of Fe(III) ions in the mineral. From EPR studies, the parameters of g for Fe(III) and g, A and D for Mn(II) are evaluated and the data confirm that the ions are in distorted octahedron. Optical absorption studies reveal that Fe(III) is in distorted octahedron. The bands in NIR spectra are due to the overtones and combinations of water molecules. Thus EPR and optical absorption spectral studies have proven useful for the study of the chemistry of dolomite.

Small molecule–biopolymer interactions : Ultraviolet–visible and fluorescence spectroscopy and chemometrics

Interactions between small molecules with biopolymers e.g. the bovine serum albumin (BSA protein), are important, and significant information is recorded in the UV–vis and fluorescence spectra of their reaction mixtures. The extraction of this information is difficult conventionally and principally because there is significant overlapping of the spectra of the three analytes in the mixture. The interaction of berberine chloride (BC) and the BSA protein provides an interesting example of such complex systems. UV–vis and fluorescence spectra of BC and BSA mixtures were investigated in pH 7.4 Tris–HCl buffer at 37 °C. Two sample series were measured by each technique: (1) [BSA] was kept constant and the [BC] was varied and (2) [BC] was kept constant and the [BSA] was varied. This produced four spectral data matrices, which were combined into one expanded spectral matrix. This was processed by the multivariate curve resolution–alternating least squares method (MCR–ALS). The results produced: (1) the extracted pure BC, BSA and the BC–BSA complex spectra from the measured heavily overlapping composite responses, (2) the concentration profiles of BC, BSA and the BC–BSA complex, which are difficult to obtain by conventional means, and (3) estimates of the number of binding sites of BC.

Theoretical and numerical investigation of plasmon nanofocusing in metallic tapered rods and grooves

Effective focusing of electromagnetic (EM) energy to nanoscale regions is one of the major challenges in nano-photonics and plasmonics. The strong localization of the optical energy into regions much smaller than allowed by the diffraction limit, also called nanofocusing, offers promising applications in nano-sensor technology, nanofabrication, near-field optics or spectroscopy. One of the most promising solutions to the problem of efficient nanofocusing is related to surface plasmon propagation in metallic structures. Metallic tapered rods, commonly used as probes in near field microscopy and spectroscopy, are of a particular interest. They can provide very strong EM field enhancement at the tip due to surface plasmons (SP’s) propagating towards the tip of the tapered metal rod. A large number of studies have been devoted to the manufacturing process of tapered rods or tapered fibers coated by a metal film. On the other hand, structures such as metallic V-grooves or metal wedges can also provide strong electric field enhancements but manufacturing of these structures is still a challenge. It has been shown, however, that the attainable electric field enhancement at the apex in the V-groove is higher than at the tip of a metal tapered rod when the dissipation level in the metal is strong. Metallic V-grooves also have very promising characteristics as plasmonic waveguides. This thesis will present a thorough theoretical and numerical investigation of nanofocusing during plasmon propagation along a metal tapered rod and into a metallic V-groove. Optimal structural parameters including optimal taper angle, taper length and shape of the taper are determined in order to achieve maximum field enhancement factors at the tip of the nanofocusing structure. An analytical investigation of plasmon nanofocusing by metal tapered rods is carried out by means of the geometric optics approximation (GOA), which is also called adiabatic nanofocusing. However, GOA is applicable only for analysing tapered structures with small taper angles and without considering a terminating tip structure in order to neglect reflections. Rigorous numerical methods are employed for analysing non-adiabatic nanofocusing, by tapered rod and V-grooves with larger taper angles and with a rounded tip. These structures cannot be studied by analytical methods due to the presence of reflected waves from the taper section, the tip and also from (artificial) computational boundaries. A new method is introduced to combine the advantages of GOA and rigorous numerical methods in order to reduce significantly the use of computational resources and yet achieve accurate results for the analysis of large tapered structures, within reasonable calculation time. Detailed comparison between GOA and rigorous numerical methods will be carried out in order to find the critical taper angle of the tapered structures at which GOA is still applicable. It will be demonstrated that optimal taper angles, at which maximum field enhancements occur, coincide with the critical angles, at which GOA is still applicable. It will be shown that the applicability of GOA can be substantially expanded to include structures which could be analysed previously by numerical methods only. The influence of the rounded tip, the taper angle and the role of dissipation onto the plasmon field distribution along the tapered rod and near the tip will be analysed analytically and numerically in detail. It will be demonstrated that electric field enhancement factors of up to ~ 2500 within nanoscale regions are predicted. These are sufficient, for instance, to detect single molecules using surface enhanced Raman spectroscopy (SERS) with the tip of a tapered rod, an approach also known as tip enhanced Raman spectroscopy or TERS. The results obtained in this project will be important for applications for which strong local field enhancement factors are crucial for the performance of devices such as near field microscopes or spectroscopy. The optimal design of nanofocusing structures, at which the delivery of electromagnetic energy to the nanometer region is most efficient, will lead to new applications in near field sensors, near field measuring technology, or generation of nanometer sized energy sources. This includes: applications in tip enhanced Raman spectroscopy (TERS); manipulation of nanoparticles and molecules; efficient coupling of optical energy into and out of plasmonic circuits; second harmonic generation in non-linear optics; or delivery of energy to quantum dots, for instance, for quantum computations.

Corona discharges on the surfaces of high voltage composite insulators

The degradation of high voltage electrical insulation is a prime factor that can significantly influence the reliability performance and the costs of maintaining high voltage electricity networks. Little information is known about the system of localized degradation from corona discharges on the relatively new silicone rubber sheathed composite insulators that are now being widely used in high voltage applications. This current work focuses on the fundamental principles of electrical corona discharge phenomena to provide further insights to where damaging surface discharges may localize and examines how these discharges may degrade the silicone rubber material. Although water drop corona has been identified by many authors as a major cause of deterioration of silicone rubber high voltage insulation until now no thorough studies have been made of this phenomenon. Results from systematic measurements taken using modern digital instrumentation to simultaneously record the discharge current pulses and visible images associated with corona discharges from between metal electrodes, metal electrodes and water drops, and between waters drops on the surface of silicone rubber insulation, using a range of 50 Hz voltages are inter compared. Visual images of wet electrodes show how water drops can play a part in encouraging flashover, and the first reproducible visual images of water drop corona at the triple junction of water air and silicone rubber insulation are presented. A study of the atomic emission spectra of the corona produced by the discharge from its onset up to and including spark-over, using a high resolution digital spectrometer with a fiber optic probe, provides further understanding of the roles of the active species of atoms and molecules produced by the discharge that may be responsible for not only for chemical changes of insulator surfaces, but may also contribute to the degradation of the metal fittings that support the high voltage insulators. Examples of real insulators and further work specific to the electrical power industry are discussed. A new design concept to prevent/reduce the damaging effects of water drop corona is also presented.

Raman spectroscopic study of the uranyl mineral pseudojohannite Cu6.5[(UO2)4O4(SO4)2]2(OH)5.25H2O

Raman spectra of pseudojohannite were studied and related to the structure of the mineral. Observed bands were assigned to the stretching and bending vibrations of (UO2)2+ and (SO4)2- units and of water molecules. The published formula of pseudojohannite is Cu6.5(UO2)8\[O8](OH)5\[(SO4)4].25H2O; however Raman spectroscopy does not detect any hydroxyl units. Raman bands at 805 and 810 cm-1 are assigned to (UO2)2+ stretching modes. The Raman bands at 1017 and 1100 cm-1 are assigned to the (SO4)2- symmetric and antisymmetric stretching vibrations. The three Raman bands at 423, 465 and 496 cm-1 are assigned to the (SO4)2- ν2 bending modes. The bands at 210 and 279 cm-1 are assigned to the doubly degenerate ν2 bending vibration of the (UO2)2+ units. U-O bond lengths in uranyl and O-H…O hydrogen bond lengths were calculated from the Raman and infrared spectra.