Sample records for solid-state structural studies

  1. A high-resolution solid-state NMR approach for the structural studies of bicelles.

    Dvinskikh, Sergey; Dürr, Ulrich; Yamamoto, Kazutoshi; Ramamoorthy, Ayyalusamy


    Bicelles are increasingly being used as membrane mimicking systems in NMR experiments to investigate the structure of membrane proteins. In this study, we demonstrate the effectiveness of a 2D solid-state NMR approach that can be used to measure the structural constraints, such as heteronuclear dipolar couplings between 1H, 13C, and 31P nuclei, in bicelles without the need for isotopic enrichment. This method does not require a high radio frequency power unlike the presently used rotating-frame separated-local-field (SLF) techniques, such as PISEMA. In addition, multiple dipolar couplings can be measured accurately, and the presence of a strong dipolar coupling does not suppress the weak couplings. High-resolution spectra obtained from magnetically aligned DMPC:DHPC bicelles even in the presence of peptides suggest that this approach will be useful in understanding lipid-protein interactions that play a vital role in shaping up the function of membrane proteins.

  2. A High Resolution Solid State NMR Approach for the Structural Studies of Bicelles

    Dvinskikh, Sergey; Dürr, Ulrich; Yamamoto, Kazutoshi; Ramamoorthy, Ayyalusamy


    Bicelles are increasingly being used as membrane mimicking systems in NMR experiments to investigate the structure of membrane proteins. In this study, we demonstrate the effectiveness of a 2D solid-state NMR approach that can be used to measure the structural constraints such as heteronuclear dipolar couplings between 1H, 13C and 31P nuclei in bicelles without the need for isotopic enrichment. This method does not require a high radio frequency power unlike the presently used rotating-frame separated-local-field (SLF) techniques like PISEMA. In addition, multiple dipolar couplings can be measured accurately and the presence of a strong dipolar coupling does not suppress the weak couplings. High resolution spectra obtained from magnetically aligned DMPC:DHPC bicelles even in the presence of peptides suggest that this approach will be useful in understanding lipid-protein interactions that play a vital role in shaping up the function of membrane proteins. PMID:16683791

  3. Applications of Solid State NMR to the Study of Molecular Structure

    Curtis, Ronald Dean

    This thesis illustrates several applications of dilute spin I = 1over2 solid state nmr spectroscopy to the study of molecular structure in systems of chemical interest. Specifically, the compounds studied include benzylideneaniline and several related imines, the first stable iminophosphenium cation containing a N,P triple bond and several tetracyclines. The first two applications describe the use of dipolar-chemical shift nmr of "isolated" spin-pairs to fully characterize chemical shift tensors. For example, the carbon and nitrogen shift tensors of the C=N linkage of the Schiff base benzylideneaniline have been completely specified. The most shielded principal component of both carbon and nitrogen shift tensors is approximately perpendicular to the imine fragment. For the imine carbon, the intermediate component of the shift tensor is directed approximately along the C=N bond whereas the corresponding component of the nitrogen shift tensor is oriented along the direction of the nitrogen lone pair. Examination of the nitrogen chemical shift parameters for several related imines suggests that variations in the least shielded principal component are mainly responsible for changes in the nitrogen shieldings in the imine system. For the N,P moiety of the iminophosphenium cation, the most shielded principal component of both nitrogen and phosphorus tensors is oriented along the N,P bond axis. Comparison of both shift tensors with those of related compounds suggests that the electronic environment surrounding the N,P moiety is similar to other systems containing a formal triple bond. The final application section demonstrates the utility of high-resolution ^{13} C and ^{15}N cp/mas nmr for studying the molecular structure of solid tetracycline antibiotics. Comparison of ^{15} C chemical shifts in the solid state to those determined in (CD_3)_2SO solutions indicates for the first time that the structural integrity of the A ring of the tetracyclines is maintained in

  4. Structural studies of proteins by paramagnetic solid-state NMR spectroscopy

    Jaroniec, Christopher P.


    Paramagnetism-based nuclear pseudocontact shifts and spin relaxation enhancements contain a wealth of information in solid-state NMR spectra about electron-nucleus distances on the ∼20 Å length scale, far beyond that normally probed through measurements of nuclear dipolar couplings. Such data are especially vital in the context of structural studies of proteins and other biological molecules that suffer from a sparse number of experimentally-accessible atomic distances constraining their three-dimensional fold or intermolecular interactions. This perspective provides a brief overview of the recent developments and applications of paramagnetic magic-angle spinning NMR to biological systems, with primary focus on the investigations of metalloproteins and natively diamagnetic proteins modified with covalent paramagnetic tags.

  5. Structural studies of proteins by paramagnetic solid-state NMR spectroscopy

    Jaroniec, Christopher P.


    Paramagnetism-based nuclear pseudocontact shifts and spin relaxation enhancements contain a wealth of information in solid-state NMR spectra about electron-nucleus distances on the ~20 Å length scale, far beyond that normally probed through measurements of nuclear dipolar couplings. Such data are especially vital in the context of structural studies of proteins and other biological molecules that suffer from a sparse number of experimentally-accessible atomic distances constraining their three-dimensional fold or intermolecular interactions. This perspective provides a brief overview of the recent developments and applications of paramagnetic magic-angle spinning NMR to biological systems, with primary focus on the investigations of metalloproteins and natively diamagnetic proteins modified with covalent paramagnetic tags. PMID:25797004


    FURuowen; HuangWenqiang; 等


    The solid state C13-NMR spectra of different ACFs from various precursor fibers were recorded in this paper,The effects of activation conditions on chemical structures of ACFs,as well as the changes of chemical structures during carbonization and redox reaction were inverstigated by NMR technique,At same time,the soild state P31-NMR spectra of ACFS are studied.The C13-NMR spectra of ACFs can be divided into six bands that are assigned to methyl and methylene groups,hydroxyl and ether groups.acetal (or methylenedioxy) carbon,graphite-like aromatic carbon structure,phenol,and quinone groups,respectively.Only phosphorous pentoxide exists on ACFs and CFs.Moreover,most of them are stuck over the crystal face but not at the edge of graphite-like micro-crystal.The carbonization and activation conditions affect the C13-NMR spectra of ACFs.The experimental rsults indicate that the redox reaction of ACFs with oxidants greatly consumes C-H group.


    Drobny, Gary P.; Long, J. R.; Karlsson, T.; Shaw, Wendy J.; Popham, Jennifer M.; Oyler, N.; Bower, Paula M.; Stringer, J.; Gregory, D.; Mehta, M.; Stayton, Patrick S.


    Proteins directly control the nucleation and growth of biominerals, but the details of molecular recognition at the protein-biomineral interface remain poorly understood. The elucidation of recognition mechanisms at this interface may provide design principles for advanced materials development in medical and ceramic composites technologies. Here, we describe both the theory and practice of double-quantum solid-stateNMR(ssNMR) structure-determination techniques, as they are used to determine the secondary structures of surface-adsorbed peptides and proteins. In particular, we have used ssNMR dipolar techniques to provide the first high-resolution structural and dynamic characterization of a hydrated biomineralization protein, salivary statherin, adsorbed to its biologically relevant hydroxyapatite (HAP) surface. Here, we also review NMR data on peptides designed to adsorb from aqueous solutions onto highly porous hydrophobic surfaces with specific helical secondary structures. The adsorption or covalent attachment of biological macromolecules onto polymer materials to improve their biocompatibility has been pursued using a variety of approaches, but key to understanding their efficacy is the verification of the structure and dynamics of the immobilized biomolecules using double-quantum ssNMR spectroscopy.

  8. Molecular structure of crude beeswax studied by solid-state 13C NMR.

    Kameda, Tsunenori


    13C solid-state NMR experiments were performed to investigate the structure of beeswax in the native state (crude beeswax) for the first time. From quantitative direct polarization 13C MAS NMR spectrum, it was found that the fraction of internal-chain methylene (int-(CH2)) component compared to other components of crude beeswax was over 95%. The line shape of the int-(CH2) carbon resonance region was comprehensively analyzed in terms of NMR chemical shift. The 13C broad peak component covering from 31 to 35 ppm corresponds to int-(CH2) carbons with trans conformation in crystalline domains, whereas the sharp signal at 30.3 ppm corresponds to gauche conformation in the non-crystalline domain. From peak deconvolution of the aliphatic region, it was found that over 85% of the int-(CH2) has a crystal structure and several kinds of molecular packing for int-(CH2), at least three, exist in the crystalline domain.

  9. On the structure of amorphous calcium carbonate--a detailed study by solid-state NMR spectroscopy.

    Nebel, Holger; Neumann, Markus; Mayer, Christian; Epple, Matthias


    The calcium carbonate phases calcite, aragonite, vaterite, monohydrocalcite (calcium carbonate monohydrate), and ikaite (calcium carbonate hexahydrate) were studied by solid-state NMR spectroscopy ( (1)H and (13)C). Further model compounds were sodium hydrogencarbonate, potassium hydrogencarbonate, and calcium hydroxide. With the help of these data, the structure of synthetically prepared additive-free amorphous calcium carbonate (ACC) was analyzed. ACC contains molecular water (as H 2O), a small amount of mobile hydroxide, and no hydrogencarbonate. This supports the concept of ACC as a transient precursor in the formation of calcium carbonate biominerals.

  10. Regenerated silk fibers: Structural studies and solid state NMR techniques for efficient multiple distance determinations in proteins

    Liivak, Oskar


    Material Science is the science of understanding the relationship between the molecular level structure of a material and its macroscopic properties. Such research requires both the ability to determine molecular structure and the ability to control and modify the molecular structure. The present research into silks, especially the dragline silk from the spider Nephila clavipes , is occurring at a time when these two criteria are beginning to be met for proteins like spider silk. Genetic engineering has evolved to the point where material scientists have full control over the primary sequence of amino acids that comprise proteins. In addition, solid state nuclear magnetic resonance (NMR) techniques exist which allow us to probe molecular structure. This work applies solid state NMR to the study of the structure of silk fibers. In particular, we focus on techniques of fiber regeneration from solution. The purpose is not only to develop the techniques by which genetically engineered fibers could be spun into fibers for mass production but also as a tool into fundamental silk research. Results on these regenerated fibers show a correlation between the fraction of the silk's alanine residues which are in the β-sheet conformation and the ultimate tensile strength of the fibers. In addition, in a clever mating of the fiber regeneration technique and the solid state NMR distance measurement experiment, rotational echo double resonance (REDOR), we investigate the supramolecular topology of the alanine β-sheet crystals. Even though the REDOR technique has failings for the complicated ISn spin systems found in the silk samples, a qualitative analysis does indicate that the β-sheet crystals are intermolecular. Finally, we investigate a new class of REDOR-like experiments which are designed to overcome the failings of REDOR in ISn spin systems. Experimental data is shown to validate these ideas. An alternate pulse sequence is also introduced and verified with experimental

  11. Band structure of fcc-C60 solid state crystal study

    S Javanbakht


    Full Text Available We studied the architecture of the C60 cluster to drive its atomic positions which can be seen at room temperature. We then used the obtained carbon positions as a basis set for the fcc structure to construct the fcc-C60 compound. Self consistent calculations were performed based on the density functional theory (DFT utilizing the accurate WIEN2K code to solve the single-particle Kohen-Sham equation within the augmented plane waves plus local orbital (APW+lo method. The cohesive energy has been found to be 1.537 eV for the fcc-C60 . The calculated small cohesive energy that results from the weak Van der Waals-London interactions among a C60 cluster with its nearest neighbors is in good agreement with experiment. The electron densities of states (DOSs were calculated for a C60 macromolecule as well as the fcc-C60 compound and the results were compared with each other. The band gap from DOS calculations has been found to be 0.7 eV. Band structures were also calculated within the generalized gradient approximation (GGA. The band structure calculation results in 1.04 eV for the direct band gap. Two kinds of σ and π bonds were determined in the band structure. Our results are in good agreement with experiment and pseudopotential calculations.

  12. Variable-temperature 13C solid-state NMR study of the molecular structure of honeybee wax and silk.

    Kameda, Tsunenori; Tamada, Yasushi


    To elucidate the native-state crystal structure of beeswax from the Japanese bee, Apis cerana japonica, we determined the relationship between temperature and the 13C solid-state nuclear magnetic resonance (NMR) chemical shift of methylene carbon of beeswax, with comparison to n-alkanes and polyethylene in the orthorhombic, monoclinic, or triclinic crystal form. Variable-temperature 13C solid-state NMR observations of n-alkanes and polyethylene revealed that the chemical shifts of methylene carbon in the orthorhombic crystal form increased linearly with increasing temperature, that of the triclinic form decreased, and that of the monoclinic form was unaltered. These relations were compared with results of variable-temperature 13C solid-state NMR observation of beeswax. Results clarified that the two crystal forms comprising the beeswax in the native state are orthorhombic and monoclinic. The variable-temperature 13C solid-state NMR observations were also applied to interpret the differential scanning calorimetry (DSC) curve of beeswax. They were used to clarify the structural changes of beeswax for widely various temperatures. For beeswax secreted by the Japanese bee, the transition from the orthorhombic form to the rotator phase occurred at 36 degrees C, that is from the crystalline to the intermediate state at 45 degrees C. Moreover, the variable-temperature 13C solid-state NMR spectrum of honeybee silk in the native state was observed. Results demonstrated that the secondary structures of honeybee silk proteins in the native state comprised coexisting alpha-helix and beta-sheet conformations and that the amount of alpha-helices was greater. The alpha-helix content of honeybee silk was compared with that of hornet silk produced by Vespa larvae.

  13. Bonding, structure and solid-state chemistry

    Ladd, Mark


    This book is aimed at undergraduate students in both chemistry and those degree subjects in which chemistry forms a significant part. It does not reflect any particular academic year, and so finds a place during the normal span of degree studies in the physical sciences. An A-level standard in science and mathematics is presumed; additional mathematical treatments are discussed in Appendices. An introductory first chapter leads into the main subject matter, which is treated through four chapters in terms of the principle bonding forces of cohesion in the solid state; a further chapter discusses nanosize materials. Important applications of the study topics are interspersed at appropriate points within the text. Each chapter is provided with a set of problems of varying degrees of difficulty, so as to assist the reader in gaining a facility with the subject matter and its applications. The problems are supplemented by detailed tutorial solutions, some of which present additional relevant material that indicate...

  14. Solid state lighting devices and methods with rotary cooling structures

    Koplow, Jeffrey P.


    Solid state lighting devices and methods for heat dissipation with rotary cooling structures are described. An example solid state lighting device includes a solid state light source, a rotating heat transfer structure in thermal contact with the solid state light source, and a mounting assembly having a stationary portion. The mounting assembly may be rotatably coupled to the heat transfer structure such that at least a portion of the mounting assembly remains stationary while the heat transfer structure is rotating. Examples of methods for dissipating heat from electrical devices, such as solid state lighting sources are also described. Heat dissipation methods may include providing electrical power to a solid state light source mounted to and in thermal contact with a heat transfer structure, and rotating the heat transfer structure through a surrounding medium.

  15. Molecular-level secondary structure, polymorphism, and dynamics of full-length -synuclein fibrils studied by solid-state NMR

    Heise, Henrike; Hoyer, Wolfgang; Becker, Stefan; Andronesi, Ovidiu C.; Riedel, Dietmar; Baldus, Marc


    The 140-residue protein -synuclein (AS) is able to form amyloid fibrils and as such is the main component of protein inclusions involved in Parkinson's disease. We have investigated the structure and dynamics of full-length AS fibrils by high-resolution solid-state NMR spectroscopy. Homonuclear and heteronuclear 2D and 3D spectra of fibrils grown from uniformly 13C/15N-labeled AS and AS reverse-labeled for two of the most abundant amino acids, K and V, were analyzed. 13C and 15N signals exhibited linewidths of HR ALIGN=LEFT WIDTH=50% NOSHADE SIZE=1>

  16. Solid State Structure-Reactivity Studies on Bixbyites, Fluorites and Perovskites Belonging to the Vanadate, Titanate and Cerate Families

    Shafi, Shahid P.

    This thesis primarily focuses on the systematic understanding of structure-reactivity relationships in two representative systems: bixbyite and related structures as well as indium doped CeO2. Topotactic reaction routes have gained significant attention over the past two decades due to their potential to access kinetically controlled metastable materials. This has contributed substantially to the understanding of solid state reaction pathways and provided first insights into mechanisms. Contrary to the widely used ex-situ methods, in-situ techniques including powder x-ray diffraction and thermogravimetric-differential thermal analysis have been employed extensively throughout this work in order to follow the reaction pathways in real time. Detailed analysis of the AVO3 (A = In, Sc) bixbyite reactivity under oxidative conditions has been carried out and a variety of novel metastable oxygen defect phases have been identified and characterized. The novel metastable materials have oxygen deficient fluorite structures and consequently are potential ion conductors. Structural aspects of the topotactic vs. reconstructive transformations are illustrated with this model system. The structure-reactivity study of AVO3 phases was extended to AVO3 perovskite family. Based on the research methodologies and results from AVO3 bixbyite reactivity studies a generalized mechanistic oxidation pathway has been established with a non-vanadium phase, ScTiO3 bixbyite. However, there is stark contrast in terms of structural stability and features beyond this stability limit during AVO3 and ScTiO3 bixbyite reaction pathways. A series of complex reaction sequences including phase separation and phase transitions were identified during the investigation of ScTiO3 reactivity. The two-step formation pathway for the fluorite-type oxide ion conductor Ce1-xInxO2-delta (0 ≤ x ≤ 0.3) is being reported. The formation of the BaCe1-xInxO 3-delta perovskites and the subsequent CO2-capture reaction

  17. Solution-phase mechanistic study and solid-state structure of a tris(bipyridinium radical cation) inclusion complex.

    Fahrenbach, Albert C; Barnes, Jonathan C; Lanfranchi, Don Antoine; Li, Hao; Coskun, Ali; Gassensmith, Jeremiah J; Liu, Zhichang; Benítez, Diego; Trabolsi, Ali; Goddard, William A; Elhabiri, Mourad; Stoddart, J Fraser


    The ability of the diradical dicationic cyclobis(paraquat-p-phenylene) (CBPQT(2(•+))) ring to form inclusion complexes with 1,1'-dialkyl-4,4'-bipyridinium radical cationic (BIPY(•+)) guests has been investigated mechanistically and quantitatively. Two BIPY(•+) radical cations, methyl viologen (MV(•+)) and a dibutynyl derivative (V(•+)), were investigated as guests for the CBPQT(2(•+)) ring. Both guests form trisradical complexes, namely, CBPQT(2(•+))⊂MV(•+) and CBPQT(2(•+))⊂V(•+), respectively. The structural details of the CBPQT(2(•+))⊂MV(•+) complex, which were ascertained by single-crystal X-ray crystallography, reveal that MV(•+) is located inside the cavity of the ring in a centrosymmetric fashion: the 1:1 complexes pack in continuous radical cation stacks. A similar solid-state packing was observed in the case of CBPQT(2(•+)) by itself. Quantum mechanical calculations agree well with the superstructure revealed by X-ray crystallography for CBPQT(2(•+))⊂MV(•+) and further suggest an electronic asymmetry in the SOMO caused by radical-pairing interactions. The electronic asymmetry is maintained in solution. The thermodynamic stability of the CBPQT(2(•+))⊂MV(•+) complex was probed by both isothermal titration calorimetry (ITC) and UV/vis spectroscopy, leading to binding constants of (5.0 ± 0.6) × 10(4) M(-1) and (7.9 ± 5.5) × 10(4) M(-1), respectively. The kinetics of association and dissociation were determined by stopped-flow spectroscopy, yielding a k(f) and k(b) of (2.1 ± 0.3) × 10(6) M(-1) s(-1) and 250 ± 50 s(-1), respectively. The electrochemical mechanistic details were studied by variable scan rate cyclic voltammetry (CV), and the experimental data were compared digitally with simulated data, modeled on the proposed mechanism using the thermodynamic and kinetic parameters obtained from ITC, UV/vis, and stopped-flow spectroscopy. In particular, the electrochemical mechanism of association

  18. Physicochemical analyses of a bioactive 4-aminoantipyrine analogue - synthesis, crystal structure, solid state interactions, antibacterial, conformational and docking studies.

    Alam, Mohammad Sayed; Lee, Dong-Ung


    A novel Schiff base derivative of 4-aminoantipyrine, that is, (E)-4-(2-methoxybenzylideneamino)-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one (MBA-dMPP), was synthesized and characterized by FT-IR, (1)H-NMR, and EI-MS. Single-crystal X-ray diffraction data revealed MBA-dMPP adopts a trans configuration around its central C=N double bond, and forms orthorhombic crystals. XRD revealed that MBA-dMPP possess two different planes, in which the pyrazolone and benzylidene groups attached to C9 of the pyrazolone ring are almost coplanar and the phenyl ring connected to the N1 atom of the pyrazolone moiety lies in another plane. The intermolecular, host-guest C-H…O, C-H…N, and C-H…C van der Waals interactions were found to form a 3D network and confer stability to the MBA-dMPP crystal structure. The quantitative and qualitative solid state behaviors of MBA-dMPP were subjected to 3D Hirshfeld surface analysis and 2D fingerprint plotting. Reciprocal H…H contacts contributed most (52.9 %) to the Hirshfeld surface, followed by C…H/H…C contacts (30.2 %), whereas, O…H/H…O and N…H/H…N interactions contributed 15.5 % to the Hirshfeld surface. Electrostatic potentials were mapped over the Hirshfeld surface to analyze electrostatic complementarities within the MBA-dMPP crystal. In addition, geometrical descriptors were also analyzed to the extent of surface interactions. MBA-dMPP was also investigated for in vitro antibacterial activity against Gram-positive and Gram-negative bacterial strains, and showed highest activity against Bacillus cereus (MIC = 12.5 μg mL(-1)) and Salmonellatythimurium (MIC = 50 μg mL(-1)). In silico screening was conducted by docking MBA-dMPP on the active site of S12 bacterial protein (an important therapeutic target of antibacterial agents) and its binding properties were compared with those of ciprofloxacin. Moreover, a field points map of MBA-dMPP ligand was studied to determine electrostatic and van der Waals forces, hydrophobic

  19. Physicochemical analyses of a bioactive 4-aminoantipyrine analogue - synthesis, crystal structure, solid state interactions, antibacterial, conformational and docking studies

    Alam, Mohammad Sayed; Lee, Dong-Ung


    A novel Schiff base derivative of 4-aminoantipyrine, that is, (E)-4-(2-methoxybenzylideneamino)-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one (MBA-dMPP), was synthesized and characterized by FT-IR, 1H-NMR, and EI-MS. Single-crystal X-ray diffraction data revealed MBA-dMPP adopts a trans configuration around its central C=N double bond, and forms orthorhombic crystals. XRD revealed that MBA-dMPP possess two different planes, in which the pyrazolone and benzylidene groups attached to C9 of the pyrazolone ring are almost coplanar and the phenyl ring connected to the N1 atom of the pyrazolone moiety lies in another plane. The intermolecular, host-guest C-H…O, C-H…N, and C-H…C van der Waals interactions were found to form a 3D network and confer stability to the MBA-dMPP crystal structure. The quantitative and qualitative solid state behaviors of MBA-dMPP were subjected to 3D Hirshfeld surface analysis and 2D fingerprint plotting. Reciprocal H…H contacts contributed most (52.9 %) to the Hirshfeld surface, followed by C…H/H…C contacts (30.2 %), whereas, O…H/H…O and N…H/H…N interactions contributed 15.5 % to the Hirshfeld surface. Electrostatic potentials were mapped over the Hirshfeld surface to analyze electrostatic complementarities within the MBA-dMPP crystal. In addition, geometrical descriptors were also analyzed to the extent of surface interactions. MBA-dMPP was also investigated for in vitro antibacterial activity against Gram-positive and Gram-negative bacterial strains, and showed highest activity against Bacillus cereus (MIC = 12.5 μg mL-1) and Salmonella tythimurium (MIC = 50 μg mL-1). In silico screening was conducted by docking MBA-dMPP on the active site of S12 bacterial protein (an important therapeutic target of antibacterial agents) and its binding properties were compared with those of ciprofloxacin. Moreover, a field points map of MBA-dMPP ligand was studied to determine electrostatic and van der Waals forces, hydrophobic potentials

  20. Solid-State Structure of Abeta (Aβ) in Alzheimer's Disease.

    Lu, Jun-Xia; Dong, Xing-Qi; Zhang, Jian-Jun


    Alzheimer's disease (AD) has become the most common neurodegenerative disease. The deposition of amyloid fibrils in the brain is one of the characteristics of AD. The fibrils are composed of amyloid-β peptide (Aβ). Aβ is produced through a series event of protease cleavage of a transmembrane protein called β-amyloid precursor protein (APP) which is commonly expressed in the brain. The production of Aβ and its propensity to aggregation to form oligomers and fibrils are believed to initiate a sequence of events that lead to AD dementia. The production of Aβ is influenced by the transmembrane domain (TM) structure of APP. The structure variety of different Aβ assemblies including oligomers and fibrils may result in different neurotoxicity to the brain. Therefore, enormous work has been carried out to study the structure of APP TM and various Aβ assemblies. Solid-state NMR has advantages in studying immobile protein structures with large molecular weight. In this review, solid-state NMR structure of APP TM and different Aβ assemblies will be discussed, especially various Aβ amyloid fibril structures. This structural information greatly enhanced our understanding in AD, providing fundamental knowledge that will help in finding a treatment for AD. Copyright© Bentham Science Publishers; For any queries, please email at

  1. Solid state synthesis of Mn5Ge3 in Ge/Ag/Mn trilayers: Structural and magnetic studies

    Myagkov, V. G.; Bykova, L. E.; Matsynin, A. A.; Volochaev, M. N.; Zhigalov, V. S.; Tambasov, I. A.; Mikhlin, Yu L.; Velikanov, D. A.; Bondarenko, G. N.


    The thin-film solid-state reaction between elemental Ge and Mn across chemically inert Ag layers with thicknesses of (0, 0.3, 1 and 2.2 μm) in Ge/Ag/Mn trilayers was studied for the first time. The initial samples were annealed at temperatures between 50 and 500 °C at 50 °C intervals for 1 h. The initiation temperature of the reaction for Ge/Mn (without a Ag barrier layer) was 120 °C and increased slightly up to 250 °C when the Ag barrier layer thickness increased up to 2.2 μm. In spite of the Ag layer, only the ferromagnetic Mn5Ge3 compound and the Nowotny phase were observed in the initial stage of the reaction after annealing at 500 °C. The cross-sectional studies show that during Mn5Ge3 formation the Ge is the sole diffusing species. The magnetic and cross-sectional transmission electron microscopy (TEM) studies show an almost complete transfer of Ge atoms from the Ge film, via a 2.2 μm Ag barrier layer, into the Mn layer. We attribute the driving force of the long-range transfer to the long-range chemical interactions between reacting Mn and Ge atoms.

  2. Solid-state NMR structures of integral membrane proteins.

    Patching, Simon G


    Solid-state NMR is unique for its ability to obtain three-dimensional structures and to measure atomic-resolution structural and dynamic information for membrane proteins in native lipid bilayers. An increasing number and complexity of integral membrane protein structures have been determined by solid-state NMR using two main methods. Oriented sample solid-state NMR uses macroscopically aligned lipid bilayers to obtain orientational restraints that define secondary structure and global fold of embedded peptides and proteins and their orientation and topology in lipid bilayers. Magic angle spinning (MAS) solid-state NMR uses unoriented rapidly spinning samples to obtain distance and torsion angle restraints that define tertiary structure and helix packing arrangements. Details of all current protein structures are described, highlighting developments in experimental strategy and other technological advancements. Some structures originate from combining solid- and solution-state NMR information and some have used solid-state NMR to refine X-ray crystal structures. Solid-state NMR has also validated the structures of proteins determined in different membrane mimetics by solution-state NMR and X-ray crystallography and is therefore complementary to other structural biology techniques. By continuing efforts in identifying membrane protein targets and developing expression, isotope labelling and sample preparation strategies, probe technology, NMR experiments, calculation and modelling methods and combination with other techniques, it should be feasible to determine the structures of many more membrane proteins of biological and biomedical importance using solid-state NMR. This will provide three-dimensional structures and atomic-resolution structural information for characterising ligand and drug interactions, dynamics and molecular mechanisms of membrane proteins under physiological lipid bilayer conditions.

  3. Novel Secondary Structure of Calcitonin in Solid State as Revealed by Circular Dichroism Spectroscopy

    DU,Hai-Ning(杜海宁); DING,Jin-Guo(丁金国); CUI,Da-Fu(崔大敷); HU,Hong-Yu(胡红雨)


    The solid-state circular dichroic study reveals that salmon calcitonin presents a typical α-helical structure while human calcitonin appears to form a β-sheet in solid state, although both of them adopt random coil structures in aqueous solution.

  4. Study of crystalline morphology and phase structure in poly(styrene-b-ethylene oxide-b-styrene) triblock copolymers bu solid state RMN spin diffusion

    Mantovani, Gerson L., E-mail: [Universidade Federal do ABC (UFABC), Santo Andre, SP (Brazil). Centro de Engenharia, Modelagem e Ciencias Sociais Aplicadas; Bonk, Fabio A. [Universidade Estadual de Campinas (IQ/UNICAMP) SP (Brazil). Inst. de Quimica; Caldarelli, Stefano Caldarelli [Aix-Marseille Universite ISm2, Site de Saint Jerome, Marseille (France); Phan, Trang; Bertin, Denis [Universite de Provence, Site de Saint Jerome, Marseille (France); Azevedo, Eduardo R. de; Bonagamba, Tito J. [Universidade de Sao Paulo (IF/USP), Sao Carlos, SP (Brazil). Inst. de Fisica


    The phase structure and crystalline morphology of a series of polystyrene-b-polyethylene oxide-b-polystyrene (PS-b- PEO-b-PS) triblock copolymers, with different compositions and molecular weights, has been studied by solid-state NMR. WAXS and DSC measurements were used to detect the presence of crystalline domains of polyethylene oxide (PEO) blocks at room temperature as a function of the copolymer composition. {sup 1}H NMR spin diffusion analyses provided an estimation of the size of the dispersed phases of the nano structured copolymers. (author)

  5. Solid state NMR study of bone mineral

    Wu, Y.


    In high field (9.4 T) CP MASS (cross polarization magic angle sample spinning) studies, in contrast to the scheme in the literature that infers the presence of minor constituents in spectra, we developed a new scheme to suppress the main part of the spectra to show the minor constituents. In order to perform in vivo solid state NMR studies, a double tuned two port surface coil probe was constructed. This probe is a modified version of the traditional Cross probe, which utilizes two 1/4 wave length 50 ohm transmission line, one with open ended and the other with shorted end, to isolate the high and low frequency circuits. The two resonance frequencies in Cross probe were proton and carbon. Our probe is designed to resonate at the proton and phosphorus frequencies, which are much closer to each other and hence more difficult to be tuned and matched simultaneously. Our approach to solve this problem is that instead of using standard 50 ohm transmission lines, we constructed a low capacity open end coaxial transmission line and low inductance shorted end coaxial transmission line. The Q of the phosphorus channel is high. We developed a short contact time cross polarization technique for non-MASS spectroscopy which reduces the signal of the major component of bone mineral to emphasize the minor component. By applying this technique on intact pork bone samples with our home made surface coil, we observed the wide line component, acid phosphate, for the first time. Hydroxyapatite, brushite and octacalcium are considered in the literature to be the model compounds for bone mineral. Cross polarization dynamics has been studied on hydroxyapatite and brushite, which yielded an NMR value for the distance between proton and phosphorus. One and two dimensional CP MASS spectroscopy of octacalcium phosphate were also studied, which revealed the different cross polarization rates and anisotropic channel shifts of acid phosphate and phosphate ions in octacalcium phosphate.

  6. Studies of Structure and Dynamics of Light Harvesting Complex 1 of R. Sphaeroides by Solid State NMR

    McDermott, Ann E [Columbia Univ., New York, NY (United States)


    Studies of the structure and dynamics of a light harvesting complex from photosynthetic bacteria are described. Using Nuclear Magnetic Resonance methods, we explored the idea that optical properties are modulated via a conformational switch in the BChl chromophores, in a way that provides benefits for the efficiency of energy conversion.

  7. Solid-State NMR Studies of Chemically Lithiated CFx

    Leifer, N. D.; Johnson, V. S.; Ben-Ari, R.; Gan, H.; Lehnes, J. M.; Guo, R.; Lu, W.; Muffoletto, B. C.; Reddy, T.; Stallworth, P. E.; Greenbaum, S. G.


    Three types of fluorinated carbon, all in their original form and upon sequential chemical lithiations via n-butyllithium, were investigated by 13C and 19F solid-state NMR methods. The three starting CFx materials [where x = 1 (nominally)] were fiber based, graphite based, and petroleum coke based. The aim of the current study was to identify, at the atomic/molecular structural level, factors that might account for differences in electrochemical performance among the different kinds of CFx. Differences were noted in the covalent F character among the starting compounds and in the details of LiF production among the lithiated samples. PMID:20676233

  8. Fourier transform IR spectroscopic study of hydration-induced structure changes in the solid state of omega-gliadins.

    Wellner, N; Belton, P S; Tatham, A S


    The hydration of omega-gliadins and party deamidated and esterified omega-gliadins has been studied by Fourier transform IR spectroscopy. The secondary structure of the fully hydrated proteins was a mixture of beta-turns and extended chains, with a small amount of intermolecular beta-sheets. The absorption of the glutamine side chain amide groups contributed considerably to the amide I band with two well-defined peaks at 1658 and 1610 cm-1. the amide I band of the dry native sample could not be resolved into single component bands. There the backbone structure seemed to be distorted by extensive hydrogen bonding involving glutamine side chains. With increasing water content, these hydrogen bonds were broken successively by water molecules, resulting in an increase in extended, hydrated structures, which gave rise to the formation of intermolecular beta-sheet structures. Above 35% (w/w) water the beta-sheet content fell sharply and was replaced by extensively hydrated extended structures. An amide I band similar to dissolved poly-L-proline proved that parts of the polymer were in a solution-like state. The replacement of many glutamine side chains in the esterified protein produced more resolved secondary structures even in the dry sample. The beta-sheet content of the dry sample was higher than in the native omega-gliadins, but hydration generally caused very similar changes. At all hydration levels the spectra indicated a more ordered structure than in the native sample. Overall, the modification caused changes that go beyond the simple presence or absence of glutamine bands.

  9. Molecular Structure of Humin and Melanoidin via Solid State NMR

    Herzfeld, Judith; Rand, Danielle; Matsuki, Yoh; Daviso, Eugenio; Mak-Jurkauskas, Melody; Mamajanov, Irena


    Sugar-derived humins and melanoidins figure significantly in food chemistry, agricultural chemistry, biochemistry and prebiotic chemistry. Despite wide interest and significant experimental attention, the amorphous and insoluble nature of the polymers has made them resistant to conventional structural characterization. Here we make use of solid-state NMR methods, including selective 13C substitution, 1H-dephasing, and double quantum filtration. The spectra, and their interpretation, are simpl...

  10. The importance of screening solid-state phases of a racemic modification of a chiral drug: thermodynamic and structural characterization of solid-state phases of etiracetam.

    Herman, Christelle; Vermylen, Valérie; Norberg, Bernadette; Wouters, Johan; Leyssens, Tom


    In this contribution different solid-state forms of the racemic compound (RS)-2-(2-oxo-pyrrolidin-1yl)-butyramide are studied from a structural and thermal point of view. Three different solid-state phases were identified, including two polymorphs and one hydrate phase. Comparison is made with the structure of the (S)-enantiomer, for which only one solid-state phase is known. The basic structural motif found in both polymorphs of the racemic compound is similar, but the basic motif observed for the hydrate differs. These synthons could in principle be used in future polymorph prediction studies to screen for possible alternative forms of the enantiopure compound. Based on the structure of the hydrate, further efforts should therefore be made in order to identify a hydrate structure of the enantiopure compound. Studying the different phases of a racemic compound can therefore help to guide polymorphic screening of an enantiopure compound.

  11. Use of solid-state 13C NMR in structural studies of humic acids and humin from Holocene sediments

    Hatcher, P.G.; VanderHart, D.L.; Earl, W.L.


    13C NMR spectra of solid humic substances in Holocene sediments have been obtained using cross polarization with magic-angle sample spinning techniques. The results demonstrate that this technique holds great promise for structural characterizations of complex macromolecular substances such as humin and humic acids. Quantifiable distinctions can be made between structural features of aquatic and terrestrial humic substances. The aliphatic carbons of the humic substances are dominant components suggestive of input from lipid-like materials. An interesting resemblance is also noted between terrestrial humic acid and humin spectra. ?? 1980.

  12. Structural biology applications of solid state MAS DNP NMR

    Akbey, Ümit; Oschkinat, Hartmut


    Dynamic Nuclear Polarization (DNP) has long been an aim for increasing sensitivity of nuclear magnetic resonance (NMR) spectroscopy, delivering spectra in shorter experiment times or of smaller sample amounts. In recent years, it has been applied in magic angle spinning (MAS) solid-state NMR to a large range of samples, including biological macromolecules and functional materials. New research directions in structural biology can be envisaged by DNP, facilitating investigations on very large complexes or very heterogeneous samples. Here we present a summary of state of the art DNP MAS NMR spectroscopy and its applications to structural biology, discussing the technical challenges and factors affecting DNP performance.

  13. Structural, dielectric and conductivity studies of LiNi0.75Mg0.25-xCuxPO4 synthesized by solid state reaction method

    Kotamalige Anand


    Full Text Available The olivine structured LiNi0.75Mg0.25-xCuxPO4 (x = 0, 0.05 and 0.1 cathode materials were synthesized by solid state reaction method. The XRD, FTIR and FESEM studies were conducted to investigate the phase purity, crystal structure, lattice parameters and morphology, respectively. The powder X-ray diffraction studies confirmed the single phase formation of the pure and doped compounds which are found to be orthorhombic with the parent LiNiPO4. Morphology and grain sizes of the materials were investigated through FESEM. The FTIR technique was used to characterize the stretching and bending vibrational modes of different functional groups existing in the materials. The cathode properties were analysed through impedance spectroscopy and indicated on improved electrical properties of the doped samples as compared to the pure LiNiPO4. The conductivity and modulus analyses of the samples were carried out at different temperatures and frequencies using the complex impedance spectroscopy technique.

  14. A 13C solid-state NMR study of the structure and the dynamics of the polymorphs of sulphanilamide

    Frydman, Lucio; Olivieri, Alejandro C.; Diaz, Luis E.; Frydman, Benjamin; Schmidt, Asher; Vega, Shimon

    The 13C CPMAS NMR spectra of four crystalline forms of p-aminobenzenesulphonamide (sulphanilamide) were recorded at room temperature. Three of these forms (α, β, and γ) showed doublings in the resonances of the carbon atoms ortho to the amino group, but only a single signal was obtained from those ortho to the asymmetric sulphonamide group. A variabletemperature study allowed the interconversion of the α and β forms to the γ form to be monitored. Changes were also observed in the spectrum of the γ form as the temperature was increased, and were ascribed to the presence of 180° flips of the phenyl rings about their para axis. This interpretation was confirmed by analysis of the broadenings introduced by the assumed motion on the centreband and sidebands in the 13C CPMAS NMR spectrum of the exchanging nuclei. Variable-temperature spectra of the γ form were simulated in order to obtain information about the geometry, the rates and the activation parameters involved in the process. These calculations were in good agreement with the experimental data. The possible relevance that the observed doublings and ring motion may have for the mode of action of sulphonamides is also discussed.


    WU Rongrui; DENG Yuan; HUANG Guanbao; DENG Jianyuan; LI Huiping


    The kinetic data of solid state polycondensation of PET and its copolymers are determined.It is shown that the reaction rate of copolycondensation is higher than that of PET polycondensation, and increases with the comonomers content. But the reaction rate of copolycondensation in melt state of this kind of copolymers is lower than that of PET. It is considered that the chemical reactivity of comonomer is the main factor which affect the polycondensation in melt state,whereas the aggregative structure of the polymer is the main factor in solid state. The crystallinity and crystallite size of the copolymers have been measured by X-ray method.

  16. Solid state NMR study calcium phosphate ceramics

    Miquel, J.L.; Facchini, L.; Legrand, A.P. (Laboratoire de Physique Quantique, Paris (France). CNRS, URA421, ESPCI); Rey, C. (CNRS, Toulouse (France). ENSC. Laboratoire de Physico-chimie des Solides); Lemaitre, J. (EPF Lausanne (France). Laboratoire de Technologie des Poudres)


    High-resolution {sup 31}P and {sup 1}H NMR spectra at 40 and 121 MHz {sup 31}P and 300 MHz {sup 1}H of synthetic and biological samples of calcium phosphates have been obtained by magic angle spinning (MAS) at spinning speeds up to 6.5 kHz, and high power proton decoupling. The samples include crystalline hydroxyapatite, a deficient hydroxyapatite characterized by a Ca/P atomic ratio of 1.5, a poorly crystallized hydroxyapatite, monetite, brushite, octacalcium phosphate, {beta}-tricalcium phosphate and rabbit femoral bone. The interactions between nuclei in unlike structures and the mobility of acid protons are discussed. (author). 11 refs.; 2 figs.; 1 tab.

  17. Structural, optical and magnetic study of (1-x)ZnO-xMgO composites prepared through solid state reaction method

    Adhlakha, Nidhi [Smart Materials Research Laboratory, Department of Physics, Indian Institute of Technology Roorkee, Roorkee 247667 (India); Yadav, K.L., E-mail: [Smart Materials Research Laboratory, Department of Physics, Indian Institute of Technology Roorkee, Roorkee 247667 (India); Kumar, Amit; Patel, Piyush Kumar; Rani, Jyoti; Rawat, Meera [Smart Materials Research Laboratory, Department of Physics, Indian Institute of Technology Roorkee, Roorkee 247667 (India)


    We report the study of structural, optical and magnetic properties of (1-x)ZnO-xMgO (x=0.35, 0.40, 0.45 and 0.50) composites prepared by solid state reaction method. X-ray diffraction pattern confirms the presence of both the phases associated with ZnO (hexagonal) and MgO (cubic), which is revealed through the existence of (1 1 1) and (2 0 0) peaks in addition to ZnO peaks. The lattice parameter c as calculated using X-ray analysis undergoes shrinkage with increasing content of MgO. Microstructural analysis suggests that there is no variation in spherical elongated shape of grains with increasing concentration of MgO, where the average grain size is found to be {approx}600 nm. The band gap as calculated from optical absorption spectra obtained by diffuse reflectance method recorded at room temperature is tuned from 3.16 to 3.55 eV. Photoluminescence spectra consist of near band edge UV emission (389 nm) and defect level emission (503 nm). The increase of MgO concentration leads to blue shift of UV emission peaks. The magnetic measurements conducted using SQUID at 5 K temperature reveals ferromagnetism along with paramagnetic and superparamagnetic components. Saturation magnetisation (M{sub s}) is observed to be enhanced with MgO doping.

  18. Theory of the electronic and structural properties of solid state oxides

    Chelikowsky, J.R.


    Studies on electronic and structural properties of solid state oxides continued. This quarter, studies have concentrated on silica. Progress is discussed in the following sections: interatomic potentials and the structural properties of silica; chemical reactivity and covalent/metallic bonding on Si clusters; and surface and thermodynamic interatomic forces fields for silicon. 64 refs., 20 figs., 5 tabs. (CBS)

  19. Multidimensional solid-state NMR studies of the structure and dynamics of pectic polysaccharides in uniformly 13C-labeled Arabidopsis primary cell walls

    Dick-Perez, Marilu; Wang, Tuo; Salazar, Andre; Zabotina, Olga A.; Hong, Mei


    Plant cell wall (CW) polysaccharides are responsible for the mechanical strength and growth of plant cells; however, the high-resolution structure and dynamics of the CW polysaccharides are still poorly understood because of the insoluble nature of these molecules. Here, we use 2D and 3D magic-angle-spinning (MAS) solid-state NMR (SSNMR) to investigate the structural role of pectins in the plant CW. Intact and partially depectinated primary CWs of Arabidopsis thaliana were uniformly labeled with 13C and their NMR spectra were compared. Recent 13C resonance assignment of the major polysaccharides in Arabidopsis thaliana CWs allowed us to determine the effects of depectination on the intermolecular packing and dynamics of the remaining wall polysaccharides. 2D and 3D correlation spectra show the suppression of pectin signals, confirming partial pectin removal by chelating agents and sodium carbonate. Importantly, higher cross peaks are observed in 2D and 3D 13C spectra of the depectinated CW, suggesting higher rigidity and denser packing of the remaining wall polysaccharides compared with the intact CW. 13C spin–lattice relaxation times and 1H rotating-frame spin–lattice relaxation times indicate that the polysaccharides are more rigid on both the nanosecond and microsecond timescales in the depectinated CW. Taken together, these results indicate that pectic polysaccharides are highly dynamic and endow the polysaccharide network of the primary CW with mobility and flexibility, which may be important for pectin functions. This study demonstrates the capability of multidimensional SSNMR to determine the intermolecular interactions and dynamic structures of complex plant materials under near-native conditions. Copyright © 2012 John Wiley & Sons, Ltd.

  20. In situ microscopic studies on the structures and phase behaviors of SF/PEG films using solid-state NMR and Raman imaging.

    Chen, Congheng; Yao, Ting; Tu, Sidong; Xu, Weijie; Han, Yi; Zhou, Ping


    In order to overcome the drawbacks of silk fibroin (SF)-based materials, SF has been blended with some polymers. Before using the blend material, understanding of the structures and phase behaviors of the blend is thought to be essential. In this study, solid-state (13)C CP-MAS NMR and Raman imaging techniques were used to study the structures and phase behaviors of blends of SF with polyethylene glycol (PEG) at a molecular weight that varied from 2 to 20 kDa and a blend ratio of SF/PEG from 95/5 to 70/30 (w/w%) at the molecular and microscopic levels. It is found that the conformational transition of SF to the β-sheet increased as the PEG content increased, while the amount of the formed β-sheet conformers was decreased as the PEG molecular weight increased for a given content. It is also observed that SF was incompatible with PEG to some extent. The phase separation into "sea" and "island" domains took place in the SF/PEG blend films. SF was dominantly present in the "sea" domain, while PEG in the "island" domains. The conformation of SF in the interface between SF and PEG was changed to the β-sheet, while that in the protein-rich domain remained in the random coil and/or helix conformation. These observations suggest that the specifically expected materials, for example, the silk-based microspheres or scaffold materials can be manufactured by controlling the molecular weight and content of PEG in the blend system.

  1. Solid State Synthesis and Crystal Structure of K3SI

    ZHAO Zhen-Qian; LIU Xi; CHEN Wen-Tong; LI Yan; WU A-Qing; ZENG Hui-Yi; GUO Guo-Cong; HUANG Jin-Shun


    A new ternary alkali metal chalcogenide halide, K3SI, has been synthesized by solid state reaction method and structurally characterized by X-ray crystallography. The crystal belongs to hexagonal, space group P63cm with a = 11.699(1), c = 5.8279(9) (A), Mr = 276.26, V = 690.8(1)(A)3, Z = 6, Dc = 3.985 g/cm3, F(000) = 756, μ= 9.913 mm-1, S = 1.004, R = 0.0719 and wR = 0.2204. The title compound is the first example containing S anion in the ternary alkali metal chalcogenide halides family M3QX (M = alkali metal, Q = chalcogenide, X = halide), which crystallizes in the hexagonal anti-perovskite structure type.

  2. Structural and vibrational spectroscopic elucidation of sulpiride in solid state.

    Kecel-Gunduz, Serda; Celik, Sefa; Ozel, Aysen E; Akyuz, Sevim


    The study on the conformational and vibrational behaviors of sulpiride molecule which is known as a neuroleptic or antipsychotic drug that is widely used clinically in the treatment of schizophrenic or depressive disorders is an important scientific and practical task. In here, a careful enough study of monomer and dimeric forms of sulpiridine {5-(aminosulfonyl)-N-[(1-ethyl-2-pyrrolidinyl) ethyl]-2-methoxy-benzamide (C(15)H(23)N(3)O(4)S)} is undertaken by density functional theory (DFTB3LYP) method with the B3LYP/6-31 G(d,p) basis set. The conformations of free molecule were searched by means of torsion potential energy surfaces scan studies through dihedral angles D1 (8 N, 18 C, 20 C, 23 N), D2 (18 C, 20 C, 23 N, 25 C) and D3 (28 C, 30 C, 41 S, 44 N) in electronically ground state, employing 6-31 G basic set. The final geometrical parameters for the obtained stable conformers were determined by means of geometry optimization, carried out at DFT/B3LYP/6-31 G(d,p) theory level. Afterwards, the possible dimer forms of the molecule were formed and their energetically preferred conformations were investigated. Moreover, the effect of basis set superposition error on the structure and energy of the three energetically favourable sulpiride dimers has been determined. The optimized structural parameters of the most stable monomer and three low energy dimer forms were used in the vibrational wavenumber calculations. Raman and IR (4000-400 cm(-1)) spectra of sulpiride have been recorded in the solid state. The assignment of the bands was performed based on the potential energy distribution data. The natural bond orbital analysis has been performed on both monomer and dimer geometries in order to elucidate delocalization of electron density within the molecule. The predicted frontier molecular orbital energies at DFT/B3LYP/6-31 G(d,p) theory level show that charge transfer occurs within the molecule. The first-order hyperpolarizability (β0) and related properties (μ and

  3. Uses of pulsed electron beam to solid-states studies

    Itoh, Noriaki; Nakayama, Takeyoshi; Tanimura, Katsumi; Chong, Taisu; Saidoh, Masahiro


    A survey is given on the use of the pulsed electron beams to studies of solid states. Even though main emphasis is placed on the studies carried out at the Faculty of Engineering, Nagoya University, using the Pulsed Electron Facilities installed in 1970, the works carried out at other institutes are also included. Only the studies of crystalline solids with simple structures, such as alkali halides and aromatic hydrocarbons are covered. In the first place several instrumentations which have extended utilities of pulsed-electron beams are presented. Then we discuss the studies of the dynamic of excitons, emphasizing the advantages and disadvantages of the usage of the electron pulses. Then usages of the pulsed-electron beam for the studies of the excited states of the quasi-stable defects are described. Application of the electron pulse for studies of the excitation spectroscopy of the photochemistry is described. The dynamic studies of defects introduced by electron-pulse bombardment is discussed finally. A summary is given, which includes also the possible future experiments.

  4. Understanding the solid-state forms of fenofibrate - a spectroscopic and computational study

    Heinz, Andrea; Gordon, Keith C; McGoverin, Cushla M;


    The aim of this study was to investigate the structure of different solid-state forms of fenofibrate, a drug that lacks strong intermolecular interactions such as hydrogen bonding. In addition to a structural analysis of crystalline and amorphous fenofibrate using infrared and Raman spectroscopy...... structures with the experimental vibrational spectra of crystalline and amorphous fenofibrate revealed conformational differences in the orientation of the two benzyl rings in the fenofibrate molecule and structural differences between the different solid-state forms in aliphatic parts of the drug molecule...... and multivariate analysis revealed multiple solid-state forms of fenofibrate, including the metastable crystalline form II, which were structurally analyzed with reference to the quantum chemical calculations. Overall, the study showed that vibrational spectroscopy, multivariate analysis, and quantum chemical...

  5. Sintered Cathodes for All-Solid-State Structural Lithium-Ion Batteries

    Huddleston, William; Dynys, Frederick; Sehirlioglu, Alp


    All-solid-state structural lithium ion batteries serve as both structural load-bearing components and as electrical energy storage devices to achieve system level weight savings in aerospace and other transportation applications. This multifunctional design goal is critical for the realization of next generation hybrid or all-electric propulsion systems. Additionally, transitioning to solid state technology improves upon battery safety from previous volatile architectures. This research established baseline solid state processing conditions and performance benchmarks for intercalation-type layered oxide materials for multifunctional application. Under consideration were lithium cobalt oxide and lithium nickel manganese cobalt oxide. Pertinent characteristics such as electrical conductivity, strength, chemical stability, and microstructure were characterized for future application in all-solid-state structural battery cathodes. The study includes characterization by XRD, ICP, SEM, ring-on-ring mechanical testing, and electrical impedance spectroscopy to elucidate optimal processing parameters, material characteristics, and multifunctional performance benchmarks. These findings provide initial conditions for implementing existing cathode materials in load bearing applications.

  6. Elements of solid state electronics based on soi-structures and si whiskers for cryogenic temperatures

    Druzhinin A. A.


    Full Text Available The paper presents the study results of electrical properties of polycrystalline silicon films in silicon-on-insulator structures and Si whiskers in the temperature range of 4,2—70 K obtained by impedance measurements in the frequency range from 10 Hz to 250 kHz and the possibility of their use in solid-state electronics, functioning at cryogenic temperatures. Characteristics of samples obtained with impedance measurements allow to predict certain specifications of reactive elements of solid state electronics based on polycrystalline and single crystalline silicon, operable at low temperatures. Using the established dependencies, separate elements in the form of solid-state electronics capacitive and inductive elements as well as a combined system in an oscillatory circuit, operable at cryogenic temperatures, have been suggested. The features of developed system depend on the structure of samples and their doping level, which allows to change the required parameters of the elements of solid state electronics in a wide range.

  7. Structure and disorder in iron-bearing sodium silicate glasses and melts: High-resolution 29Si and 17O solid-state NMR study

    Kim, H.; Lee, S.


    Understanding of the effect of iron content on the structure (Si coordination environment and the degree of polymerization) of iron-bearing silicate melts and glasses is essential for studying their macroscopic properties and diverse geological processes in Earth's interior. Although the recent advances in high-resolution solid-state NMR techniques provide detailed structural information of a diverse iron-free oxide glasses with varying composition (e.g., Lee, P. Natl. Acad. Sci. USA., 2011, 108, 6847; Lee and Sung, Chem. Geol., 2008, 256, 326; Park and Lee, Geochim. Cosmochim. Acta, 2012, 80, 125; Lee et al., Phys. Rev., 103, 095501, 2009), their application to iron-bearing silicate glasses has a limited usefulness in resolving atomic configurations due to the effect of paramagnetic cation (i.e., Fe) on the NMR spectra. Here, we report the first ^{29}Si and ^{17}O NMR spectra for sodium-iron silicate glasses with varying iron content (Na_{2}O-Fe_{2}O_{3}-SiO_{2} glasses, up to 34.60 wt% Fe_{2}O_{3}), revealing previously unknown details of iron-induced changes in structure and disorder. While signal intensity decreases and peak width increases exponentially with increasing iron content [=Fe_{2}O_{3}/(Na_{2}O+Fe_{2}O_{3})], ^{29}Si MAS NMR spectra for sodium-iron silicate glasses present the slight peak shift and an asymmetrical peak broadening toward higher Q^{n} species with increasing iron content. This result implies an increase in the degree of polymerization with increasing iron content. Additionally, ^{29}Si spin-relaxation time (T_{1}) for the glasses decreases with increasing of iron content by several orders of magnitude. ^{17}O 3QMAS NMR spectra for the glasses show well-resolved non-bridging oxygen (NBO, Na-O-Si) and bridging oxygen (BO, Si-O-Si) even at relatively high iron content, providing the first direct experimental estimation of the degree of polymerization. In sodium-iron silicate glasses, the fraction of NBO decreases with increasing iron

  8. Protein structural studies by paramagnetic solid-state NMR spectroscopy aided by a compact cyclen-type Cu(II) binding tag

    Sengupta, Ishita; Gao, Min; Arachchige, Rajith J.; Nadaud, Philippe S. [The Ohio State University, Department of Chemistry and Biochemistry (United States); Cunningham, Timothy F.; Saxena, Sunil [University of Pittsburgh, Department of Chemistry (United States); Schwieters, Charles D. [National Institutes of Health, Center for Information Technology (United States); Jaroniec, Christopher P., E-mail: [The Ohio State University, Department of Chemistry and Biochemistry (United States)


    Paramagnetic relaxation enhancements (PREs) are a rich source of structural information in protein solid-state NMR spectroscopy. Here we demonstrate that PRE measurements in natively diamagnetic proteins are facilitated by a thiol-reactive compact, cyclen-based, high-affinity Cu{sup 2+} binding tag, 1-[2-(pyridin-2-yldisulfanyl)ethyl]-1,4,7,10-tetraazacyclododecane (TETAC), that overcomes the key shortcomings associated with the use of larger, more flexible metal-binding tags. Using the TETAC–Cu{sup 2+} K28C mutant of B1 immunoglobulin-binding domain of protein G as a model, we find that amino acid residues located within ∼10 Å of the Cu{sup 2+} center experience considerable transverse PREs leading to severely attenuated resonances in 2D {sup 15}N–{sup 13}C correlation spectra. For more distant residues, electron–nucleus distances are accessible via quantitative measurements of longitudinal PREs, and we demonstrate such measurements for {sup 15}N–Cu{sup 2+} distances up to ∼20 Å.

  9. In situ solid-state NMR and XRD studies of the ADOR process and the unusual structure of zeolite IPC-6

    Morris, Samuel A.; Bignami, Giulia P. M.; Tian, Yuyang; Navarro, Marta; Firth, Daniel S.; Čejka, Jiří; Wheatley, Paul S.; Dawson, Daniel M.; Slawinski, Wojciech A.; Wragg, David S.; Morris, Russell E.; Ashbrook, Sharon E.


    The assembly-disassembly-organization-reassembly (ADOR) mechanism is a recent method for preparing inorganic framework materials and, in particular, zeolites. This flexible approach has enabled the synthesis of isoreticular families of zeolites with unprecedented continuous control over porosity, and the design and preparation of materials that would have been difficult—or even impossible—to obtain using traditional hydrothermal techniques. Applying the ADOR process to a parent zeolite with the UTL framework topology, for example, has led to six previously unknown zeolites (named IPC-n, where n = 2, 4, 6, 7, 9 and 10). To realize the full potential of the ADOR method, however, a further understanding of the complex mechanism at play is needed. Here, we probe the disassembly, organization and reassembly steps of the ADOR process through a combination of in situ solid-state NMR spectroscopy and powder X-ray diffraction experiments. We further use the insight gained to explain the formation of the unusual structure of zeolite IPC-6.

  10. Theoretical solid state physics

    Haug, Albert


    Theoretical Solid State Physics, Volume 1 focuses on the study of solid state physics. The volume first takes a look at the basic concepts and structures of solid state physics, including potential energies of solids, concept and classification of solids, and crystal structure. The book then explains single-electron approximation wherein the methods for calculating energy bands; electron in the field of crystal atoms; laws of motion of the electrons in solids; and electron statistics are discussed. The text describes general forms of solutions and relationships, including collective electron i

  11. Studies of the fundamentals of solids state batteries

    Abraham, K. M.; Alamgir, M.


    Several methods have been developed to dimensionally stabilize polymer electrolytes based on poly-(bis (methoxy ethoxy ethoxide) phosphazene), known as MEEP. In contrast to the poor dimensional stability exhibited by complexes of MEEP with most Li salts, those prepared with LiAlCl4 have been isolated as the first example of free-standing MEEP-(LiX)n films. The mechanical properties of dimensionally unstable MEEP-(LIX)n complexes can be significantly improved by forming composites with polymers such as poly(ethylene oxide), poly(propylene oxide), poly(ethylene glycol diacrylate) and poly(vinyl pyrrolidinone). The conductivity of 6.7 x 10(exp -5) ohm(exp -1) cm(exp -1) at 25 C exhibited by 55 w/o MEEP/45 w/o PEO-(LiN(CF3SO2)2)0.13 is among the highest values reported to date for a dimensionally stable electrolyte. The preparation, and conductivity, calorimetric and electrochemical studies of these electrolytes are described. Cyclic voltammetric data indicated that these electrolytes have anodic stability at least up to 4.5V versus Li(+)/Li. They have shown excellent compatibility with Li metal making them suitable for use as Li(+) conductive solid electrolytes in solid-state Li batteries. Li/TiS2 solid-state cells utilizing some of these electrolytes have exceeded 200 cycles.

  12. Solid-state NMR and ESR studies of activated carbons produced from pecan shells

    Activated carbon from pecan shells has shown promise as an adsorbent in water treatment and sugar refining. However, the chemistry of the material is complex and not fully understood. We report here the application of solid state NMR and ESR to study the chemical structure, mobility, and pore volu...

  13. Solid-state (79/81)Br NMR and gauge-including projector-augmented wave study of structure, symmetry, and hydration state in alkaline earth metal bromides.

    Widdifield, Cory M; Bryce, David L


    Bromine-79/81 solid-state NMR (SSNMR) spectroscopy is established as a tool to characterize the local structure and symmetry about bromide ions in inorganic systems. Benchmark experimental (79/81)Br SSNMR data are acquired for CaBr(2), SrBr(2), BaBr(2), MgBr(2).6H(2)O, SrBr(2).6H(2)O, BaBr(2).2H(2)O, and CaBr(2).xH(2)O using the Solomon echo and/or QCPMG pulse sequences in magnetic fields of 11.75 and 21.1 T. Analytical line-shape analysis provides (79/81)Br electric field gradient (EFG) tensor parameters (including (79)Br quadrupolar coupling constants, C(Q)((79)Br), of up to 75.1(5) MHz in CaBr(2)), chemical shift tensor parameters (including the largest reported anisotropy), and the relative orientation of the tensor principal axis systems. These data are interpreted in terms of structure and symmetry. Our results indicate that ionic bromide systems should be generally accessible to characterization by (79/81)Br SSNMR despite sizable quadrupolar interactions. The resolving capabilities of (79/81)Br SSNMR spectroscopy are illustrated, using samples which possess up to four magnetically inequivalent sites, and through a rare example of (79)Br magic-angle spinning NMR for a Br in a noncubic lattice. Bromine-79/81 SSNMR spectroscopy is demonstrated to be sensitive to the presence of hydrates (i.e., pseudopolymorphism), via drastic changes in C(Q) and delta(iso). The changes are diagnostic to an extent that the composition of the mixture CaBr(2).xH(2)O is determined for the first time. This technique should therefore be applicable to characterize other unknown mixtures or polymorphs. Important instances where (79)Br nuclear quadrupole resonance data were found to be deficient are noted and corrected. GIPAW DFT computations are shown to be generally in very good agreement with the experimental (79/81)Br SSNMR observations. Finally, it is demonstrated that the origin of the EFG at the Br nuclei cannot be described quantitatively using a point charge model, even after

  14. Solid state nuclear magnetic resonance studies of prion peptides and proteins

    Heller, Jonathan [Univ. of California, Berkeley, CA (United States)


    High-resolution structural studies using x-ray diffraction and solution nuclear magnetic resonance (NMR) are not feasible for proteins of low volubility and high tendency to aggregate. Solid state NMR (SSNMR) is in principle capable of providing structural information in such systems, however to do this efficiently and accurately, further SSNMR tools must be developed This dissertation describes the development of three new methods and their application to a biological system of interest, the priori protein (PrP).

  15. Relationship between crystal structure and solid-state properties of pharmaceuticals

    Sheth, Agam R.

    This thesis strives to understand the structure-property relationships of some pharmaceutical crystals at the molecular level with emphasis on the effect of secondary processing on the solid phase. Using single crystal X-ray diffractometry (SCXRD), the structure of warfarin sodium 2-propanol adduct (W) was established to be a true solvate, contrary to previous reports. Using dynamic water vapor sorption, optical and environmental scanning electron microscopy, SCXRD, powder X-ray diffractometry (PXRD), volume computations and molecular modeling, the effect of relative humidity and temperature on the crystal structure of W was investigated. Ab initio calculations on piroxicam showed that the difference in energy between the two polymorphs, I and II, arises predominantly from the difference between their lattice energies. The detailed hydrogen bonding networks of the two polymorphs are described and compared using graph sets. Despite stabilization of the polymorphs by hydrogen bonds, pair-wise distribution function transforms show a loss of polymorphic memory upon cryogrinding the two polymorphs, leading to a difference in recrystallization behavior between amorphous piroxicam prepared from polymorphs I and II. Structural and solid-state changes of piroxicam polymorphs under mechanical stress were investigated using cryogenic grinding, PXRD, diffuse-reflectance solid-state ultraviolet-visible spectroscopy, 13C solid-state nuclear magnetic resonance spectroscopy, and diffuse-reflectance solid-state Fourier-transform infrared spectroscopy. Intermolecular proton transfer was found to accompany changes in phase and color observed upon cryogrinding the two polymorphs. Model-free and model-fitting studies of the dehydration kinetics of piroxicam monohydrate (PM) showed the dependence of activation energy ( Ea) on both isothermal and non-isothermal heating conditions, and on the fraction of conversion. In the constant-E a region, isothermal dehydration follows the two

  16. 2010 Ceramics, Solid State Studies in Gordon Research Conference

    John Halloran


    The 2010 Gordon Conference on Solid State Studies in Ceramics will present forefront research on ceramic materials in energy conversion, storage, and environmental sustainability. Oxide materials in advanced Li-ion batteries will be featured, including first principles computational methods, new experimental methods, novel synthesis, and the design of batteries that exploit nanoscale cathode materials. Several speakers address advances in oxides for solar applications, including photo-catalysts for solar hydrogen production and dye sensitized solar cells, along with thin film photovoltaics. Fast ionic conducting ceramics in electrochemical energy conversion and storage will be addressed for fuel cells and electrochemical storage. New concepts for electrochemical capacitor materials will be addressed, as will thermoelectric, geopolymers, and ceramics in nuclear energy. The Conference will bring together investigators at the forefront of their field as well as junior scientists in a collegial atmosphere, with programmed discussion sessions and informal gatherings in the afternoons and evenings. Poster presentations provide opportunities for junior scientists and graduate students to present their work and exchange ideas with leaders in the field. This Conference provides an avenue for scientists from different disciplines to explore new ideas and promotes cross-disciplinary collaborations in the various research areas represented.

  17. Solid state NMR studies of gels derived from low molecular mass gelators.

    Nonappa; Kolehmainen, E


    Since its invention more than six decades ago, nuclear magnetic resonance (NMR) spectroscopy has evolved as an inevitable part of chemical as well as structural analysis of small molecules, polymers, biomaterials and hybrid materials. In the solution state, due to the increased viscosity of complex viscoelastic fluids such as gels, liquid crystals and other soft materials, the rate of molecular tumbling is reduced, which in turn affects the chemical shift anisotropy, dipolar and quadrupolar interactions. As a consequence the solution state NMR spectra show broad lines, and therefore, extracting detailed structural information is a challenging task. In this context, solid state (SS) NMR has the ability to distinguish between a minute amount of polymorphic forms, conformational changes, and the number of non-equivalent molecules in an asymmetric unit of a crystal lattice, and to provide both qualitative as well as quantitative analytical data with a short-range order. Therefore, SS NMR has continued to evolve as an indispensable tool for structural analysis and gave birth to a new field called NMR crystallography. Solid state cross polarization (CP) and high resolution (HR) magic angle spinning (MAS) NMR spectroscopy has been used to study weak interactions in polymer gels. However, the application of SS NMR spectroscopy to study gels derived from low molecular weight gelators has been limited until recently. In this review, we will focus on the importance of solid state NMR spectroscopy in understanding and elucidating the structure of supramolecular gels derived from low molecular weight gelators with selected examples.

  18. Solid state NMR studies of gels derived from low molecular mass gelators

    Kolehmainen, E.


    Since its invention more than six decades ago, nuclear magnetic resonance (NMR) spectroscopy has evolved as an inevitable part of chemical as well as structural analysis of small molecules, polymers, biomaterials and hybrid materials. In the solution state, due to the increased viscosity of complex viscoelastic fluids such as gels, liquid crystals and other soft materials, the rate of molecular tumbling is reduced, which in turn affects the chemical shift anisotropy, dipolar and quadrupolar interactions. As a consequence the solution state NMR spectra show broad lines, and therefore, extracting detailed structural information is a challenging task. In this context, solid state (SS) NMR has the ability to distinguish between a minute amount of polymorphic forms, conformational changes, and the number of non-equivalent molecules in an asymmetric unit of a crystal lattice, and to provide both qualitative as well as quantitative analytical data with a short-range order. Therefore, SS NMR has continued to evolve as an indispensable tool for structural analysis and gave birth to a new field called NMR crystallography. Solid state cross polarization (CP) and high resolution (HR) magic angle spinning (MAS) NMR spectroscopy has been used to study weak interactions in polymer gels. However, the application of SS NMR spectroscopy to study gels derived from low molecular weight gelators has been limited until recently. In this review, we will focus on the importance of solid state NMR spectroscopy in understanding and elucidating the structure of supramolecular gels derived from low molecular weight gelators with selected examples. PMID:27374054

  19. Structure study of BaCe0.85Y0.15O3-Δ as solid state fuel cell material

    Krezhov, K.; Vladikova, D.; Raikova, G.; Genov, I.; Malakova, T.; Dimitrov, D.; Svab, E.; Fabian, M.


    The structural details of powder, dense and porous samples of BaCe0.85Y0.15O3-δ (BCY15) used recently in an innovative monolithic design of SOFC were studied from multiple Rietveld analysis of neutron and x-ray diffraction patterns. The 3-layered monolithic assembly built from BCY15 material works as oxide ion conductor in the oxygen space, as proton conductor in the hydrogen area and as mixed conductor in the central membrane. We find that in all the samples of studied BCY15 based materials there are no indications of difference in crystallographic symmetry and the structure refinements did produce best agreement factors in orthorhombic Pnma space group.

  20. Exploring Solid-State Structure and Physical Properties: A Molecular and Crystal Model Exercise

    Bindel, Thomas H.


    A crystal model laboratory exercise is presented that allows students to examine relations among the microscopic-macroscopic-symbolic levels, using crystalline mineral samples and corresponding crystal models. Students explore the relationship between solid-state structure and crystal form. Other structure-property relationships are explored. The…

  1. Exploring Solid-State Structure and Physical Properties: A Molecular and Crystal Model Exercise

    Bindel, Thomas H.


    A crystal model laboratory exercise is presented that allows students to examine relations among the microscopic-macroscopic-symbolic levels, using crystalline mineral samples and corresponding crystal models. Students explore the relationship between solid-state structure and crystal form. Other structure-property relationships are explored. The…

  2. Solid State Structure of Poly(9,9-dinonylfluorene)

    Torkkeli, Mika; Galbrecht, Frank; Scherf, Ullrich


    We report on X-ray diffraction and grazing-incidence X-ray diffraction data of poly(9,9-dinonylfluorene) (PF9) in bulk, thin films and in the 1% methylcyclohexane gel. We denote the main crystalline phase as alpha phase and propose that the unit cell is monoclinic (a = 29.31 angstrom, b = 23...... polymer chains) and to the stacking of aromatic main chain units along the b-axis. The polymer chains are aligned along the c-axis. Monoclinic structure agrees with the layer spacing of 14.6 angstrom, the stacking period d(040) = 5.89 angstrom and the monomer repeat distance of 8.33 angstrom. The alpha...

  3. Structural and Functional Models for the Dinuclear Copper Active Site in Catechol Oxidases: Syntheses, X-ray Crystal Structures, Magnetic and Spectral Properties, and X-ray Absorption Spectroscopic Studies in Solid State and in Solution.

    Zippel, Frank; Ahlers, Friedhelm; Werner, Rüdiger; Haase, Wolfgang; Nolting, Hans-Friedrich; Krebs, Bernt


    Two novel tridentate dinucleating ligands containing benzimidazole were prepared, 1,3-bis(2-benzimidazolyl)-2-propanol (Hbbp, 1) and 1,5-bis(2-benzimidazolyl)-3-pentanol (Hbbpen, 2). Their complexing properties toward copper were studied in order to obtain structural and functional models for catechol oxidases. Syntheses and crystal structures of dinuclear Cu(II) complexes derived from these ligands are reported. [Cu(2)bbp(2)](ClO(4))(2).2MeOH, 3, crystallizes in the triclinic space group P&onemacr; with the following unit cell parameters: a = 7.702(3) Å, b = 10.973(6) Å, c = 12.396(6) Å, alpha = 100.59(4) degrees, beta = 99.02(4) degrees, gamma = 98.90(4) degrees, V = 998.7(8) Å(3), and Z = 1. [Cu(2)bbpen(2)](ClO(4))(2).3MeOH, 4, crystallizes in the orthorhombic space group Pccn, with the following unit cell parameters: a = 17.478(9) Å, b = 18.795(8) Å, c = 13.888(6) Å, V = 4562.2(4) Å(3), and Z = 4. Magnetic susceptibility measurements in the temperature ranges 4.6-459 K (3) and 4.6-425 K (4) indicate an antiferromagnetic coupling between the Cu(II) centers of both complexes. In order to determine the structures of the complexes in solution, XAS spectra (EXAFS and XANES) were recorded in the solid state and in solution. The interpretation of these data, including multiple scattering calculations, together with UV-vis titrations, shows that the complexes have the same structure in the crystalline state as well as in methanolic solution. Complex 4 is able to oxidize 3,5-di-tert-butylcatechol (3,5-DTBC) to the quinone (catecholase activity). This reaction was also studied by XAS and UV-vis spectroscopy. These measurements reveal the reduction of Cu(II) to Cu(I) accompanied by a decrease of the coordination number.

  4. Solid state NMR: The essential technology for helical membrane protein structural characterization.

    Cross, Timothy A; Ekanayake, Vindana; Paulino, Joana; Wright, Anna


    NMR spectroscopy of helical membrane proteins has been very challenging on multiple fronts. The expression and purification of these proteins while maintaining functionality has consumed countless graduate student hours. Sample preparations have depended on whether solution or solid-state NMR spectroscopy was to be performed - neither have been easy. In recent years it has become increasingly apparent that membrane mimic environments influence the structural result. Indeed, in these recent years we have rediscovered that Nobel laureate, Christian Anfinsen, did not say that protein structure was exclusively dictated by the amino acid sequence, but rather by the sequence in a given environment (Anfinsen, 1973) [106]. The environment matters, molecular interactions with the membrane environment are significant and many examples of distorted, non-native membrane protein structures have recently been documented in the literature. However, solid-state NMR structures of helical membrane proteins in proteoliposomes and bilayers are proving to be native structures that permit a high resolution characterization of their functional states. Indeed, solid-state NMR is uniquely able to characterize helical membrane protein structures in lipid environments without detergents. Recent progress in expression, purification, reconstitution, sample preparation and in the solid-state NMR spectroscopy of both oriented samples and magic angle spinning samples has demonstrated that helical membrane protein structures can be achieved in a timely fashion. Indeed, this is a spectacular opportunity for the NMR community to have a major impact on biomedical research through the solid-state NMR spectroscopy of these proteins. Copyright © 2013 Elsevier Inc. All rights reserved.

  5. 1 : 2 Adducts of copper(I) halides with 1,2-bis(di-2-pyridylphosphino)ethane: solid state and solution structural studies and antitumour activity.

    Bowen, Richard J; Navarro, Maribel; Shearwood, Anne-Marie J; Healy, Peter C; Skelton, Brian W; Filipovska, Aleksandra; Berners-Price, Susan J


    The 1 : 2 adducts of copper(I) halides with 1,2-bis(2-pyridylphosphino)ethane (d2pype) have been synthesized and solution properties characterized by variable temperature (1)H, (31)P and (65)Cu NMR spectroscopy. Single-crystal structure determinations for the chloride, bromide and iodide complexes show these to crystallize from acetonitrile in the triclinic space group P1 as isostructural centrosymmetric dimers [(d2pype)Cu(mu-d2pype)(2)Cu(d2pype)]X(2).(solvent) with a approximately 12.6, b approximately 12.7, c approximately 15.3 A, alpha approximately 84, beta approximately 67, gamma approximately 84 degrees. In contrast to the analogous AuCl:2(d2pype) and AgNO(3):2(d2pype) adducts, in solution these CuX:2(d2pype) adducts (where X = Cl, Br and I) exist almost exclusively as bis-chelated monomeric [Cu(d2pype)(2)]X; evidence for an equilibrium between monomeric and dimeric forms is detected only for the CuCl adduct in methanol. Cytotoxicity studies in two human breast cancer lines and two matched liver progenitor cell lines indicate that [Cu(d2pype)(2)]Cl is non selectively toxic to both non-tumourigenic and tumourigenic cells. However, the analogous Au(I) compound [Au(d2pype)(2)]Cl, is toxic to highly tumourigenic cells and more selective in its toxicity to tumourigenic cells compared to non-tumourigenic cells. The significance of these results to the further development of selective, mitochondria-targeted, Au(I) antitumour complexes is discussed.

  6. Intercalation complex of proflavine with DNA: Structure and dynamics by solid-state NMR

    Tang, Pei; Juang, Chilong; Harbison, G.S. (State Univ. of New York, Stony Brook (USA))


    The structure of the complex formed between the intercalating agent proflavine and fibrous native DNA was studied by one- and two-dimensional high-resolution solid-state nuclear magnetic resonance (NMR). Carbon-13-labeled proflavine was used to show that the drug is stacked with the aromatic ring plane perpendicular to the fiber axis and that it is essentially immobile. Natural abundance carbon-13 NMR of the DNA itself shows that proflavine binding does not change the puckering of the deoxyribose ring. However, phosphorus-31 NMR spectra show profound changes in the orientation of the phosphodiester grouping on proflavine binding, with some of the phosphodiesters tilting almost parallel to the helix axis, and a second set almost perpendicular. The first group to the phosphodiesters probably spans the intercalation sites, whereas the tilting of the second set likely compensates for the unwinding of the DNA by the intercalator.

  7. Protein oligomers studied by solid-state NMR – the case of the full-length nucleoid-associated protein histone-like nucleoid structuring protein

    Renault, M.A.M.; García, J.; Cordeiro, T.N.; Baldus, M.; Pons, M.


    Members of the histone-like nucleoid structuring protein (H-NS) family play roles both as architectural proteins and as modulators of gene expression in Gram-negative bacteria. The H-NS protein participates in modulatory processes that respond to environmental changes in osmolarity, pH, or temperatu

  8. Effect of iron content on the structure and disorder of iron-bearing sodium silicate glasses: A high-resolution 29Si and 17O solid-state NMR study

    Kim, Hyo-Im; Sur, Jung Chul; Lee, Sung Keun


    increase with iron content and that Fe3+ is predominantly a network-former. The 17O NMR spectra suggest a moderate degree of preferential partitioning of iron between NBO and BO clusters. The present results bear strong promise for studying iron-bearing silicate glasses using solid-state NMR techniques, constraining the effect of iron content on the degree of polymerization. The observed changes in atomic structures of iron-bearing sodium silicate glasses will be helpful for unraveling atomic origins of the properties of natural silicate melts.

  9. Lithium substitution in strontium chlorapatite studied by solid state NMR spectroscopy

    Subramanian, S.; Sairam, T. N., E-mail:; Amarendra, G. [Materials Science Group, Indira Gandhi Centre for Atomic Research, Kalpakkam-603102 (India); Maji, B. K.; Jena, H. [Chemical Group, Indira Gandhi Centre for Atomic Research, Kalpakkam-603102 (India)


    Strontium Chlorapatites with various amounts of Li substitution (Sr{sub 10-x}Li{sub x}(PO{sub 4}){sub 6}Cl{sub 2-δ}) were prepared by solid state reaction method and characterized by powder XRD and solid state NMR spectroscopy. XRD reveals shortening of lattice parameters upon Li incorporation. The linewidth of {sup 31}P solid state Magic Angle Spinning NMR spectra decreases with increase in Li content within the apatite phase. This study confirms Li uptake within the apatite phase.

  10. A comparative study of the lipase yield by solid state and submerged ...



    Jan 5, 2009 ... A comparative study of lipase enzyme yields by solid state fermentation (SSF) and submerged fermentation (SmF) ... modern technology by using advanced machinery. With more than .... helps in solving pollution problems.

  11. The study of disk resonators diode modules, solid-state generators active

    B. A. Kotserzhinskii


    Full Text Available The results of an experimental study of disk resonators diode modules, solid-state active microwave generators. The effect of current leads, as well as errors in the manufacture of resonators their characteristics.

  12. Exploratory studies on coordination chemistry of a redox-active bridging ligand: synthesis, properties and solid state structures of the complexes.

    Ran, Ying-Fen; Liu, Shi-Xia; Sereda, Olha; Neels, Antonia; Decurtins, Silvio


    The explorative coordination chemistry of the bridging ligand TTF-PPB is presented. Its strong binding ability to Co(II) and then to Ni(II) or Cu(II) in the presence of hexafluoroacetylacetonate (hfac(-)), forming new mono- and dinuclear complexes 1-3, is described. X-ray crystallographic studies have been conducted in the case of the free ligand TTF-PPB as well as its complexes [Co(TTF-PPB)(hfac)(2)] (1) and [Co(hfac)(2)(μ-TTF-PPB)Ni(hfac)(2)] (2). Each metal ion is bonded to two bidentate hfac(-) anions through their oxygen atoms and two nitrogen atoms of the PPB moiety with a distorted octahedral coordination geometry. Specifically, nitrogen donor atoms of TTF-PPB adopt a cis-coordination but not in the equatorial plane, which is quite rare. Electronic absorption, photoinduced intraligand charge transfer ((1)ILCT), and electrochemical behaviour of 1-3 have been investigated. UV-Vis spectroscopy shows very strong bands in the UV region consistent with ligand centred π-π* transitions and an intense broad band in the visible region corresponding to a spin-allowed π-π* (1)ILCT transition. Upon coordination, the (1)ILCT band is bathochromically shifted by 3100, 6100 and 5900 cm(-1) on going from 1 to 3. The electrochemical studies reveal that all of them undergo two reversible oxidation and one reversible reduction processes, ascribed to the successive oxidations of the TTF moiety and the reduction of the PPB unit, respectively. This journal is © The Royal Society of Chemistry 2011

  13. Solid state SPS microwave generation and transmission study. Volume 1: Phase 2

    Maynard, O. E.


    The solid state sandwich concept for Solar Power Station (SPS) was investigated. The design effort concentrated on the spacetenna, but did include some system analysis for parametric comparison reasons. The study specifically included definition and math modeling of basic solid state microwave devices, an initial conceptual subsystems and system design, sidelobe control and system selection, an assessment of selected system concept and parametric solid state microwave power transmission system data relevant to the SPS concept. Although device efficiency was not a goal, the sensitivities to design of this efficiency were parametrically treated. Sidelobe control consisted of various single step tapers, multistep tapers, and Gaussian tapers. A preliminary assessment of a hybrid concept using tubes and solid state is also included. There is a considerable amount of thermal analysis provided with emphasis on sensitivities to waste heat radiator form factor, emissivity, absorptivity, amplifier efficiency, material and junction temperature.

  14. Solid state SPS microwave generation and transmission study. Volume 1: Phase 2

    Maynard, O. E.


    The solid state sandwich concept for Solar Power Station (SPS) was investigated. The design effort concentrated on the spacetenna, but did include some system analysis for parametric comparison reasons. The study specifically included definition and math modeling of basic solid state microwave devices, an initial conceptual subsystems and system design, sidelobe control and system selection, an assessment of selected system concept and parametric solid state microwave power transmission system data relevant to the SPS concept. Although device efficiency was not a goal, the sensitivities to design of this efficiency were parametrically treated. Sidelobe control consisted of various single step tapers, multistep tapers, and Gaussian tapers. A preliminary assessment of a hybrid concept using tubes and solid state is also included. There is a considerable amount of thermal analysis provided with emphasis on sensitivities to waste heat radiator form factor, emissivity, absorptivity, amplifier efficiency, material and junction temperature.

  15. In situ x-ray diffraction study of crystal structure of Pd during hydrogen isotope loading by solid-state electrolysis at moderate temperatures 250−300 °C

    Fukada, Yoshiki, E-mail: [Toyota Motor Corporation, 1200 Mishuku, Susono-shi, Shizuoka-ken, 410-1193 (Japan); Hioki, Tatsumi; Motohiro, Tomoyoshi [Toyota Central R& D Labs.,Inc, 41-1, Yokomichi, Nagakute, Aichi, 480-1192 (Japan); Green Mobility Collaborative Research Center & Graduate School of Engineering Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8603 (Japan); Ohshima, Shigeki [Toyota Central R& D Labs.,Inc, 41-1, Yokomichi, Nagakute, Aichi, 480-1192 (Japan)


    Hydrogen isotopes and metal interaction with respect to Pd under high hydrogen isotope potential at moderate temperature region around 300 °C was studied. A dry electrolysis technique using BaZr{sub 1−x} Y{sub x}O{sub 3} solid state electrolyte was developed to generate high hydrogen isotope potential. Hydrogen or deuterium was loaded into a 200 nm thick Pd cathode. The cathode is deposited on SiO{sub 2} substrate and covered with the solid state electrolyte and a Pd anode layer. Time resolved in situ monochromatic x-ray diffraction measurement was performed during the electrolysis. Two phase states of the Pd cathodes with large and small lattice parameters were observed during the electrolysis. Numerous sub-micron scale voids in the Pd cathode and dendrite-like Pd precipitates in the solid state electrolyte were found from the recovered samples. Hydrogen induced super-abundant-vacancy may take role in those phenomena. The observed two phase states may be attributed to phase separation into vacancy-rich and vacancy-poor states. The voids formed in the Pd cathodes seem to be products of vacancy coalescence. Isotope effects were also observed. The deuterium loaded samples showed more rapid phase changes and more formation of voids than the hydrogen doped samples. - Highlights: • High amount hydrogen loading into Pd by all solid-state electrolysis was performed. • Two phase states with large and small lattice parameters were observed. • Lattice contractions were observed suggesting formations of super-abundant-vacancy. • The absence of mechanical pressure might stimulate the formation of the vacancy. • Sub-micron void formations were found in the Pd from recovered samples.

  16. Quantification of protein secondary structure by (13)C solid-state NMR.

    Andrade, Fabiana Diuk; Forato, Lucimara Aparecida; Bernardes Filho, Rubens; Colnago, Luiz Alberto


    High-resolution (13)C solid-state NMR stands out as one of the most promising techniques to solve the structure of insoluble proteins featuring biological and technological importance. The simplest nuclear magnetic resonance (NMR) spectroscopy method to quantify the secondary structure of proteins uses the areas of carbonyl and alpha carbon peaks. The quantification obtained by fitting procedures depends on the assignment of the peaks to the structure, type of line shape, number of peaks to be used, and other parameters that are set by the operator. In this paper, we demonstrate that the analysis of (13)C NMR spectra by a pattern recognition method-based on the singular value decomposition (SVD) regression, which does not depend on the operator-shows higher correlation coefficients for α-helix and β-sheet (0.96 and 0.91, respectively) than Fourier transform infrared spectroscopy (FTIR) method. Therefore, the use of (13)C solid-state NMR spectra and SVD is a simple and reliable method for quantifying the secondary structures of insoluble proteins in solid-state.

  17. High-resolution solid-state NMR study of the effect of composition on network connectivity and structural disorder in multi-component glasses in the diopside and jadeite join: Implications for structure of andesitic melts

    Park, Sun Young; Lee, Sung Keun


    The structural evolution of andesitic melts with varying compositions remains one of the unsolved questions in high-temperature geochemistry and petrology. In this article, we report the structural details of model andesitic glasses [CaO-MgO-Na2O-Al2O3-SiO2 (CMNAS)] in the diopside (CaMgSi2O6) and jadeite (NaAlSi2O6) join using high-resolution, multi-nuclear, solid-state nuclear magnetic resonance (NMR). The 27Al NMR spectra of CMNAS glasses confirm that [4]Al is dominant. While a minor fraction of [5]Al is observed, its presence is only prevalent in the glasses with higher Ca-Mg content. Topological disorder in the glass network also tends to increase with Ca-Mg content as evidenced by the increase in the quadrupolar coupling constant (Cq) of [4]Al for glasses with increasing diopside contents (XDiopside). Despite the complex nature of the glasses studied here (with five oxide components), the 17O 3QMAS NMR spectra resolve diverse bridging oxygens (BOs) and non-bridging oxygens (NBOs), from which the degree of Al avoidance among framework cations (Si and Al) and preferential proximity among non-network cations (Ca2+, Mg2+, and Na+) and each oxygen site can be estimated: presence of Al-O-Al in jadeite glass implies a violation of the Al-avoidance rule in the glasses and the decrease in the fraction of NBOs with increasing XDiopside is consistent with a decrease in their viscosity. Analysis of the peak position of {Ca, Mg}-mixed NBOs, along with the absence of Na-NBO peak, and the peak shape of Si-O-Al reveals preferential partitioning of Ca2+ and Mg2 into NBOs and the proximity of Na+ to BOs. The fraction of highly coordinated Al has been linked to thermodynamic and transport properties of the melts. Considering all the experimental Al coordination environments available in the literature, together with the current experimental studies, we attempt to establish the relationship between the fractions of highly coordinated Al and composition, particularly average

  18. Investigation of bacterial spore structure by high resolution solid-state nuclear magnetic resonance spectroscopy and transmission electron microscopy.

    Leuschner, R G; Lillford, P J


    High resolution solid-state nuclear magnetic resonance spectroscopy (NMR) in combination with transmission electron microscopy (TEM) of spores of Bacillus cereus, an outer coatless mutant B. subtilis 322, an inner coatless mutant B. subtilis 325 and of germinated spores of B. subtilis CMCC 604 were carried out. Structural differences in the coats, mainly protein of spores were reflected by NMR spectra which indicated also differences in molecular mobility of carbohydrates which was partially attributed to the cortex. Dipicolinic acid (DPA) of spores of B. cereus displayed a high degree of solid state order and may be crystalline. Heat activation was studied on spores of B. subtilis 357 lux + and revealed a structural change when analysed by TEM but this was not associated with increases in molecular mobility since no effects were measured by NMR.

  19. Analysis of Structural Variability in Pharmaceutical Excipients Using Solid-State NMR Spectroscopy

    Sperger, Diana M.; Munson, Eric Jon


    Polysaccharide-based excipients comprise the majority of most solid dosage forms and can vary dramatically in terms of structural and functionally related properties. Analytical methods for characterizing these important formulation components are crucial. Solid-state NMR spectroscopy (SSNMR) can provide a wealth of information on these materials while offering the advantages of non-destructive sample preparation and selectivity. The overall objective of this work is to identify SSNMR paramet...

  20. Atomic-resolution structure of cytoskeletal bactofilin by solid-state NMR.

    Shi, Chaowei; Fricke, Pascal; Lin, Lin; Chevelkov, Veniamin; Wegstroth, Melanie; Giller, Karin; Becker, Stefan; Thanbichler, Martin; Lange, Adam


    Bactofilins are a recently discovered class of cytoskeletal proteins of which no atomic-resolution structure has been reported thus far. The bacterial cytoskeleton plays an essential role in a wide range of processes, including morphogenesis, cell division, and motility. Among the cytoskeletal proteins, the bactofilins are bacteria-specific and do not have a eukaryotic counterpart. The bactofilin BacA of the species Caulobacter crescentus is not amenable to study by x-ray crystallography or solution nuclear magnetic resonance (NMR) because of its inherent noncrystallinity and insolubility. We present the atomic structure of BacA calculated from solid-state NMR-derived distance restraints. We show that the core domain of BacA forms a right-handed β helix with six windings and a triangular hydrophobic core. The BacA structure was determined to 1.0 Å precision (heavy-atom root mean square deviation) on the basis of unambiguous restraints derived from four-dimensional (4D) HN-HN and 2D C-C NMR spectra.

  1. The unusual solid state structures of pentasubstituted bis(cyclopentadienyl)zinc compounds: Bis(pentamethylcyclopentadienyl)zinc and Bis(tetramethylphenyl- cyclo-pentadienyl)zinc

    Koten, G. van; Fisher, B.; Wijkens, P.; Budzelaar, P.H.M.; Boersma, J.


    The replacement of all hydrogen atoms of Zn(C5H5)2 by methyl groups causes a major change in the solid state structure. Whereas Zn(C5H5)2 is polymeric in the solid state, an X-ray diffraction study of Zn(C5Me5)2 has shown it to be a monomer, with one 5- and one 1-bonded ring. The crystals are monocl

  2. The unusual solid state structures of pentasubstituted bis(cyclopentadienyl)zinc compounds: Bis(pentamethylcyclopentadienyl)zinc and Bis(tetramethylphenyl- cyclo-pentadienyl)zinc

    Koten, G. van; Fisher, B.; Wijkens, P.; Budzelaar, P.H.M.; Boersma, J.


    The replacement of all hydrogen atoms of Zn(C5H5)2 by methyl groups causes a major change in the solid state structure. Whereas Zn(C5H5)2 is polymeric in the solid state, an X-ray diffraction study of Zn(C5Me5)2 has shown it to be a monomer, with one 5- and one 1-bonded ring. The crystals are monocl

  3. Synthesis, Structure and Solid State Properties of Cyclohexanemethylamine Substituted Phenalenyl Based Molecular Conductor

    Robert C. Haddon


    Full Text Available We report the preparation, crystallization and solid state characterization of a cyclohexanemethylamine substituted spirobiphenalenyl radical; in the solid state the compound is iso-structural with its dehydro-analog (benzylamine-substitued compound, and the molecules packed in a one-dimensional fashion that we refer to as a π-step stack. Neighboring molecules in the stack interact via the overlap of one pair of active (spin bearing carbon atoms per phenalenyl unit. The magnetic susceptibility measurement indicates that in the solid state the radical remains paramagnetic and the fraction of Curie spins is 0.75 per molecule. We use the analytical form of the Bonner-Fisher model for the S = 1/2 antiferromagnetic Heisenberg chain of isotropically interacting spins with intrachain spin coupling constant J = 6.3 cm−1, to fit the experimentally observed paramagnetism [χp (T] in the temperature range 4–330 K. The measured room temperature conductivity (σRT = 2.4 × 10–3 S/cm is comparable with that of the iso-structural benzyl radical, even though the calculated band dispersions are smaller than that of the unsaturated analog.

  4. Solid State NMR Studies of Energy Conversion and Storage Materials

    Jankuru Hennadige, Sohan Roshel De Silva

    NMR (Nuclear magnetic resonance) spectroscopy is utilized to study energy conversion and storage materials. Different types of NMR techniques including Magic Angle Spinning, Cross-polarization and relaxation measurement experiments were employed. Four different projects are discussed in this dissertation. First, three types of CFx battery materials were investigated. Electrochemical studies have demonstrated different electrochemical performances by one type, delivering superior performance over the other two. 13C and 19F MAS NMR techniques are employed to identify the atomic/molecular structural factors that might account for differences in electrochemical performance among different types. Next as the second project, layered polymer dielectrics were investigated by NMR. Previous studies have shown that thin film capacitors are improved by using alternate layers of two polymers with complementary properties: one with a high breakdown strength and one with high dielectric constant as opposed to monolithic layers. 13C to 1H cross-polarization techniques were used to investigate any inter-layer properties that may cause the increase in the dielectric strength. The third project was to study two types of thermoelectric materials. These samples were made of heavily doped phosphorous and boron in silicon by two different methods: ball-milled and annealed. These samples were investigated by NMR to determine the degree of disorder and obtain insight into the doping efficiency. The last ongoing project is on a lithium-ion battery system. The nature of passivating layers or the solid electrolyte interphase (SEI) formed on the electrodes surface is important because of the direct correlation between the SEI and the battery life time/durability. Multinuclear (7Li, 19F, 31P) techniques are employed to identify the composition of the SEI formation of both positive and negative electrodes.

  5. Thermodynamic study of (anthracene + phenanthrene) solid state mixtures

    Rice, James W.; Fu, Jinxia; Sandström, Emma; Ditto, Jenna C.; Suuberg, Eric M.


    Polycyclic aromatic hydrocarbons (PAH) are common components of many materials, such as petroleum and various types of tars. They are generally present in mixtures, occurring both naturally and as byproducts of fuel processing operations. It is important to understand the thermodynamic properties of such mixtures in order to understand better and predict their behavior (i.e., fate and transport) in the environment and in industrial operations. To characterize better the thermodynamic behavior of PAH mixtures, the phase behavior of a binary (anthracene + phenanthrene) system was studied by differential scanning calorimetry, X-ray diffraction, and the Knudsen effusion technique. Mixtures of (anthracene + phenanthrene) exhibit non-ideal mixture behavior. They form a lower-melting, phenanthrene-rich phase with an initial melting temperature of 372 K (identical to the melting temperature of pure phenanthrene) and a vapor pressure of roughly lnP/Pa = −2.38. The phenanthrene-rich phase coexists with an anthracene-rich phase when the mole fraction of phenanthrene (xP) in the mixture is less than or equal to 0.80. Mixtures initially at xP = 0.90 consist entirely of the phenanthrene-rich phase and sublime at nearly constant vapor pressure and composition, consistent with azeotrope-like behavior. Quasi-azeotropy was also observed for very high-content anthracene mixtures (2.5 < xP < 5) indicating that anthracene may accommodate very low levels of phenanthrene in its crystal structure. PMID:26973354

  6. Thermodynamic study of (anthracene + phenanthrene) solid state mixtures.

    Rice, James W; Fu, Jinxia; Sandström, Emma; Ditto, Jenna C; Suuberg, Eric M


    Polycyclic aromatic hydrocarbons (PAH) are common components of many materials, such as petroleum and various types of tars. They are generally present in mixtures, occurring both naturally and as byproducts of fuel processing operations. It is important to understand the thermodynamic properties of such mixtures in order to understand better and predict their behavior (i.e., fate and transport) in the environment and in industrial operations. To characterize better the thermodynamic behavior of PAH mixtures, the phase behavior of a binary (anthracene + phenanthrene) system was studied by differential scanning calorimetry, X-ray diffraction, and the Knudsen effusion technique. Mixtures of (anthracene + phenanthrene) exhibit non-ideal mixture behavior. They form a lower-melting, phenanthrene-rich phase with an initial melting temperature of 372 K (identical to the melting temperature of pure phenanthrene) and a vapor pressure of roughly lnP/Pa = -2.38. The phenanthrene-rich phase coexists with an anthracene-rich phase when the mole fraction of phenanthrene (xP) in the mixture is less than or equal to 0.80. Mixtures initially at xP = 0.90 consist entirely of the phenanthrene-rich phase and sublime at nearly constant vapor pressure and composition, consistent with azeotrope-like behavior. Quasi-azeotropy was also observed for very high-content anthracene mixtures (2.5 anthracene may accommodate very low levels of phenanthrene in its crystal structure.

  7. Solid-state NMR studies on surface structure of modified SiO2%固体核磁共振研究改性纳米 SiO2的表面结构

    陈慧娟; 朱建君; 韩培娟; 张慧


    A series of KH550 modified nano-SiO2 with different compositions were prepared and studied by solid-state NMR.29 Si MAS NMR spectroscopy was applied to characterize surface structure and hydroxyl content .Hydrophilicity was measured via 1 H MAS NMR.1 H-29 Si CP/MAS NMR spectroscopy characterized the interaction at the organic-inorganic interface .The above studies show that with the increase of the degree of modification ,the surface hydroxyl content and hydrophilicity of samples were decreased . And the activity of surface proton was reduced with the increase of the degree of modification .%  以纳米 SiO2和 KH550改性纳米 SiO2为研究对象,分别利用29 Si 魔角旋转核磁共振谱(29 Si MAS NMR)、1H魔角旋转核磁共振谱(1H MAS NMR)和1H-29Si 交叉极化/魔角旋转核磁共振谱(1H-29Si CP/MAS NMR)对纳米SiO2和KH550改性纳米SiO2的表面结构、表面羟基含量、亲水性和界面相互作用等进行了研究。实验结果表明,纳米SiO2经过KH550的改性,随着改性程度的增加,样品表面的羟基含量降低、亲水性降低、亲油性增加、表面质子运动活性随改性程度增加而减弱。

  8. Salicylamide cocrystals: screening, crystal structure, sublimation thermodynamics, dissolution, and solid-state DFT calculations.

    Manin, Alex N; Voronin, Alexander P; Manin, Nikolay G; Vener, Mikhail V; Shishkina, Anastasia V; Lermontov, Anatoly S; Perlovich, German L


    A new cocrystal of 2-hydroxybenzamide (A) with 4-acetamidobenzoic acid (B) has been obtained by the DSC screening method. Thermophysical analysis of the aggregate [A:B] has been conducted and a fusion diagram has been plotted. Cocrystal formation from melts was studied by using thermomicroscopy. A cocrystal single-crystal was grown and its crystal structure was determined. The pattern of noncovalent interactions has been quantified using the solid-state DFT computations coupled with the Bader analysis of the periodic electron density. The sublimation processes of A-B cocrystal have been studied and its thermodynamic functions have been calculated. The classical method of substance transfer by inert gas-carrier was chosen to investigate sublimation processes experimentally. The lattice energy is found to be 143 ± 4 kJ/mol. It is lower than the sum of the corresponding values of the cocrystal pure components. The theoretical value of the lattice energy, 156 kJ/mol, is in reasonable agreement with the experimental one. A ternary phase diagram of solubility (A-B-ethanol) has been plotted and the areas with solutions for growing thermodynamically stable cocrystals have been determined.

  9. Applications of Advanced Solid-State NMR Techniques in Studying the Structure and Dynamics of Polymers%先进固体 NMR 技术研究高分子结构与动力学

    张荣纯; 孙平川


    With the advances in NMR theories and spectrometer hardware technology, NMR is playing an increasingly important role in studying multi-scale structure and dynamics of polymers. In this paper, the newest developments in solid-state 1H and 13C NMR techniques and their applications in the studies of polymer structures and dynamics were reviewed. High-resolution solid-state 1H NMR techniques, such as multiple-pulse and fast magic angle spinning (MAS) , have made it possible to determine the chemical structures of polymers and to detect the intra- and inter-polymer interactions effectively. Taking advantages of through-bond (/ coupling) and through-space (dipolar coupling) interactions, two dimensional heteronuclear correlation NMR experiments now can be used to resolve the microstructures of complex polymer chains. The recoupling techniques allow dipolar interactions and chemical shift anisotropy to be observed under MAS conditions, thus enabling simultaneous detection of high-resolution 1H or 13C signals and quasi-static anisotropic interactions. The domain sizes and interphase thickness in multiphase polymers and miscibility in polymer blends can now be determined effectively using the dipolar filter techniques. In the dynamics studies, it is now possible to obtain information on local fast motions of a single bond and super-slow chain dynamics by efficient suppression of spin-diffusion among protons and recoupling of chemical shift anisotropy. In summary, the advanced solid-state NMR techniques have enabled detailed studies on polymer microstructure, phase separation and dynamic behavior at different time and length scales, and on the relationship between the microstructure and macroscopic properties of polymers.%随着固体NMR理论和谱仪硬件技术的不断发展,近年来固体NMR技术在高分子多尺度结构与动力学研究领域中正发挥着越来越重要的作用.多脉冲及高速魔角旋转(MAS)等质子高分辨技术的发展使得

  10. Structural investigation of aluminium doped ZnO nanoparticles by solid-state NMR spectroscopy.

    Avadhut, Yamini S; Weber, Johannes; Hammarberg, Elin; Feldmann, Claus; Schmedt auf der Günne, Jörn


    The electrical conductivity of aluminium doped zinc oxide (AZO, ZnO:Al) materials depends on doping induced defects and grain structure. This study aims at relating macroscopic electrical conductivity of AZO nanoparticles with their atomic structure, which is non-trivial because the derived materials are heavily disordered and heterogeneous in nature. For this purpose we synthesized AZO nanoparticles with different doping levels and narrow size distribution by a microwave assisted polyol method followed by drying and a reductive treatment with forming gas. From these particles electrically conductive, optically transparent films were obtained by spin-coating. Characterization involved energy-dispersive X-ray analysis, wet chemical analysis, X-ray diffraction, electron microscopy and dynamic light scattering, which provided a basis for a detailed structural solid-state NMR study. A multinuclear ((27)Al, (13)C, (1)H) spectroscopic investigation required a number of 1D MAS NMR and 2D MAS NMR techniques (T(1)-measurements, (27)Al-MQMAS, (27)Al-(1)H 2D-PRESTO-III heteronuclear correlation spectroscopy), which were corroborated by quantum chemical calculations with an embedded cluster method (EEIM) at the DFT level. From the combined data we conclude that only a small part of the provided Al is incorporated into the ZnO structure by substitution of Zn. The related (27)Al NMR signal undergoes a Knight shift when the material is subjected to a reductive treatment with forming gas. At higher (formal) doping levels Al forms insulating (Al, H and C containing) side-phases, which cover the surface of the ZnO:Al particles and increase the sheet resistivity of spin-coated material. Moreover, calculated (27)Al quadrupole coupling constants serve as a spectroscopic fingerprint by which previously suggested point-defects can be identified and in their great majority be ruled out.

  11. Probing Membrane Protein Structure Using Water Polarization Transfer Solid-State NMR

    Williams, Jonathan K.; Hong, Mei


    Water plays an essential role in the structure and function of proteins, lipid membranes and other biological macromolecules. Solid-state NMR heteronuclear-detected 1H polarization transfer from water to biomolecules is a versatile approach for studying water-protein, water-membrane, and water-carbohydrate interactions in biology. We review radiofrequency pulse sequences for measuring water polarization transfer to biomolecules, the mechanisms of polarization transfer, and the application of this method to various biological systems. Three polarization transfer mechanisms, chemical exchange, spin diffusion and NOE, manifest themselves at different temperatures, magic-angle-spinning frequencies, and pulse irradiations. Chemical exchange is ubiquitous in all systems examined so far, and spin diffusion plays the key role in polarization transfer within the macromolecule. Tightly bound water molecules with long residence times are rare in proteins at ambient temperature. The water polarization-transfer technique has been used to study the hydration of microcrystalline proteins, lipid membranes, and plant cell wall polysaccharides, and to derive atomic-resolution details of the kinetics and mechanism of ion conduction in channels and pumps. Using this approach, we have measured the water polarization transfer to the transmembrane peptide of the influenza M2 protein to obtain information on the structure of this tetrameric proton channel. At short mixing times, the polarization transfer rates are site-specific and depend on the pH, labile protons, sidechain conformation, as well as the radial position of the residues in this four-helix bundle. Despite the multiple dependences, the initial transfer rates reflect the periodic nature of the residue positions from the water-filled pore, thus this technique provides a way of gleaning secondary structure information, helix tilt angle, and the oligomeric structure of membrane proteins. PMID:25228502

  12. Structural, Optical, and Magnetic Properties of Co Doped CdTe Alloy Powders Prepared by Solid-State Reaction Method

    M. Rigana Begam


    Full Text Available Co doped CdTe powder samples were prepared by solid-state reaction method. In the present work effect of Co doping on structural, optical, and magnetic properties has been studied. X-ray diffraction studies confirm zinc blend structure for all the samples. The lattice parameter showed linear increase with the increase in Co content. The elemental constituents were characterized by EDAX. Optical studies showed the increase in band gap with increase in Co level. The samples were diluted magnetic semiconductors and exhibited clear hysteresis loop showing room temperature ferromagnetism as confirmed by vibrating sample magnetometer.

  13. Inclusion of trans-resveratrol in methylated cyclodextrins: synthesis and solid-state structures

    Lee Trollope


    Full Text Available The phytoalexin trans-resveratrol, 5-[(1E-2-(4-hydroxyphenylethenyl]-1,3-benzenediol, is a well-known, potent antioxidant having a variety of possible biomedical applications. However, its adverse physicochemical properties (low stability, poor aqueous solubility limit such applications and its inclusion in cyclodextrins (CDs has potential for addressing these shortcomings. Here, various methods of the attempted synthesis of inclusion complexes between trans-resveratrol and three methylated cyclodextrins (permethylated α-CD, permethylated β-CD and 2,6-dimethylated β-CD are described. Isolation of the corresponding crystalline 1:1 inclusion compounds enabled their full structure determination by X-ray analysis for the first time, revealing a variety of guest inclusion modes and unique supramolecular crystal packing motifs. The three crystalline inclusion complexes were also fully characterized by thermal analysis (hot stage microscopy, thermogravimetric analysis and differential scanning calorimetry. To complement the solid-state data, phase-solubility studies were conducted using a series of CDs (native and variously derivatised to establish their effect on the aqueous solubility of trans-resveratrol and to estimate association constants for complex formation.

  14. Study of coals by high resolution solid state nuclear magnetic resonance

    杨保联; 冯继文; 周建威; 李丽云; 叶朝辉


    By using high resolution solid state nuclear magnetic resonance method, six coal samples coming from four countries were investigated. Twelve structural parameters of these samples were measured and compared with those of Chinese coals. Spectral editing experiment was carried out and 15N NMR spectrum was obtained.

  15. Feasibility Study on Advanced Solid-State Oxygen Sensors.


    CaO-ZrO2) structure.. 6..............6 3 A typical galvanic cell using a zirconia oxygen ion electrolyte . 8 4 The closed-loop concept of engine...0.645 90.4 6 Sm203 0.869 97.2 Zirconia Electrolyte Cell A typical galvanic cell using a zirconia solid electrolyte is shown in Figure 3 (18, 23, 25-28...oxygen determined by oxygen partial electrolyte oxygen partial pressure P p pressure Po0 0? 0---- Figure 3. A typical galvanic cell using a zirconia V

  16. Study of upscaling possibilities for antimony sulfide solid state sensitized solar cells

    Nikolakopoulou, Archontoula; Raptis, Dimitrios; Dracopoulos, Vasilios; Sygellou, Lamprini; Andrikopoulos, Konstantinos S.; Lianos, Panagiotis


    Solid state solar cells of inverted structure were constructed by successive deposition of nanoparticulate titania, antimony sulfide sensitizer and P3HT on FTO electrodes with PEDOT:PSS:Ag as counter electrode. Sensitized photoanode electrodes were characterized by XRD, Raman, XPS, FESEM and UV-vis. Small laboratory scale cells were first constructed and optimized. Functional cells were obtained by annealing the antimony sulfide film either in air or in inert atmosphere. High short-circuit currents were recorded in both cases with air-annealed sample producing more current but lower voltage. Small unit cells were combined to form cell modules. Connection of unit cells in parallel increased current but not proportionally to that of the unit cell. Connection in series preserved current and generated voltage multiplication. Cells were constructed and studied under ambient conditions, without encapsulation. The results encourage upscaling of antimony sulfide solar cells.

  17. Solid State Division

    Green, P.H.; Watson, D.M. (eds.)


    This report contains brief discussions on work done in the Solid State Division of Oak Ridge National Laboratory. The topics covered are: Theoretical Solid State Physics; Neutron scattering; Physical properties of materials; The synthesis and characterization of materials; Ion beam and laser processing; and Structure of solids and surfaces. (LSP)

  18. Solid-state high performance flexible supercapacitors based on polypyrrole-MnO2-carbon fiber hybrid structure

    Tao, Jiayou; Liu, Nishuang; Ma, Wenzhen; Ding, Longwei; Li, Luying; Su, Jun; Gao, Yihua


    A solid-state flexible supercapacitor (SC) based on organic-inorganic composite structure was fabricated through an "in situ growth for conductive wrapping" and an electrode material of polypyrrole (PPy...

  19. Flexible solid-state supercapacitors based on carbon nanoparticles/MnO2 nanorods hybrid structure.

    Yuan, Longyan; Lu, Xi-Hong; Xiao, Xu; Zhai, Teng; Dai, Junjie; Zhang, Fengchao; Hu, Bin; Wang, Xue; Gong, Li; Chen, Jian; Hu, Chenguo; Tong, Yexiang; Zhou, Jun; Wang, Zhong Lin


    A highly flexible solid-state supercapacitor was fabricated through a simple flame synthesis method and electrochemical deposition process based on a carbon nanoparticles/MnO(2) nanorods hybrid structure using polyvinyl alcohol/H(3)PO(4) electrolyte. Carbon fabric is used as a current collector and electrode (mechanical support), leading to a simplified, highly flexible, and lightweight architecture. The device exhibited good electrochemical performance with an energy density of 4.8 Wh/kg at a power density of 14 kW/kg, and a demonstration of a practical device is also presented, highlighting the path for its enormous potential in energy management.

  20. Synthesis in solid state, structural regularity and reaction mechanism for [VS4-Cun] clusters

    余秀芬; 郑发鲲; 黄锦顺


    The reaction system (NH4)3VS4/CuCl/PPh3/Et4NBr afforded a series of [VS4-Cun] dusters with various core configurations in the solid state at low heating temperature. The structural regularity of [VS4-Cun] dusters and the influence of the CuCl:(NH4)3VS4 ratio as well as that of reaction temperature and time on the formation of duster core have been summarized. The reaction mechanism of forming V-Cu-S clusters has also been explored.

  1. Photochromism and thermochromism of Schiff bases in the solid state: structural aspects.

    Hadjoudis, Eugene; Mavridis, Irene M


    This tutorial review describes in a brief historical perspective the most important organic compounds that exhibit photochromism in the crystalline state since its discovery in 1867 up to now and considers in detail Schiff bases of salicylaldehyde with amines (anils). The latter comprise a chemical system undergoing hydrogen-atom tautomerism between enol and keto forms and show the phenomena of solid state photochromism and thermochromism. The system has been investigated extensively. Thus it has been shown that the photochromic property is a characteristic of the molecules but their chromobehaviour is influenced by the crystal structure of the compounds. Anils, apart from their fundamental interest, have potential for various applications.

  2. Studies of Molecular Dynamics by Solid State Deuterium NMR Spectroscopy

    Zhao, Baiyi

    The rotational dynamics of molecules in a number of solid systems were followed by variable temperature deuterium (^2H), nuclear magnetic resonance (NMR) spectroscopy via changes in the spectral lineshapes and spin-lattice relaxation times (T _1). First the pure solid trimethylamine-borane adduct, (CH_3)_3NBH_3, was studied. For a methyl deuterated sample, T _1 measurements yielded two T_1 minima, 6.9 ms and 4.3 ms corresponding to the slowing of methyl and trimethyl rotation, respectively, with decreasing temperature. Activation energies for methyl and trimethyl rotation, obtained from fitting the T _1 curve as a function of temperature, were 32.8 and 15.0 kJ/mol, respectively; simulations of the spectral lineshapes gave 26.6 and 18.9 kT/mol, respectively. Fitting of the ^2H T_1 curve for the borane deuterated sample gave a BH _3 rotation activation energy of 14.1 kT/mol and a ^2H quadrupolar coupling constant, chi, of 101 kHz. The activation energy for BH_3 rotation obtained from the spectral lineshape simulations gave 12.6 kT/mol. A series of deuterated organic chalcogen cations: (CH_3)_3S^+, (CH_3)_3Se^+ and (CH_3)_3Te^+, were ion exchanged into the cavities of sodium Mordenite LZ-M5 and the dynamics of these guests within the hydrated zeolite were followed by ^2H NMR. All three undergo isotropic motion above about -80 to -90^circC. Below this temperature two superimposed ^2H powder spectra appear; the broad lineshape is consistent with only methyl rotation in a hindered, coordinated site, and the other narrow lineshape is due to both methyl and trimethyl rotation in a less hindered, uncoordinated site. As the temperature is lowered the population of the lower energy coordinated site increases. Relative peak areas yield adsorption enthalpies of 6.7, 7.8 and 10.0 kJ/mol for (CH_3)_3S^+, (CH_3)_3Se^+ and (CH_3)_3Te^+, respectively. The series of methyl deuterated ammonium and phosphonium cations: (CH_3)NH_3^+ , (CH_3)_2NH^+ , (CH_3)_3NH^+ and (CH_3)_4P^+ , were

  3. Crystal structure and tautomerism of Pigment Yellow 138 determined by X-ray powder diffraction and solid-state NMR

    Gumbert, Silke D.; Körbitzer, Meike; Alig, Edith;


    The crystal structure of C.I. Pigment Yellow 138 was determined from X-ray powder diffraction data using real-space methods with subsequent Rietveld refinements. The tautomeric state was investigated by solid-state 1D and 2D multinuclear NMR experiments. In the crystals, the compound exhibits...... the NH-tautomer with a hydrogen atom situated at the nitrogen of the quinoline moiety. Direct evidence of the presence of the NH-tautomer is provided by 1H–14N HMQC solid-state NMR at very fast MAS. Solid-state dispersion-corrected density functional theory calculations with BLYP-D3 confirm...

  4. Friction surface cladding: An exploratory study of a new solid state cladding process

    Liu, S.J.; Bor, T.C.; Stelt, van der A.A.; Geijselaers, H.J.M.; Kwakernaak, C.; Kooijman, A.M.; Mol, J.M.C.; Akkerman, R.; Boogaard, van den A.H.


    Friction surface cladding is a newly developed solid state cladding process to manufacture thin metallic layers on a substrate. In this study the influence of process conditions on the clad layer appearance and the mechanical properties of both the clad layer and the substrate were investigated. Thi

  5. High-resolution membrane protein structure by joint calculations with solid-state NMR and X-ray experimental data

    Tang Ming; Sperling, Lindsay J.; Berthold, Deborah A. [University of Illinois at Urbana-Champaign, Department of Chemistry (United States); Schwieters, Charles D. [National Institutes of Health, Division of Computational Bioscience, Center for Information Technology (United States); Nesbitt, Anna E.; Nieuwkoop, Andrew J.; Gennis, Robert B.; Rienstra, Chad M., E-mail: [University of Illinois at Urbana-Champaign, Department of Chemistry (United States)


    X-ray diffraction and nuclear magnetic resonance spectroscopy (NMR) are the staple methods for revealing atomic structures of proteins. Since crystals of biomolecular assemblies and membrane proteins often diffract weakly and such large systems encroach upon the molecular tumbling limit of solution NMR, new methods are essential to extend structures of such systems to high resolution. Here we present a method that incorporates solid-state NMR restraints alongside of X-ray reflections to the conventional model building and refinement steps of structure calculations. Using the 3.7 A crystal structure of the integral membrane protein complex DsbB-DsbA as a test case yielded a significantly improved backbone precision of 0.92 A in the transmembrane region, a 58% enhancement from using X-ray reflections alone. Furthermore, addition of solid-state NMR restraints greatly improved the overall quality of the structure by promoting 22% of DsbB transmembrane residues into the most favored regions of Ramachandran space in comparison to the crystal structure. This method is widely applicable to any protein system where X-ray data are available, and is particularly useful for the study of weakly diffracting crystals.

  6. The potential for the indirect crystal structure verification of methyl glycosides based on acetates' parent structures: GIPAW and solid-state NMR approaches

    Szeleszczuk, Łukasz; Gubica, Tomasz; Zimniak, Andrzej; Pisklak, Dariusz M.; Dąbrowska, Kinga; Cyrański, Michał K.; Kańska, Marianna


    A convenient method for the indirect crystal structure verification of methyl glycosides was demonstrated. Single-crystal X-ray diffraction structures for methyl glycoside acetates were deacetylated and subsequently subjected to DFT calculations under periodic boundary conditions. Solid-state NMR spectroscopy served as a guide for calculations. A high level of accuracy of the modelled crystal structures of methyl glycosides was confirmed by comparison with published results of neutron diffraction study using RMSD method.

  7. Odd-numbered oxacalix[n]arenes (n = 5, 7): synthesis and solid-state structures.

    Van Rossom, Wim; Robeyns, Koen; Ovaere, Magriet; Van Meervelt, Luc; Dehaen, Wim; Maes, Wouter


    The critical synthetic access to odd-numbered calix[n]arenes has evidently resulted in less attention for these macrocycles, although specific molecular recognition phenomena have been observed for some of them. A straightforward fragment coupling approach has been designed, applying kinetically controlled nucleophilic aromatic substitution reaction conditions, affording odd-numbered oxacalix[n]arenes (n = 5, 7) selectively in high yields. The solid-state conformational behavior and the oxacalix[n]arene cavity size were explored by single-crystal X-ray diffraction studies.

  8. Carbonyl Diisocyanate CO(NCO)2: Synthesis and Structures in Solid State and Gas Phase.

    Klapötke, Thomas M; Krumm, Burkhard; Rest, Sebastian; Scharf, Regina; Schwabedissen, Jan; Stammler, Hans-Georg; Mitzel, Norbert W


    A modified synthesis for carbonyl diisocyanate, CO(NCO)2, starting from trichloroisocyanuric acid and diphosgene is described. In addition to the previously reported (13)C NMR resonances, the (15)N NMR shift is determined for the first time. The structure in the solid state was determined by X-ray diffraction (XRD) on in situ grown crystals, that in the gas phase was experimentally determined by electron diffraction (GED) and for single molecules theoretically by quantum-chemical calculations. The structures are compared and discussed with related systems. Quantum-chemical calculations as well as GED and XRD prove syn-syn to be the conformation of lowest energy. In quantum-chemical calculations and GED the presence of a syn-anti conformer was confirmed and the structure of this conformer was determined.

  9. Structure and dynamics of cationic membrane peptides and proteins: Insights from solid-state NMR

    Hong, Mei; Su, Yongchao


    Many membrane peptides and protein domains contain functionally important cationic Arg and Lys residues, whose insertion into the hydrophobic interior of the lipid bilayer encounters significant energy barriers. To understand how these cationic molecules overcome the free energy barrier to insert into the lipid membrane, we have used solid-state NMR spectroscopy to determine the membrane-bound topology of these peptides. A versatile array of solid-state NMR experiments now readily yields the conformation, dynamics, orientation, depth of insertion, and site-specific protein–lipid interactions of these molecules. We summarize key findings of several Arg-rich membrane peptides, including β-sheet antimicrobial peptides, unstructured cell-penetrating peptides, and the voltage-sensing helix of voltage-gated potassium channels. Our results indicate the central role of guanidinium-phosphate and guanidinium-water interactions in dictating the structural topology of these cationic molecules in the lipid membrane, which in turn account for the mechanisms of this functionally diverse class of membrane peptides. PMID:21344534

  10. Solid-State Millimeter-Wave Source Study: A Study of Two Novel Concepts for Generation of CW Millimeter Waves.



  11. Structural Dynamics and Conformational Equilibria of SERCA Regulatory Proteins in Membranes by Solid-State NMR Restrained Simulations

    De Simone, Alfonso; Mote, Kaustubh R.; Veglia, Gianluigi


    Solid-state NMR spectroscopy is emerging as a powerful approach to determine structure, topology, and conformational dynamics of membrane proteins at the atomic level. Conformational dynamics are often inferred and quantified from the motional averaging of the NMR parameters. However, the nature of these motions is difficult to envision based only on spectroscopic data. Here, we utilized restrained molecular dynamics simulations to probe the structural dynamics, topology and conformational transitions of regulatory membrane proteins of the calcium ATPase SERCA, namely sarcolipin and phospholamban, in explicit lipid bilayers. Specifically, we employed oriented solid-state NMR data, such as dipolar couplings and chemical shift anisotropy measured in lipid bicelles, to refine the conformational ensemble of these proteins in lipid membranes. The samplings accurately reproduced the orientations of transmembrane helices and showed a significant degree of convergence with all of the NMR parameters. Unlike the unrestrained simulations, the resulting sarcolipin structures are in agreement with distances and angles for hydrogen bonds in ideal helices. In the case of phospholamban, the restrained ensemble sampled the conformational interconversion between T (helical) and R (unfolded) states for the cytoplasmic region that could not be observed using standard structural refinements with the same experimental data set. This study underscores the importance of implementing NMR data in molecular dynamics protocols to better describe the conformational landscapes of membrane proteins embedded in realistic lipid membranes. PMID:24940774

  12. Polyfunctional Lewis acids: intriguing solid-state structure and selective detection and discrimination of nitroaromatic explosives.

    Swamy P, Chinna Ayya; Thilagar, Pakkirisamy


    Synthesis and crystal structures of three porphyrin-based polyfunctional Lewis acids 1-3 are reported. Intermolecular HgCl⋅⋅⋅HgCl (linear and μ-type) interactions in the solid state of the peripherally ArHgCl-decorated compound 3 lead to a fascinating 3D supramolecular architecture. Compound 3 shows a selective fluorescence quenching response to picric acid and discriminates other nitroaromatic-based explosives. For the first time, an electron-deficient polyfunctional Lewis acid is shown to be useful for the selective detection and discrimination of nitroaromatic explosives. The Stern-Volmer quenching constant and detection limits of compound 3 for picric acid are the best among the reported small-molecular receptors for nitroaromatic explosives. The electronic structure, Lewis acidity, and selective sensing characteristics of 3 are well corroborated by DFT calculations. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Solid state nuclear magnetic resonance studies of cross polarization from quadrupolar nuclei

    De Paul, Susan M. [Univ. of California, Berkeley, CA (United States)


    The development of solid-state Nuclear Magnetic Resonance (NMR) has, to a large extent, focused on using spin-1/2 nuclei as probes to investigate molecular structure and dynamics. For such nuclei, the technique of cross polarization is well-established as a method for sensitivity enhancement. However, over two-thirds of the nuclei in the periodic table have a spin-quantum number greater than one-half and are known as quadrupolar nuclei. Such nuclei are fundamental constituents of many inorganic materials including minerals, zeolites, glasses, and gels. It is, therefore, of interest to explore the extent to which polarization can be transferred from quadrupolar nuclei. In this dissertation, solid-state NMR experiments involving cross polarization from quadrupolar nuclei to spin-1/2 nuclei under magic-angle spinning (MAS) conditions are investigated in detail.

  14. 固体NMR研究PMMA纳米复合材料结构与受限链运动%Solid-State NMR Studies on the Structure and Confined Segmental Dynamics of PMMA Nanocomposite

    刘源; 陈胜利; 吴强; 陈铁红; 孙平川


    Solid-state NMR techniques were used to study the structure and confined dynamics of poly-methyl methacrylate (PMMA)/laponite nanocomposite. 1H magic angle spinning (MAS) spectra and relaxation experiments indicate that organic modifiers (AIBA) interact strongly with laponite nano-sheets, and the structure of PMMA nanocomposite is homogenous at the scale of several nanometers. The results of 13C spin-lattice relaxation times (T1,C) experiments indicate that mobility of the PMMA segments, especially the carbonyl groups, in nanocomposite decreases under the confinement of laponite nano-sheets. 13C SUPER experiments further indicate that the incorporation of laponite induce a slight change of the CSA line shape of PMMA carbonyl groups.%聚合物/无机纳米复合材料的微观结构和动力学决定了其宏观性能,阐明无机纳米材料对复合材料结构和动力学的影响,对认识材料结构-性能关系及设计新材料都具有重要意义.该文通过乳液聚合方法合成了聚甲基丙烯酸甲酯/锂藻土(PMMA/Laponite)纳米复合材料,采用1H MAS和13C CPMAS、弛豫时间及13C化学位移各向异性谱(SUPER)等多种固体 NMR 技术,详细研究了无机纳米材料的界面改性及其对纳米复合材料的微观结构和动力学的影响.1H MAS和13C CPMAS实验表明,有机改性剂与锂藻土形成强的有机-无机界面相互作用,13C 纵向弛豫时间实验表明,PMMA 及其锂藻土纳米复合物均含有刚性和柔性两个组分,而纳米复合物中的聚合物链运动相对较低,特别是其中PMMA的酯基分子运动明显受限.进一步的13C SUPER实验表明,PMMA酯基的化学位移各向异性在加入锂藻土后发生变化,预示酯基与锂藻土表面的羟基可能存在氢键作用而导致聚合物的链段运动进一步受限,上述纳米尺度受限效应提高了复合材料的玻璃化转变温度.

  15. Controlling polymorphic structures and investigating electric properties of Ca-doped zirconia using solid state ceramic method

    Emam, W.I. [Solid State Physics Department, National Research Center, Dokki, Cairo (Egypt); Mabied, Ahmed F., E-mail: [Solid State Physics Department, National Research Center, Dokki, Cairo (Egypt); Hashem, H.M. [Physics Department, Faculty of Science, Helwan University, Helwan (Egypt); Selim, M.M. [Physical Chemistry Department, National Research Center, Dokki, Cairo (Egypt); El-Shabiny, A.M.; Ahmed Farag, I.S. [Solid State Physics Department, National Research Center, Dokki, Cairo (Egypt)


    Structural study of Zr{sub 1−x}Ca{sub x}O{sub 2−x} samples with x=0.01–0.15 were prepared using solid state ceramic method. X-ray diffraction analysis revealed a mixture of the high temperature phase and the monoclinic one for the samples with x≤0.05. On the other hand, the formation of a single high temperature cubic phase was observed within a concentration range of x=0.06–0.10. At concentrations higher than 0.10 the calcium zirconate phase was observed besides the dominant high temperature one. Rietveld refinement of the single phase data clearly revealed, that substitution of zirconium by calcium increases both the lattice parameters as well as the tetrahedral bond length. Ionic to electronic conductivity ratio enhanced considerably as Ca-doping level ascends. The dielectric constant shows strong temperature dependence at lower frequencies. The dielectric loss factor increases rapidly with the increase in temperature at lower frequencies, while decreases with the increase in frequency at higher temperatures. The ionic conduction is considered as the dominant process at higher temperatures. - Graphical abstract: Forming a high temperature cubic zirconia phase at 1200 °C using ceramic solid state method and aliovalent cation. - Highlights: • Formation the high temperature cubic polymorph of zirconia using Ca-doping. • Solid state ceramic method was used for preparing the cubic Ca-doped zirconia. • Substitution of zirconium by calcium increases the lattice parameters and the bond length. • Ionic to electronic conductivity ratio enhanced considerably as Ca-doping level increases.

  16. Solid-state and unilateral NMR study of deterioration of a Dead Sea Scroll fragment.

    Masic, A; Chierotti, M R; Gobetto, R; Martra, G; Rabin, I; Coluccia, S


    Unilateral and solid-state nuclear magnetic resonance (NMR) analyses were performed on a parchment fragment of the Dead Sea Scroll (DSS). The analyzed sample belongs to the collection of non-inscribed and nontreated fragments of known archaeological provenance from the John Rylands University Library in Manchester. Therefore, it can be considered as original DSS material free from any contamination related to the post-discovery period. Considering the paramount significance of the DSS, noninvasive approaches and portable in situ nondestructive methods are of fundamental importance for the determination of composition, structure, and chemical-physical properties of the materials under study. NMR studies reveal low amounts of water content associated with very short proton relaxation times, T(1), indicating a high level of deterioration of collagen molecules within scroll fragments. In addition, (13)C cross-polarization magic-angle-spinning (CPMAS) NMR spectroscopy shows characteristic peaks of lipids whose presence we attribute to the production technology that did not involve liming. Extraction with chloroform led to the reduction of both lipid and protein signals in the (13)C CPMAS spectrum indicating probable involvement of lipids in parchment degradation processes. NMR absorption and relaxation measurements provide nondestructive, discriminative, and sensitive tools for studying the deterioration effects on the organization and properties of water and collagen within ancient manuscripts.

  17. Solvent dependence of the solid-state structures of salicylaldiminate magnesium amide complexes.

    Rood, Jeffrey A; Landis, Ashley M; Forster, Daniel R; Goldkamp, Timothy; Oliver, Allen G


    There are challenges in using magnesium coordination complexes as reagents owing to their tendency to adopt varying aggregation states in solution and thus impacting the reactivity of the complexes. Many magnesium complexes are prone to ligand redistribution via Schlenk equilibrium due to the ionic character within the metal-ligand interactions. The role of the supporting ligand is often crucial for providing stability to the heteroleptic complex. Strategies to minimize ligand redistribution in alkaline earth metal complexes could include using a supporting ligand with tunable sterics and electronics to influence the degree of association to the metal atom. Magnesium bis(hexamethyldisilazide) was reacted with salicylaldimines [(1)L = N-(2,6-diisopropylphenyl)salicylaldimine and (2)L = 3,5-di-tert-butyl-N-(2,6-diisopropylphenyl)salicylaldimine] in either nondonor (toluene) or donor solvents [tetrahydrofuran (THF) or pyridine]. The structures of the magnesium complexes were studied in the solid state via X-ray diffraction. In the nondonor solvent, i.e. toluene, the heteroleptic complex bis{μ-2-[(2,6-diisopropylphenyl)iminomethyl]phenolato}-κ(3)N,O:O;κ(3)O:N,O-bis[(hexamethyldisilazido-κN)magnesium(II)], [Mg2(C19H22NO)2(C6H18NSi2)2] or [(1)LMgN(SiMe3)2]2, (1), was favored, while in the donor solvent, i.e. pyridine (pyr), the formation of the homoleptic complex {2,4-di-tert-butyl-6-[(2,6-diisopropylphenyl)iminomethyl]phenolato-κ(2)N,O}bis(pyridine-κN)magnesium(II) toluene monosolvate, [Mg(C27H38NO)2(C5H5N)2]·C5H5N or [{(2)L2Mg2(pyr)2}·pyr], (2), predominated. Heteroleptic complex (1) was crystallized from toluene, while homoleptic complexes (2) and the previously reported [(1)L2Mg·THF] [Quinque et al. (2011). Eur. J. Inorg. Chem. pp. 3321-3326] were crystallized from pyridine and THF, respectively. These studies support solvent-dependent ligand redistribution in solution. In-situ (1)H NMR experiments were carried out to further probe the solution behavior of

  18. Protein secondary structure of Green Lynx spider dragline silk investigated by solid-state NMR and X-ray diffraction.

    Xu, Dian; Shi, Xiangyan; Thompson, Forrest; Weber, Warner S; Mou, Qiushi; Yarger, Jeffery L


    In this study, the secondary structure of the major ampullate silk from Peucetia viridans (Green Lynx) spiders is characterized by X-ray diffraction and solid-state NMR spectroscopy. From X-ray diffraction measurement, β-sheet nanocrystallites were observed and found to be highly oriented along the fiber axis, with an orientational order, fc≈0.98. The size of the nanocrystallites was determined to be on average 2.5nm×3.3nm×3.8nm. Besides a prominent nanocrystalline region, a partially oriented amorphous region was also observed with an fa≈0.89. Two-dimensional (13)C-(13)C through-space and through-bond solid-state NMR experiments were employed to elucidate structure details of P. viridans silk proteins. It reveals that β-sheet nanocrystallites constitutes 40.0±1.2% of the protein and are dominated by alanine-rich repetitive motifs. Furthermore, based upon the NMR data, 18±1% of alanine, 60±2% glycine and 54±2% serine are incorporated into helical conformations. Copyright © 2015 Elsevier B.V. All rights reserved.

  19. Structure-Property Relationships of Solid State Additive Manufactured Aluminum Alloy 2219 and Inconel 625

    Rivera Almeyda, Oscar G.

    In this investigation, the processing-structure-property relations are correlated for solid state additively manufactured (SSAM) Inconel 625 (IN 625) and a SSAM aluminum alloy 2219 (AA2219). This is the first research of these materials processed by a new SSAM method called additive friction stir (AFS). The AFS process results in a refined grain structure by extruding solid rod through a rotating tool generating heat and severe plastic deformation. In the case of the AFS IN625, the IN625 alloy is known for exhibiting oxidation resistance and temperature mechanical stability, including strength and ductility. This study is the first to investigate the beneficial grain refinement and densification produced by AFS in IN625 that results in advantageous mechanical properties (YS, UTS, epsilonf) at both quasi-static and high strain rate. Electron Backscatter Diffraction (EBSD) observed dynamic recrystallization and grain refinement during the layer deposition in the AFS specimens, where the results identified fine equiaxed grain structures formed by dynamic recrystallization (DRX) with even finer grain structures forming at the layer interfaces. The EBSD quantified grains as fine as 0.27 microns in these interface regions while the average grain size was approximately 1 micron. Additionally, this is the first study to report on the strain rate dependence of AFS IN625 through quasi-static (QS) (0.001/s) and high strain rate (HR) (1500/s) tensile experiments using a servo hydraulic frame and a direct tension-Kolsky bar, respectively, which captured both yield and ultimate tensile strengths increasing as strain rate increased. Fractography performed on specimens showed a ductile fracture surface on both QS, and HR. Alternatively, the other AFS material system investigated in this study, AA2219, is mostly used for aerospace applications, specifically for rocket fuel tanks. EBSD was performed in the cross-section of the AA2219, also exhibiting DRX with equiaxed microstructure

  20. Test of Variational Methods for Studying Molecular and Solid State Properties by Application to Sodium Atom

    Das, T. P.; Pink, R. H.; Dubey, Archana; Scheicher, R. H.; Chow, Lee


    As part of our continuing test of accuracy of the variational methods, Variational Hartree-Fock Many Body Perturbation Theory (VHFMBPT) and Variational Density Functional Theory (VDFT) for study of energy and wave-function dependent properties in molecular and solid state systems we are studying the magnetic hyperfine interactions in the ground state of sodium atom for comparison by these methods with the available results from experiment 1 and the linked cluster many-body many body perturbation theory (LCMBPT) for atoms 2 , which has provided very accurate results for the one-electron and many-electron contributions and total hyperfine constants in atomic systems. Comparison will also be made with the corresponding results obtained already from the (VHFMBPT) and (VDFT) methods in lithium 3 to draw general conclusions about the nature of possible improvements needed for the variational methods. 1. M. Arditi and R. T. Carver, Phys. Rev. 109, 1012 (1958); 2. T. Lee, N.C. Dutta, and T.P. Das, Hyperfine Structure of Sodium, Phys. Rev. A 1, 995 (1970); 3. Third Joint HFI-NQI International Conference on Hyperfine Interactions, CERN, Geneva, September 2010.

  1. Solid state NMR method development and studies of biological and biomimetic nanocomposites

    Hu, Yanyan [Iowa State Univ., Ames, IA (United States)


    This thesis describes application and development of advanced solid-state nuclear magnetic resonance techniques for complex materials, in particular organic-inorganic nanocomposites and thermoelectric tellurides. The apatite-collagen interface, essential for understanding the biomineralization process in bone and engineering the interface for controlled bio-mimetic synthesis and optimized mechanical properties, is buried within the nanocomposite of bone. We used multinuclear solid-state NMR to study the composition and structure of the interface. Citrate has been identified as the main organic molecule strongly bound to the apatite surface with a density of 1/(2 nm)2, covering 1/6 of the total surface area in bovine bone. Citrate provides more carboxylate groups, one of the key functional groups found to affect apatite nucleation and growth, than all the non-collagenous proteins all together in bone; thus we propose that citrate stabilizes apatite crystals at a very small thickness of ~3 nm (4 unit cells) to increase bone fracture tolerance. The hypothesis has been confirmed in vitro by adding citrate in the bio-mimetic synthesis of polymerhydroxyapatite nanocomposites. The results have shown that the size of hydroxyapatite nanocrystals decreases as increasing citrate concentration. With citrate concentrations comparable to that in body fluids, similar-sized nanocrystals as in bone have been produced. Besides the dimensions of the apatite crystals, the composition of bone also affects its biofunctional and macroscopic mechanical properties; therefore, our team also extended its effort to enhance the inorganic portion in our bio-mimetic synthesis from originally 15 wt% to current 50 wt% compared to 65 wt% in bovine bone, by using Lysine-Leucine hydroxyapatite nucleating diblock co-polypeptide, which forms a gel at very low concentration. In this thesis, various advanced solid state NMR techniques have been employed to characterize nanocomposites

  2. Thermogravimetric analysis and kinetic study of formation of lithium titanate by solid state route

    Sonak, Sagar; Jain, Uttam [Fusion Reactor Materials Section, Bhabha Atomic Research Centre, Mumbai 400 085 (India); Sahu, Ashok Kumar [Glass and advanced Materials Division, Bhabha Atomic Research Centre, Mumbai 400 085 (India); Kumar, Sanjay; Krishnamurthy, Nagaiyar [Fusion Reactor Materials Section, Bhabha Atomic Research Centre, Mumbai 400 085 (India)


    The kinetics of formation of lithium titanate from the solid state reaction of lithium carbonate and titanium oxide was studied using non-isothermal thermogravimetric technique. Thermogravimetric data for the reaction of lithium carbonate and titanium oxide was obtained at various heating rates. The methods such as Flynn–Wall–Ozawa and Kissinger–Akahira–Sunose were used to estimate the kinetic parameters from the obtained thermogravimetric data. The average activation energy for the formation of lithium titanate by solid state route was found to be 243 kJ/mol K. The reaction mechanism was determined by the method given by Malek. It was found that the three dimensional diffusion model best describes the reaction kinetics. A kinetic equation describing the reaction is proposed and reaction mechanism is discussed.

  3. Study of the neutron radiography characteristics for the solid state nuclear track detector Makrofol-DE

    Pugliesi, R


    In this work, the track-etch method was employed for Neutron Radiography purposes. A combination of the Solid State Nuclear Track Detector Makrofol-DE with a natural boron converter screen has been used to register the image. The radiography characteristics such as, track size, track production rate, characteristic curves and spatial resolution, have been studied. The detectors were irradiated up to neutron exposures about 5x10 sup 1 sup 0 n/cm sup 2 , in a radiography facility installed at the IEA-R1 Nuclear Research Reactor, and etched in a KOH aqueous solution at a constant temperature of 70 deg. C. The obtained results were compared with those reported by other and discussed according to the theory of the image formation in solid state nuclear track detectors. The experimental conditions to obtain the best image contrast, and the corresponding value of the spatial resolution, were also determined.

  4. Composition and solution properties of fluorinated block copolymers and their surface structures in the solid state


    A series of diblock copolymers composed of methyl methacrylate and 2-perfluorooctylethyl methacry-late(PMMA144-b-PFMAn) with various PFMA block lengths were prepared by atom transfer radical po-lymerization(ATRP).The surface structures and properties of these polymers in the solid state and in solution were investigated using contact angle measurement,X-ray photoelectron spectroscopy(XPS),sum frequency generation(SFG) vibrational spectroscopy,surface tension and dynamic laser light scattering(DLS).It was found that with increasing PFMA block length,water and oil repellency de-creased,the ratio of F/C increased with increasing film depth,and the degree of ordered packing of the perfluoroalkyl side chains at the surface decreased.When the number of PFMA block units reached 10,PMMA segments were detected at the copolymer surface,which was attributed to the PFMA block length affecting molecular aggregation structure of the copolymer in the solution and the interfacial structure at the air/liquid interface,which in turn affects surface structure formation during solution solidification.The results suggest that copolymer solution properties play an important role in struc-ture formation on the solid surface.

  5. Structure and backbone dynamics of a microcrystalline metalloprotein by solid-state NMR.

    Knight, Michael J; Pell, Andrew J; Bertini, Ivano; Felli, Isabella C; Gonnelli, Leonardo; Pierattelli, Roberta; Herrmann, Torsten; Emsley, Lyndon; Pintacuda, Guido


    We introduce a new approach to improve structural and dynamical determination of large metalloproteins using solid-state nuclear magnetic resonance (NMR) with (1)H detection under ultrafast magic angle spinning (MAS). The approach is based on the rapid and sensitive acquisition of an extensive set of (15)N and (13)C nuclear relaxation rates. The system on which we demonstrate these methods is the enzyme Cu, Zn superoxide dismutase (SOD), which coordinates a Cu ion available either in Cu(+) (diamagnetic) or Cu(2+) (paramagnetic) form. Paramagnetic relaxation enhancements are obtained from the difference in rates measured in the two forms and are employed as structural constraints for the determination of the protein structure. When added to (1)H-(1)H distance restraints, they are shown to yield a twofold improvement of the precision of the structure. Site-specific order parameters and timescales of motion are obtained by a gaussian axial fluctuation (GAF) analysis of the relaxation rates of the diamagnetic molecule, and interpreted in relation to backbone structure and metal binding. Timescales for motion are found to be in the range of the overall correlation time in solution, where internal motions characterized here would not be observable.

  6. Composition and solution properties of fluorinated block copolymers and their surface structures in the solid state

    NI HuaGang; XUE DongWu; WANG XiaoFang; ZHANG Wei; WANG XinPing; SHEN ZhiQuan


    A series of diblock copolymers composed of methyl methacrylate and 2-perfluorooctylethyl methacry-late (PMMA144-b-PFMAn) with various PFMA block lengths were prepared by atom transfer radical po-lymerization (ATRP). The surface structures and properties of these polymers in the solid state and in solution were investigated using contact angle measurement, X-ray photoelectron spectroscopy (XPS), sum frequency generation (SFG) vibrational spectroscopy, surface tension and dynamic laser light scattering (DLS). It was found that with increasing PFMA block length, water and oil repellency de-creased, the ratio of F/C increased with increasing film depth, and the degree of ordered packing of the perfluoroalkyl side chains at the surface decreased. When the number of PFMA block units reached 10, PMMA segments were detected at the copolymer surface, which was attributed to the PFMA block length affecting molecular aggregation structure of the copolymer in the solution and the interfacial structure at the air/liquid interface, which in turn affects surface structure formation during solution solidification. The results suggest that copolymer solution properties play an important role in struc-ture formation on the solid surface.

  7. Solid-State NMR Studies of HIV-1 Capsid Protein Assemblies

    HAN, YUN; Ahn, Jinwoo; Concel, Jason; Byeon, In-Ja L.; Gronenborn, Angela M.; YANG, Jun; Polenova, Tatyana


    In mature HIV-1 virions, a 26.6 kDa CA protein is assembled into a characteristic cone shaped core (capsid) that encloses the RNA viral genome. The assembled capsid structure is best described by a fullerene cone model that is made up from a hexameric lattice containing a variable number of CA pentamers, thus allowing for closure of tubular or conical structures. In this report, we present a solid-state NMR analysis of the wild type HIV-1 CA protein, prepared as conical and spherical assembli...

  8. Structural and optical properties of zinc oxide doped by V2O5 synthesized by solid-state reaction

    Abaira, R.; Dammak, T.; Matoussi, A.; Younes, A.


    Vanadium doped zinc oxide with different vanadium concentration were synthesized by conventional solid state reaction. The structural and optical properties of ZnO: V2O5 pellets were studied by using a panalytic diffraktometer (X'pert) with Cu-K radiation, the UV-visible spectrophotometer and photoluminescence (PL). X-ray diffraction (XRD) show that all the samples have a wurtzite structure and grow mainly in the (101) orientation, we show also the presence of dominated phase Zn3 (VO4)2, Optical studied indicate a decrease in optical band gap energy, and photoluminescence (PL) spectra showed a strong visible emission band, energy position and intensity of this emission depends on the temperature measurement. The activate energy Ea has been fitted and studied using Arunis equation.

  9. Exploration of structure and function in biomolecules through solid-state NMR and computational methods

    Heider, Elizabeth M.

    Solid-State Nuclear Magnetic Resonance (SSNMR) spectroscopy and quantum mechanical calculations are powerful analysis tools. Leveraged independently, each method yields important nuclear and molecular information. Used in concert, SSNMR and computational techniques provide complementary data about the structure of solids. These methods are particularly useful in characterizing the structures of microcrystalline organic compounds and revealing mechanisms of biological activity. Such applications may possess special relevance in analysis of pharmaceutical products; 90% of all pharmaceuticals are marketed as solids and bioactivity is strongly linked with molecular conformation. Accordingly, this dissertation employs both SSNMR and quantum mechanical computation to study three bioactive molecules: citrinin, two forms of Atrasentan (Abt-627), and paclitaxel (Taxol RTM). First, a computational study is utilized to determine the mechanism for unusual antioxidant activity in citrinin. Here, molecular geometries and bond dissociation enthalpies (BDE) of the citrinin O--H groups are calculated from first principles (ab initio). The total molecular Hamiltonian is determined by approximating the individual contributors to energy including electronic energy and contributions from modes of molecular vibration. This study of citrinin clearly identifies specific reaction sites in the active form, establishing the central role of intramolecular hydrogen bonding in this activity. Notably, it is discovered that citrinin itself is not the active species. Instead, a pair of hydrated Michael addition products of citrinin act as radical scavengers via O--H bond dissociation. Next, two separate compounds of the anticancer drug Abt-627 (form I and form II) are examined via SSNMR. The three principal values of the 13C diagonalized chemical shift tensor are acquired through the high resolution 2D experiment, FIREMAT. Isotropic chemical shift assignments are made utilizing both dipolar

  10. Characterizing the secondary protein structure of black widow dragline silk using solid-state NMR and X-ray diffraction.

    Jenkins, Janelle E; Sampath, Sujatha; Butler, Emily; Kim, Jihyun; Henning, Robert W; Holland, Gregory P; Yarger, Jeffery L


    This study provides a detailed secondary structural characterization of major ampullate dragline silk from Latrodectus hesperus (black widow) spiders. X-ray diffraction results show that the structure of black widow major ampullate silk fibers is comprised of stacked β-sheet nanocrystallites oriented parallel to the fiber axis and an amorphous region with oriented (anisotropic) and isotropic components. The combination of two-dimensional (2D) (13)C-(13)C through-space and through-bond solid-state NMR experiments provide chemical shifts that are used to determine detailed information about the amino acid motif secondary structure in black widow spider dragline silk. Individual amino acids are incorporated into different repetitive motifs that make up the majority of this protein-based biopolymer. From the solid-state NMR measurements, we assign distinct secondary conformations to each repetitive amino acid motif and, hence, to the amino acids that make up the motifs. Specifically, alanine is incorporated in β-sheet (poly(Alan) and poly(Gly-Ala)), 3(1)-helix (poly(Gly-Gly-Xaa), and α-helix (poly(Gln-Gln-Ala-Tyr)) components. Glycine is determined to be in β-sheet (poly(Gly-Ala)) and 3(1)-helical (poly(Gly-Gly-X(aa))) regions, while serine is present in β-sheet (poly(Gly-Ala-Ser)), 3(1)-helix (poly(Gly-Gly-Ser)), and β-turn (poly(Gly-Pro-Ser)) structures. These various motif-specific secondary structural elements are quantitatively correlated to the primary amino acid sequence of major ampullate spidroin 1 and 2 (MaSp1 and MaSp2) and are shown to form a self-consistent model for black widow dragline silk.

  11. The Effect of Cellulose Crystal Structure and Solid-State Morphology on the Activity of Cellulases

    Stipanovic, Arthur J [SUNY College of Environmental Science and Forestry


    Consistent with the US-DOE and USDA “Roadmap” objective of producing ethanol and chemicals from cellulosic feedstocks more efficiently, a three year research project entitled “The Effect of Cellulose Crystal Structure and Solid-State Morphology on the Activity of Cellulases” was initiated in early 2003 under DOE sponsorship (Project Number DE-FG02-02ER15356). A three year continuation was awarded in June 2005 for the period September 15, 2005 through September 14, 2008. The original goal of this project was to determine the effect of cellulose crystal structure, including allomorphic crystalline form (Cellulose I, II, III, IV and sub-allomorphs), relative degree of crystallinity and crystallite size, on the activity of different types of genetically engineered cellulase enzymes to provide insight into the mechanism and kinetics of cellulose digestion by “pure” enzymes rather than complex mixtures. We expected that such information would ultimately help enhance the accessibility of cellulose to enzymatic conversion processes thereby creating a more cost-effective commercial process yielding sugars for fermentation into ethanol and other chemical products. Perhaps the most significant finding of the initial project phase was that conversion of native bacterial cellulose (Cellulose I; BC-I) to the Cellulose II (BC-II) crystal form by aqueous NaOH “pretreatment” provided an increase in cellulase conversion rate approaching 2-4 fold depending on enzyme concentration and temperature, even when initial % crystallinity values were similar for both allomorphs.

  12. Analysis of structural variability in pharmaceutical excipients using solid-state NMR spectroscopy.

    Sperger, Diana M; Munson, Eric Jon


    Polysaccharide-based excipients comprise the majority of most solid dosage forms and can vary dramatically in terms of structural and functionally related properties. Analytical methods for characterizing these important formulation components are crucial. Solid-state NMR spectroscopy (SSNMR) can provide a wealth of information on these materials while offering the advantages of non-destructive sample preparation and selectivity. The overall objective of this work is to identify SSNMR parameters that can be used to detect differences among these excipients. Excipients were obtained from a wide range of suppliers and analyzed as received; (13)C SSNMR spectra were acquired using a Chemagnetics CMX-300 spectrometer operating at approximately 75 MHz. The resolution of SSNMR signals of many excipients allows for positive identification of the major form present. Alginic acid and sodium alginate can be differentiated based on carbonyl peak position. Analysis of relative peak intensities provides insight into the purity of a carrageenan sample compared to known standards. The SSNMR spectrum of starch can be used to identify the source and to quantitate the amorphous and crystalline content. Relaxation values and peak areas of starch derivatives can be related to the degree of hydrolysis, providing an alternative method for determining dextrose equivalent. Differences in peak intensities and relaxation time values of HPMC samples can be correlated to the amount of methoxy subsituent groups. Important characteristics of excipients such as form identification, structural differences, crystalline and amorphous content, and water content variations can be detected using SSNMR spectroscopy.

  13. A combined solid-state NMR and X-ray crystallography study of the bromide ion environments in triphenylphosphonium bromides.

    Burgess, Kevin M N; Korobkov, Ilia; Bryce, David L


    Multinuclear ((31)P and (79/81)Br), multifield (9.4, 11.75, and 21.1 T) solid-state nuclear magnetic resonance experiments are performed for seven phosphonium bromides bearing the triphenylphosphonium cation, a molecular scaffold found in many applications in chemistry. This is undertaken to fully characterise their bromine electric field gradient (EFG) tensors, as well as the chemical shift (CS) tensors of both the halogen and the phosphorus nuclei, providing a rare and novel insight into the local electronic environments surrounding them. New crystal structures, obtained from single-crystal X-ray diffraction, are reported for six compounds to aid in the interpretation of the NMR data. Among them is a new structure of BrPPh(4), because the previously reported one was inconsistent with our magnetic resonance data, thereby demonstrating how NMR data of non-standard nuclei can correct or improve X-ray diffraction data. Our results indicate that, despite sizable quadrupolar interactions, (79/81)Br magnetic resonance spectroscopy is a powerful characterisation tool that allows for the differentiation between chemically similar bromine sites, as shown through the range in the characteristic NMR parameters. (35/37)Cl solid-state NMR data, obtained for an analogous phosphonium chloride sample, provide insight into the relationship between unit cell volume, nuclear quadrupolar coupling constants, and Sternheimer antishielding factors. The experimental findings are complemented by gauge-including projector-augmented wave (GIPAW) DFT calculations, which substantiate our experimentally determined strong dependence of the largest component of the bromine CS tensor, δ(11), on the shortest Br-P distance in the crystal structure, a finding that has possible application in the field of NMR crystallography. This trend is explained in terms of Ramsey's theory on paramagnetic shielding. Overall, this work demonstrates how careful NMR studies of underexploited exotic nuclides, such

  14. Solvent-free methylthiomethyllithium [LiCH2SMe]infinity: solid state structure and thermal decomposition.

    Ruth, Kai; Dinnebier, Robert E; Tönnes, Stefan W; Alig, Edith; Sänger, Ingeborg; Lerner, Hans-Wolfram; Wagner, Matthias


    Solvent-free [LiCH2SMe]infinity forms a layer structure consisting of four- (Li2C2), five- (Li2CS2), and six-membered (Li2C2S2) rings in the solid state; the compound violently explodes upon heating to T=160+/-5 degrees C under an argon atmosphere.

  15. Structural analysis of a melaminium polyphosphate from X-ray powder diffraction and solid-state NMR data

    Brodski, V.; Peschar, R.; Schenk, H.; Brinkmann, A.; Bloemberg, T.G.; Eck, E.R.H. van; Kentgens, A.P.M.


    The crystal structure of the environmentally friendly flame retardant melaminium polyphosphate (MPoly) (2,4,6-triamino-1,3,5-triazinium-PO3)(n) was determined by a direct-space global optimization technique from X-ray powder diffraction data. Solid-state NMR was used to corroborate the proposed

  16. Synthesis and structure determination of potassium copper selenide nanowires and solid-state supercapacitor application

    Zhang, Kaiyou; Chen, Hong; Wang, Xue; Guo, Donglin; Hu, Chenguo; Wang, Shuxia; Sun, Junliang; Leng, Qiang


    The new ternary alkali metal copper chalcogenide KCu4Se8 nanowires with average length of 30 μm are synthesized using a modified composite-hydroxide mediated (M-CHM) approach. The prepared KCu4Se8 is characterized by XRD, EDS, FESEM and TEM analysis. The structure is determined by the newly developed Rotation Electron Diffraction technique. It is identified to be a body center tetragonal phase. The prepared KCu4Se8 is used to fabricate solid-state supercapacitors in which the thin film of the electrodes are made with pressure of 0 MPa, 5 MPa and 10 MPa, and their electrochemical properties are tested. It is found that 0 MPa supercapacitor displays best electrochemical performance and the specific capacitance of 25.3 F g-1 is obtained at the scan rate of 5 mV s-1. It also shows good long-term cycle property by recording 5000 cycles of galvanostatic charge/discharge operation. The specific capacitance can be enhanced to 93.7 F g-1 at the scan rate of 5 mV s-1 by coating 0.1 mg V2O5 nanowire on 0 MPa KCu4Se8 electrode.

  17. Solid-state NMR/NQR and first-principles study of two niobium halide cluster compounds.

    Perić, Berislav; Gautier, Régis; Pickard, Chris J; Bosiočić, Marko; Grbić, Mihael S; Požek, Miroslav


    Two hexanuclear niobium halide cluster compounds with a [Nb6X12](2+) (X=Cl, Br) diamagnetic cluster core, have been studied by a combination of experimental solid-state NMR/NQR techniques and PAW/GIPAW calculations. For niobium sites the NMR parameters were determined by using variable Bo field static broadband NMR measurements and additional NQR measurements. It was found that they possess large positive chemical shifts, contrary to majority of niobium compounds studied so far by solid-state NMR, but in accordance with chemical shifts of (95)Mo nuclei in structurally related compounds containing [Mo6Br8](4+) cluster cores. Experimentally determined δiso((93)Nb) values are in the range from 2,400 to 3,000 ppm. A detailed analysis of geometrical relations between computed electric field gradient (EFG) and chemical shift (CS) tensors with respect to structural features of cluster units was carried out. These tensors on niobium sites are almost axially symmetric with parallel orientation of the largest EFG and the smallest CS principal axes (Vzz and δ33) coinciding with the molecular four-fold axis of the [Nb6X12](2+) unit. Bridging halogen sites are characterized by large asymmetry of EFG and CS tensors, the largest EFG principal axis (Vzz) is perpendicular to the X-Nb bonds, while intermediate EFG principal axis (Vyy) and the largest CS principal axis (δ11) are oriented in the radial direction with respect to the center of the cluster unit. For more symmetrical bromide compound the PAW predictions for EFG parameters are in better correspondence with the NMR/NQR measurements than in the less symmetrical chlorine compound. Theoretically predicted NMR parameters of bridging halogen sites were checked by (79/81)Br NQR and (35)Cl solid-state NMR measurements.

  18. Solid-state structures of peapod bearings composed of finite single-wall carbon nanotube and fullerene molecules.

    Sato, Sota; Yamasaki, Takashi; Isobe, Hiroyuki


    A supramolecular combination of carbon nanotube and fullerene, so-called a peapod, has attracted much interest, not solely because of its physical properties but also for its unique assembled structures of carbonaceous entities. However, the detailed structural information available was not sufficient for in-depth understanding of its structural chemistry or for exploratory research inspired by novel physical phenomena, mainly because of the severely inhomogeneous nature of currently available carbon nanotubes. We herein report solid-state structures of a molecular peapod. This structure, solved with a belt-persistent finite carbon nanotube molecule at the atomic level by synchrotron X-ray diffraction, revealed the presence of a smooth, inflection-free Hirshfeld surface inside the tube, and the smoothness permitted dynamic motion of the C60 guest molecule even in the solid state. This precise structural information may inspire the molecular design of carbonaceous machines assembled purely through van der Waals contacts between two neutral molecules.

  19. Solid state NMR and pair distribution function studies of silicon electrodes for lithium-ion batteries

    Key, Baris

    observed in the in situ NMR experiments; this mechanism results in self-discharge, and potentially capacity loss. The rate of this self-discharge process is much slower when CMC (carboxymethylcellulose) is used as the binder. Previous work has shown that the electrochemical performance of nanoparticulate crystalline silicon is different from the bulk. The lithiation and delithiation mechanisms of nano-Si for lithium ion batteries are studied by using ex-situ solid state MAS NMR and PDF analysis. The main differences vs. bulk lithiation and delithiation are identified by characterizing the amorphous phases formed.

  20. Structure and properties of solid-state synthesized poly (3,4-propylenedioxythiophene)/nano-ZnO composite

    Ahmat Ali; Ruxangul Jamal; Weiwei shao; Adalet Rahman; Yakupjan Osman; Tursun Abdiryim


    Poly(3,4-propylenedioxythiophene)/nano-Zinic Oxide (PProDOT/ZnO) composites with the content of 3-7 wt% nano-ZnO were synthesized by the solid-state method with FeCl3 as oxidant. The structure and morphology of the composites were characterized by Fourier transform infrared (FTIR) spectroscopy, ultraviolet-visible (UV-vis) absorption spectroscopy, X-ray diffraction (XRD) and transmission electron microscopy (TEM). The electrochemical performances of the composites were investigated by galvanostatic charge-discharge, cyclic voltammetry and electrochemical impedance spectroscopy (EIS). The photocatalytic activities of the composites were investigated by the degradation of methylene blue (MB) dyes in aqueous medium under UV light irradiation. The results from FTIR and UV-vis spectra showed that the PProDOT/ZnO composites were successfully synthesized by solid-state method, and nano-ZnO had great influences on the conjugation length and oxidation degree of the polymers. Furthermore, the PProDOT/5 wt%ZnO had the highest conjugation and oxidation degree among the composites. The results of XRD analysis indicated that there were some FeC14? ions as doping agent in the PProDOT matrix, and the content of ZnO had no effect on diffraction pattern of PProDOT. Morphological studies revealed that the pure PProDOT and composites had similar morphological structure, and all the composites displayed an irregular sponge like morphology. The results of electrochemical tests showed that the PProDOT/5 wt%ZnO had a higher electrochemical activity with a specific capacitance value of 220 Fg ? 1 than others. The results from photocatalytic activities of the composites indicated that the PProDOT/5 wt%ZnO had better photocatalytic activity than other composites.

  1. Advanced solid-state NMR techniques for characterization of membrane protein structure and dynamics: application to Anabaena Sensory Rhodopsin.

    Ward, Meaghan E; Brown, Leonid S; Ladizhansky, Vladimir


    Studies of the structure, dynamics, and function of membrane proteins (MPs) have long been considered one of the main applications of solid-state NMR (SSNMR). Advances in instrumentation, and the plethora of new SSNMR methodologies developed over the past decade have resulted in a number of high-resolution structures and structural models of both bitopic and polytopic α-helical MPs. The necessity to retain lipids in the sample, the high proportion of one type of secondary structure, differential dynamics, and the possibility of local disorder in the loop regions all create challenges for structure determination. In this Perspective article we describe our recent efforts directed at determining the structure and functional dynamics of Anabaena Sensory Rhodopsin, a heptahelical transmembrane (7TM) protein. We review some of the established and emerging methods which can be utilized for SSNMR-based structure determination, with a particular focus on those used for ASR, a bacterial protein which shares its 7TM architecture with G-protein coupled receptors.

  2. Advanced solid-state NMR techniques for characterization of membrane protein structure and dynamics: Application to Anabaena Sensory Rhodopsin

    Ward, Meaghan E.; Brown, Leonid S.; Ladizhansky, Vladimir


    Studies of the structure, dynamics, and function of membrane proteins (MPs) have long been considered one of the main applications of solid-state NMR (SSNMR). Advances in instrumentation, and the plethora of new SSNMR methodologies developed over the past decade have resulted in a number of high-resolution structures and structural models of both bitopic and polytopic α-helical MPs. The necessity to retain lipids in the sample, the high proportion of one type of secondary structure, differential dynamics, and the possibility of local disorder in the loop regions all create challenges for structure determination. In this Perspective article we describe our recent efforts directed at determining the structure and functional dynamics of Anabaena Sensory Rhodopsin, a heptahelical transmembrane (7TM) protein. We review some of the established and emerging methods which can be utilized for SSNMR-based structure determination, with a particular focus on those used for ASR, a bacterial protein which shares its 7TM architecture with G-protein coupled receptors.

  3. The Surface of Nanoparticle Silicon as Studied by Solid-State NMR

    Gary E. Maciel


    Full Text Available The surface structure and adjacent interior of commercially available silicon nanopowder (np-Si was studied using multinuclear, solid-state NMR spectroscopy. The results are consistent with an overall picture in which the bulk of the np-Si interior consists of highly ordered (“crystalline” silicon atoms, each bound tetrahedrally to four other silicon atoms. From a combination of 1H, 29Si and 2H magic-angle-spinning (MAS NMR results and quantum mechanical 29Si chemical shift calculations, silicon atoms on the surface of “as-received” np-Si were found to exist in a variety of chemical structures, with apparent populations in the order (a (Si–O–3Si–H > (b (Si–O–3SiOH > (c (HO–nSi(Sim(–OSi4−m−n ≈ (d (Si–O–2Si(HOH > (e (Si–O–2Si(–OH2 > (f (Si–O–4Si, where Si stands for a surface silicon atom and Si represents another silicon atom that is attached to Si by either a Si–Si bond or a Si–O–Si linkage. The relative populations of each of these structures can be modified by chemical treatment, including with O2 gas at elevated temperature. A deliberately oxidized sample displays an increased population of (Si–O–3Si–H, as well as (Si–O–3SiOH sites. Considerable heterogeneity of some surface structures was observed. A combination of 1H and 2H MAS experiments provide evidence for a substantial population of silanol (Si–OH moieties, some of which are not readily H-exchangeable, along with the dominant Si–H sites, on the surface of “as-received” np-Si; the silanol moieties are enhanced by deliberate oxidation. An extension of the DEPTH background suppression method is also demonstrated that permits measurement of the T2 relaxation parameter simultaneously with background suppression.

  4. Four Thermochromic o-Hydroxy Schiff Bases of α-Aminodiphenylmethane: Solution and Solid State Study

    Marija Zbačnik


    Full Text Available More than a hundred years after the first studies of the photo- and thermochromism of o-hydroxy Schiff bases (imines, it is still an intriguing topic that fascinates several research groups around the world. The reasons for such behavior are still under investigation, and this work is a part of it. We report the solution-based and mechanochemical synthesis of four o-hydroxy imines derived from α-aminodiphenylmethane. The thermochromic properties were studied for the single crystal and polycrystalline samples of the imines. The supramolecular impact on the keto-enol tautomerism in the solid state was studied using SCXRD and NMR, while NMR spectroscopy was used for the solution state. All four imines are thermochromic, although the color changes of the single crystals are not as strong as of the polycrystalline samples. One of the imines shows negative thermochromism, and that one is in keto-amine tautomeric form, both in the solid state as in solution.

  5. {sup 13}C solid-state NMR analysis of heterogeneous structure of beeswax in native state

    Kameda, Tsunenori [National Institute of Agrobiological Sciences, Tsukuba, Ibaraki, 305-8634 (Japan)


    I investigated the molecular structure of natural wax from Japanese bees (Apis cerana japonica) in its native state (neither purified nor recrystallized) by {sup 13}C and {sup 1}H solid-state NMR. Two strong {sup 13}C peaks at 32.9 and 34.0 ppm were attributed to signals from internal-chain methylene carbons [int-(CH{sub 2})] in two types of crystal form. The peak at 32.9 ppm was assigned to an orthorhombic crystal form, and that at 34.0 ppm was assigned to a triclinic or monoclinic form. In both crystalline regions, bi-exponential decay of {sup 13}C spin-lattice relaxation [T{sub 1}(C)] for the crystalline peaks due to chain diffusion was observed. {sup 1}H spin-lattice relaxation [T{sub 1}(H)] values for protons of the CH{sub 3} group and for int-(CH{sub 2}) in the crystalline and amorphous regions were identical; this was interpreted as being due to averaging of the T{sub 1}(H) relaxation rates via spin diffusion. In contrast, although the T{sub 1{sub {rho}}}(H) decay curves for protons of the CH{sub 3} group and for int-(CH{sub 2}) in the amorphous and orthorhombic forms were almost identical, those of the triclinic or monoclinic forms were different. This unhomogeneous character of T{sub 1{sub {rho}}}(H) was interpreted as resulting from differences in the molecular composition of each crystal form. Moreover, two components with long and short {sup 1}H spin-spin relaxation [T{sub 2}(H)] values, arising from the mobile and rigid phases, respectively, were observed at above about -30 deg. C.

  6. 13C solid-state NMR analysis of heterogeneous structure of beeswax in native state

    Kameda, Tsunenori


    I investigated the molecular structure of natural wax from Japanese bees (Apis cerana japonica) in its native state (neither purified nor recrystallized) by 13C and 1H solid-state NMR. Two strong 13C peaks at 32.9 and 34.0 ppm were attributed to signals from internal-chain methylene carbons [int-(CH2)] in two types of crystal form. The peak at 32.9 ppm was assigned to an orthorhombic crystal form, and that at 34.0 ppm was assigned to a triclinic or monoclinic form. In both crystalline regions, bi-exponential decay of 13C spin-lattice relaxation [T1(C)] for the crystalline peaks due to chain diffusion was observed. 1H spin-lattice relaxation [T1(H)] values for protons of the CH3 group and for int-(CH2) in the crystalline and amorphous regions were identical; this was interpreted as being due to averaging of the T1(H) relaxation rates via spin diffusion. In contrast, although the T_{{1}_{\\rho}}(H) decay curves for protons of the CH3 group and for int-(CH2) in the amorphous and orthorhombic forms were almost identical, those of the triclinic or monoclinic forms were different. This unhomogeneous character of T_{{1}_{\\rho}}(H) was interpreted as resulting from differences in the molecular composition of each crystal form. Moreover, two components with long and short 1H spin-spin relaxation [T2(H)] values, arising from the mobile and rigid phases, respectively, were observed at above about -30 °C.

  7. Applications of Solid-State NMR Spectroscopy for the Study of Lipid Membranes with Polyphilic Guest (MacroMolecules

    Ruth Bärenwald


    Full Text Available The incorporation of polymers or smaller complex molecules into lipid membranes allows for property modifications or the introduction of new functional elements. The corresponding molecular-scale details, such as changes in dynamics or features of potential supramolecular structures, can be studied by a variety of solid-state NMR techniques. Here, we review various approaches to characterizing the structure and dynamics of the guest molecules as well as the lipid phase structure and dynamics by different high-resolution magic-angle spinning proton and 13C NMR experiments as well as static 31P NMR experiments. Special emphasis is placed upon the incorporation of novel synthetic polyphilic molecules such as shape-persistent T- and X-shaped molecules as well as di- and tri-block copolymers. Most of the systems studied feature dynamic heterogeneities, for instance those arising from the coexistence of different phases; possibilities for a quantitative assessment are of particular concern.

  8. Fabrication of All-Solid-State Lithium-ion Cells using Three-Dimensionally Structured Solid Electrolyte Li7La3Zr2O12 Pellets



    Full Text Available All-solid-state lithium-ion batteries using Li+-ion conducting ceramic electrolytes have been focused on as attractive future batteries for electric vehicles and renewable energy conversion systems because high safety can be realized due to non-flammability of ceramic electrolytes. In addition, a higher volumetric energy density than that of current lithium-ion batteries is expected since the all-solid-state lithium-ion batteries can be made in bipolar cell configurations. However, the special ideas and techniques based on ceramic processing are required to construct the electrochemical interface for all-solid-state lithium-ion batteries since the battery development has been done so far based on liquid electrolyte system over 100 years. As one of promising approaches to develop practical all-solid-state batteries, we have been focusing on three-dimensionally (3D structured cell configurations such as an interdigitated combination of 3D pillars of cathode and anode, which can be realized by using solid electrolyte membranes with hole-array structures. The application of such kinds of 3D structures effectively increases the interface between solid electrode and solid electrolyte per unit volume, lowering the internal resistance of all-solid-state lithium-ion batteries. In this study, Li6.25Al0.25La3Zr2O12 (LLZAl, which is a Al-doped Li7La3Zr2O12 (LLZ with Li+-ion conductivity of ~10–4 S cm–1 at room temperature and high stability against lithium-metal, was used as a solid electrolyte, and its pellets with 700 um depth holes in 700 x 700 um2 area were fabricated to construct 3D-structured all-solid-state batteries with LiCoO2 / LLZAl / lithium-metal configuration. It is expected that the LiCoO2-LLZAl interface is formed by point to point contact even when the LLZAl pellet with 3D hole-array structure is applied. Therefore, the application of mechanically soft Li3BO3 with a low melting point at around 700 °C was also performed as a supporting

  9. Solid-state structure of gelatin-mono epoxy terminated polydimethylsiloxane polymer: effect of electrostatic and hydrophobic interactions.

    Xu, Jing; Xia, Yongmei; Qiao, Cong-De; Zhu, Weiyue; Wang, Yuexia; Li, Tian-Duo


    In this study, a hybrid synthetic gelatin-mono epoxy terminated polydimethylsiloxane polymer (PDMS-E grafted gelatin (PGG)) was successfully synthesized on a large scale. Supramolecular structure of gelatin, which was decided by the sophisticated inter- and intra-molecular interactions, significantly affected the self-assembly and phase behavior of PGG. Interestingly, the supramolecular organization of PGG could be tuned finely by negatively charged surfactants, such as sodium dodecyl sulfate (SDS) and sodium tetradecyl sulfonate (STSo), as revealed by high-resolution transmission electron microscopy (HR-TEM), scanning electron microscopy (SEM), light microscopy (LM), and atomic force microscopy (AFM). SEM images exhibited the presence of spherical aggregates in PGG/SDS films while hexagonal array was observed in PGG/STSo films. The results of LM revealed that when PGG/STSo solution was dried, a successive structural transformation from spheres to hexagons, via sticks and butterfly-shaped aggregates as intermediates, was observed. However, the morphologies of the aggregates formed in PGG/SDS system did not exhibit any obvious change upon drying. Attenuated total reflection-Fourier transform infrared spectra combined with AFM observations indicated that the secondary structure and aggregation behavior of gelatin was modified with the change in the electrostatic and hydrophobic interactions, leading to the formation of diversified solid-state structures of PGG.

  10. Solid-State Devices.

    Sutliff, Ronald D.; And Others

    This self-study course is designed to familiarize Marine Corps enlisted personnel with the principles of solid-state devices and their functions. The course contains four study units. Each study unit begins with a general objective, which is a statement of what the student should learn from the unit. The study units are divided into numbered work…

  11. Structural analysis of pyridine-imino boronic esters involving secondary interactions on solid state

    Sánchez-Portillo, Paola; Arenaza-Corona, Antonino; Hernández-Ahuactzi, Irán F.; Barba, Victor


    Twelve boronic esters (1a-1l) synthesized from 4-halo- substituted arylboronic acids (halo = F, Cl, Br, I and CF3) with 2-amino-2- alkyl (H, Me) -1,3-propanediol in presence of (3- or 4)-pyridine carboxaldehyde are described. A solvent mixture toluene/methanol 1:4 ratio was used. All compounds include both donor/acceptor functional groups, which are the necessary elements to self-assembly of the molecular species. Several secondary interactions as I⋯N, Br⋯Br, Br⋯B, F⋯B, Csbnd H⋯N, Csbnd H⋯O, Br⋯π and Csbnd H⋯π support the 1D and 2D polymeric frameworks in solid state. The coordination of the nitrogen atom from the pyridine moiety with the boron atom was not observed in either solution or solid state.

  12. A Comparative Study of New Aspergillus Strains for Proteolytic Enzymes Production by Solid State Fermentation

    Gastón Ezequiel Ortiz


    Full Text Available A comparative study of the proteolytic enzymes production using twelve Aspergillus strains previously unused for this purpose was performed by solid state fermentation. A semiquantitative and quantitative evaluation of proteolytic activity were carried out using crude enzymatic extracts obtained from the fermentation cultures, finding seven strains with high and intermediate level of protease activity. Biochemical, thermodynamics, and kinetics features such as optimum pH and temperature values, thermal stability, activation energy (Ea, quotient energy (Q10, Km, and Vmax were studied in four enzymatic extracts from the selected strains that showed the highest productivity. Additionally, these strains were evaluated by zymogram analysis obtaining protease profiles with a wide range of molecular weight for each sample. From these four strains with the highest productivity, the proteolytic extract of A. sojae ATCC 20235 was shown to be an appropriate biocatalyst for hydrolysis of casein and gelatin substrates, increasing its antioxidant activities in 35% and 125%, respectively.

  13. Solid state 31NMR studies of the conversion of amorphous tricalcium phosphate to apatitic tricalcium phosphate.

    Roberts, J E; Heughebaert, M; Heughebaert, J C; Bonar, L C; Glimcher, M J; Griffin, R G


    The hydrolytic conversion of a solid amorphous calcium phosphate of empirical formula Ca9 (PO4)6 to a poorly crystalline apatitic phase, under conditions where Ca2+ and PO4(3-) were conserved, was studied by means of solid-state magic-angle sample spinning 31P-NMR (nuclear magnetic resonance). Results showed a gradual decrease in hydrated amorphous calcium phosphate and the formation of two new PO4(3-)-containing components: an apatitic component similar to poorly crystalline hydroxyapatite and a protonated PO4(3-), probably HPO4(2-) in a dicalcium phosphate dihydrate (DCPD) brushite-like configuration. This latter component resembles the brushite-like HPO4(2-) component previously observed by 31P-NMR in apatitic calcium phosphates of biological origin. Results were consistent with previous studies by Heughebaert and Montel [18] of the kinetics of the conversion of amorphous calcium phosphate to hydroxyapatite under the same conditions.

  14. Studies on Ferromagnetic and Photoluminescence Properties of ITO and Cu-Doped ITO Nanoparticles Synthesized by Solid State Reaction

    Babu, S. Harinath; Kaleemulla, S.; Rao, N. Madhusudhana; Krishnamoorthi, C.


    Cubic structured indium-tin-oxide (ITO) and copper-doped ITO nanoparticles were synthesized by solid state reaction. The structure, morphology, chemical, magnetic, and photoluminescence properties of the synthesized nanoparticles were studied by x-ray diffraction, field emission scanning electron microscopy, x-ray photoelectron spectroscopy, vibrating sample magnetometry, and photoluminescence spectrophotometry, respectively. Magnetic studies confirmed that the ITO nanoparticles were ferromagnetic at room temperature (300 K) and at 100 K, and it was believed that the observed ferromagnetism may be due to oxygen vacancies and defects present in the system. No hysteresis loop was observed in copper-doped ITO nanoparticles at room temperature and 100 K. The ITO and Cu-doped ITO nanoparticles exhibited two broad emission peaks in the visible region of the electromagnetic spectrum.

  15. Solid-state diffusion in amorphous zirconolite

    Yang, C.; Dove, M. T.; Trachenko, K. [School of Physics and Astronomy, Queen Mary University of London, Mile End Road, London E1 4NS (United Kingdom); Zarkadoula, E. [School of Physics and Astronomy, Queen Mary University of London, Mile End Road, London E1 4NS (United Kingdom); Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831-6138 (United States); Todorov, I. T. [STFC Daresbury Laboratory, Warrington WA4 1EP (United Kingdom); Geisler, T. [Steinmann-Institut für Geologie, Mineralogie und Paläontologie, University of Bonn, D-53115 Bonn (Germany); Brazhkin, V. V. [Institute for High Pressure Physics, RAS, 142190 Moscow (Russian Federation)


    We discuss how structural disorder and amorphization affect solid-state diffusion, and consider zirconolite as a currently important case study. By performing extensive molecular dynamics simulations, we disentangle the effects of amorphization and density, and show that a profound increase of solid-state diffusion takes place as a result of amorphization. Importantly, this can take place at the same density as in the crystal, representing an interesting general insight regarding solid-state diffusion. We find that decreasing the density in the amorphous system increases pre-factors of diffusion constants, but does not change the activation energy in the density range considered. We also find that atomic species in zirconolite are affected differently by amorphization and density change. Our microscopic insights are relevant for understanding how solid-state diffusion changes due to disorder and for building predictive models of operation of materials to be used to encapsulate nuclear waste.

  16. Neutron scattering studies of solid-state polymorphism in dimethyl butanol glass formers

    Juszynska, E. [H. Niewodniczanski Institute of Nuclear Physics, Polish Academy of Sciences, Radzikowskiego 152, 31-342 Cracow (Poland); Massalska-Arodz, M. [H. Niewodniczanski Institute of Nuclear Physics, Polish Academy of Sciences, Radzikowskiego 152, 31-342 Cracow (Poland)], E-mail:; Natkaniec, I. [H. Niewodniczanski Institute of Nuclear Physics, Polish Academy of Sciences, Radzikowskiego 152, 31-342 Cracow (Poland); Frank Laboratory of Neutron Physics, JINR, 141980 Dubna (Russian Federation); Krawczyk, J. [H. Niewodniczanski Institute of Nuclear Physics, Polish Academy of Sciences, Radzikowskiego 152, 31-342 Cracow (Poland)


    Inelastic incoherent neutron scattering (IINS) and neutron powder diffraction (NPD) studies have been performed for two dimethyl 1-butanols and two dimethyl 2-butanols with CH{sub 3} side molecular groups. Low-temperature vibrational density of states confirmed solid-state polymorphism detected by calorimetric methods, i.e., existence of crystalline and ODIC phases for all isomers, orientationally disordered glass for 2,2-DM 1-B and 3,3-DM 2-B, and glass of isotropic phase for 3,3-DM 1-B. Difference in vibrational density of states between glass and the ordered crystal has shown the so-called Boson peak. Influence of the OH group position in the molecules on their vibrational dynamics up to 50 meV is discussed.

  17. Solid-State FTIR Spectroscopic Study of Two Binary Mixtures: Cefepime-Metronidazole and Cefoperazone-Sulbactam

    Hassan Refat H. Ali


    Full Text Available The structural information of the pharmaceuticals and insights on the modes of molecular interactions are very important aspects in drug development. In this work, two cephalosporins and antimicrobial combinations, cefepime-metronidazole and cefoperazone-sulbactam, were studied in the solid state using FTIR spectroscopy for the first time. Quantitation of the studied drugs and their binary mixtures was performed by integrating the peak areas of the characteristic well-resolved bands: υ (C=O band at 1773 cm−1 for cefepime and ring torsion band at 826 cm−1 for metronidazole and υ (C=O band at 1715 cm−1 for cefoperazone and ring torsion band at 1124 cm−1 for sulbactam. The results of this work were compared with the relevant spectrophotometric reported methods. This study provides data that can be used for the preparative process monitoring of the studied drugs in various dosage forms.

  18. Crystal structure, magnetism, {sup 89}Y solid state NMR, and {sup 121}Sb Moessbauer spectroscopic investigations of YIrSb

    Benndorf, Christopher [Institut fuer Physikalische Chemie, Universitaet Muenster (Germany); Institut fuer Anorganische und Analytische Chemie, Universitaet Muenster (Germany); Heletta, Lukas; Block, Theresa; Poettgen, Rainer [Institut fuer Anorganische und Analytische Chemie, Universitaet Muenster (Germany); Eckert, Hellmut [Institut fuer Physikalische Chemie, Universitaet Muenster (Germany); Institute of Physics in Sao Carlos, University of Sao Paulo, Sao Carlos (Brazil)


    The ternary antimonide YIrSb was synthesized from the binary precursor YIr and elemental antimony by a diffusion controlled solid-state reaction. Single crystals were obtained by a flux technique with elemental bismuth as an inert solvent. The YIrSb structure (TiNiSi type, space group Pnma) was refined from single-crystal X-ray diffractometer data: a = 711.06(9), b = 447.74(5), c = 784.20(8) pm, wR{sub 2} = 0.0455, 535 F{sup 2} values, 20 variables. {sup 89}Y solid state MAS NMR and {sup 121}Sb Moessbauer spectra show single resonance lines in agreement with single-crystal X-ray data. YIrSb is a Pauli paramagnet. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  19. Glass for Solid State Devices

    Bailey, R. F.


    Glass film has low intrinsic compressive stress for isolating active layers of magnetic-bubble and other solid-state devices. Solid-state device structure incorporates low-stress glasses as barrier and spacer layers. Glass layers mechanically isolate substrate, conductor, and nickel/iron layers.

  20. Investigations of the structure and "interfacial" surface chemistry of Bioglass (RTM) materials by solid-state multinuclear NMR spectroscopy

    Sarkar, Gautam

    Bioactive materials such as BioglassRTM 45S5 (45% SiO 2, 24.5% CaO, 24.5% Na2O, and 6% P2O5 by weight) are sodium-phosphosilicate glasses containing independent three-dimensional silicate and phosphate networks and Na+ and Ca2+ ions as modifying cations. Due to their bioactivity, these materials are currently used as implants and for other surgical and clinical applications. The bioactivity of BioglassesRTM is due to their unique capability to form chemical bonds to tissues through an octacalciumphosphate (OCP)- and/or hydroxyapatite-like (HA) "interfacial" matrix. The formation of OCP and/or HA is preceded by the formation of a silica-rich surface layer and the subsequent growth of an amorphous calcium phosphate (a-CP) layer. Structural characterization of a series of commercial and synthesized Bioglass materials 45S5 52S, 55S, 60S, and synthesized 17O-labelled "Bioglass materials 45S, 52S, 55S and 60S" have been obtained using solid-state single-pulse magic-angle spinning (SP/MAS) 17O, 23Na, 29Si and 31P NMR. The 17O NMR isotropic chemical shifts and estimates of the quadrupole coupling constants (Cq) [at fixed asymmetry parameter ( hQ ) values of zero] have been obtained from solid-state spin-echo 17O SP/MAS NMR spectra of 17O-labelled "Bioglasses". The simulation results of these spectra reveal the presence of both bridging-oxygens (BO, i.e. ≡ Si-17OSi ≡ ) and non-bridging oxygens (NBO, i.e. ≡ Si-17O-Na+/Ca2+ ) in the silicate networks in these materials. 17O NMR spectra of these Bioglass materials do not show any direct evidence for the presence of BO and NBO atoms in the phosphate units; however, they are expected to be present in small amounts. In vitro reactions of BioglassRTM 45S5, 60S and 77S powders have been used to study the "interfacial" surface chemistry of these materials in simulated body-fluid (SBF, Kyoto or K9 solution) and/or 17O-enriched tris-buffer solution. 29Si and 31P SP/MAS NMR have been used to identify and quantify the extent of

  1. Solid-state memcapacitor

    Martinez, J; Di Ventra, M.; Pershin, Yu. V.


    We suggest a possible realization of a solid-state memory capacitive (memcapacitive) system. Our approach relies on the slow polarization rate of a medium between plates of a regular capacitor. To achieve this goal, we consider a multi-layer structure embedded in a capacitor. The multi-layer structure is formed by metallic layers separated by an insulator so that non-linear electronic transport (tunneling) between the layers can occur. The suggested memcapacitor shows hysteretic charge-voltag...

  2. Solid state physics at ISOLDE

    Deicher, M; Wichert, T


    Radioactive atoms have been used in solid state physics and in materials science for decades. Besides their classical applications as tracers for diffusion studies, nuclear techniques such as Mossbauer spectroscopy, perturbed gamma gamma angular correlation, beta -NMR, and emission channeling make use of nuclear properties (via hyperfine interactions or emitted alpha or beta particles) to gain microscopic information on structural and dynamical properties of solids. During the last decade, the availability of many different radioactive isotopes as clean ion beams at ISOL facilities like ISOLDE/CERN has triggered a new era involving methods sensitive to the optical and electronic properties of solids, especially in the field of semiconductor physics. This overview will browse through ongoing solid state physics experiments with radioactive ion beams at ISOLDE. A wide variety of problems is under study, involving bulk properties, surfaces and interfaces in many different systems like semiconductors, superconduc...

  3. Conformational Analysis, Molecular Structure and Solid State Simulation of the Antiviral Drug Acyclovir (Zovirax Using Density Functional Theory Methods

    Margarita Clara Alvarez-Ros


    Full Text Available The five tautomers of the drug acyclovir (ACV were determined and optimised at the MP2 and B3LYP quantum chemical levels of theory. The stability of the tautomers was correlated with different parameters. On the most stable tautomer N1 was carried out a comprehensive conformational analysis, and the whole conformational parameters (R, β, Φ, φ1, φ2, φ3, φ4, φ5 were studied as well as the NBO Natural atomic charges. The calculations were carried out with full relaxation of all geometrical parameters. The search located at least 78 stable structures within 8.5 kcal/mol electronic energy range of the global minimum, and classified in two groups according to the positive or negative value of the torsional angle j1. In the nitrogen atoms and in the O2' and O5' oxygen atoms of the most stable conformer appear a higher reactivity than in the natural nucleoside deoxyguanosine. The solid state was simulated through a dimer and tetramer forms and the structural parameters were compared with the X-ray crystal data available. Several general conclusions were emphasized.

  4. Structural and dynamic properties of amorphous solid dispersions: the role of solid-state nuclear magnetic resonance spectroscopy and relaxometry.

    Paudel, Amrit; Geppi, Marco; Van den Mooter, Guy


    Amorphous solid dispersions (ASDs) are one of the frontier strategies to improve solubility and dissolution rate of poorly soluble drugs and hence tackling the growing challenges in oral bioavailability. Pharmaceutical performance, physicochemical stability, and downstream processability of ASD largely rely on the physical structure of the product. This necessitates in-depth characterization of ASD microstructure. Solid-state nuclear magnetic resonance (SS-NMR) techniques bear the ultimate analytical capabilities to provide the molecular level information on the dynamics and phase compositions of amorphous dispersions. SS-NMR spectroscopy/relaxometry, as a single and nondestructive technique, can reveal diverse and critical structural information of complex ASD formulations that are barely amenable from any other existing technique. The purpose of the current article is to review the recent most important studies on various sophisticated and information-rich one-dimensional and two-dimensional SS-NMR spectroscopy/relaxometry for the analysis of molecular mobility, miscibility, drug-carrier interactions, crystallinity, and crystallization in ASD. Some specific examples on microstructural elucidations of challenging ASD using multidimensional and multinuclear SS-NMR are presented. Additionally, some relevant examples on the utility of solution-NMR and NMR-imaging techniques for the investigation of the dissolution behavior of ASD are gathered.

  5. Integrating solid-state NMR and computational modeling to investigate the structure and dynamics of membrane-associated ghrelin.

    Gerrit Vortmeier

    Full Text Available The peptide hormone ghrelin activates the growth hormone secretagogue receptor 1a, also known as the ghrelin receptor. This 28-residue peptide is acylated at Ser3 and is the only peptide hormone in the human body that is lipid-modified by an octanoyl group. Little is known about the structure and dynamics of membrane-associated ghrelin. We carried out solid-state NMR studies of ghrelin in lipid vesicles, followed by computational modeling of the peptide using Rosetta. Isotropic chemical shift data of isotopically labeled ghrelin provide information about the peptide's secondary structure. Spin diffusion experiments indicate that ghrelin binds to membranes via its lipidated Ser3. Further, Phe4, as well as electrostatics involving the peptide's positively charged residues and lipid polar headgroups, contribute to the binding energy. Other than the lipid anchor, ghrelin is highly flexible and mobile at the membrane surface. This observation is supported by our predicted model ensemble, which is in good agreement with experimentally determined chemical shifts. In the final ensemble of models, residues 8-17 form an α-helix, while residues 21-23 and 26-27 often adopt a polyproline II helical conformation. These helices appear to assist the peptide in forming an amphipathic conformation so that it can bind to the membrane.

  6. Structural and optical properties of solid-state synthesized Au dendritic structures

    Gentile, A. [Dipartimento di Fisica ed Astronomia - Università di Catania, via S. Sofia 64, 95123 Catania (Italy); MATIS IMM-CNR, via S. Sofia 64, 95123 Catania (Italy); Ruffino, F., E-mail: [Dipartimento di Fisica ed Astronomia - Università di Catania, via S. Sofia 64, 95123 Catania (Italy); MATIS IMM-CNR, via S. Sofia 64, 95123 Catania (Italy); Romano, L. [Dipartimento di Fisica ed Astronomia - Università di Catania, via S. Sofia 64, 95123 Catania (Italy); MATIS IMM-CNR, via S. Sofia 64, 95123 Catania (Italy); Boninelli, S. [MATIS IMM-CNR, via S. Sofia 64, 95123 Catania (Italy); Reitano, R.; Piccitto, G. [Dipartimento di Fisica ed Astronomia - Università di Catania, via S. Sofia 64, 95123 Catania (Italy); Grimaldi, M.G. [Dipartimento di Fisica ed Astronomia - Università di Catania, via S. Sofia 64, 95123 Catania (Italy); MATIS IMM-CNR, via S. Sofia 64, 95123 Catania (Italy)


    Graphical abstract: - Highlights: • Au dendritic structures were produced on surfaces. • The chemical and structural properties of the dendritic structures are presented. • The optical properties of the dendritic structures are presented. • The ability of the dendritic structures to serve as light scattering centers is presented. - Abstract: Au dendrites (Au Ds) are synthesized, on various substrates, by a simple physical methodology involving the deposition of a thin Au film on a Si surface followed by thermal processes at high temperatures (>1273 K) in an inert ambient (N{sub 2}), using fast heating and cooling rates (1273 K/min). Microscopic analyses reveal the evolution, thanks to the thermal processes, of the Au film from a continuous coating to dendritic structures covering the entire sample surface. In particular, transmission electron microscopy analyses indicate that, below the Au surface, the dendritic structures consist of Si atoms originating from the substrate. Furthermore, optical characterizations reveal the ability of the Au Ds to serve as scattering centers in the infrared region. Finally, on the basis of the experimental observations, a phenomenological model for the growth of the Au Ds is proposed.

  7. Solid state SPS microwave generation and transmission study. Volume 2, phase 2: Appendices

    Maynard, O. E.


    The solid state sandwich concept for SPS was further defined. The design effort concentrated on the spacetenna, but did include some system analysis for parametric comparison reasons. Basic solid state microwave devices were defined and modeled. An initial conceptual subsystems and system design was performed as well as sidelobe control and system selection. The selected system concept and parametric solid state microwave power transmission system data were assessed relevant to the SPS concept. Although device efficiency was not a goal, the sensitivities to design of this efficiency were parametrically treated. Sidelobe control consisted of various single step tapers, multistep tapers and Gaussian tapers. A hybrid concept using tubes and solid state was evaluated. Thermal analyses are included with emphasis on sensitivities to waste heat radiator form factor, emissivity, absorptivity, amplifier efficiency, material and junction temperature.

  8. Luminescence and the solid state

    Ropp, Richard C


    Since the discovery of the transistor in 1948, the study of the solid state has been burgeoning. Recently, cold fusion and the ceramic superconductor have given cause for excitement. There are two approaches possible to this area of science, namely, that of solid state physics and solid state chemistry, although both overlap extensively. The former is more concerned with electronic states in solids (including electromagnetics) whereas the latter is more concerned with interactions of atoms in solids. The area of solid state physics is well documented, however, there are very few texts which de

  9. Toward a structure determination method for biomineral-associated protein using combined solid- state NMR and computational structure prediction.

    Masica, David L; Ash, Jason T; Ndao, Moise; Drobny, Gary P; Gray, Jeffrey J


    Protein-biomineral interactions are paramount to materials production in biology, including the mineral phase of hard tissue. Unfortunately, the structure of biomineral-associated proteins cannot be determined by X-ray crystallography or solution nuclear magnetic resonance (NMR). Here we report a method for determining the structure of biomineral-associated proteins. The method combines solid-state NMR (ssNMR) and ssNMR-biased computational structure prediction. In addition, the algorithm is able to identify lattice geometries most compatible with ssNMR constraints, representing a quantitative, novel method for investigating crystal-face binding specificity. We use this method to determine most of the structure of human salivary statherin interacting with the mineral phase of tooth enamel. Computation and experiment converge on an ensemble of related structures and identify preferential binding at three crystal surfaces. The work represents a significant advance toward determining structure of biomineral-adsorbed protein using experimentally biased structure prediction. This method is generally applicable to proteins that can be chemically synthesized.

  10. A combination of novel solid-state NMR methods and related software to study molecular assemblies and biomolecules

    Gradmann, S.H.E.


    Solid-state Nuclear Magnetic Resonance (ssNMR) is a versatile spectroscopic method that can be applied to various samples relevant in life and material science and provides atomic insight into molecular structure, dynamics and assembly. The present thesis describes the diversity and utility of ssNMR

  11. Plutonium and americium monazite materials: Solid state synthesis and X-ray diffraction study

    Bregiroux, D. [DEN/DEC/SPUA, Commissariat a l' Energie Atomique, Cadarache, 13108 Saint Paul Lez Durance (France); Laboratoire Science des Procedes Ceramiques et de Traitements de Surface, UMR CNRS-Universite no. 6638, Batiment Chimie, 123 avenue Albert Thomas, 87060 Limoges (France); E-mail:; Belin, R. [DEN/DEC/SPUA, Commissariat a l' Energie Atomique, Cadarache, 13108 Saint Paul Lez Durance (France); Valenza, P. [DEN/DEC/SPUA, Commissariat a l' Energie Atomique, Cadarache, 13108 Saint Paul Lez Durance (France); Audubert, F. [DEN/DEC/SPUA, Commissariat a l' Energie Atomique, Cadarache, 13108 Saint Paul Lez Durance (France); Bernache-Assollant, D. [Ecole Nationale Superieure des Mines, 158 Cours Fauriel, 42023 Saint Etienne (France)


    High-temperature solid state syntheses of monazite powders containing plutonium (III), plutonium (IV) and americium (III) were performed. Resulting powders were characterized by X-ray diffraction. Pu{sup 3+}PO{sub 4} was readily obtained as a single phase by heating a Pu{sup 4+}O{sub 2}-NH{sub 4}H{sub 2}PO{sub 4} mixture under argon atmosphere. Traces of tetravalent plutonium phosphate Pu{sup 4+}P{sub 2}O{sub 7} were detected when synthesized under air atmosphere. The incorporation of (Pu{sup 4+},Ca{sup 2+}) in the monazite structure was investigated under air and argon atmosphere. We showed that Pu{sup 4+} is fully reduced in Pu{sup 3+} under argon atmosphere whereas, under air, the compound with the formula Pu{sub 0.4}{sup 3+}Pu{sub 0.3}{sup 4+}Ca{sub 0.3}{sup 2+}PO{sub 4} was obtained. Pure Am{sup 3+}PO{sub 4} was also synthesized under argon atmosphere. X-ray patterns revealed a complete amorphisation of the monazite structure at a relatively low cumulative alpha dose for {sup 241}AmPO{sub 4}.

  12. The interplay of hydrogen bonds in the solid state structure of NH-pyrazoles bearing cyano and amino substituents

    Emelina, Elena E.; Petrov, Alexander A.; Borissova, Alexandra O.; Filyukov, Dmitriy V.; Antipin, Mikhail Yu.


    The annular tautomeric equilibrium of two 4-cyano-3(5)-aminopyrazoles having hydrogen atom or methyl group in position 5(3) was studied by X-ray crystallography for the solid compounds and by DFT B3LYP/6-31G** and CBS-QB3 calculations for the free molecules. The 3-amino tautomer was found to be the more favorable form for the free molecules and the sole form in the solid state.

  13. Towards hybrid quantum systems: Trapping a single atom near a nanoscale solid-state structure

    Tiecke T.G.


    Full Text Available We describe and demonstrate a method to deterministically trap single atoms near nanoscale solid-state objects. The trap is formed by the interference of an optical tweezer and its reflection from the nano object, creating a one-dimensional optical lattice where the first lattice site is at z0 ∼ λ/4 from the surface. Using a tapered optical fiber as the nanoscopic object, we characterize the loading into different lattice sites by means of the AC-Stark shift induced by a guided fiber mode. We demonstrate a loading efficiency of 94(6% into the first lattice site, and measure the cooperativity for the emission of the atom into the guided mode of the nanofiber. We show that by tailoring the dimensions of the nanofiber the distance of the trap to the surface can be adjusted. This method is applicable to a large variety of nanostructures and represents a promising starting point for interfacing single atoms with arbitrary nanoscale solid-state systems.

  14. Towards a lattice-matching solid-state battery: synthesis of a new class of lithium-ion conductors with the spinel structure.

    Rosciano, Fabio; Pescarmona, Paolo P; Houthoofd, Kristof; Persoons, Andre; Bottke, Patrick; Wilkening, Martin


    Lithium ion batteries have conquered most of the portable electronics market and are now on the verge of deployment in large scale applications. To be competitive in the automotive and stationary sectors, however, they must be improved in the fields of safety and energy density (W h L(-1)). Solid-state batteries with a ceramic electrolyte offer the necessary advantages to significantly improve the current state-of-the-art technology. The major limit towards realizing a practical solid-state lithium-ion battery lies in the lack of viable ceramic ionic conductors. Only a few candidate materials are available, each carrying a difficult balance between advantages and drawbacks. Here we introduce a new class of possible solid-state lithium-ion conductors with the spinel structure. Such compounds could be coupled with spinel-type electrode materials to obtain a "lattice matching" solid device where low interfacial resistance could be achieved. Powders were prepared by wet chemistry, their structure was studied by means of diffraction techniques and magic angle spinning NMR, and Li(+) self-diffusion was estimated by static NMR line shape measurements. Profound differences in the Li(+) diffusion properties were observed depending on the composition, lithium content and cationic distribution. Local Li(+) hopping in the spinel materials is accompanied by a low activation energy of circa 0.35 eV being comparable with that of, e.g., LLZO-type garnets, which represent the current benchmark in this field. We propose these novel materials as a building block for a lattice-matching all-spinel solid-state battery with low interfacial resistance.

  15. Solid State Physics Introduction to the Theory

    Patterson, James D


    Learning Solid State Physics involves a certain degree of maturity, since it involves tying together diverse concepts from many areas of physics. The objective is to understand, in a basic way, how solid materials behave. To do this one needs both a good physical and mathematical background. One definition of Solid State Physics is it is the study of the physical (e.g. the electrical, dielectric, magnetic, elastic, and thermal) properties of solids in terms of basic physical laws. In one sense, Solid State Physics is more like chemistry than some other branches of physics because it focuses on common properties of large classes of materials. It is typical that Solid State Physics emphasizes how physics properties link to electronic structure. We have retained the term Solid State Physics, even though Condensed Matter Physics is more commonly used. Condensed Matter Physics includes liquids and non-crystalline solids such as glass, which we shall not discuss in detail. Modern Solid State Physics came of age in ...

  16. Applications of solid state nuclear magnetic resonance techniques to the study of coals and polymers. [Ph. D. thesis; 125 references

    Pembleton, R.G.


    The use of Nuclear Magnetic Resonance (NMR) to study molecules in the solid state has grown rapidly over the past several years. This is due to the advent of techniques which allow for the removal of certain interactions in the solid state which previously have thwarted most attempts at obtaining chemical shift or their anisotropies. With these parameters and others now available, NMR has become an important tool to be used in the understanding of the chemistry of solids. The work reported in this dissertation applies the techniques of solid state NMR to a number of chemical systems. Specific applications are made to crystallinity in polymers, to combined sample spinning and multiple pulse techniques, and to aromatic and aliphatic content of vitrain portions of coals of varying carbon content.

  17. An explanation for the high stability of polycarboxythiophenes in photovoltaic devices—A solid-state NMR dipolar recoupling study

    Bierring, M.; Nielsen, J.S.; Siu, Ana


    observed in photovoltaic devices employing polythiophene substituted with carboxylic-acid moieties under oxygen free conditions. H-1 and C-13 solid-state NMR, IR, and ESR spectroscopy of unmodified and isotopically labeled polythiophenes were studied. Distances between the isotopically labeled carboxylic...... acid carbon atoms were measured by C-13 solid-state magic-angle-spinning (MAS) NMR using symmetry-based double-quantum (2Q) dipolar recoupling. This revealed the presence of C-13-C-13 distances of 3.85 angstrom, which correspond to the C-C distance in hydrogen-bonded carboxylic acid dimers. In spite...... of the presence of carboxylic groups in the polymer as demonstrated by C-13 CP/MAS NMR and IR spectroscopy, the absence of carboxylic protons in solid state H-1 NMR spectra indicate that they are mobile. We link the extraordinary stability of this system to the rigid nature, cross-linking through a hydrogen...

  18. High-efficiency, solid-state, dye-sensitized solar cells using hierarchically structured TiO₂ nanofibers.

    Hwang, Daesub; Jo, Seong Mu; Kim, Dong Young; Armel, Vanessa; MacFarlane, Douglas R; Jang, Sung-Yeon


    High-performance, room-temperature (RT), solid-state dye-sensitized solar cells (DSSCs) were fabricated using hierarchically structured TiO₂ nanofiber (HS-NF) electrodes and plastic crystal (PC)-based solid-state electrolytes. The electrospun HS-NF photoelectrodes possessed a unique morphology in which submicrometer-scale core fibers are interconnected and the nanorods are dendrited onto the fibers. This nanorod-in-nanofiber morphology yielded porosity at both the mesopore and macropore level. The macropores, steming from the interfiber space, afforded high pore volumes to facilitate the infiltration of the PC electrolytes, whereas the mesoporous nanorod dendrites offered high surface area for enhanced dye loading. The solid-state DSSCs using HS-NFs (DSSC-NF) demonstrated improved power conversion efficiency (PCE) compared to conventional TiO₂ nanoparticle (NP) based DSSCs (DSSC-NP). The improved performance (>2-fold) of the DSSC-NFs was due to the reduced internal series resistance (R(s)) and the enhanced charge recombination lifetime (τ(r)) determined by electrochemical impedance spectroscopy and intensity modulated photocurrent/photovoltage spectroscopy. The easy penetration of the PC electrolytes into HS-NF layers via the macropores reduces R(s) significantly, improving the fill factor (FF) of the resulting DSSC-NFs. The τ(r) difference between the DSSC-NF and DSSC-NP in the PC electrolytes was extraordinary (~14 times) compared to reported results in conventional organic liquid electrolytes. The optimized PCE of DSSC-NF using the PC electrolytes was 6.54, 7.69, and 7.93% at the light intensity of 100, 50, and 30 mW cm⁻², respectively, with increased charge collection efficiency (>40%). This is the best performing RT solid-state DSSC using a PC electrolyte. Considering the fact that most reported quasi-solid state or nonvolatile electrolytes require higher iodine contents for efficient ion transport, our HS-NFs are a promising morphology for such

  19. Study on microbial protein and the mechanism of solid-state fermentation with periodical dynamic changes of air

    FU Xiaoguo; CHEN Hongzhang; LI Hongqiang; MA Runyu


    The effect of different extraction and purification conditions on the microbial protein obtained from solid-state fermentation (SSF) and the effect of periodical dynamic changes of air on protein have been studied.The mechanism of solid-state ermentation with periodical dynamic changes of air is also discussed.Compared with static solid-state fermentation,periodical dynamic changes of air afford a higher protein mass; from 1 g of the fermentation microbe,5.3 mg of the intracellular protein (an increase of 34.63%)and 9.09 mg of the extracellular protein (an increase of 17.8%)were obtained on the sixth day of fermentation.The filter paper activity and carboxymethyl cellulose activity (FPA and CMCase) of the extracellular protein are 1.739 μmol/s and 109.592 μmol/s,respectively,which represent increases of 60.1% and 21.2% over the corresponding values for static solid-state fermentation.The FPA and CMCase of the intracellular protein are 0.245 μmol/s and 6.392 μmol/s,respec tively,which represent decreases of 22.2% and 38.7% over the corresponding values for static solid-state fermentation.The enzyme activity of the microbial extracellular protein in solid-state fermentation with periodical dynamic changes of air on the fifth day is nearly equal to that on the sixth day without periodical dynamic changes of air,so the period of fermentation can be shortened.The sodium dodecyl sulfatepolyacrylamide gel electrophoresis (SDS-PAGE) experiments suggest that pulsating air pressure stimulation leads to a decrease in the amount of protein component with molecule mass of about 80400Da,and an increase in the amount of protein component with molecule mass of about 28520Da.

  20. Solid State Laser


    The Titan-CW Ti:sapphire (titanium-doped sapphire) tunable laser is an innovation in solid-state laser technology jointly developed by the Research and Solid State Laser Divisions of Schwartz Electro-optics, Inc. (SEO). SEO is producing the laser for the commercial market, an outgrowth of a program sponsored by Langley Research Center to develop Ti:sapphire technology for space use. SEO's Titan-CW series of Ti:sapphire tunable lasers have applicability in analytical equipment designed for qualitative analysis of carbohydrates and proteins, structural analysis of water, starch/sugar analyses, and measurements of salt in meat. Further applications are expected in semiconductor manufacture, in medicine for diagnosis and therapy, and in biochemistry.

  1. Oriented solid-state NMR spectrosocpy

    Bertelsen, Kresten

    This thesis is concerned with driving forward oriented solid-state NMR spectroscopy as a viable technique for studying peptides in membrane bilayers. I will show that structural heterogeneity is an intrinsic part of the peptide/lipid system and that NMR can be used to characterize static...... and dynamic structural features of the peptides and its local surroundings. In fact one need to take into account the dynamical features of the system in order to correctly predict the structure from oriented solid-state NMR spectra.      ...

  2. An experimental study on ultrafast lamps for an ultraviolet solid state laser

    Alderighi, Daniele; Toci, Guido; Vannini, Matteo


    In this work we present an accurate experimental study of Xenon filled flash-lamps developed to achieve a fast submicrosecond light pulse with high emission in the ultraviolet (UV) spectral range. This study has been initiated to obtain an efficient pump for solid state lasers with Ce3+ activated crystal as active medium. For Ce3+ doped fluorides the absorption bands lie in the UV spectrum, in the region between 248 and 288nm. Due to the very short lifetime (-4Ons) of the upper level ofthe laser transition (5d->4f), Cerium activated hosts must be pumped with a fast rising light pulse. To our best knowledge, no direct ultraviolet laser action from a Ce3+ activated host with incoherent pumping has been reported. To achieve a threshold population inversion, an unusually fast lamp pulse is required making necessary the development of a lamp system opposite to what it is usually required in terms of duration and stability. We present here a detailed characterization of the lamp and ofthe discharge circuit parameters. Furthermore we discuss the opportunity to use an excimer mixture or a Silicon-Xenon based gas mixture to optimize the spectral coupling of lamp emission to the active medium adsorption.

  3. Structural Investigations of Portland Cement Components, Hydration, and Effects of Admixtures by Solid-State NMR Spectroscopy

    Skibsted, Jørgen Bengaard; Andersen, Morten D.; Jakobsen, Hans Jørgen


    Solid-state, magic-angle spinning (MAS) NMR spectroscopy represents a valuable tool for structural investigations on the nanoscale of the most important phases in anhydrous and hydrated Portland cements and of various admixtures. This is primarily due to the fact that the method reflects the firs.......% flourine. Finally, the detection and quantification of strätlingite (2CaO·Al2O3·SiO2·8H2O) in Portland cement mixtures containing metakaolin will be demonstrated....

  4. Structural Investigations of Portland Cement Components, Hydration, and Effects of Admixtures by Solid-State NMR Spectroscopy

    Skibsted, Jørgen Bengaard; Andersen, Morten D.; Jakobsen, Hans Jørgen


    Solid-state, magic-angle spinning (MAS) NMR spectroscopy represents a valuable tool for structural investigations on the nanoscale of the most important phases in anhydrous and hydrated Portland cements and of various admixtures. This is primarily due to the fact that the method reflects the first...... in the cement phases. The role of flouride ions is of special interest for mineralized Portland cements and it demonstrated that the location of these anions in anhydrous and hydrated Portland cements can be clarified using 19F MAS or 29Si{19F} CP/MAS NMR despite these cements contain only about 0.2 wt...

  5. Study of dual wavelength composite output of solid state laser based on adjustment of resonator parameters

    Wang, Lei; Nie, Jinsong; Wang, Xi; Hu, Yuze


    The 1064nm fundamental wave (FW) and the 532nm second harmonic wave (SHW) of Nd:YAG laser have been widely applied in many fields. In some military applications requiring interference in both visible and near-infrared spectrum range, the de-identification interference technology based on the dual wavelength composite output of FW and SHW offers an effective way of making the device or equipment miniaturized and low cost. In this paper, the application of 1064nm and 532nm dual-wavelength composite output technology in military electro-optical countermeasure is studied. A certain resonator configuration that can achieve composite laser output with high power, high beam quality and high repetition rate is proposed. Considering the thermal lens effect, the stability of this certain resonator is analyzed based on the theory of cavity transfer matrix. It shows that with the increase of thermal effect, the intracavity fundamental mode volume decreased, resulting the peak fluctuation of cavity stability parameter. To explore the impact the resonator parameters does to characteristics and output ratio of composite laser, the solid-state laser's dual-wavelength composite output models in both continuous and pulsed condition are established by theory of steady state equation and rate equation. Throughout theoretical simulation and analysis, the optimal KTP length and best FW transmissivity are obtained. The experiment is then carried out to verify the correctness of theoretical calculation result.

  6. Solid state drug-polymer miscibility studies using the model drug ABT-102.

    Jog, Rajan; Gokhale, Rajeev; Burgess, Diane J


    Amorphous solid dispersions typically suffer storage stability issues due to: their amorphous nature, high drug loading, uneven drug:stabilizer ratio and plasticization effects as a result of hygroscopic excipients. An extensive solid state miscibility study was conducted to aid in understanding the mechanisms involved in drug/stabilizer interactions. ABT-102 (model drug) and nine different polymers with different molecular weights and viscosities were selected to investigate drug/polymer miscibility. Three different polymer:drug ratios (1:3, 1:1 and 3:1, w/w) were analyzed using: DSC, FTIR and PXRD. Three different techniques were used to prepare the amorphous solid dispersions: serial dilution, solvent evaporation and spray drying. Spray drying was the best method to obtain amorphous solid dispersions. However, under certain conditions amorphous formulations could be obtained using solvent evaporation. Melting point depression was used to calculate interaction parameters and free energy of mixing for the various drug polymer mixtures. The spray dried solid dispersions yielded a negative free energy of mixing which indicated strong drug-polymer miscibility compared to the solvent evaporation and serial dilution method. Soluplus was the best stabilizer compared to PVP and HPMC, which is probably a consequence of strong hydrogen bonding between the two CO moieties of soluplus and the drug NH moieities. Copyright © 2016. Published by Elsevier B.V.

  7. (13)C and (15)N solid-state NMR studies on albendazole and cyclodextrin albendazole complexes.

    Ferreira, M João G; García, A; Leonardi, D; Salomon, Claudio J; Lamas, M Celina; Nunes, Teresa G


    (13)C and (15)N solid-state nuclear magnetic resonance (NMR) spectra were recorded from albendazole (ABZ) and from ABZ:β-cyclodextrin, ABZ:methyl-β-cyclodextrin, ABZ:hydroxypropyl-β-cyclodextrin and ABZ:citrate-β-cyclodextrin, which were prepared by the spray-drying technique. ABZ signals were typical of a crystalline solid for the pure drug and of an amorphous compound obtained from ABZ:cyclodextrin samples. Relevant spectral differences were correlated with chemical interaction between ABZ and cyclodextrins. The number and type of complexes revealed a strong dependence on the cyclodextrin group substituent. Solid-state NMR data were consistent with the presence of stable inclusion complexes.

  8. Study of p-type ZnO and MgZnO Thin Films for Solid State Lighting

    Liu, Jianlin [Univ. of California, Riverside, CA (United States)


    This project on study of p-type ZnO and MgZnO thin films for solid state lighting was carried out by research group of Prof. Jianlin Liu of UCR during the four-year period between August 2011 and July 2015. Tremendous progress has been made on the proposed research. This final report summarizes the important findings.

  9. Solid state devices


    The Solid State Device research program is directed toward developing innovative devices for space remote and in-situ sensing, and for data processing. Innovative devices can result from the standard structures in innovative materials such as low and high temperature superconductors, strained layer superlattices, or diamond films. Innovative devices can also result from innovative structures achieved using electron tunneling or nanolithography in standard materials. A final step is to use both innovative structures and innovative materials. A new area of emphasis is the miniaturization of sensors and instruments molded by using the techniques of electronic device fabrication to micromachine silicon into micromechanical and electromechanical sensors and actuators.

  10. Solid state characterization and crystal structure from X-ray powder diffraction of two polymorphic forms of ranitidine base.

    de Armas, Héctor Novoa; Peeters, Oswald M; Blaton, Norbert; Van Gyseghem, Elke; Martens, Johan; Van Haele, Gerrit; Van Den Mooter, Guy


    Ranitidine hydrochloride (RAN-HCl), a known anti-ulcer drug, is the product of reaction between HCl and ranitidine base (RAN-B). RAN-HCl has been extensively studied; however this is not the case of the RAN-B. The solid state characterization of RAN-B polymorphs has been carried out using different analytical techniques (microscopy, thermal analysis, Fourier transform infrared spectrometry in the attenuated total reflection mode, (13)C-CPMAS-NMR spectroscopy and X-ray powder diffraction). The crystal structures of RAN-B form I and form II have been determined using conventional X-ray powder diffraction in combination with simulated annealing and whole profile pattern matching, and refined using rigid-body Rietveld refinement. RAN-B form I is a monoclinic polymorph with cell parameters: a = 7.317(2), b = 9.021(2), c = 25.098(6) A, beta = 95.690(1) degrees and space group P2(1)/c. The form II is orthorhombic: a = 31.252(4), b = 13.052(2), c = 8.0892(11) A with space group Pbca. In RAN-B polymorphs, the nitro group is involved in a strong intramolecular hydrogen bond responsible for the existence of a Z configuration in the enamine portion of the molecules. A tail to tail packing motif can be denoted via intermolecular hydrogen bonds. The crystal structures of RAN-B forms are compared to those of RAN-HCl polymorphs. RAN-B polymorphs are monotropic polymorphic pairs.

  11. αB-Crystallin. A Hybrid Solid-State/Solution-State NMR Investigation Reveals Structural Aspects of the Heterogeneous Oligomer

    Jehle, Stefan [Freie Univ., Berlin (Germany); Leibniz Inst. for Molecular Pharmacology, Berlin (Germany); van Rossum, Barth [Leibniz Inst. for Molecular Pharmacology, Berlin (Germany); Stout, Joseph R. [Univ. of Washington, Seattle, WA (United States); Noguchi, Satoshi M. [Univ. of Washington, Seattle, WA (United States); Falber, Katja [Leibniz Inst. for Molecular Pharmacology, Berlin (Germany); Rehbein, Kristina [Leibniz Inst. for Molecular Pharmacology, Berlin (Germany); Oschkinat, Hartmut [Freie Univ., Berlin (Germany); Leibniz Inst. for Molecular Pharmacology, Berlin (Germany); Klevit, Rachel E. [Univ. of Washington, Seattle, WA (United States); Rajagopal, Ponni [Univ. of Washington, Seattle, WA (United States)


    Atomic-level structural information on αB-Crystallin (αB), a prominent member of the small heat-shock protein family, has been a challenge to obtain due its polydisperse oligomeric nature. We show that magic-angle spinning solid-state NMR can be used to obtain high-resolution information on an ~580-kDa human αB assembled from 175-residue 20-kDa subunits. An ~100-residue α-crystallin domain is common to all small heat-shock proteins, and solution-state NMR was performed on two different α- crystallin domain constructs isolated from αB. In vitro, the chaperone-like activities of full-length αB and the isolated α-crystallin domain are identical. Chemical shifts of the backbone and Cβ resonances have been obtained for residues 64–162 (α-crystallin domain plus part of the C-terminus) in αB and the isolated α-crystallin domain by solid-state and solution-state NMR, respectively. Both sets of data strongly predict six β-strands in the α-crystallin domain. A majority of residues in the α-crystallin domain have similar chemical shifts in both solid-state and solution-state, indicating similar structures for the domain in its isolated and oligomeric forms. Sites of intersubunit interaction are identified from chemical shift differences that cluster to specific regions of the α-crystallin domain. Multiple signals are observed for the resonances of M68 in the oligomer, identifying the region containing this residue as existing in heterogeneous environments within αB. Evidence for a novel dimerization motif in the human α-crystallin domain is obtained by a comparison of (i) solid-state and solution-state chemical shift data and (ii) 1H–15N heteronuclear single quantum coherence spectra as a function of pH. The isolated α-crystallin domain undergoes a dimer–monomer transition over the pH range 7.5–6.8. This steep pHdependent switch may be important for αB to function optimally (e.g., to preserve the filament integrity

  12. Fine refinement of solid state structure of racemic form of phospho-tyrosine employing NMR Crystallography approach.

    Paluch, Piotr; Pawlak, Tomasz; Oszajca, Marcin; Lasocha, Wieslaw; Potrzebowski, Marek J


    We present step by step facets important in NMR Crystallography strategy employing O-phospho-dl-tyrosine as model sample. The significance of three major techniques being components of this approach: solid state NMR (SS NMR), X-ray diffraction of powdered sample (PXRD) and theoretical calculations (Gauge Invariant Projector Augmented Wave; GIPAW) is discussed. Each experimental technique provides different set of structural constraints. From the PXRD measurement the size of the unit cell, space group and roughly refined molecular structure are established. SS NMR provides information about content of crystallographic asymmetric unit, local geometry, molecular motion in the crystal lattice and hydrogen bonding pattern. GIPAW calculations are employed for validation of quality of elucidation and fine refinement of structure. Crystal and molecular structure of O-phospho-dl-tyrosine solved by NMR Crystallography is deposited at Cambridge Crystallographic Data Center under number CCDC 1005924.

  13. Structural and Magnetic Characterizations of Nano Sized Grain Zinc Ferrite/Hydroxyapatite Ceramic Prepared by Solid State Reaction Route.

    Pankaew, Piyapong; Klumdoung, Pattarinee


    A promising composite of bioactive hydroxyapatite (HAp) and zinc ferrite (ZnFe2O4) has potentials for future bone reinforcing formation. In present study, HAp and ZnFe2O4 composite ceramic was prepared by solid state reaction route for easier control of structural and magnetic characteristics and with low cost. HAp powder was synthesized by precipitation method from chicken eggshell. Mixed powders with varying ZnFe2O4/HAp weight ratios from 2-10 wt% were milled together and uniaxially pressed and then sintered at 1200 degrees C for 3 hours. The XRD results showing no other phases of composite ceramics with only HAp and ZnFe2O4 phases were identified, indicating high stability of HAp property. Phase fractions of ZnFe2O4 were found to increase from 10.8 to 18.73 wt% with increasing content of ZnFe2O4. FT-IR results were only revealed vibration bands of standard HAp phase. SEM results revealed primary grains sizes of the prepared ceramics in nano scale. The BET surface area and pore volume increased with increasing content of ZnFe2O4 in composite ceramics. The VSM results of composites with increasing ZnFe2O4 content had been shown with increasing magnetization from 0.05 to 1.85 emu/g while their coercivities were decreased from 44 to 24 Oe. Higher magnetization as well as higher super paramagnetic behavior could be achieved with increasing the studied ZnFe2O4 weight ratios in ZnFe2O4/HAp composite ceramics, which can be tailored for specific applications.

  14. Solid state phenomena

    Lawrance, R


    Solid State Phenomena explores the fundamentals of the structure and their influence on the properties of solids. This book is composed of five chapters that focus on the electrical and thermal conductivities of crystalline solids. Chapter 1 describes the nature of solids, particularly metals and crystalline materials. This chapter also presents a model to evaluate crystal structure, the forces between atom pairs, and the mechanism of plastic and elastic deformation. Chapter 2 demonstrates random vibrations of atoms in a solid using a one-dimensional array, while Chapter 3 examines the resista

  15. Calcination products of gibbsite studied by X-ray diffraction, XPS and solid-state NMR

    Malki, A. [Laboratoire des structures, propriétés et interactions inter atomiques (LASPI2A), Faculté des sciences et technologies, Université Abbes Laghrour, Khenchela 40000 (Algeria); Mekhalif, Z.; Detriche, S.; Fonder, G. [Laboratoire de Chimie et Electrochimie des Surfaces, Facultés Universitaires Notre-Dame de la Paix, Rue de Bruxelles 61, B-5000 Namur (Belgium); Boumaza, A., E-mail: [Laboratoire des structures, propriétés et interactions inter atomiques (LASPI2A), Faculté des sciences et technologies, Université Abbes Laghrour, Khenchela 40000 (Algeria); Djelloul, A. [Laboratoire des structures, propriétés et interactions inter atomiques (LASPI2A), Faculté des sciences et technologies, Université Abbes Laghrour, Khenchela 40000 (Algeria)


    The changes caused by heat treatment of gibbsite powder at 300–1473 K were studied using the X-ray diffraction (XRD), X-ray photoemission (XPS) spectra and {sup 27}Al magic angle spinning nuclear magnetic resonance spectroscopy ({sup 27}Al MAS NMR). XRD analysis indicates that the transformation sequence involves the formation of κ-Al{sub 2}O{sub 3} as an intermediate phase between χ- and α-Al{sub 2}O{sub 3}. The crystallite size of χ-Al{sub 2}O{sub 3} is as small as 10 nm. XPS analysis indicates that the ratio of aluminium atoms to oxygen atoms in χ-Al{sub 2}O{sub 3} and κ-Al{sub 2}O{sub 3} increases, whereas the expected ratio is observed in α-Al{sub 2}O{sub 3}. The percentage of AlO{sub 4} units in the transition aluminas follows the same behaviour as the ratio of Al/O. - Graphical abstract: The percentage of AlO{sub 4} units in transition aluminas follows the same behaviour as the ratio of Al/O. - Highlights: • Calcination products of gibbsite studied by XRD, XPS and solid-state NMR. • The crystallite size of χ-Al{sub 2}O{sub 3} is as small as 10 nm. • The Al/O atomic ratio determined by XPS is larger than 2/3 in χ-Al{sub 2}O{sub 3} and κ-Al{sub 2}O{sub 3}. • The percentage of AlO{sub 4} in the aluminas follows the same behaviour as the Al/O atomic ratio.

  16. sup 3 sup 1 P high resolution solid state NMR studies of phosphoorganic compounds of biological interest

    Potrzebowski, M J; Kazmierski, S


    In this review several applications of sup 3 sup 1 P high resolution solid state NMR spectroscopy in structural studies of bioorganic samples is recorded. The problem of pseudopolymorphism of bis[6-O,6'-O-(1,2:3,4diisopropylidene-alpha-D-galactopyranosyl) phosphothionyl] disulfide (1) and application of sup 3 sup 1 P C/MAS experiment to investigate of this phenomenon is discussed. The influence of weak C-H--S intermolecular contacts on molecular packing of 1,6-anhydro-2-O-tosyl-4-S- (5,5-dimethyl-2-thioxa-1,3,2-dioxaphosphophorinan-2-= yl)-beta-D-glucopyranose (2) and S sub P , R sub P diastereomers of deoxyxylothymidyl-3'-O-acetylthymidyl (3',5')-O-(2-cyanoethyl) phosphorothioate (3) and their implication on sup 3 sup 1 P NMR spectra is shown. The final part of review describes the recent progress in structural studies of O-phosphorylated amino acids (serine, threonine, tyrosine), relationship between molecular structure and sup 3 sup 1 P chemical shift parameters delta sub i sub i and influence of hydrogen ...

  17. Determination of structural changes of dispersed clay platelets in a polymer blend during solid-state rheological property measurement by small-angle X-ray scattering

    Bandyopadhyay, J


    Full Text Available -1 Polymer Volume 52, Issue 12, 26 May 2011, Pages 2628?2642 Determination of structural changes of dispersed clay platelets in a polymer blend during solid-state rheological property measurement by small-angle X-ray scattering ? Jayita Bandyopadhyaya... frequency and temperature sweep tests. Graphical abstract Keywords ? Blend composites; ? Small-angle X-ray scattering; ? Solid-state rheology ...

  18. Structural, optical and magnetic properties of Sn doped ZnS nano powders prepared by solid state reaction

    Kumar, K. Chaitanya; Rao, N. Madhusudhana; Kaleemulla, S.; Rao, G. Venugopal


    Tin doped ZnS powders (Zn1-xSnxS, x = 0.00, 0.02, 0.05&0.08) were synthesized by a simple Solid state reaction and were characterized by Powder X-ray diffractometer (XRD), UV-Vis-NIR diffuse reflectance spectrophotometer, fluorescence spectrophotometer, scanning electron microscope (SEM) and vibrating sample magnetometer (VSM). The XRD studies revealed that no change in crystal structure was observed by the substitution of Sn into ZnS lattice. The crystallite size was calculated by Scherrer's formula and found that the crystallize size of Sn doped ZnS powders were in the range of 35-45 nm. From the diffused reflectance spectra, the band gap values of Zn1-xSnxS powders were estimated, and they were found to be in the range of 3.53-3.58 eV. The pure ZnS particles showed higher optical absorption in visible region than that of Sn doped ZnS nano particles. The Photoluminescence (PL) spectra of Zn1-xSnxS powders were recorded in the range of 400-700 nm with an excitation wavelength of 360 nm. The Zn1-xSnxS powders exhibited ferromagnetism at low temperature (100 K) and super paramagnetism at room temperature (300 K). The strength of magnetization increased with increase of Sn doping concentration from 0.015 emu/g to 0.18 emu/g, when x increased from 0.00-0.05.

  19. Experimental study on solid state reduction of chromite with rising temperature

    Kekkonen, M.; Syynimaa, A.; Holappa, L.


    The solid state reduction of preoxidized sintered chromite pellets, raw pellets, process pellets and lumpy ores have been studied with rising temperature 700-1520 deg C under CO-atmosphere in order to better simulate the conditions in the upper part of a real submerged arc furnace. According to the reduction degree curves the reduction behaviour of chromite pellets seems to be similar. The reduction rate was slow at the beginning but increased rapidly when the temperature reached about 1000 deg C. The final reduction degree was highest in the case of process pellets and lowest in the case of raw pellet. In the case of preoxidized pellets there was not much difference of the reduction rate and final reduction degree between different oxidation states. In the case of lumpy ores the reduction rate and the final reduction degree was much lower compared to the pellets. Optical photographs, phase and microanalysis show that the reduction has proceeded further in the surface of the samples and confirmed also that the reduction degree remained lower in the case of raw pellet and lumpy ores which was also seen from the reduction degree curves. According to the experiments in the case of preoxidized pellets the effect of oxidation state on the reduction rate was not observed due to small difference in the oxidation state of the samples. But when comparing the reduction of preoxidized pellets and unoxidised raw pellet we can say that preoxidation promotes the reduction. The final reduction degree of the raw pellet remained lower than in the case of preoxidized pellets. (orig.)

  20. Dynamic Nuclear Polarization (DNP) solid-state NMR spectroscopy, a new approach to study humic material?

    Knicker, Heike; Lange, Sascha; van Rossum, Barth; Oschkinat, Hartmut


    Compared to solution NMR spectroscopy, solid-state NMR spectra suffer from broad resonance lines and low resolution. This could be overcome by the use of 2-dimenstional solid-state NMR pulse sequences. Until recently, this approach has been unfeasible as a routine tool in soil chemistry, mainly because of the low NMR sensitivity of the respective samples. A possibility to circumvent those sensitivity problems represents high-field Dynamic Nuclear Polarization (DNP) solid-state NMR spectroscopy (Barnes et al., 2008), allowing considerable signal enhancements (Akbey et al., 2010). This is achieved by a microwave-driven transfer of polarization from a paramagnetic center to nuclear spins. Application of DNP to MAS spectra of biological systems (frozen solutions) showed enhancements of the factor 40 to 50 (Hall et al., 1997). Enhancements of this magnitude, thus may enable the use of at least some of the 2D solid-state NMR techniques that are presently already applied for pure proteins but are difficult to apply to soil peptides in their complex matrix. After adjusting the required acquisition parameters to the system "soil organic matter", lower but still promising enhancement factors were achieved. Additional optimization was performed and allowed the acquisition of 2D 13C and 15N solid-state NMR spectra of humified 13C and 15N enriched plant residues. Within the present contribution, the first solid-state DNP NMR spectra of humic material are presented. Those data demonstrate the great potential of this approach which certainly opens new doors for a better understanding of biochemical processes in soils, sediments and water. Akbey, Ü., Franks, W.T., Linden, A., Lange, S., Griffin, R.G., van Rossum, B.-J., Oschkinat, H., 2010. Dynamic nuclear polarization of deuterated proteins. Angewandte Chemie International Edition 49, 7803-7806. Barnes, A.B., De Paëpe, G., van der Wel, P.C.A., Hu, K.N., Joo, C.G., Bajaj, V.S., Mak-Jurkauskas, M.L., Sirigiri, J.R., Herzfeld, J

  1. The Effect of a Small Amount of Water on the Structure and Electrochemical Properties of Solid-State Synthesized Polyaniline

    Shao, Weiwei; Jamal, Ruxangul; Xu, Feng; Ubul, Aminam; Abdiryim, Tursun


    A series of polyaniline (PANI) salts were synthesized with the presence of a small amount of water varying from 0 to 1 mL at the beginning of solid-state polymerization. The structure and morphology of the samples were characterized by fourier transform infrared (FTIR) spectra, ultraviolet-visible (UV-Vis) absorption spectra, X-ray diffraction (XRD) and transmission electron microscopy (TEM). The electrochemical performances of the products were investigated by galvanostatic charge-discharge, cyclic voltammetry, cycling stability and electrochemical impedance spectroscopy (EIS). The results showed that the amounts of water can affect the oxidation degree, conjugate level and crystallinity of PANI salts. All PANI salts showed spherical morphology with the diameter of about 60 nm as shown by TEM. The electrochemical tests showed the highest specific capacitance value 593.3 F.g−1 in 1 M H2SO4 for PANI prepared with the addition of 0.5 mL of water at the beginning of solid-state polymerization.

  2. FT-Raman and FTIR spectra of photoactive aminobenzazole derivatives in the solid state: A combined experimental and theoretical study

    Alves, Rodrigo Martins [Universidade Federal do Pampa, Campus Bagé, Grupo de Pesquisa em Espectroscopia de Materiais Fotônicos, 96400-970 Bagé, RS (Brazil); Rodembusch, Fabiano Severo [Universidade Federal do Rio Grande do Sul, Grupo de Pesquisa em Fotoquímica Orgânica Aplicada, Av. Bento Gonçalves 9500, CEP 91501-970 Porto Alegre, RS (Brazil); Habis, Charles [Northern Virginia Community College, Manassas, VA (United States); Moreira, Eduardo Ceretta, E-mail: [Universidade Federal do Pampa, Campus Bagé, Grupo de Pesquisa em Espectroscopia de Materiais Fotônicos, 96400-970 Bagé, RS (Brazil)


    This study reports the experimental investigation of two photoactive aminobenzazole derivatives in the solid state by FT-Raman and Infrared Spectroscopies (FTIR) and its comparison with theoretical models. The optimized molecular structure, vibrational frequencies, and corresponding vibrational assignments of these compounds have been investigated experimentally and theoretically using Spanish Initiative for Electronic Simulations with Thousands of Atoms (SIESTA) and Gaussian03 Software Package. The FT-Raman and FTIR spectra were acquired with high resolution and emission frequencies identified by simulating the vibrational modes. The most intense peak observed in the FT-Raman spectra is the in-plane deformation vibrational of O–H bond that could be related to the vibrational region responsible for the stabilization of the enol conformer in the ground state which undergoes ESIPT to form a keto tautomer in the excited state. Additionally, the position of the amino group played an important role on the vibrational characteristics of the studied compounds. Also, the simulations proved to be a good approach in undertaking the FTIR and FT-Raman experiments. The use of graphic correlations helps us to determine the method and basis that best fit the experimental results. - Highlights: • Structural and vibrational properties of two aminobenzazoles were reported. • Comparison between experimental techniques and theoretical models. • The position of the amino group played an important role on the vibrational characteristics of the studied compounds.

  3. Photoluminescence study of Tb3+ doped CaCO3 synthesized by solid state metathesis

    Muke, A. M.; Ugemuge, N. S.; Moharil, S. V.


    Conventional solid-state reaction or simple solution precipitation techniques suffer from several limitations, i.e. a high processing temperature, relatively high preparation cost and more time of preparation, highly complicated synthesis, in-stoichiometric compositions and poor crystallinity. Preparation of inorganic phosphors by microwave assisted Solid state metathesis is one of the superior methods of synthesis. Time duration required for synthesis by microwave assisted synthesis is relatively low. The required reaction temperature can be attempted using domestic microwave oven with consumption of relatively low energy. CaCO3 is one of the most abundant biological minerals in nature and has found many important applications in industry, such as pigments, paper makings, plastics, rubbers, and so on.

  4. Solid-state 13C NMR and molecular modeling studies of acetyl aleuritolic acid obtained from Croton cajucara Benth

    da Silva San Gil, Rosane Aguiar; Albuquerque, Magaly Girão; de Alencastro, Ricardo Bicca; da Cunha Pinto, Angelo; do Espírito Santo Gomes, Fabiano; de Castro Dantas, Tereza Neuma; Maciel, Maria Aparecida Medeiros


    Solid-state 13C nuclear magnetic resonance ( 13C NMR) with magic-angle spinning (MAS) and with cross-polarization and magic-angle spinning (CP/MAS) spectra, and differential scanning calorimetry (DSC) techniques were used to obtain structural data from a sample of acetyl aleuritolic acid (AAA) extracted from the stem bark of Croton cajucara Benth. (Euphorbiaceae) and recrystallized from acetone. Since solid-state 13C NMR results suggested the presence of more than one molecule in the unitary cell for the AAA, DSC analysis and molecular modeling calculations were used to access this possibility. The absence of phase transition peaks in the DSC spectra and the dimeric models of AAA simulated using the semi-empirical PM3 method are in agreement with that proposal.

  5. Solid-state (17)O NMR study of 2-acylbenzoic acids and warfarin.

    Kong, Xianqi; Dai, Yizhe; Wu, Gang

    We report synthesis and solid-state (17)O NMR characterization of four site-specifically (17)O-labeled 2-acylbenzoic acids (2-RC(O)C6H4COOH) where R=H and CH3): 2-[3-(17)O]formylbenzoic acid, 2-[1,2-(17)O2]formylbenzoic acid, 2-[3-(17)O]acetylbenzoic acid, and 2-[1,2,3-(17)O3]acetylbenzoic acid. In the solid state, both 2-formyl- and 2-acetyl-benzoic acids exist as the cyclic phthalide form each containing a five-membered lactone ring and a cyclic hemiacetal/hemiketal group. Static and magic-angle-spinning (17)O NMR spectra were recorded at 14.1 and 21.1T for these compounds, from which the (17)O chemical shift and nuclear quadrupolar coupling tensors were determined for each oxygen site. These results represent the first time that (17)O NMR tensors are fully characterized for lactone, cyclic hemiacetal, and cyclic hemiketal functional groups. We also report solid-state (17)O NMR data for the cyclic hemiketal group an anticoagulant drug, warfarin. Experimental (17)O NMR tensors in these compounds were compared with computational results obtained with a periodic DFT code BAND. Copyright © 2016 Elsevier Inc. All rights reserved.

  6. Solid state physics

    Grosso, Giuseppe


    Solid State Physics is a textbook for students of physics, material science, chemistry, and engineering. It is the state-of-the-art presentation of the theoretical foundations and application of the quantum structure of matter and materials. This second edition provides timely coverage of the most important scientific breakthroughs of the last decade (especially in low-dimensional systems and quantum transport). It helps build readers' understanding of the newest advances in condensed matter physics with rigorous yet clear mathematics. Examples are an integral part of the text, carefully de

  7. 2D 31P solid state NMR spectroscopy, electronic structure and thermochemistry of PbP7

    Benndorf, Christopher; Hohmann, Andrea; Schmidt, Peer; Eckert, Hellmut; Johrendt, Dirk; Schäfer, Konrad; Pöttgen, Rainer


    Phase pure polycrystalline PbP7 was prepared from the elements via a lead flux. Crystalline pieces with edge-lengths up to 1 mm were obtained. The assignment of the previously published 31P solid state NMR spectrum to the seven distinct crystallographic sites was accomplished by radio-frequency driven dipolar recoupling (RFDR) experiments. As commonly found in other solid polyphosphides there is no obvious correlation between the 31P chemical shift and structural parameters. PbP7 decomposes incongruently under release of phosphorus forming liquid lead as remainder. The thermal decomposition starts at T>550 K with a vapor pressure almost similar to that of red phosphorus. Electronic structure calculations reveal PbP7 as a semiconductor according to the Zintl description and clearly shows the stereo-active Pb-6s2 lone pairs in the electron localization function ELF.

  8. Lanthanide(III) complexes of 4,10-bis(phosphonomethyl)-1,4,7,10-tetraazacyclododecane-1,7-diacetic acid (trans-H6do2a2p) in solution and in the solid state: structural studies along the series.

    Campello, M Paula C; Lacerda, Sara; Santos, Isabel C; Pereira, Giovannia A; Geraldes, Carlos F G C; Kotek, Jan; Hermann, Petr; Vanek, Jakub; Lubal, Premysl; Kubícek, Vojtech; Tóth, Eva; Santos, Isabel


    Complexes of 4,10-bis(phosphonomethyl)-1,4,7,10-tetraazacyclododecane-1,7-diacetic acid (trans-H(6)do2a2p, H(6)L) with transition metal and lanthanide(III) ions were investigated. The stability constant values of the divalent and trivalent metal-ion complexes are between the corresponding values of H(4)dota and H(8)dotp complexes, as a consequence of the ligand basicity. The solid-state structures of the ligand and of nine lanthanide(III) complexes were determined by X-ray diffraction. All the complexes are present as twisted-square-antiprismatic isomers and their structures can be divided into two series. The first one involves nona-coordinated complexes of the large lanthanide(III) ions (Ce, Nd, Sm) with a coordinated water molecule. In the series of Sm, Eu, Tb, Dy, Er, Yb, the complexes are octa-coordinated only by the ligand donor atoms and their coordination cages are more irregular. The formation kinetics and the acid-assisted dissociation of several Ln(III)-H(6)L complexes were investigated at different temperatures and compared with analogous data for complexes of other dota-like ligands. The [Ce(L)(H(2)O)](3-) complex is the most kinetically inert among complexes of the investigated lanthanide(III) ions (Ce, Eu, Gd, Yb). Among mixed phosphonate-acetate dota analogues, kinetic inertness of the cerium(III) complexes is increased with a higher number of phosphonate arms in the ligand, whereas the opposite is true for europium(III) complexes. According to the (1)H NMR spectroscopic pseudo-contact shifts for the Ce-Eu and Tb-Yb series, the solution structures of the complexes reflect the structures of the [Ce(HL)(H(2)O)](2-) and [Yb(HL)](2-) anions, respectively, found in the solid state. However, these solution NMR spectroscopic studies showed that there is no unambiguous relation between (31)P/(1)H lanthanide-induced shift (LIS) values and coordination of water in the complexes; the values rather express a relative position of the central ions between the N(4

  9. A Study of Position-Sensitive Solid-State Photomultiplier Signal Properties.

    Schmall, Jeffrey P; Du, Junwei; Judenhofer, Martin S; Dokhale, Purushottam; Christian, James; McClish, Mickel; Shah, Kanai S; Cherry, Simon R


    We present an analysis of the signal properties of a position-sensitive solid-state photomultiplier (PS-SSPM) that has an integrated resistive network for position sensing. Attractive features of PS-SSPMs are their large area and ability to resolve small scintillator crystals. However, the large area leads to a high detector capacitance, and in order to achieve high spatial resolution a large network resistor value is required. These inevitably create a low-pass filter that drastically slows what would be a fast micro-cell discharge pulse. Significant changes in the signal shape of the PS-SSPM cathode output as a function of position are observed, which result in a position-dependent time delay when using traditional time pick-off methods such as leading edge discrimination and constant fraction discrimination. The timing resolution and time delay, as a function of position, were characterized for two different PS-SSPM designs, a continuous 10 mm × 10 mm PS-SSPM and a tiled 2 × 2 array of 5 mm × 5 mm PS-SSPMs. After time delay correction, the block timing resolution, measured with a 6 × 6 array of 1.3 × 1.3 × 20 mm(3) LSO crystals, was 8.6 ns and 8.5 ns, with the 10 mm PS-SSPM and 5 mm PS-SSPM respectively. The effect of crystal size on timing resolution was also studied, and contrary to expectation, a small improvement was measured when reducing the crystal size from 1.3 mm to 0.5 mm. Digital timing methods were studied and showed great promise for allowing accurate timing by implementation of a leading edge time pick-off. Position-dependent changes in signal shape on the anode side also are present, which complicates peak height data acquisition methods used for positioning. We studied the effect of trigger position on signal amplitude, flood histogram quality, and depth-of-interaction resolution in a dual-ended readout detector configuration. We conclude that detector timing and positioning can be significantly improved by implementation of digital timing

  10. Density functional theory in the solid state.

    Hasnip, Philip J; Refson, Keith; Probert, Matt I J; Yates, Jonathan R; Clark, Stewart J; Pickard, Chris J


    Density functional theory (DFT) has been used in many fields of the physical sciences, but none so successfully as in the solid state. From its origins in condensed matter physics, it has expanded into materials science, high-pressure physics and mineralogy, solid-state chemistry and more, powering entire computational subdisciplines. Modern DFT simulation codes can calculate a vast range of structural, chemical, optical, spectroscopic, elastic, vibrational and thermodynamic phenomena. The ability to predict structure-property relationships has revolutionized experimental fields, such as vibrational and solid-state NMR spectroscopy, where it is the primary method to analyse and interpret experimental spectra. In semiconductor physics, great progress has been made in the electronic structure of bulk and defect states despite the severe challenges presented by the description of excited states. Studies are no longer restricted to known crystallographic structures. DFT is increasingly used as an exploratory tool for materials discovery and computational experiments, culminating in ex nihilo crystal structure prediction, which addresses the long-standing difficult problem of how to predict crystal structure polymorphs from nothing but a specified chemical composition. We present an overview of the capabilities of solid-state DFT simulations in all of these topics, illustrated with recent examples using the CASTEP computer program.

  11. Solid-state structure and solution conformation of the nootropic agent N[2-( N,N-Diisopropylamino)ethyl]-2-oxo-1-pyrrolidinacetamide sulphate. X-ray and homonuclear two-dimensional 1H NMR studies

    Bandoli, Giuliano; Nicolini, Marino; Pappalardo, Giuseppe C.; Grassi, Antonio; Perly, Bruno


    The crystal and molecular structure of the nootropic agent N-[2-( N,N-diisopropyl-amino)ethyl]-2-oxo-1-pyrrolidinacetamide sulphate was determined by X-ray analysis. The conformational properties in the solution state were deduced from the 1H-NMR spectrum run in 2H 2O at 500 MHz. Spectral assignments were made with the aid of the COSY 45 shift correlation experiment. Crystals were triclinic with unit cell dimensions a = 13.410(10), b = 11.382(8), c = 6.697(4) », α = 83.80(3), β = 88.61(3)and γ = 72.25(6)° ; space group Poverline1. The structure was determined from 1047 three-dimensional counter data and refined to a value of 7.5% for the conventional discrepancy factor R. One molecule of the solvent acetonitrile is incorporated per two of the (C 14H 28N 3O 2) +-(HSO 4) -. The five-membered heterocyclic ring is in an envelope ( Cs) conformation and the "flap" atom deviates by 0.31 » from the plane of the other four. This plane forms a dihedral angle of 71.4° with the amide group, with the CO fragment directed toward the ring. All bond angles and distances are in good agreement with expected standard values. A strong OH⋯O intermolecular bond (2.61 ») links the cation of the hydrogen-sulphate anion, while the loosely held MeCN molecule is trapped in the polar pockets. The molecular conformation in the solid was compared with results from 1H NMR spectral analysis which showed that in solution wide torsional oscillations can occur about the bonds of the chain bonded to the N(1) atom.

  12. Applications of solid-state Nuclear Magnetic Resonance (NMR) in studies of Portland cements-based materials

    Skibsted, Jørgen; Andersen, Morten Daugaard; Jakobsen, Hans Jørgen


    Solid-state NMR spectroscopy represents an important research tool in the characterization of a range of structural properties for cement-based materials. Different approaches of the technique can be used to obtain information on hydration kinetics, mobile and bound water, porosity, and local...... atomic structures. After a short introduction to these NMR techniques, it is exemplified how magic-angle spinning (MAS) NMR can provide quantitative and structural information about specific phases in anhydrous and hydrated Portland cements with main emphasis on the incorporation of Al3+ ions...

  13. Structural and electronic properties of solid-state (LiMPO4∣γ-Li3PO4)[010] electrochemical interface (M = Fe and Co)

    Chandrasekaran, S. Selva; Murugan, P.


    First principles density functional calculations are carried out to investigate the structural, electronic, and electrochemical properties of the bilayered nanocomposite, which is composed of LiMPO4 (M = Fe and Co) as a positive electrode and γ-Li3PO4 as a solid-state electrolyte. The calculated interfacial energy reveals that the Li-O atomic layer terminated (010) LiMPO4 surface gives better stability than its Fe-O layer termination, for constructing the solid state interface with γ-Li3PO4. Further, structural optimization shows that inter-layer distances at the interface and surface of the electrolyte are increased ≈0.1 and 0.06 Å, respectively, from its bulk value. Moreover, electronic structure calculations infer that the energy of top most occupied level in the electrode strongly depends on its thickness, whereas, this energy is almost constant for different thick electrolytes. Thus, our study suggests that by varying the thickness of LiMPO4-electrode, Li-ion vacancy formation and electrochemical performance of the nanocomposite can be altered favourably.

  14. Structural Role of Alkali Cations in Calcium Aluminosilicate Glasses as Examined Using Oxygen-17 Solid-State Nuclear Magnetic Resonance Spectroscopy

    Sukenaga, Sohei; Kanehashi, Koji; Shibata, Hiroyuki; Saito, Noritaka; Nakashima, Kunihiko


    The structural roles of alkali and calcium cations are important for understanding the physical and chemical properties of aluminosilicate melts and glasses. Recently, oxygen-17 nuclear magnetic resonance (17O NMR) studies of calcium-sodium aluminosilicate glasses showed that these structural roles are not randomly given, but rather each cation has its own preferential role. However, the relationship between cation type and role preference in calcium aluminosilicate glass is not completely understood. In the present study, the structural roles of lithium, sodium, and potassium cations in selected calcium aluminosilicate glasses are investigated using 17O solid-state NMR experiments. Data from these experiments clearly show that potassium cations have a notably stronger tendency to act as charge compensators within the network structure, compared to sodium and lithium cations. The result of 17O NMR experiment also showed that sodium and lithium cations in part act as network modifier alongside with calcium cations.

  15. Hexameric Capsules Studied by Magic Angle Spinning Solid-State NMR Spectroscopy: Identifying Solvent Molecules in Pyrogallol[4]arene Capsules.

    Avram, Liat; Goldbourt, Amir; Cohen, Yoram


    Powders of pyrogallol[4]arene hexamers were produced by evaporation from organic solvents and were studied, for the first time, by magic angle spinning solid-state NMR (MAS ssNMR). Evaporation selectively removed non-encapsulated solvent molecules leaving stable hexameric capsules encapsulating solvent molecules. After exposure of the powder to solvent vapors, (1)H/(13)C heteronuclear correlation MAS ssNMR experiments were used to assign the signals of the external and encapsulated solvent molecules. The formed capsules were stable for months and the process of solvent encapsulation was reversible. According to the ssNMR experiments, the encapsulated solvent molecules occupy different sites and those sites differ in their mobility. The presented approach paves the way for studying guest exchange, guest affinity, and gas storage in hexamers of this type in the solid state.

  16. Study of Mg-based materials to be used in a functional solid state hydrogen reservoir for vehicular applications

    Maddalena, Amedeo; Petris, Milo; Palade, Petru; Sartori, Sabrina; Principi, Giovanni [Settore Materiali and CNISM, Dipartimento di Ingegneria Meccanica, Universita di Padova, via Marzolo 9, 35131 Padova (Italy); Settimo, Eliseo [Celco-Profil, via dell' Artigianato 4, 30030 Vigonovo (Venezia) (Italy); Molinas, Bernardo [Venezia Tecnologie, via delle Industrie 39, 30175 Marghera (Venezia) (Italy); Lo Russo, Sergio [Dipartimento di Fisica and CNISM, Universita di Padova, via Marzolo 8, 35131 Padova (Italy)


    Powders mixtures of nanosized MgH{sub 2} and suitable additives, obtained by high energy milling, have been studied as materials to be used in a functional solid state hydrogen reservoir. A prototype of a two stages reservoir is under development (patent pending). The hydrogen release from the main stage, with high capacity Mg-based hydrides, is primed by a primer stage containing commercial hydrides able to operate at room temperature. (author)

  17. Study of corrosion in steel sculptures by means of solid state voltammetry at paraffin-impregnated graphite electrodes

    DOMENECH CARBO, ANTONIO; Roig Salom, José Luís; Domenech Carbo, Mª Teresa


    Solid-state voltammetry is used for studying the composition of corrosion products in a series of sculptures from the Contemporary Sculpture Collection of the Universidad Politècnica de Valencia (Spain). Upon attachment to paraffin-impregnated graphite electrodes, well-defined voltammetric responses were obtained upon immersion in 0.10 M HCl. A hematite with a variable degree of hydration and crystallinity, accompanied by FeO(OH) forms, is identified as the main corrosion product. La volta...

  18. One-pot preparation of new copolymer electrolytes with tunable network structure for all-solid-state lithium battery

    Chen, Bo; Xu, Qiang; Huang, Zhen; Zhao, Yanran; Chen, Shaojie; Xu, Xiaoxiong


    A new class of copolymer electrolytes with tunable network structure is successfully designed and prepared via a facile one-pot reaction. The trimethylolpropane triglycidyl ether (TMPEG) is cross-linked with poly (ethylene glycol) diamine (NPEG) to create well-defined solid network polymer electrolyte (SNPE). The network structure could be tuned by changing the molar ratio of TMPEG and NPEG or the molecular weight of NPEG. The effects of molecular weight of NPEG and molar ratio of EO/Li+ on the ionic conductivity are systematically investigated. The optimal electrolyte TMPEG-NPEG4K[2:1]-16:1 presents a maximum conductivity of 1.10 × 10-4 S cm-1 under 30 °C, and an 18-fold ionic conductivity enhancement in that of PEO-based electrolyte. Furthermore, it also exhibits wide electrochemical window (0-5.4 V), excellent compatibility with metallic Li, and superior mechanical properties. The all-solid-state lithium batteries LiFePO4/Li are assembled with TMPEG-NPEG4K[2:1]-16:1 electrolyte, and present good cycling and rate performance under 60 °C. The initial discharge specific capacities of the batteries are 161.7 mAh g-1 at 0.2 C and 132.7 mAh g-1 at 1 C, and the capacity retention ratio can be retained at 90.6% and 90.5% after 100 cycles. This new copolymer electrolyte may become a promising candidate for applications in all-solid-state lithium battery.

  19. Two new two-dimensional coordination polymers based on isophthalate and a flexible N-donor ligand containing benzimidazole and pyridine rings: synthesis, crystal structures and a solid-state UV-Vis study.

    Hasi, Qi Meige; Fan, Yan; Hou, Chen; Yao, Xiao Qiang; Liu, Jia Cheng


    In coordination chemistry and crystal engineering, many factors influence the construction of coordination polymers and the final frameworks depend greatly on the organic ligands used. N-Donor ligands with diverse coordination modes and conformations have been employed to assemble metal-organic frameworks. Carboxylic acid ligands can deprotonate completely or partially when bonding to metal ions and can also act as donors or acceptors of hydrogen bonds and are thus good candidates for the construction of supramolecular architectures. Two new transition metal complexes, namely poly[diaqua(μ4-1,4-bis{[1-(pyridin-3-ylmethyl)-1H-benz[d]imidazol-2-yl]methoxy}benzene)bis(μ2-isophthalato)dicobalt(II)], [Co(C8H4O4)(C34H28N6O2)0.5(H2O)]n, (1), and poly[diaqua(μ4-1,4-bis{[1-(pyridin-3-ylmethyl)-1H-benz[d]imidazol-2-yl]methoxy}benzene)bis(μ2-isophthalato)dicadmium(II)], [Cd(C8H4O4)(C34H28N6O2)0.5(H2O)]n, have been constructed using a symmetric N-donor ligand and a carboxylate ligand under hydrothermal conditions. X-ray crystallographic studies reveal that complexes (1) and (2) are isostructural, both of them exhibiting three-dimensional supramolecular architectures built by hydrogen bonds in which the coordinated water molecules serve as donors, while the O atoms of the carboxylate groups act as acceptors. Furthermore, (1) and (2) have been characterized by elemental, IR spectroscopic, powder X-ray diffraction (PXRD) and thermogravimetric analyses. The UV-Vis absorption spectrum of complex (1) has also been investigated.

  20. Atomic-Level Structure Characterization of Biomass Pre- and Post-Lignin Treatment by Dynamic Nuclear Polarization-Enhanced Solid-State NMR.

    Perras, Frédéric A; Luo, Hao; Zhang, Ximing; Mosier, Nathan S; Pruski, Marek; Abu-Omar, Mahdi M


    Lignocellulosic biomass is a promising sustainable feedstock for the production of biofuels, biomaterials, and biospecialty chemicals. However, efficient utilization of biomass has been limited by our poor understanding of its molecular structure. Here, we report a dynamic nuclear polarization (DNP)-enhanced solid-state (SS)NMR study of the molecular structure of biomass, both pre- and postcatalytic treatment. This technique enables the measurement of 2D homonuclear (13)C-(13)C correlation SSNMR spectra under natural abundance, yielding, for the first time, an atomic-level picture of the structure of raw and catalytically treated biomass samples. We foresee that further such experiments could be used to determine structure-function relationships and facilitate the development of more efficient, and chemically targeted, biomass-conversion technologies.

  1. Solid-State Lasers for Bathymetry and Communications. Studies of Four Rare-Earth Materials.


    The envelope was cerium -doped quartz, to reduce UV emission. The lamp was operated in simmer mode. The pulse forming network contained a 50-PF...class of solid state lasing materials called rare-earth fluorides . In these materials, the host lattice is LiYF4 (often called YLF), and the active...1971-1973 in which terbium-doped rare-earth fluorides were grown, and spectroscopy and lasing measurements conducted. A sample of Tb:LiGdF4 was lased

  2. Studies on the solid-state ion exchange of nickel ions into zeolites using DRS technique

    Zanjanchi, M. A.; Ebrahimian, A.


    The coordination of Ni 2+ ions in the dehydrated nickel-exchanged zeolites was investigated from the analysis of diffuse reflectance spectra. Solid-state ion exchange method was used to prepare nickel-containing mordenite, Y, L and mazzite zeolites. In the dehydrated mordenite and zeolite Y, nickel cations are presented in both forms of tetrahedral and distorted tetrahedral symmetries. The relative amount of tetrahedral and distorted tetrahedral nickel species are related to the heating temperature and heating time used for calcinations. In the dehydrated zeolite L and mazzite, Ni 2+ ions are mainly in the distorted octahedral symmetries.

  3. A solid state NMR study of layered double hydroxides intercalated with para-amino salicylate, a tuberculosis drug

    Jensen, Nicholai Daugaard; Bjerring, Morten; Nielsen, Ulla Gro


    Para-amino salicylate (PAS), a tubercolosis drug, was intercalated in three different layered double hydroxides (MgAl, ZnAl, and CaAl-LDH) and the samples were studied by multi-nuclear (1H, 13C, and 27Al) solid state NMR (SSNMR) spectroscopy in combination with powder X-ray diffraction (PXRD......), elemental analysis and IR-spectroscopy to gain insight into the bulk and atomic level structure of these LDHs especially with a view to the purity of the LDH-PAS materials and the concentration of impurities. The intercalations of PAS in MgAl-, ZnAl-, and CaAl-LDH's were confirmed by 13C SSNMR and PXRD...... showed that the M(II):Al ratio was higher than predicted from the bulk metal composition of MgAl-PAS and ZnAl-PAS. Moreover, the first high-resolution 1H SSNMR spectra of a CaAl LDH is reported and assigned using 1H single and double quantum experiments in combination with 27Al{1H} HETCOR....

  4. Materials space of solid-state electrolytes: unraveling chemical composition-structure-ionic conductivity relationships in garnet-type metal oxides using cheminformatics virtual screening approaches.

    Kireeva, Natalia; Pervov, Vladislav S


    The organic electrolytes of most current commercial rechargeable Li-ion batteries (LiBs) are flammable, toxic, and have limited electrochemical energy windows. All-solid-state battery technology promises improved safety, cycling performance, electrochemical stability, and possibility of device miniaturization and enables a number of breakthrough technologies towards the development of new high power and energy density microbatteries for electronics with low processing cost, solid oxide fuel cells, electrochromic devices, etc. Currently, rational materials design is attracting significant attention, which has resulted in a strong demand for methodologies that can accelerate the design of materials with tailored properties; cheminformatics can be considered as an efficient tool in this respect. This study was focused on several aspects: (i) identification of the parameters responsible for high Li-ion conductivity in garnet structured oxides; (ii) development of quantitative models to elucidate composition-structure-Li ionic conductivity relationships, taking into account the experimental details of sample preparation; (iii) circumscription of the materials space of solid garnet-type electrolytes, which is attractive for virtual screening. Several candidate compounds have been recommended for synthesis as potential solid state electrolyte materials.

  5. Spectroscopic studies of solid-state forms of donepezil free base and salt forms with various salicylic acids

    Brittain, Harry G.


    The polymorphic forms of donepezil free base have been studied using X-ray powder diffraction, Fourier transform infrared absorption spectroscopy, and differential scanning calorimetry. None of the free base crystal forms was observed to exhibit detectable fluorescence in the solid state under ambient conditions. Crystalline salt products were obtained by the reaction of donepezil with salicylic and methyl-substituted salicylic acids, with the salicylate and 4-methylsalicylate salts being obtained as non-solvated products, and the 3-methylsalicylate and 5-methylsalicylate salts being obtained as methanol solvated products. The intensity of solid-state fluorescence from donepezil salicylate and donepezil 4-methylsalicylate was found to be reduced relative to the fluorescence intensity of the corresponding free acids, while the solid-state fluorescence intensity of donepezil 3-methylsalicylate methanolate and donepezil 5-methylsalicylate methanolate was greatly increased relative to the fluorescence intensity of the corresponding free acids. Desolvation of the solvated salt products led to formation of glassy solids that exhibited strong green fluorescence.

  6. An optimization study of solid-state fermentation: xanthophylls extraction from marigold flowers.

    Luis, Navarrete-Bolaños José; Hugo, Jiménez-Islas; Enrique, Botello-Alvarez; Ramiro, Rico-Martínez; Octavio, Paredes-López


    Marigold flowers are the main natural source of xanthophylls, and marigold saponified extract is used as an additive in several food and pharmaceutical industries. In this work, the use of a solid-state fermentation (ensilage) process for increasing the yield of xanthophylls extracted from fermented marigold flowers was examined. The process consisted of a mixed culture of three microorganisms (Flavobacterium IIb, Acinetobacter anitratus, and Rhizopus nigricans), part of the normal microbiota associated with the marigold flower. These microorganisms had been previously isolated, and were identified as relevant for the ensilage process due to their capacity to produce cellulolytic enzymes. Based on experimental design strategies, optimum operation values were determined for aeration, moisture, agitation, and marigold-to-inoculum ratio in the proposed solid-state fermentation equipment, leading to a xanthophylls yield of 17.8-g/kg dry weight. The optimum achieved represents a 65% increase with respect to the control. HPLC analysis indicated conservation of extracted oleoresin. Based on the experimental results, interactions were identified that could be associated with the heat and mass-transfer reactions taking place within the bioreactor. The insight gained allows conditions that limit growth and metabolic activity to be avoided.

  7. Solid-state NMR paramagnetic relaxation enhancement immersion depth studies in phospholipid bilayers

    Chu, Shidong


    A new approach for determining the membrane immersion depth of a spin-labeled probe has been developed using paramagnetic relaxation enhancement (PRE) in solid-state NMR spectroscopy. A DOXYL spin label was placed at different sites of 1-palmitoyl-2-stearoyl-sn-glycero-3-phosphocholine (PSPC) phospholipid bilayers as paramagnetic moieties and the resulting enhancements of the longitudinal relaxation (T1) times of 31P nuclei on the surface of the bilayers were measured by a standard inversion recovery pulse sequence. The 31P NMR spin-lattice relaxation times decrease steadily as the DOXYL spin label moves closer to the surface as well as the concentration of the spin-labeled lipids increase. The enhanced relaxation vs. the position and concentration of spin-labels indicate that PRE induced by the DOXYL spin label are significant to determine longer distances over the whole range of the membrane depths. When these data were combined with estimated correlation times τc, the r-6-weighted, time-averaged distances between the spin-labels and the 31P nuclei on the membrane surface were estimated. The application of using this solid-state NMR PRE approach coupled with site-directed spin labeling (SDSL) may be a powerful method for measuring membrane protein immersion depth. © 2010 Elsevier Inc. All rights reserved.

  8. Monitoring the refinement of crystal structures with (15)N solid-state NMR shift tensor data.

    Kalakewich, Keyton; Iuliucci, Robbie; Mueller, Karl T; Eloranta, Harriet; Harper, James K


    The (15)N chemical shift tensor is shown to be extremely sensitive to lattice structure and a powerful metric for monitoring density functional theory refinements of crystal structures. These refinements include lattice effects and are applied here to five crystal structures. All structures improve based on a better agreement between experimental and calculated (15)N tensors, with an average improvement of 47.0 ppm. Structural improvement is further indicated by a decrease in forces on the atoms by 2-3 orders of magnitude and a greater similarity in atom positions to neutron diffraction structures. These refinements change bond lengths by more than the diffraction errors including adjustments to X-Y and X-H bonds (X, Y = C, N, and O) of 0.028 ± 0.002 Å and 0.144 ± 0.036 Å, respectively. The acquisition of (15)N tensors at natural abundance is challenging and this limitation is overcome by improved (1)H decoupling in the FIREMAT method. This decoupling dramatically narrows linewidths, improves signal-to-noise by up to 317%, and significantly improves the accuracy of measured tensors. A total of 39 tensors are measured with shifts distributed over a range of more than 400 ppm. Overall, experimental (15)N tensors are at least 5 times more sensitive to crystal structure than (13)C tensors due to nitrogen's greater polarizability and larger range of chemical shifts.

  9. Solid state physics for metallurgists

    Weiss, Richard J


    Metal Physics and Physical Metallurgy, Volume 6: Solid State Physics for Metallurgists provides an introduction to the basic understanding of the properties that make materials useful to mankind. This book discusses the electronic structure of matter, which is the domain of solid state physics.Organized into 12 chapters, this volume begins with an overview of the electronic structure of free atoms and the electronic structure of solids. This text then examines the basis of the Bloch theorem, which is the exact periodicity of the potential. Other chapters consider the fundamental assumption in

  10. Solid-state proton conductors

    Jewulski, J.R.; Osif, T.L.; Remick, R.J.


    The purpose of this program was to survey the field of solid-state proton conductors (SSPC), identify conductors that could be used to develop solid-state fuel cells suitable for use with coal derived fuel gases, and begin the experimental research required for the development of these fuel cells. This document covers the following topics: the history of developments and current status of the SSPC, including a review of proton conducting electrolyte structures, the current status of the medium temperature SSPC development, electrodes for moderate temperature (SSPC) fuel cell, basic material and measurement techniques applicable for SSPC development, modeling and optimization studies. Correlation and optimization studies, to include correlation studies on proton conduction and oxide cathode optimization for the SSPC fuel cell. Experiments with the SSPC fuel cells including the fabrication of the electrolyte disks, apparatus for conducting measurements, the strontium-cerium based electrolyte, the barium-cerium based electrolyte with solid foil electrodes, the barium-cerium based electrolyte with porous electrodes, and conduction mechanisms. 164 refs., 27 figs., 13 tabs.

  11. Solid-state proton conductors

    Jewulski, J. R.; Osif, T. L.; Remick, R. J.


    The purpose of this program was to survey the field of solid-state proton conductors (SSPC), identify conductors that could be used to develop solid-state fuel cells suitable for use with coal derived fuel gases, and begin the experimental research required for the development of these fuel cells. This document covers the following topics: the history of developments and current status of the SSPC, including a review of proton conducting electrolyte structures, the current status of the medium temperature SSPC development, electrodes for moderate temperature (SSPC) fuel cell, basic material and measurement techniques applicable for SSPC development, modeling, and optimization studies. Correlation and optimization studies are described which include correlation studies on proton conduction and oxide cathode optimization for the SSPC fuel cell. Experiments with the SSPC fuel cells are presented which include the fabrication of the electrolyte disks, apparatus for conducting measurements, the strontium-cerium based electrolyte, the barium-cerium based electrolyte with solid foil electrodes, the barium-cerium based electrolyte with porous electrodes, and conduction mechanisms.

  12. Solid state video cameras

    Cristol, Y


    Solid State Video Cameras reviews the state of the art in the field of solid-state television cameras as compiled from patent literature. Organized into 10 chapters, the book begins with the basic array types of solid-state imagers and appropriate read-out circuits and methods. Documents relating to improvement of picture quality, such as spurious signal suppression, uniformity correction, or resolution enhancement, are also cited. The last part considerssolid-state color cameras.

  13. III-Nitride Micro and Nano Structures for Solid State Lightning

    Ben Slimane, Ahmed


    Visible light emitting diodes (LEDs) are widely used in daily consumer electronics systems, such as general lighting, displays, communication, sensing, and also biomedical applications. To mitigate the ever increasing technology demand, there are tremendous on-going efforts in improving material properties and micro-fabrication techniques. In general, visible LEDs are environmentally friendly, robust and reliable light emitters with small device footprint, and are capable of delivering high luminous efficacy. Typically, LEDs rely on group-III-nitride materials to generate visible light. One of the techniques to generate white light is to coat blue LEDs with yellow phosphor, or ultraviolet (UV) LEDs with red-green-blue (RGB) phosphor. Other scheme relies on combination of RGB LEDs, where high brightness green and blue LEDs are generally grown on robust sapphire substrate. But the current challenges in high threading dislocation density of III-Nitride materials on sapphire or hetero-substrate, phosphor degradation, and bulk-LED mechanical design constraints imposed by the supporting substrate wafer motivate further scientific investigations into strain-engineering, novel reliable phosphor-semiconductor, color-tuning techniques, and transferrable III-nitride vertical LEDs. The current research presents a significant step towards the utilization of annealed porous GaN as a template for subsequent growth of fully relaxed GaN-based epitaxy materials. In our study, we observed significant compressive strain relaxation of 0.41 ± 0.04 GPa in annealed porous GaN fabricated using UV-assisted electroless etching. Moreover the use of GaN nanoparticles with large wavelength tunability and 10 µm InGaN microstructures with different indium composition ushers a new way of making reliable phosphor for white light generation. We also investigate the epitaxial lift-off of InGaN LED structures by selectively etching unintentionally doped GaN sacrificial buffer layer. High Ga

  14. A structural model for Alzheimer's β-amyloid fibrils based on experimental constraints from solid state NMR

    Petkova, Aneta T.; Ishii, Yoshitaka; Balbach, John J.; Antzutkin, Oleg N.; Leapman, Richard D.; Delaglio, Frank; Tycko, Robert


    We present a structural model for amyloid fibrils formed by the 40-residue β-amyloid peptide associated with Alzheimer's disease (Aβ1–40), based on a set of experimental constraints from solid state NMR spectroscopy. The model additionally incorporates the cross-β structural motif established by x-ray fiber diffraction and satisfies constraints on Aβ1–40 fibril dimensions and mass-per-length determined from electron microscopy. Approximately the first 10 residues of Aβ1–40 are structurally disordered in the fibrils. Residues 12–24 and 30–40 adopt β-strand conformations and form parallel β-sheets through intermolecular hydrogen bonding. Residues 25–29 contain a bend of the peptide backbone that brings the two β-sheets in contact through sidechain-sidechain interactions. A single cross-β unit is then a double-layered β-sheet structure with a hydrophobic core and one hydrophobic face. The only charged sidechains in the core are those of D23 and K28, which form salt bridges. Fibrils with minimum mass-per-length and diameter consist of two cross-β units with their hydrophobic faces juxtaposed. PMID:12481027

  15. Solid state physics

    Burns, Gerald


    Solid State Physics, International Edition covers the fundamentals and the advanced concepts of solid state physics. The book is comprised of 18 chapters that tackle a specific aspect of solid state physics. Chapters 1 to 3 discuss the symmetry aspects of crystalline solids, while Chapter 4 covers the application of X-rays in solid state science. Chapter 5 deals with the anisotropic character of crystals. Chapters 6 to 8 talk about the five common types of bonding in solids, while Chapters 9 and 10 cover the free electron theory and band theory. Chapters 11 and 12 discuss the effects of moveme

  16. Applications of the diffraction technique in solid state chemistry from "ab-initio" structure solution to final structure refinement: powder and single crystal

    Napolitano, Emilio


    Establishing the crystal structure in solid state chemistry is often a pre-requisite for understanding and predicting the function and technological properties of the matter. The single crystal and powder diffraction approaches play a fundamental role to achieve this goal. These two methods are non-destructive analytical techniques which provide detailed information about the internal lattice of crystalline substances, unit cell dimensions, bond-lengths, bond-angles, and details of site-or...

  17. Numerical Simulations of Pillar Structured Solid State Thermal Neutron Detector Efficiency and Gamma Discrimination

    Conway, A; Wang, T; Deo, N; Cheung, C; Nikolic, R


    This work reports numerical simulations of a novel three-dimensionally integrated, {sup 10}boron ({sup 10}B) and silicon p+, intrinsic, n+ (PIN) diode micropillar array for thermal neutron detection. The inter-digitated device structure has a high probability of interaction between the Si PIN pillars and the charged particles (alpha and {sup 7}Li) created from the neutron - {sup 10}B reaction. In this work, the effect of both the 3-D geometry (including pillar diameter, separation and height) and energy loss mechanisms are investigated via simulations to predict the neutron detection efficiency and gamma discrimination of this structure. The simulation results are demonstrated to compare well with the measurement results. This indicates that upon scaling the pillar height, a high efficiency thermal neutron detector is possible.

  18. Synthesis, solid-state structure, and bonding analysis of a homoleptic beryllium azide

    Naglav, Dominik; Tobey, Briac; Lyhs, Benjamin; Roemer, Beate; Blaeser, Dieter; Woelper, Christoph; Jansen, Georg; Schulz, Stephan [Faculty of Chemistry and Center for Nanointegration Duisburg-Essen (Cenide), Duisburg-Essen Univ., Essen (Germany)


    [Ph{sub 4}P]{sub 2}[Be(N{sub 3}){sub 4}] (1) and [PNP]{sub 2}[Be(N{sub 3}){sub 4}] (2; PNP=Ph{sub 3}PNPPh{sub 3}) were synthesized by reacting Be(N{sub 3}){sub 2} with [Ph{sub 4}P]N{sub 3} and [PNP]N{sub 3}. Compound 1 represents the first structurally characterized homoleptic beryllium azide. The electronic structure and bonding situation in the tetraazidoberyllate dianion [Be(N{sub 3}){sub 4}]{sup 2-} were investigated by quantum-chemical calculations (NPA, ELF, LOL). (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  19. Solid-state structure of a degradation product frequently observed on historic metal objects.

    Dinnebier, Robert E; Runčevski, Tomče; Fischer, Andrea; Eggert, Gerhard


    In the course of the investigation of glass-induced metal corrosion processes, a microcrystalline sodium copper formate hydroxide oxide hydrate, Cu4Na4O(HCOO)8(H2O)4(OH)2, was detected on a series of antique works of art, and its crystal structure was determined ab initio from high-resolution laboratory X-ray powder diffraction data using the method of charge flipping, simulated annealing, and difference-Fourier analysis (P42/n, a = 8.425 109(97) Å, c = 17.479 62(29) Å, V = 1240.747(35) Å(3), Z = 8). In the crystal structure, the metal cations are interconnected in a two-dimensional metal-organic framework via the oxygen atoms of the formate, hydroxide, and oxide anions. Doublets of face-sharing square pyramidal Cu(2+) polyhedra are linked via a single, central oxide oxygen atom to give a paddle-wheel arrangement, while the Na(+) cations are organized in Na2O11 moieties with highly disordered, edge-sharing octahedral coordination. In addition, hydrogen bonding plays an important role in stabilizing the crystal structure.

  20. Solid state magnetism

    Crangle, John


    Solid state magnetism is important and attempts to understand magnetic properties have led to an increasingly deep insight into the fundamental make up of solids. Both experimental and theoretical research into magnetism continue to be very active, yet there is still much ground to cover before there can be a full understanding. There is a strong interplay between the developments of materials science and of magnetism. Hundreds of new materials have been dis­ covered, often with previously unobserved and puzzling magnetic prop­ erties. A large and growing technology exists that is based on the magnetic properties of materials. Very many devices used in everyday life involve magnetism and new applications are being invented all the time. Under­ standing the fundamental background to the applications is vital to using and developing them. The aim of this book is to provide a simple, up-to-date introduction to the study of solid state magnetism, both intrinsic and technical. It is designed to meet the needs a...

  1. Solid state synthesis and structural refinement of polycrystalline LaCa1-TiO3 ceramic powder

    O P Shrivastava; Narendra Kumar; I B Sharma


    Perovskite structure based ceramic precursors have a characteristic property of substitution in the ``A" site of the ABO3 structure. This makes them a potential material for nuclear waste management in synthetic rock (SYNROC) technology. In order to simulate the mechanism of rare earth fixation in perovskite, La Ca1-TiO3 (where = 0.05) has been synthesized through ceramic route by taking calculated quantities of oxides of Ca, Ti and La as starting materials. Solid state synthesis has been carried out by repeated pelletizing and sintering the finely powdered oxide mixture in a muffle furnace at 1050°C. The ceramic phase has been characterized by its powder diffraction pattern. Step analysis data has been used to determine the structure of solid solution of lanthanum substituted calcium titanate. The SEM and EDAX analyses also confirm that the CaTiO3 can act as a host for lanthanum. X-ray data has been interpreted using CRYSFIRE and POWDERCELL softwares. The ℎ, , values for different lattice planes have been generated from the experimental data. The lanthanum substituted perovskite crystallizes in orthorhombic symmetry with space group (#62). Following unit cell parameters have been calculated: = 5.410, = 7.631, = 5.382. The calculated and observed values of corresponding intensities, 2, and density show good agreement. GSAS based calculation for bond distances Ti–O, Ca–O, La–O and bond angles Ti–O–Ca, Ca–O–Ca, La–O–Ti have been reported.

  2. Unlocking the molecular structure of fungal melanin using 13C biosynthetic labeling and solid-state NMR.

    Tian, Shiying; Garcia-Rivera, Javier; Yan, Bin; Casadevall, Arturo; Stark, Ruth E


    Melanins are enigmatic pigments found in all biological kingdoms that are associated with a variety of functions, including microbial virulence. Despite being ubiquitous in nature, melanin pigments have long resisted atomic-level structural examination because of their insolubility and amorphous organization. Cryptococcus neoformans is a human pathogenic fungus that melanizes only when provided with exogenous substrate, thus offering a unique system for exploring questions related to melanin structure at the molecular level. We have exploited the requirement for exogenous substrate in melanin synthesis as well as the capabilities of high-resolution solid-state nuclear magnetic resonance (NMR) to establish the predominantly aliphatic composition of l-dopa melanin and to introduce (13)C labels that permit the identification of proximal carbons in the developing biopolymer. By swelling solid melanin samples in organic solvents and using two-dimensional heteronuclear NMR in conjunction with magic-angle spinning, we have identified chemical bonding patterns typical of alkane, alkene, alcohol, ketone, ester, and indole functional groups. These findings demonstrate the feasibility of a novel approach to determining the structure of melanin using metabolic labeling and NMR spectroscopy.

  3. Monolayer graphene saturable absorber with sandwich structure for ultrafast solid-state laser

    Zhu, Hongtong; Zhao, Lina; Liu, Jie; Xu, Shicai; Cai, Wei; Jiang, Shouzhen; Zheng, Lihe; Su, Liangbi; Xu, Jun


    The uniform-quality, large-area, monolayer graphene saturable absorber (SA) with sandwich structure was fabricated, tested, and successfully applied for the generation of diode-pumped Yb:Y2SiO5 mode-locked laser. Without extra negative dispersion elements, the shortest pulse with duration of ˜883 fs was obtained at 1042.6 nm with an output power of ˜1 W. These promising experimental results suggested that the low-cost, high-quality graphene SA could potentially be employed in practical, high-power, ultrafast mode-locking laser systems.

  4. Synthesis, structures of four coordination compounds constructed from o-methacrylamidobenzoic acid and their relationship between structure and solid state luminescence

    Chen, Hong-Xia; Ma, Yong; Zhou, Feng; Wu, Bing [Key Laboratory of Organic Synthesis of Jiangsu Province, School of Chemistry, Chemical Engineering and Materials Science, Soochow University(DuShuHu Campus), 199 Renai Road, Suzhou, 215123 (China); Key Laboratory of Energy-Saving And Environmental Protection Materials Test and Technical Service Center of Jiangsu Province, Soochow University (DuShuHu Campus), 199 Renai Road, Suzhou, 215123 (China); Xu, Qing-Feng, E-mail: [Key Laboratory of Organic Synthesis of Jiangsu Province, School of Chemistry, Chemical Engineering and Materials Science, Soochow University(DuShuHu Campus), 199 Renai Road, Suzhou, 215123 (China); Key Laboratory of Energy-Saving And Environmental Protection Materials Test and Technical Service Center of Jiangsu Province, Soochow University (DuShuHu Campus), 199 Renai Road, Suzhou, 215123 (China); Lu, Jian-Mei, E-mail: [Key Laboratory of Organic Synthesis of Jiangsu Province, School of Chemistry, Chemical Engineering and Materials Science, Soochow University(DuShuHu Campus), 199 Renai Road, Suzhou, 215123 (China); Key Laboratory of Energy-Saving And Environmental Protection Materials Test and Technical Service Center of Jiangsu Province, Soochow University (DuShuHu Campus), 199 Renai Road, Suzhou, 215123 (China); Ge, Jian-Feng [Key Laboratory of Organic Synthesis of Jiangsu Province, School of Chemistry, Chemical Engineering and Materials Science, Soochow University(DuShuHu Campus), 199 Renai Road, Suzhou, 215123 (China); Key Laboratory of Energy-Saving And Environmental Protection Materials Test and Technical Service Center of Jiangsu Province, Soochow University (DuShuHu Campus), 199 Renai Road, Suzhou, 215123 (China)


    Four new coordination compounds, namely, Zn(o-MAABA){sub 2}(Phen) (1), [Cd(o-MAABA){sub 2}·2H{sub 2}O]{sub 2} (2), ([Pb{sub 2}Cl{sub 2}(o-MAABA){sub 2}(Phen){sub 4}])·2H{sub 2}O (3·2H{sub 2}O), [Pb(NO{sub 3})(o-MAABA)(Phen)]{sub n} (4), where o-MAABA=o-methacrylamidobenzoic acid and phen=1, 10-phenanthroline, have been synthesized. All compounds were fully confirmed by FT-IR, elemental analysis and TGA analysis. Their structures were determined by single crystal X-ray diffraction, in which compound 1 shows a mononuclear structure, compounds 2 and 3 have binuclear structures and compound 4 shows an infinite chain. In 2 and 4, the adjacent chains are extended into a 3D supramolecular architecture via π–π interactions. Solid-state room temperature luminescence spectra revealed that emission bands of compound 1 were located at 524 nm (λ{sub ex}=352 nm) and compound 4 at 479 and 584 nm (λ{sub ex}=390 nm) assigned to the excimer formation. The emission at 454 nm (λ{sub ex}=340 nm) of compound 2 was mainly ascribed to the Ligand–Metal Charge Transfer (LMCT). - Graphical abstract: Four coordination compounds constructed by o-methacrylamidobenzoic, phenanthroline and metal ions are reported. The photoluminescent properties is studied, which is affected by the molecular stacking and LMCT.

  5. X-ray diffraction study of laser-driven solid-state diffusional mixing and new phase formation in Ni-Pt multilayers

    Kelly, B. G.; Loether, A.; Unruh, K. M.; DeCamp, M. F.; DiChiara, A. D.


    An in situ optical pump and x-ray probe technique has been utilized to study photoinitiated solid-state diffusion in a Ni-Pt multilayer system. Hard x-ray diffraction has been used to follow the systematic growth of the NiPt alloy as a function of laser intensity and total energy deposited. It is observed that new phase growth can be driven in as little as one laser pulse, and that repeated photoexcitation can completely convert the entire multilayer structure into a single metallic alloy. The data suggest that lattice strain relaxation takes place prior to atomic diffusion and the formation of a NiPt alloy.

  6. Solid-state transformation of nanocrystalline phyllomanganate into tectomanganate: influence of initial layer and interlayer structure.

    Grangeon, Sylvain; Lanson, Bruno; Lanson, Martine


    In surficial environments, the fate of many elements is influenced by their interactions with the phyllomanganate vernadite, a nano-sized and turbostratic variety of birnessite. To advance our understanding of the surface reactivity of vernadite as a function of pH, synthetic vernadite (δ-MnO2) was equilibrated at pH ranging from 3 to 10 and characterized structurally using chemical methods, thermogravimetry and modelling of powder X-ray diffraction (XRD) patterns. With decreasing pH, the number of vacant layer sites increases in the octahedral layers of δ-MnO2 (from 0.14 per layer octahedron at pH 10 to 0.17 at pH 3), whereas the number of layer Mn(3+) is, within errors, equal to 0.12 per layer octahedron over the whole pH range. Vacant layer sites are capped by interlayer Mn(3+) sorbed as triple corner-sharing surface complexes (TC sites). The increasing number of interlayer Mn(3+) with decreasing pH (from 0.075 per layer octahedron at pH 10 to 0.175 at pH 3) results in the decrease of the average Mn oxidation degree (from 3.80 ± 0.01 at pH 10 to 3.70 ± 0.01 at pH 3) and in the lowering of the Na/Mn ratio (from 27.66 ± 0.20 at pH 10 to 6.99 ± 0.16 at pH 3). In addition, in-plane unit-cell parameters are negatively correlated to the number of interlayer Mn at TC sites and decrease with decreasing pH (from b = 2.842 Å at pH 10 to b = 2.834 Å at pH 3), layer symmetry being systematically hexagonal with a = b × 3(1/2). Finally, modelling of X-ray diffraction (XRD) patterns indicates that crystallite size in the ab plane and along the c* axis decreases with decreasing pH, ranging respectively from 7 nm to 6 nm, and from 1.2 nm to 1.0 nm (pH 10 and 3, respectively). Following their characterization, dry samples were sealed in polystyrene vials, kept in the dark, and re-analysed 4 and 8 years later. With ageing time and despite the dry state, layer Mn(3+) extensively migrates to the interlayer most likely to minimize steric strains

  7. Structural features of a bituminous coal and their changes during low-temperature oxidation and loss of volatiles investigated by advanced solid-state NMR spectroscopy

    Mao, J.-D.; Schimmelmann, A.; Mastalerz, Maria; Hatcher, P.G.; Li, Y.


    Quantitative and advanced 13C solid-state NMR techniques were employed to investigate (i) the chemical structure of a high volatile bituminous coal, as well as (ii) chemical structural changes of this coal after evacuation of adsorbed gases, (iii) during oxidative air exposure at room temperature, and (iv) after oxidative heating in air at 75 ??C. The solid-state NMR techniques employed in this study included quantitative direct polarization/magic angle spinning (DP/MAS) at a high spinning speed of 14 kHz, cross polarization/total sideband suppression (CP/TOSS), dipolar dephasing, CH, CH2, and CHn selection, 13C chemical shift anisotropy (CSA) filtering, two-dimensional (2D) 1H-13C heteronuclear correlation NMR (HETCOR), and 2D HETCOR with 1H spin diffusion. With spectral editing techniques, we identified methyl CCH 3, rigid and mobile methylene CCH2C, methine CCH, quaternary Cq, aromatic CH, aromatic carbons bonded to alkyls, small-sized condensed aromatic moieties, and aromatic C-O groups. With direct polarization combined with spectral-editing techniques, we quantified 11 different types of functional groups. 1H-13C 2D HETCOR NMR experiments indicated spatial proximity of aromatic and alkyl moieties in cross-linked structures. The proton spin diffusion experiments indicated that the magnetization was not equilibrated at a 1H spin diffusion time of 5 ms. Therefore, the heterogeneity in spatial distribution of different functional groups should be above 2 nm. Recoupled C-H long-range dipolar dephasing showed that the fraction of large charcoal-like clusters of polycondensed aromatic rings was relatively small. The exposure of this coal to atmospheric oxygen at room temperature for 6 months did not result in obvious chemical structural changes of the coal, whereas heating at 75 ??C in air for 10 days led to oxidation of coal and generated some COO groups. Evacuation removed most volatiles and caused a significant reduction in aliphatic signals in its DP

  8. Numerical study for selective excitation of Mathieu-Gauss modes in end-pumped solid-state laser systems.

    Chu, Shu-Chun; Tsai, Ko-Fan


    This study reports a possible first systematic approach to the selective excitations of all Mathieu-Gauss modes (MGMs) in end-pumped solid-state lasers with a new kind of axicon-based stable laser resonator. The study classifies MGMs into two categories, and explores and verifies the approach to excite each MGM category using numerical simulations. Controlling both the "cavity mode gain" and the "cavity conical asymmetry" of the axicon-based stable laser resonator achieves the proposed selective MGM-excitation approach.

  9. Detection of low-level PTFE contamination: An application of solid-state NMR to structure elucidation in the pharmaceutical industry.

    Pham, Tran N; Day, Caroline J; Edwards, Andrew J; Wood, Helen R; Lynch, Ian R; Watson, Simon A; Bretonnet, Anne-Sophie Z; Vogt, Frederick G


    We report a novel use of solid-state ¹⁹F nuclear magnetic resonance to detect and quantify polytetrafluoroethylene contamination from laboratory equipment, which due to low quantity (up to 1% w/w) and insolubility remained undetected by standard analytical techniques. Solid-state ¹⁹F NMR is shown to be highly sensitive to such fluoropolymers (detection limit 0.02% w/w), and is demonstrated as a useful analytical tool for structure elucidation of unknown solid materials.

  10. Lipid Dynamics Studied by Calculation of 31P Solid-State NMR Spectra Using Ensembles from Molecular Dynamics Simulations

    Hansen, Sara Krogh; Vestergaard, Mikkel; Thøgersen, Lea;


    We present a method to calculate 31P solid-state NMR spectra based on the dynamic input from extended molecular dynamics (MD) simulations. The dynamic information confered by MD simulations is much more comprehensive than the information provided by traditional NMR dynamics models based on......, for example, order parameters. Therefore, valuable insight into the dynamics of biomolecules may be achieved by the present method. We have applied this method to study the dynamics of lipid bilayers containing the antimicrobial peptide alamethicin, and we show that the calculated 31P spectra obtained...

  11. Some studies on a solid-state sulfur probe for coal gasification systems

    Jacob, K. T.; Rao, D. B.; Nelson, H. G.


    As a part of a program for the development of a sulfur probe for monitoring the sulfur potential in coal gasification reactors, an investigation was conducted regarding the efficiency of the solid electrolyte cell Ar+H2+H2S/CaS+CaF2+(Pt)//CaF2//Pt)+CaF2+CaS/H2S+H2+Ar. A demonstration is provided of the theory, design, and operation of a solid-state sulfur probe based on CaF2 electrolyte. It was found that the cell responds to changes in sulfur potential in a manner predicted by the Nernst equation. The response time of the cell at 1225 K, after a small change in temperature or gas composition, was 2.5 Hr, while at a lower temperature of 990 K the response time was approximately 9 hr. The cell emf was insensitive to a moderate increase in the flow rate of the test gas and/or the reference gas. The exact factors affecting the slow response time of galvanic cells based on a CaF2 electrolyte have not yet been determined. The rate-limiting steps may be either the kinetics of electrode reactions or the rate of transport through the electrolyte.

  12. Studies on a wideband, solid-state driven RF system for the CERN PS booster

    Paoluzzi, M M; Arnaudon, L; Chritin, N S; Mikulec, B; Hanke, K; Tardy, T


    In the framework of the LHC Injectors Upgrade project (LIU) the PS Booster (PSB) will undergo in depth consolidation and upgrade programs [1]. The aim is increasing the extraction energy to 2 GeV, exploiting the potential of Linac4 and allowing reliable operations during the next 25 years. For the RF system, substantial improvements could come from the replacement of the existing narrowband, tuned systems covering the h=1 and h=2 frequency ranges (0.6 ÷ 1.8 MHz and 1.2 ÷ 3.6 MHz respectively) with wideband (0.5 ÷ 4 MHz) Finemet® loaded cavities. The new system would be modular, allow multi-harmonic operation, use solid-state power stages and include fast RF feedback to compensate beam loading effects to some extent. A proof of principle system providing ≈3.0 kV accelerating voltage has been designed, constructed and installed in one of the PSB rings. This paper provides details on the design and measurements as well as information on the project status.

  13. The local physical structure of amorphous hydrogenated boron carbide: insights from magic angle spinning solid-state NMR spectroscopy.

    Paquette, Michelle M; Li, Wenjing; Sky Driver, M; Karki, Sudarshan; Caruso, A N; Oyler, Nathan A


    Magic angle spinning solid-state nuclear magnetic resonance spectroscopy techniques are applied to the elucidation of the local physical structure of an intermediate product in the plasma-enhanced chemical vapour deposition of thin-film amorphous hydrogenated boron carbide (B(x)C:H(y)) from an orthocarborane precursor. Experimental chemical shifts are compared with theoretical shift predictions from ab initio calculations of model molecular compounds to assign atomic chemical environments, while Lee-Goldburg cross-polarization and heteronuclear recoupling experiments are used to confirm atomic connectivities. A model for the B(x)C:H(y) intermediate is proposed wherein the solid is dominated by predominantly hydrogenated carborane icosahedra that are lightly cross-linked via nonhydrogenated intraicosahedral B atoms, either directly through B-B bonds or through extraicosahedral hydrocarbon chains. While there is no clear evidence for extraicosahedral B aside from boron oxides, ∼40% of the C is found to exist as extraicosahedral hydrocarbon species that are intimately bound within the icosahedral network rather than in segregated phases.

  14. Synthesis and Electronic Structures and Linear Optics of SolidState Compound SrB2O4

    CHENG, Wen-Dan; ZHENG, Fa-Kun; CHEN, Jim-Tong


    The chuster(SrB2O4)2 existubg in crystalline states is emplotedto model the electronic structure and linear optical propertiesof solid state compound State compound SrB2O4.This clmpound is synthesized by high temperature solution reaction,and it crystallizes inthe orthorhombic space group tbcn with cell dimenions a= 1.1995(3), b=0.4337(1), c=0.6575(1)nm, V=0.34202nm3,and Z=4, μ=15.14cm-1, Dcalcd=3.36g/cm3.Thedynamic refractive indices are obtained in terms of INDO/SCIfollowing combination with the Sum-Otates method.Awidth of the calculated gap is 4.424 eV between the valenceband and conduction band,and the calculated,average refractive index is 10980 at a wavelength of 1.065μm.The charge transfers from o2 amion orbitals to Sr2+ cation orbetals make the significant contributions to linear polarizability in terms ofanalyses of atomic state density contributing the valence and conduction bands.

  15. Combining (27)Al Solid-State NMR and First-Principles Simulations To Explore Crystal Structure in Disordered Aluminum Oxynitride.

    Tu, Bingtian; Liu, Xin; Wang, Hao; Wang, Weimin; Zhai, Pengcheng; Fu, Zhengyi


    The nuclear magnetic resonance (NMR) technique gives insight into the local information in a crystal structure, while Rietveld refinement of powder X-ray diffraction (PXRD) sketches out the framework of a crystal lattice. In this work, first-principles calculations were combined with the solid-state NMR technique and Rietveld refinement to explore the crystal structure of a disordered aluminum oxynitride (γ-alon). The theoretical NMR parameters (chemical shift, δiso, quadrupolar coupling constants, CQ, and asymmetry parameter, η) of Al22.5O28.5N3.5, predicted by the gauge-including projector augmented wave (GIPAW) algorithm, were used to facilitate the analytical investigation of the (27)Al magic-angle spinning (MAS) NMR spectra of the as-prepared sample, whose formula was confirmed to be Al2.811O3.565N0.435 by quantitative analysis. The experimental δiso, CQ, and η of (27)Al showed a small discrepancy compared with theoretical models. The ratio of aluminum located at the 8a to 16d sites was calculated to be 0.531 from the relative integration of peaks in the (27)Al NMR spectra. The occupancies of aluminum at the 8a and 16d positions were determined through NMR investigations to be 0.9755 and 0.9178, respectively, and were used in the Rietveld refinement to obtain the lattice parameter and anion parameter of Al2.811O3.565N0.435. The results from (27)Al NMR investigations and PXRD structural refinement complemented each other. This work provides a powerful and accessible strategy to precisely understand the crystal structure of novel oxynitride materials with multiple disorder.

  16. Structure of 1,5-benzodiazepinones in the solid state and in solution: Effect of the fluorination in the six-membered ring

    Marta Pérez-Torralba


    Full Text Available Two novel tetrafluorinated 1,5-benzodiazepinones were synthesized and their X-ray structures determined. 6,7,8,9-Tetrafluoro-4-methyl-1,3-dihydro-2H-1,5-benzodiazepin-2-one crystallizes in the monoclinic P21/c space group and 6,7,8,9-tetrafluoro-1,4-dimethyl-1,3-dihydro-2H-1,5-benzodiazepin-2-one in the triclinic P−1 space group. Density functional theory studies at the B3LYP/6-311++G(d,p level were carried out on these compounds and on four non-fluorinated derivatives, allowing to calculate geometries, tautomeric energies and ring-inversion barriers, that were compared with the experimental results obtained by static and dynamic NMR in solution and in solid state.

  17. Three novel photoisomeric compounds of the 4-acyl pyrazolone derivants: Crystal structures and substituent effects on photo-isomerism in solid state

    WANG JunHua; LIU Lang; LIU GuangFei; GUO JiXi; JIA DianZeng


    Three new photoisomeric compounds: 1,3-diphenyl-4-benzal-5-pyrazolone 4-methylthiosemicarbazone (DPBP-MTSC), 1,3-diphenyl-4-(4'-methylbenzal)-5-pyrazolone 4-methylthiosemicarbazone (DP4MBP-MTSC), and 1,3-diphenyl-4-(4'-bromobenzal)-5-pyrazolone 4-methylthiosemicarbazone (DP4BrBP-MTSC) were synthesized by direct condensation of pyrazolones and 4-methylthiosemicarbazone. Their struc-tures were confirmed using 1H NMR, IR, elemental analyses, and X-ray crystallographic analyses. The photoisomeric properties in the solid state were studied under UV light irradiation and the photo-isomerization phenomena were interpreted by the double proton-transfer mechanism. Moreover, the effects of different substituent groups at the 4-position of the benzal in the three compounds on the photoisomeric properties were discussed.

  18. Structural Basis for Asymmetric Conductance of the Influenza M2 Proton Channel Investigated by Solid-State NMR Spectroscopy.

    Mandala, Venkata S; Liao, Shu-Yu; Kwon, Byungsu; Hong, Mei


    The influenza M2 protein forms an acid-activated proton channel that is essential for virus replication. The transmembrane H37 selects for protons under low external pH while W41 ensures proton conduction only from the N terminus to the C terminus and prevents reverse current under low internal pH. Here, we address the molecular basis for this asymmetric conduction by investigating the structure and dynamics of a mutant channel, W41F, which permits reverse current under low internal pH. Solid-state NMR experiments show that W41F M2 retains the pH-dependent α-helical conformations and tetrameric structure of the wild-type (WT) channel but has significantly altered protonation and tautomeric equilibria at H37. At high pH, the H37 structure is shifted toward the π tautomer and less cationic tetrads, consistent with faster forward deprotonation to the C terminus. At low pH, the mutant channel contains more cationic tetrads than the WT channel, consistent with faster reverse protonation from the C terminus. (15)N NMR spectra allow the extraction of four H37 pKas and show that the pKas are more clustered in the mutant channel compared to WT M2. Moreover, binding of the antiviral drug, amantadine, at the N-terminal pore at low pH did not convert all histidines to the neutral state, as seen in WT M2, but left half of all histidines cationic, unambiguously demonstrating C-terminal protonation of H37 in the mutant. These results indicate that asymmetric conduction in WT M2 is due to W41 inhibition of C-terminal acid activation by H37. When Trp is replaced by Phe, protons can be transferred to H37 bidirectionally with distinct rate constants. Copyright © 2017 Elsevier Ltd. All rights reserved.

  19. Synthesis and solid state structures of Chalcogenide compounds of Imidazolin-2-ylidene-1,1-Diphenyl-phosphinamine

    Naktode Kishor; Suman Das; Abhinanda Kundu; Hari Pada Nayek; Tarun K Panda


    We report the synthesis and solid state structures of 1,3-di-aryl-imidazolin-2-ylidine-1,1-diphenylphosphinamine [(aryl=mesityl (1a) and aryl=2,6-diisopripyl (1b)] and their chalcogenide compounds 3-di-aryl-imidazolin-2-ylidine-P, P-diphenylphosphinicamide (2a,b), 1,3-di-aryl-imidazolin-2-ylidine-P,P diphenyl-phosphinothioicamide (3a,b) and 1,3-diaryl-imidazolin-2-ylidine-P,P -diphenyl-phosphinoselenoicamide (4a,b).The compounds 1a,b were prepared in good yield by the reaction of 1,3-di-aryl-imidazolin-2-imine and chlorodiphenylphosphine in the presence of triethylamine in toluene. The reactions of 1a,b with elemental sulphur and selenium afforded the corresponding chalcogenide compounds 3a,b and 4a,b respectively.The corresponding oxo- derivative (2a,b) was obtained by reacting compound 1a,b with 30% aqueous hydrogen peroxide in THF. The molecular structures of 1a, 2a, 3a and 4a,b have been established by single crystal X-ray diffraction analyses. The molecular structures reveal that even C1–N1–P1 angle (124.62o) in compound 1a is less obtuse compared to the corresponding C1–N1–Si1 angles (157.8o) observed in related N-silylated 2-iminoimidazolines and trimethylsilyl iminophosphoranes. C1–N1–P1 angles are further widened in compounds 2a, 3a, and 4a,b due to the attachment of chalcogen atoms onto phosphorus atom.

  20. Bioconversion of biomass: a case study of ligno-cellulosics bioconversions in solid state fermentation

    Ashok Pandey


    Full Text Available Lignocellulosic residues obtained from crops cultivation form useful sources to be used as substrate for bioconversion processes. Sugarcane bagasse, which is a complex substrate obtained from the processing of sugar cane, is an important biomass among such sources. Due to its abundant availability, it can serve as an ideal substrate for microbial processes for the production of value added products. This paper reviews recent developments on biological processes developed on production of various products in solid state fermentation using sugarcane bagasse as the substrate and describes production of protein enriched feed, enzymes, amino acid, organic acids and compounds of pharmaceutical importance, etc. through microbial means.Resíduos celulósicos obtidos a partir do cultivo de plantas podem ser utilizados como substratos nos processos de bioconversão. Bagaço de cana é um importante substrato e fonte de biomassa obtido a partir do processamento da cana de açucar. Em razão da sua produção em grandes volumes o mesmo pode ser utilizado como substrato ideal em processos microbianos para obtenção de produtos de elevado valor comercial. Esse trabalho de revisão apresenta os recentes desenvolvimentos em processos biológicos utilizando a técnica da fermentação no estado sólido na obtenção de enzimas, aminoácidos, ácidos orgânicos e componentes farmacêuticos de interesse industrial.

  1. 13 C solid-state NMR study of the 13 C-labeled peptide, (E)8 GGLGGQGAG(A)6 GGAGQGGYGG as a model for the local structure of Nephila clavipes dragline silk (MaSp1) before and after spinning.

    Yazawa, Koji; Yamaguchi, Erika; Knight, David; Asakura, Tetsuo


    We prepared the water soluble model peptide, (E)(8) GGLGGQGAG(A)(6) GGAGQGGYGG, to throw light on the local structure of spidroin 1 (MaSpl) protein in spider dragline silk of Nephila clavipes before and after spinning. Solution (13) C NMR showed that the conformation of the peptide in aqueous solution was essentially random coil. Solid-state NMR was used to follow conformation-dependent (13) C chemical shifts in (13) C selectively labeled versions of the peptide. The peptide lyophilized from an aqueous solution at neutral pH (hereafter referred to as "without acid treatment)"was used to mimic the state of the spidroin stored in the spider's silk gland while the peptide precipitated from the acidic solution ("with acid treatment") was used to simulate the role of acid treatment in inducing conformation change in the natural spinning process. In without acid treatment, the fraction of random coil conformation was lowest in the N-terminal region (residues 15-18) when compared with the C-terminus. The conformational change produced by the acid treatment occurred in the sequence, G(15) AG(A)(6) GGAG(27), interposed between pairs of Gly residues pairs, Gly(12,13), and Gly(29,30). The acid treated peptide showed a remarkable decrease in the fraction of random coil conformation from A(20) to A(23) in the poly-Ala region when compared with the peptide without acid treatment. These observations taken together suggest that the peptide can be used as a model for studying the localization of the conformation change in spider silk fibroin in the natural spinning and the role of acid treatment in this process.

  2. Understanding solid state physics

    Holgate, Sharon Ann


    Where Sharon Ann Holgate has succeeded in this book is in packing it with examples of the application of solid state physics to technology. … All the basic elements of solid state physics are covered … . The range of materials is good, including as it does polymers and glasses as well as crystalline solids. In general, the style makes for easy reading. … Overall this book succeeds in showing the relevance of solid state physics to the modern world … .-Contemporary Physics, Vol. 52, No. 2, 2011I was indeed amused and inspired by the wonderful images throughout the book, carefully selected by th

  3. The solid state maser

    Orton, J W; Walling, J C; Ter Haar, D


    The Solid State Maser presents readings related to solid state maser amplifier from the first tentative theoretical proposals that appeared in the early 1950s to the successful realization of practical devices and their application to satellite communications and radio astronomy almost exactly 10 years later. The book discusses a historical account of the early developments (including that of the ammonia maser) of solid state maser; the properties of paramagnetic ions in crystals; the development of practical low noise amplifiers; and the characteristics of maser devices designed for communica

  4. Solid-state NMR of polymers

    Mirau, P


    Nuclear magnetic resonance (NMR) spectroscopy has emerged as one of the most important methods for the solid-state characterisation of polymers. The popularity of NMR is due to the fact that many molecular level features can be measured from the NMR spectra, including the polymer chain conformation, the morphology and the dynamics. The spectral features and relaxation times are affected by local interactions, so they provide information about the structure of polymers on a length scale (2-200 A) that is difficult to measure by other methods. In favourable cases, the NMR experiments provide a molecular-level explanation for the transitions observed by differential scanning calorimetry (DSC) and other methods, and the NMR properties can often be related to the bulk properties. Solid-state NMR has long been of interest in polymer science, and the first solid-state NMR studies of polymers were reported approximately a year after the discovery of nuclear resonance in bulk matter. It was reported in this initial study that the proton line width for natural rubber at room temperature is more like that of a mobile liquid than of a solid, but that the resonance broadens near the glass transition temperature (T{sub g}). This was recognised as being related to a change in chain dynamics above and below the T{sub g}. NMR methods developed rapidly after these initial observations, first for polymers in solution and, more recently, for polymers in the solid-state. Solid-state NMR studies of polymers were developed more slowly than their solution-state counterparts because solid-state NMR requires more specialised equipment. Solid-state NMR is now such an important tool that most modern spectrometers are capable of performing these studies. The interest in the NMR of solid polymers is due in part to the fact that most polymers are used in the solid state, and in many cases the NMR properties can be directly related to the macroscopic properties. Polymers have restricted mobility

  5. Effects of sintering temperature on interfacial structure and interfacial resistance for all-solid-state rechargeable lithium batteries

    Kato, Takehisa; Yoshida, Ryuji; Yamamoto, Kazuo; Hirayama, Tsukasa; Motoyama, Munekazu; West, William C.; Iriyama, Yasutoshi


    Sintering processes yield a mutual diffusion region at the electrode/solid electrolyte interface, which is considered as a crucial problem for developing large-sized all-solid-state rechargeable lithium batteries with high power density. This work focuses on the interface between LiNi1/3Co1/3Mn1/3O2 (NMC) and NASICON-structured Li+ conductive glass ceramics solid electrolyte (Li2Osbnd Al2O3sbnd SiO2sbnd P2O5sbnd TiO2sbnd GeO2: LATP sheet (AG-01)), and investigates the effects of sintering temperature on interfacial structure and interfacial resistance at the NMC/LATP sheet. Thin films of NMC were fabricated on the LATP sheets at 700 °C or 900 °C as a model system. We found that the thickness of the mutual diffusion region was almost the same, ca. 30 nm, in these two samples, but the NMC film prepared at 900 °C had three orders of magnitude larger interfacial resistance than the NMC film prepared at 700 °C. Around the interface between the NMC film prepared at 900 °C and the LATP sheet, Co in the NMC accumulates as a reduced valence and lithium-free impurity crystalline phase will be also formed. These two problems must contribute to drastic increasing of interfacial resistance. Formation of de-lithiated NMC around the interface and its thermal instability at higher temperature may be considerable reason to induce these problems.

  6. Magneto-structural transformations via a solid-state nudged elastic band method: Application to iron under pressure.

    Zarkevich, N A; Johnson, D D


    We extend the solid-state nudged elastic band method to handle a non-conserved order parameter, in particular, magnetization, that couples to volume and leads to many observed effects in magnetic systems. We apply this formalism to the well-studied magneto-volume collapse during the pressure-induced transformation in iron-from ferromagnetic body-centered cubic (bcc) austenite to hexagonal close-packed (hcp) martensite. We find a bcc-hcp equilibrium coexistence pressure of 8.4 GPa, with the transition-state enthalpy of 156 meV/Fe at this pressure. A discontinuity in magnetization and coherent stress occurs at the transition state, which has a form of a cusp on the potential-energy surface (yet all the atomic and cell degrees of freedom are continuous); the calculated pressure jump of 25 GPa is related to the observed 25 GPa spread in measured coexistence pressures arising from martensitic and coherency stresses in samples. Our results agree with experiments, but necessarily differ from those arising from drag and restricted parametrization methods having improperly constrained or uncontrolled degrees of freedom.

  7. Magneto-structural transformations via a solid-state nudged elastic band method: Application to iron under pressure

    Zarkevich, N. A., E-mail:, E-mail: [The Ames Laboratory, U.S. Department of Energy, Ames, Iowa 50011-3020 (United States); Johnson, D. D., E-mail:, E-mail: [The Ames Laboratory, U.S. Department of Energy, Ames, Iowa 50011-3020 (United States); Materials Science and Engineering, Iowa State University, Ames, Iowa 50011-2300 (United States)


    We extend the solid-state nudged elastic band method to handle a non-conserved order parameter, in particular, magnetization, that couples to volume and leads to many observed effects in magnetic systems. We apply this formalism to the well-studied magneto-volume collapse during the pressure-induced transformation in iron—from ferromagnetic body-centered cubic (bcc) austenite to hexagonal close-packed (hcp) martensite. We find a bcc-hcp equilibrium coexistence pressure of 8.4 GPa, with the transition-state enthalpy of 156 meV/Fe at this pressure. A discontinuity in magnetization and coherent stress occurs at the transition state, which has a form of a cusp on the potential-energy surface (yet all the atomic and cell degrees of freedom are continuous); the calculated pressure jump of 25 GPa is related to the observed 25 GPa spread in measured coexistence pressures arising from martensitic and coherency stresses in samples. Our results agree with experiments, but necessarily differ from those arising from drag and restricted parametrization methods having improperly constrained or uncontrolled degrees of freedom.

  8. Which kind of aromatic structures are produced during biomass charring? New insights provided by modern solid-state NMR spectroscopy

    Knicker, Heike; Paneque-Carmona, Marina; Velasco-Molina, Marta; de la Rosa, José Maria; León-Ovelar, Laura Regina; Fernandez-Boy, Elena


    Intense research on biochar and charcoal of the last years has revealed that depending on the production conditions, the chemical and physical characteristics of their aromatic network can greatly vary. Since such variations are determining the behavior and stability of charred material in soils, a better understanding of the structural changes occurring during their heating and the impact of those changes on their function is needed. One method to characterize pyrogenic organic matter (PyOM) represents solid-state 13C NMR spectroscopy applying the cross polarization (CP) magic angle spinning technique (MAS). A drawback of this technique is that the quantification of NMR spectra of samples with highly condensed and proton-depleted structures is assumed to be bias. Typical samples with such attributes are charcoals produced at temperatures above 700°C under pyrolytic conditions. Commonly their high condensation degree leads to graphenic structures that are not only reducing the CP efficiency but create also a conductive lattice which acts as a shield and prevents the entering of the excitation pulse into the sample during the NMR experiments. Since the latter can damage the NMR probe and in the most cases the obtained NMR spectra show only one broad signal assignable to aromatic C, this technique is rarely applied for characterizing high temperature chars or soot. As a consequence, a more detailed knowledge of the nature of the aromatic ring systems is still missing. The latter is also true for the aromatic domains of PyOM produced at lower temperatures, since older NMR instruments operating at low magnetic fields deliver solid-state 13C NMR spectra with low resolution which turns a more detailed analysis of the aromatic chemical shift region into a challenging task. In order to overcome this disadvantages, modern NMR spectroscopy offers not only instruments with greatly improved resolution but also special pulse sequences for NMR experiments which allow a more

  9. Advances in simultaneous DSC-FTIR microspectroscopy for rapid solid-state chemical stability studies: some dipeptide drugs as examples.

    Lin, Shan-Yang; Wang, Shun-Li


    The solid-state chemistry of drugs has seen growing importance in the pharmaceutical industry for the development of useful API (active pharmaceutical ingredients) of drugs and stable dosage forms. The stability of drugs in various solid dosage forms is an important issue because solid dosage forms are the most common pharmaceutical formulation in clinical use. In solid-state stability studies of drugs, an ideal accelerated method must not only be selected by different complicated methods, but must also detect the formation of degraded product. In this review article, an analytical technique combining differential scanning calorimetry and Fourier-transform infrared (DSC-FTIR) microspectroscopy simulates the accelerated stability test, and simultaneously detects the decomposed products in real time. The pharmaceutical dipeptides aspartame hemihydrate, lisinopril dihydrate, and enalapril maleate either with or without Eudragit E were used as testing examples. This one-step simultaneous DSC-FTIR technique for real-time detection of diketopiperazine (DKP) directly evidenced the dehydration process and DKP formation as an impurity common in pharmaceutical dipeptides. DKP formation in various dipeptides determined by different analytical methods had been collected and compiled. Although many analytical methods have been applied, the combined DSC-FTIR technique is an easy and fast analytical method which not only can simulate the accelerated drug stability testing but also at the same time enable to explore phase transformation as well as degradation due to thermal-related reactions. This technique offers quick and proper interpretations.

  10. Structure determination of uniformly {sup 13}C, {sup 15}N labeled protein using qualitative distance restraints from MAS solid-state {sup 13}C-NMR observed paramagnetic relaxation enhancement

    Tamaki, Hajime [Hokkaido University, Graduate School of Life Science (Japan); Egawa, Ayako [Osaka University, Institute for Protein Research (Japan); Kido, Kouki [Hokkaido University, Graduate School of Life Science (Japan); Kameda, Tomoshi [National Institute of Advanced Industrial Science and Technology, Biotechnology Research Institute for Drug Discovery (Japan); Kamiya, Masakatsu; Kikukawa, Takashi; Aizawa, Tomoyasu [Hokkaido University, Faculty of Advanced Life Science (Japan); Fujiwara, Toshimichi [Osaka University, Institute for Protein Research (Japan); Demura, Makoto, E-mail: [Hokkaido University, Faculty of Advanced Life Science (Japan)


    Magic angle spinning (MAS) solid-state nuclear magnetic resonance (NMR) is a powerful method for structure determination of insoluble biomolecules. However, structure determination by MAS solid-state NMR remains challenging because it is difficult to obtain a sufficient amount of distance restraints owing to spectral complexity. Collection of distance restraints from paramagnetic relaxation enhancement (PRE) is a promising approach to alleviate this barrier. However, the precision of distance restraints provided by PRE is limited in solid-state NMR because of incomplete averaged interactions and intermolecular PREs. In this report, the backbone structure of the B1 domain of streptococcal protein G (GB1) has been successfully determined by combining the CS-Rosetta protocol and qualitative PRE restraints. The derived structure has a Cα RMSD of 1.49 Å relative to the X-ray structure. It is noteworthy that our protocol can determine the correct structure from only three cysteine-EDTA-Mn{sup 2+} mutants because this number of PRE sites is insufficient when using a conventional structure calculation method based on restrained molecular dynamics and simulated annealing. This study shows that qualitative PRE restraints can be employed effectively for protein structure determination from a limited conformational sampling space using a protein fragment library.

  11. Synthesis, characterization and solid-state photoluminescence studies of six alkoxy phenylene ethynylene dinuclear palladium(II) rods.

    Figueira, João; Czardybon, Wojciech; Mesquita, José Carlos; Rodrigues, João; Lahoz, Fernando; Russo, Luca; Valkonen, Arto; Rissanen, Kari


    A rare family of six discrete binuclear [PdCl(PEt3)2] phenylene ethynylene rods with alkoxy side chains (methoxy, ethoxy and heptoxy) have been developed, and their solid-state photoluminescence results have been presented and discussed. The shorter bridging ligands are of the general formula H-C≡C-C6H2(R)2-C≡C-H, where R = H, OCH3, OC2H5, and OC7H15, whereas the longer ones are based on H-C≡C-C6H4-C≡C-C6H2(R)2-C≡C-C6H4-C≡C-H, where R = OCH3, OC2H5. These ligands display increasing length in both the main dimension (backbone length) as well as the number of carbons in the side chains (R, alkoxide side chain) that stem from the central phenylene moiety. The X-ray crystal structures of two of the prepared complexes are reported: one corresponds to a shorter rod, 1,4-bis[trans-(PEt3)2ClPd-C≡C]-2,5-diethoxybenzene (6c), while the second one is associated with a longer rod, the binuclear complex 1,4-bis[trans-(PEt3)2ClPd-4-(-C≡C-C6H4-C≡C)]-2,5-diethoxybenzene (7c). All new compounds were characterized by NMR spectroscopy ((1)H, (13)C{(1)H} and (31)P{(1)H}) as well as ESI-MS(TOF), EA, FTIR, UV-Vis, cyclic voltammetry and solid-state photoluminescence. Our work shows the influence of the alkoxy side chains on the electronic structure of the family of binuclear Pd rods by lowering its oxidation potential. In addition to this, the increase of the length of the bridge results in a higher oxidation potential. Solid state photoluminescence results indicate that Pd complexes are characterized by a marked decrease in both the emission intensity and the fluorescence lifetime values as compared to their ligands. This behaviour could be due to some degree of ligand-to-metal charge transfer.

  12. Solid state physics an introduction

    Hofmann, Philip


    A must-have textbook for any undergraduate studying solid state physics. This successful brief course in solid state physics is now in its second edition. The clear and concise introduction not only describes all the basic phenomena and concepts, but also such advanced issues as magnetism and superconductivity. Each section starts with a gentle introduction, covering basic principles, progressing to a more advanced level in order to present a comprehensive overview of the subject. The book is providing qualitative discussions that help undergraduates understand concepts even if they can?t foll

  13. Revealing protein structures in solid-phase peptide synthesis by 13C solid-state NMR: evidence of excessive misfolding for Alzheimer's β.

    Wang, Songlin; Ishii, Yoshitaka


    Solid-phase peptide synthesis (SPPS) is a widely used technique in biology and chemistry. However, the synthesis yield in SPPS often drops drastically for longer amino acid sequences, presumably because of the occurrence of incomplete coupling reactions. The underlying cause for this problem is hypothesized to be a sequence-dependent propensity to form secondary structures through protein aggregation. However, few methods are available to study the site-specific structure of proteins or long peptides that are anchored to the solid support used in SPPS. This study presents a novel solid-state NMR (SSNMR) approach to examine protein structure in the course of SPPS. As a useful benchmark, we describe the site-specific SSNMR structural characterization of the 40-residue Alzheimer's β-amyloid (Aβ) peptide during SPPS. Our 2D (13)C/(13)C correlation SSNMR data on Aβ(1-40) bound to a resin support demonstrated that Aβ underwent excessive misfolding into a highly ordered β-strand structure across the entire amino acid sequence during SPPS. This approach is likely to be applicable to a wide range of peptides/proteins bound to the solid support that are synthesized through SPPS.

  14. Anion-controlled assembly of silver-di(aminophenyl)sulfone coordination polymers: Syntheses, crystal structures, and solid state luminescence

    Zhang, Qi-Long, E-mail: [Department of Chemistry, Guiyang Medical College, Guiyang 550004 (China); Hu, Peng [Department of Chemistry, Guiyang Medical College, Guiyang 550004 (China); Zhao, Yi [Key Laboratory of Macrocyclic and Supramolecular Chemistry, Guizhou University, Guiyang 550025 (China); Feng, Guang-Wei [Department of Chemistry, Guiyang Medical College, Guiyang 550004 (China); Zhang, Yun-Qian; Zhu, Bi-Xue; Tao, Zhu [Key Laboratory of Macrocyclic and Supramolecular Chemistry, Guizhou University, Guiyang 550025 (China)


    Five silver coordination polymers, namely, ([Ag(3,3′-daps){sub 2}]·BF{sub 4}){sub n} (1), ([Ag(3,3′-daps){sub 2}]·NO{sub 3}){sub n} (2), [Ag(3,3′-daps)(CF{sub 3}SO{sub 3})]{sub n} (3), ([Ag(4,4′-daps)]·CF{sub 3}SO{sub 3}){sub n} (4), and ([Ag(4,4′-daps)]·ClO{sub 4}){sub n} (5) (3,3′-daps=di(3′-aminodiphenyl)sulfone, and 4,4′-daps=di(4′-aminodiphenyl)sulfone) have been synthesized and structural characterized by elemental analyses, IR spectra, powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction analyses. Complex 1 displays a 1D ladder-like chain with four-connected Ag ions and bridged 3,3′-daps. Complex 2 shows other 1D ladder chain modified by tentacles. Complex 3 is a 2D layer structure with both Ag ions and 3,3′-daps are 3-connected nodes. Complex 4 is another 1D ladder chain with three-connected Ag ions and 4,4′-daps. Complex 5 shows a 2D 4{sup 4}-sql net with Ag ions and 4,4′-daps as 4-connected nodes. Moreover, their solid state luminescence and thermal stabilities also have been investigated. - Graphical abstract: Pictogram: Synthetic procedures of the five anion controlled silver coordination polymers. We reported the synthetic procedures, structure, and luminescence property of the five anion controlled silver coordination polymers based on two novel di(aminophenyl)sulfone V-shaped ligands. Display Omitted - Highlights: • Five new silver coordination polymers were synthesized and characterized. • Two novel designed V-shaped di(aminophenyl)sulfone ligands were first introduced to coordination chemistry. • Anions play important roles in determining the five silver coordination polymers. • The structural diversity and photoluminescence property were also discussed.

  15. XAFS Study on Solid State Amorphization of Alloys by Mechanical Alloying


    Structural evolution of alloys by ball-milling during solid stateamorphization were studied by means of XAFS technique. The first one is amorphization process of Fe and B powder mixtures by mechanical alloying (MA), and the second one is amorphization process of ordered B2 CoZr intermetallic compound by mechanical milling (MM). The mixing process of Fe and B and disintegration process of ordered B2 CoZr intermetallic compound crystal were observed clearly in atomic level by XAFS method. The micro-mechanism of amorphization process of alloy by ball-milling was discussed.

  16. Solid-state NMR studies of bacteriorhodopsin and the purple membrane

    Mason, A J


    proteins. This technique may prove particularly useful when studying large proteins that are difficult to orient where the MAS lineshapes will remain relatively unaffected in comparison with current static NMR methods. Finally the MAOSS method was extended to the study of the lipid components of the purple membrane and the feasibility of determining structural constraints from phospholipid headgroups was assessed. The potential of using sup 3 sup 1 P NMR to observe qualitative protein-lipid interactions in both the purple membrane and reconstituted membranes containing bovine rhodopsin was also demonstrated. Following the demonstration of a new MAS NMR method for resolving orientational constraints in uni-axially oriented biological membranes (Glaubitz and Watts, 1998), experiments were performed to realise the potential of the new method on large, oriented membrane proteins. Using bacteriorhodopsin in the purple membrane as a paradigm for large membrane proteins, the protein was specifically labelled with de...

  17. Study on gamma and electron beam sterilization of third generation cephalosporins cefdinir and cefixime in solid state

    Singh, Babita K.; Parwate, Dilip V.; Das Sarma, Indrani B.; Shukla, Sudhir K.


    The effect of gamma radiation from 60Co source and 2 MeV e-beam was studied on two thermolabile cephalosporin antibiotics viz cefdinir and cefixime in solid state. The parameters studied to assess radiolytic degradation were loss of chemical and microbiological potency, change in optical rotation, electronic and vibrational absorption characteristics, thermal behavior and color modification. ESR spectroscopic study, HPLC related impurity profile, thermogram and Raman spectrum are applied in deducing the nature of radiolytic impurities and their formation hypotheses. Cefixime is radiation sensitive, whereas cefdinir has acceptable radiation resistance at 25 kGy dose. The nature of radiolytic related impurities and their concentrations indicates that the lactam ring is not highly susceptible to direct radiation attack, which otherwise is considered very sensitive to stress (thermal, chemical and photochemical).

  18. Single molecule magnet behavior of a pentanuclear Mn-based metallacrown complex: solid state and solution magnetic studies.

    Zaleski, Curtis M; Tricard, Simon; Depperman, Ezra C; Wernsdorfer, Wolfgang; Mallah, Talal; Kirk, Martin L; Pecoraro, Vincent L


    The magnetic behavior of the pentanuclear complex of formula Mn(II)(O(2)CCH(3))(2)[12-MC(Mn(III)(N)shi)-4](DMF)(6), 1, was investigated using magnetization and magnetic susceptibility measurements both in the solid state and in solution. Complex 1 has a nearly planar structure, made of a central Mn(II) ion surrounded by four peripheral Mn(III) ions. Solid state variable-field dc magnetic susceptibility experiments demonstrate that 1 possesses a low value for the total spin in the ground state; fitting appropriate expressions to the data results in antiferromangetic coupling both between the peripheral Mn(III) ions (J = -6.3 cm(-1)) and between the central Mn(II) ion and the Mn(III) ones (J' = -4.2 cm(-1)). In order to obtain a reasonable fit, a relatively large single ion magnetic anisotropy (D) value of 1 cm(-1) was necessary for the central Mn(II) ion. The single crystal magnetization measurements using a microsquid array display a very slight opening of the hysteresis loop but only at a very low temperature (0.04 K), which is in line with the ac susceptibility data where a slow relaxation of the magnetization occurs just around 2 K. In frozen solution, complex 1 displays a frequency dependent ac magnetic susceptibility signal with an energy barrier to magnetization reorientation (E) and relaxation time at an infinite temperature (τ(o)) of 14.7 cm(-1) and 1.4 × 10(-7) s, respectively, demonstrating the single molecule magnetic behavior in solution.

  19. Modeling solid-state precipitation

    Nebylov, AlexanderKozeschnik, Ernst


    Over recent decades, modeling and simulation of solid-state precipitation has attracted increased attention in academia and industry due to their important contributions in designing properties of advanced structural materials and in increasing productivity and decreasing costs for expensive alloying. In particular, precipitation of second phases is an important means for controlling the mechanical-technological properties of structural materials. However, profound physical modeling of precipitation is not a trivial task. This book introduces you to the classical methods of precipitation model

  20. Filamentous fungal diversity and community structure associated with the solid state fermentation of Chinese Maotai-flavor liquor.

    Chen, Bi; Wu, Qun; Xu, Yan


    Maotai-flavor liquor is produced by simultaneous saccharification and fermentation (SSF) process under solid state conditions, including Daqu (starter) making, stacking fermentation and alcohol fermentation stages. Filamentous fungi produce many enzymes to degrade the starch material into fermentable sugar during liquor fermentation. This study investigated the filamentous fungal community associated with liquor making process. Eight and seven different fungal species were identified by using culture-dependent and -independent method (PCR-denaturing gradient gel electrophoresis, DGGE) analyses, respectively. The traditional enumeration method showed that Daqu provided 7 fungal species for stacking fermentation. The total population of filamentous fungi increased from 3.4 × 10(3)cfu/g to 1.28 × 10(4)cfu/g in the first 3 days of stacking fermentation, and then decreased till the end. In alcohol fermentation in pits, the population continuously decreased and few fungal species survived (lower than 1 × 10(3)cfu/g) after 10 days. Therefore, stacking fermentation is an essential stage for the growth of filamentous fungi. Paecilomyces variotii, Aspergillus oryzae and Aspergillus terreus were detected by both methods, and P. variotii and A. oryzae were the predominant species. Meanwhile, P. variotii possessed the highest glucoamylase (3252 ± 526 U/g) and A. oryzae exhibited the highest α-amylase (1491 ± 324 U/g) activity among the cultivable fungal species. Furthermore, the variation of starch and reducing sugar content was consistent with the growth of P. variotii and A. oryzae in Zaopei (fermented grains) during stacking fermentation, which implied that the two filamentous fungi played an important role in producing amylase for hydrolyzing the starch.

  1. Charge-assisted triel bonding interactions in solid state chemistry: A combined computational and crystallographic study

    Bauzá, Antonio; García-Llinás, Xavier; Frontera, Antonio


    A combined energetic and geometric study of a series of triel bond complexes involving haloborane salts has been carried out at the M06-2X/def2-QZVPD level of theory. We have used 1-(dihaloboranyl)pyridin-1-ium compounds Py+BX2 (X = Cl, Br and I) as triel bond donors and Cl-, Br-, HCO2-, BF4- and ClO4- as electron donor moieties. In addition we have used Bader's theory of 'atoms in molecules' to further characterize the noncovalent interactions described herein. Finally, several examples were retrieved from the CSD (Cambridge Structural Database) in order to provide experimental support to the results presented in this work.

  2. In Situ Atomic-Scale Observation of Electrochemical Delithiation Induced Structure Evolution of LiCoO2 Cathode in a Working All-Solid-State Battery.

    Gong, Yue; Zhang, Jienan; Jiang, Liwei; Shi, Jin-An; Zhang, Qinghua; Yang, Zhenzhong; Zou, Dongli; Wang, Jiangyong; Yu, Xiqian; Xiao, Ruijuan; Hu, Yong-Sheng; Gu, Lin; Li, Hong; Chen, Liquan


    We report a method for in situ atomic-scale observation of electrochemical delithiation in a working all-solid-state battery using a state-of-the-art chip based in situ transmission electron microscopy (TEM) holder and focused ion beam milling to prepare an all-solid-state lithium-ion battery sample. A battery consisting of LiCoO2 cathode, LLZO solid state electrolyte and gold anode was constructed, delithiated and observed in an aberration corrected scanning transmission electron microscope at atomic scale. We found that the pristine single crystal LiCoO2 became nanosized polycrystal connected by coherent twin boundaries and antiphase domain boundaries after high voltage delithiation. This is different from liquid electrolyte batteries, where a series of phase transitions take place at LiCoO2 cathode during delithiation. Both grain boundaries become more energy favorable along with extraction of lithium ions through theoretical calculation. We also proposed a lithium migration pathway before and after polycrystallization. This new methodology could stimulate atomic scale in situ scanning/TEM studies of battery materials and provide important mechanistic insight for designing better all-solid-state battery.

  3. Effect of nano Co reinforcements on the structure of the Sn-3.0Ag-0.5Cu solder in liquid and after reflow solid states

    Yakymovych, Andriy, E-mail: [Department of Inorganic Chemistry – Functional Materials, University of Vienna, Währinger Str. 42, 1090 Vienna (Austria); Department of Metal Physics, Ivan Franko National University of Lviv, Kyrylo i Mephodiy Str. 8, 79005 Lviv (Ukraine); Mudry, Stepan; Shtablavyi, Ihor [Department of Metal Physics, Ivan Franko National University of Lviv, Kyrylo i Mephodiy Str. 8, 79005 Lviv (Ukraine); Ipser, Herbert [Department of Inorganic Chemistry – Functional Materials, University of Vienna, Währinger Str. 42, 1090 Vienna (Austria)


    Sn-Ag-Cu (SAC) alloys are commonly recognized as lead-free solders employed in the electronics industry. However, some disadvantages in mechanical properties and their higher melting temperatures compared to Pb-Sn solders prompt new research relating to reinforcement of existing SAC solders. One of the ways to reinforce these solder materials is the formation of composites with nanoparticles as filler materials. Accordingly, this study presents structural features of nanocomposite (Sn-3.0Ag-0.5Cu){sub 100−x}(nanoCo){sub x} solders with up to 0.8 wt% nano Co. The effect of nano-sized Co particles was investigated by means of differential thermal analysis (DTA), X-ray diffraction (XRD) in both liquid and solid states, and scanning electron microscopy (SEM). The experimental data of DTA are compared with available literature data for bulk Sn-3.0Ag-0.5Cu alloy to check the capability of minor nano-inclusions to decrease the melting temperature of the SAC solder. The combination of structural data in liquid and solid states provides important information about the structural transformations of liquid Sn-3.0Ag-0.5Cu alloys caused by minor Co additions and the phase formation during crystallization. Furthermore, scanning electron microscopy has shown the mutual substitution of Co and Cu atoms in the Cu{sub 6}Sn{sub 5} and CoSn{sub 3} phases, respectively. - Highlights: • Differential thermal analysis of nanocomposite (Sn-3.0Ag-0.5Cu){sub 100−x}(nanoCo){sub x} alloys. • Structural transformations of liquid Sn-3.0Ag-0.5Cu solder by minor Co additions. • Structure data of the solid quaternary (Sn-3.0Ag-0.5Cu){sub 100−x}(Co){sub x} alloys. • Substitution of Co and Cu atoms in the Cu{sub 6}Sn{sub 5} and CoSn{sub 3} phases.

  4. Correlations between (51)V solid-state NMR parameters and chemical structure of vanadium (V) complexes as models for related metalloproteins and catalysts.

    Fenn, Annika; Wächtler, Maria; Gutmann, Torsten; Breitzke, Hergen; Buchholz, Axel; Lippold, Ines; Plass, Winfried; Buntkowsky, Gerd


    The parameters describing the quadrupolar and CSA interactions of 51V solid-state MAS NMR investigations of model complexes mimicking vanadoenzymes as well as vanadium containing catalysts and enzyme complexes are interpreted with respect to the chemical structure. The interpretation is based on the data of 15 vanadium complexes including two new complexes with previously unpublished data and 13 complexes with data previously published by us. Correlations between the chemical structure and the 51V solid-state NMR data of this class of compounds have been established. Especially for the isotropic chemical shift delta(iso) and the chemical shift anisotropy delta(sigma), correlations with specific structural features like the coordination number of the vanadium atom, the number of coordinating nitrogens, the number of oxygen atoms and the chemical surrounding of the complex could be established for these compounds. Moreover, quantitative correlations between the solid-state NMR parameters and specific bond angles and bond lengths have been obtained. Our results can be of particular interest for future investigations concerning the structure and the mode of action of related vanadoenzymes and vanadate protein assemblies, including the use of vanadate adducts as transition state analogs for phosphate metabolizing systems.

  5. Determination of structural topology of a membrane protein in lipid bilayers using polarization optimized experiments (POE) for static and MAS solid state NMR spectroscopy.

    Mote, Kaustubh R; Gopinath, T; Veglia, Gianluigi


    The low sensitivity inherent to both the static and magic angle spinning techniques of solid-state NMR (ssNMR) spectroscopy has thus far limited the routine application of multidimensional experiments to determine the structure of membrane proteins in lipid bilayers. Here, we demonstrate the advantage of using a recently developed class of experiments, polarization optimized experiments, for both static and MAS spectroscopy to achieve higher sensitivity and substantial time-savings for 2D and 3D experiments. We used sarcolipin, a single pass membrane protein, reconstituted in oriented bicelles (for oriented ssNMR) and multilamellar vesicles (for MAS ssNMR) as a benchmark. The restraints derived by these experiments are then combined into a hybrid energy function to allow simultaneous determination of structure and topology. The resulting structural ensemble converged to a helical conformation with a backbone RMSD ~0.44 Å, a tilt angle of 24° ± 1°, and an azimuthal angle of 55° ± 6°. This work represents a crucial first step toward obtaining high-resolution structures of large membrane proteins using combined multidimensional oriented solid-state NMR and magic angle spinning solid-state NMR.

  6. Determination of structural topology of a membrane protein in lipid bilayers using polarization optimized experiments (POE) for static and MAS solid state NMR spectroscopy

    Mote, Kaustubh R. [University of Minnesota, Department of Chemistry (United States); Gopinath, T. [University of Minnesota, Department of Biochemistry, Molecular Biology and Biophysics (United States); Veglia, Gianluigi, E-mail: [University of Minnesota, Department of Chemistry (United States)


    The low sensitivity inherent to both the static and magic angle spinning techniques of solid-state NMR (ssNMR) spectroscopy has thus far limited the routine application of multidimensional experiments to determine the structure of membrane proteins in lipid bilayers. Here, we demonstrate the advantage of using a recently developed class of experiments, polarization optimized experiments, for both static and MAS spectroscopy to achieve higher sensitivity and substantial time-savings for 2D and 3D experiments. We used sarcolipin, a single pass membrane protein, reconstituted in oriented bicelles (for oriented ssNMR) and multilamellar vesicles (for MAS ssNMR) as a benchmark. The restraints derived by these experiments are then combined into a hybrid energy function to allow simultaneous determination of structure and topology. The resulting structural ensemble converged to a helical conformation with a backbone RMSD {approx}0.44 A, a tilt angle of 24 Degree-Sign {+-} 1 Degree-Sign , and an azimuthal angle of 55 Degree-Sign {+-} 6 Degree-Sign . This work represents a crucial first step toward obtaining high-resolution structures of large membrane proteins using combined multidimensional oriented solid-state NMR and magic angle spinning solid-state NMR.

  7. The stress stability of olanzapine: studies of interactions with excipients in solid state pharmaceutical formulations.

    Djordjević Filijović, Nataša; Antonijević, Milan D; Pavlović, Aleksandar; Vučković, Ivan; Nikolić, Katarina; Agbaba, Danica


    Stress stability testing represents an important part of the drug development process. It is used as an important tool for the identification of degradation products and degradation pathways, as well as for the assessment of changes in physical form of drug molecules. The impact of excipients on the stability of olanzapine confirms that levels of impurities and degradants are limiting parameters and are therefore used for stability evaluation. The major degradation product of olanzapine was identified as 2-methyl-5,10-dihydro-4H-thieno[2,3-b][1,5]benzodiazepine-4-one (III). The structure of III was determined by using LC-MS, IR and NMR. Compatibility and stress stability results demonstrated that tablet formulations of olanzapine are sensitive to temperature and moisture. In samples protected from moisture, the increase in concentration of III was shown to be highly temperature dependent and the degradation followed zero-order kinetics. In addition, studies of olanzapine with excipients and in formulated tablets revealed polymorphic phase changes in some samples, influenced by a combination of stress temperature and humidity conditions. Polymorphic transitions were monitored using x-ray powder diffraction (XRPD) analysis and exhibited no correlation between the phase change (appearance of a new polymorph) and the degradation process.

  8. Spin Equilibria in Monomeric Manganocenes: Solid State Magnetic and EXAFS Studies

    Walter, M. D.; Sofield, C. D.; Booth, C. H.; Andersen, R. A.


    Magnetic susceptibility measurements and X-ray data confirm that tert-butyl-substituted manganocenes [(Me{sub 3}C){sub n}C{sub 5}H{sub 5?n}]{sub 2}Mn (n = 1, 2) follow the trend previously observed with the methylated manganocenes; that is, electron-donating groups attached to the Cp ring stabilize the low-spin (LS) electronic ground state relative to Cp{sub 2}Mn and exhibit higher spin-crossover (SCO) temperatures. However, introducing three CMe{sub 3} groups on each ring gives a temperature-invariant high-spin (HS) state manganocene. The origin of the high-spin state in [1,2,4-(Me{sub 3}C){sub 3}C{sub 5}H{sub 2}]{sub 2}Mn is due to the significant bulk of the [1,2,4-(Me{sub 3}C){sub 3}C{sub 5}H{sub 2}]{sup -} ligand, which is sufficient to generate severe inter-ring steric strain that prevents the realization of the low-spin state. Interestingly, the spin transition in [1,3-(Me{sub 3}C){sub 2}C{sub 5}H{sub 3}]{sub 2}Mn is accompanied by a phase transition resulting in a significant irreversible hysteresis ({Delta}T{sub c} = 16 K). This structural transition was also observed by extended X-ray absorption fine-structure (EXAFS) measurements. Magnetic susceptibility studies and X-ray diffraction data on SiMe{sub 3}-substituted manganocenes [(Me{sub 3}Si){sub n}C{sub 5}H{sub 5-n}]{sub 2}Mn (n = 1, 2, 3) show high-spin configurations in these cases. Although tetra- and hexasubstituted manganocenes are high-spin at all accessible temperatures, the disubstituted manganocenes exhibit a small low-spin admixture at low temperature. In this respect it behaves similarly to [(Me{sub 3}C)(Me{sub 3}Si)C{sub 5}H{sub 3}]{sub 2}Mn, which has a constant low-spin admixture up to 90 K and then gradually converts to high-spin. Thermal spin-trapping can be observed for [(Me{sub 3}C)(Me{sub 3}Si)C{sub 5}H{sub 3}]{sub 2}Mn on rapid cooling.

  9. Luminescence study of Eu(3+) doped Li6 Y(BO3 )3 phosphor for solid-state lighting.

    Yawalkar, Mrunal M; Zade, G D; Dabre, K V; Dhoble, S J


    In this study, Li6 Y1-x Eux (BO3 )3 phosphor was successfully synthesized using a modified solid-state diffusion method. The Eu(3+) ion concentration was varied at 0.05, 0.1, 0.2, 0.5 and 1 mol%. The phosphor was characterized for phase purity, morphology, luminescent properties and molecular transmission at room temperature. The XRD pattern suggests a result closely matching the standard JCPDS file (#80-0843). The emission and excitation spectra were followed to discover the luminescence traits. The excitation spectra indicate that the current phosphor can be efficiently excited at 395 nm and at 466 nm (blue light) to give emission at 595 and 614 nm due to the (5) D0  → (7) Fj transition of Eu(3+) ions. Concentration quenching was observed at 0.5 mol% Eu(3+) in the Li6 Y1-x Eux (BO3 )3 host lattice. Strong red emission with CIE chromaticity coordinates of phosphor is x = 0.63 and y = 0.36 achieved with dominant red emission at 614 nm the (5) D0  → (7)  F2 electric dipole transition of Eu(3+) ions. The novel Li6 Y1-x Eux (BO3 )3 phosphor may be a suitable red-emitting component for solid-state lighting using double-excited wavelengths, i.e. near-UV at 395 nm and blue light at 466 nm. Copyright © 2015 John Wiley & Sons, Ltd.

  10. Ethanol production and a case study of ethanol produced from sweet sorghum stalks via solid state fermentation

    Geng, X. [China Agricultural Univ., Beijing (China). Resource and Environmental Engineering College; Tsinghua Univ., Beijing (China). Inst. of Nuclear and New Energy Technology; Li, S.Z. [Tsinghua Univ., Beijing (China). Inst. of Nuclear and New Energy Technology


    Ethanol has excellent fuel properties, such as high octane, high heat of vaporization and low photochemical reactivity in the atmosphere. It is less volatile than gasoline and there is lower smog formation from evaporative emissions of pure ethanol compared to gasoline. As such, ethanol has emerged as an important alternative energy source that is sustainable, efficient, cost effective, convenient and safe. In 2006, global production of ethanol reached 13.5 billion gallons, up from 12.1 billion gallons in 2005. However, in light of the current debate of food versus fuel, the industry must shift to non-food feedstocks. This paper described an emerging technology to cost-effectively produce ethanol from sweet sorghum stalks, the most promising alternative feedstock to corn, via solid state fermentation (SSF). Experiments of advanced solid state fermentation (ASSF) for ethanol production from sweet sorghum by Saccharomyces cerevisiae were conducted in laboratory and pilot scales studies. The process parameters were monitored during the fermentation in three scales. The highest ethanol concentration was achieved in pilot fermentation after 44 hours of incubation when a high yield of ethanol of 94.48 per cent was obtained. In comparison, corn ethanol fermentation yielded 91.5 per cent ethanol after 55 hours of incubation. Ethanol concentration decreased slowly after 44 hours of incubation due to the consumption of sugars and the inhibitory effects of ethanol. Ethanol is a typical primary metabolite whose production closely couples with the growth of yeast cell, indicating yeast is produced as a co-product. Under the same fermentation conditions the fermentation in non-sterilized medium gave the similar ethanol concentration to that of a sterilized medium, which has the advantages of saving in equipment and energy costs for industrialization of ethanol production from sweet sorghum via SSF. 39 refs., 6 figs.

  11. Solid state research

    McWhorter, Alan L.


    The Solid State division of Lexington Lincoln Lab reports on its progress for this quarter. The areas of study are: Time Dye Laser Using Integrated Optics; GaP Microlenses by Mass Transport; A New OMVPE Reactor for Growth of InP and Related Alloys; Microchannel Heat Sinks for Two-Dimensional High Power-Density Diode Laser Arrays; Novel Scalloped-Mirror Diffraction-Coupled Laser Arrays; Three-Mirror Ti:Al2O3 Ring Laser Cavity; Femtosecond TiAl2O3 Injection-Seeded Laser; End-Pumped Nd:LaF3 and Nd:LaMgA11O19 Lasers; Single Frequency Mixing of Frequency Modulated Laser Radiation; Vertical Rotating Disk OMVPE Reactor; New Electron Beam Lithography System; Dry Etching Induced Damage on Vertical Sidewalls of GaAs Channels; Homoepitaxial Semiconducting Diamond; 420 X 420 CCD Frame Transfer Imager; Technique for Monolithically Integrating GaAs/AlGaAs Lasers of Different Wavelengths; Superconducting Thin Films of BiSrCaCuO; and Nb Thin Film Capacitors for Superconductive Circuits.

  12. Solid-state circuits

    Pridham, G J


    Solid-State Circuits provides an introduction to the theory and practice underlying solid-state circuits, laying particular emphasis on field effect transistors and integrated circuits. Topics range from construction and characteristics of semiconductor devices to rectification and power supplies, low-frequency amplifiers, sine- and square-wave oscillators, and high-frequency effects and circuits. Black-box equivalent circuits of bipolar transistors, physical equivalent circuits of bipolar transistors, and equivalent circuits of field effect transistors are also covered. This volume is divided

  13. Solid state theory

    Harrison, Walter A


    ""A well-written text . . . should find a wide readership, especially among graduate students."" - Dr. J. I. Pankove, RCA.The field of solid state theory, including crystallography, semi-conductor physics, and various applications in chemistry and electrical engineering, is highly relevant to many areas of modern science and industry. Professor Harrison's well-known text offers an excellent one-year graduate course in this active and important area of research. While presenting a broad overview of the fundamental concepts and methods of solid state physics, including the basic quantum theory o

  14. Solid-State Physics Introduction to the Theory

    Patterson, James


    Learning Solid State Physics involves a certain degree of maturity, since it involves tying together diverse concepts from many areas of physics. The objective is to understand, in a basic way, how solid materials behave. To do this one needs both a good physical and mathematical background. One definition of Solid State Physics is it is the study of the physical (e.g. the electrical, dielectric, magnetic, elastic, and thermal) properties of solids in terms of basic physical laws. In one sense, Solid State Physics is more like chemistry than some other branches of physics because it focuses on common properties of large classes of materials. It is typical that Solid State Physics emphasizes how physics properties link to electronic structure. We have retained the term Solid Modern solid state physics came of age in the late thirties and forties and is now is part of condensed matter physics which includes liquids, soft materials, and non-crystalline solids. This solid state/condensed matter physics book begin...

  15. Nickel(II) complexes having Imidazol-2-ylidene-N′-phenylurea ligand in the coordination sphere – syntheses and solid state structures

    Kishor Naktode; Abhinanda Kundu; Sudeshna Saha; Hari Pada Nayek; Tarun K Panda


    We report the syntheses and structural studies of two nickel(II) complexes of imidazol-2-ylidene- N'-phenylureate ligand of composition [{ImBu NCON(H)Ph}2 Ni(acac)2] (1) and [(C6H5NH2)2 Ni(acac)2] [ImMes NCON(H)Ph] (2). The nickel complex 1 was readily prepared by the reaction of nickel(II) acetylacetonate [Ni(acac) 2 ] with imidazol-2-ylidene-N'-phenylureate ligand [ImBu NCON(H)Ph] (L1) in THF under reflux condition for 72 h. The nickel complex 2 was obtained by the reaction of [Ni(acac)2], mesityl derivative of imidazol-2-ylidene-N′-phenylureate ligand [ImMes NCON(H)Ph] (L2) in the presence of aniline as base under reflux condition in THF. Both the paramagnetic complexes have been characterized by FT-IR spectroscopy and elemental analyses. Solid-state structures of both the new complexes were established by single crystal X-ray diffraction analysis. In the molecular structures of complexes 1 and 2, each nickel(II) ion is six fold coordinated and form a distorted octahedral geometry. The optical properties of both complexes have been explored. The Hirshfeld surfaces are used to view and analyze the intermolecular contacts in crystalline state for complex 2.

  16. Determining the effects of lipophilic drugs on membrane structure by solid-state NMR spectroscopy: the case of the antioxidant curcumin.

    Barry, Jeffrey; Fritz, Michelle; Brender, Jeffrey R; Smith, Pieter E S; Lee, Dong-Kuk; Ramamoorthy, Ayyalusamy


    Curcumin is the active ingredient of turmeric powder, a natural spice used for generations in traditional medicines. Curcumin's broad spectrum of antioxidant, anticarcinogenic, antimutagenic, and anti-inflammatory properties makes it particularly interesting for the development of pharmaceutical compounds. Because of curcumin's various effects on the function of numerous unrelated membrane proteins, it has been suggested that it affects the properties of the bilayer itself. However, a detailed atomic-level study of the interaction of curcumin with membranes has not been attempted. A combination of solid-state NMR and differential scanning calorimetry experiments shows curcumin has a strong effect on membrane structure at low concentrations. Curcumin inserts deep into the membrane in a transbilayer orientation, anchored by hydrogen bonding to the phosphate group of lipids in a manner analogous to cholesterol. Like cholesterol, curcumin induces segmental ordering in the membrane. Analysis of the concentration dependence of the order parameter profile derived from NMR results suggests curcumin forms higher order oligomeric structures in the membrane that span and likely thin the bilayer. Curcumin promotes the formation of the highly curved inverted hexagonal phase, which may influence exocytotic and membrane fusion processes within the cell. The experiments outlined here show promise for understanding the action of other drugs such as capsaicin in which drug-induced alterations of membrane structure have strong pharmacological effects.

  17. Quantum Computing in Solid State Systems

    Ruggiero, B; Granata, C


    The aim of Quantum Computation in Solid State Systems is to report on recent theoretical and experimental results on the macroscopic quantum coherence of mesoscopic systems, as well as on solid state realization of qubits and quantum gates. Particular attention has been given to coherence effects in Josephson devices. Other solid state systems, including quantum dots, optical, ion, and spin devices which exhibit macroscopic quantum coherence are also discussed. Quantum Computation in Solid State Systems discusses experimental implementation of quantum computing and information processing devices, and in particular observations of quantum behavior in several solid state systems. On the theoretical side, the complementary expertise of the contributors provides models of the various structures in connection with the problem of minimizing decoherence.

  18. Permeability, strength and electrochemical studies on ceramic multilayers for solid-state electrochemical cells

    Andersen, Kjeld Bøhm; Charlas, Benoit; Stamate, Eugen


    and by electrochemical impedance spectroscopy in air at temperatures between 300 and 450 °C. The resulting structures were also evaluated with scanning electron microscopy.The work showed a dependence on the pore former composition and electrode powder pre-treatment resulting in variations in porosity, strength...

  19. Solid state physics

    Brewster, Hilary D


    Solid state physics is an exhaustive introductory text for the students of physics. Keeping in mind, this book has been prepared to present the subject-matter in an easily understandable way without sacrificing the essential details and principles an yet avoiding redundant matter and unnecessary complications. This book is expected to meet adequately the need of the students for whom it is meant.

  20. Structure and some magnetic properties of (BiFeO3x-(BaTiO31−x solid solutions prepared by solid-state sintering

    Kowal Karol


    Full Text Available This paper presents the results of the study on structure and magnetic properties of the perovskite-type (BiFeO3x-(BaTiO31−x solid solutions. The samples differing in the chemical composition (x = 0.9, 0.8, and 0.7 were produced according to the conventional solid-state sintering method from the mixture of powders. Moreover, three different variants of the fabrication process differing in the temperatures and soaking time were applied. The results of X-ray diffraction (XRD, Mössbauer spectroscopy (MS, and vibrating sample magnetometry (VSM were collected and compared for the set of the investigated materials. The structural transformation from rhombohedral to cubic symmetry was observed for the samples with x = 0.7. With increasing of BaTiO3 concentration Mössbauer spectra become broadened reflecting various configurations of atoms around 57Fe probes. Moreover, gradual decreasing of the average hyperfine magnetic field and macroscopic magnetization were observed with x decreasing.

  1. A new method to study complex materials in solid state chemistry: application to chalcogenide materials

    Lippens, P. E.; Olivier-Fourcade, J.; Jumas, J. C.


    We show that a combined application of Mössbauer spectroscopy and other experimental tools such as X-ray photoelectron spectroscopy, X-ray absorption spectroscopy and nuclear magnetic resonance provides a coherent picture of the local electronic structure in chalcogenide materials. In order to develop this idea we propose an analysis of the Sn, Sb and Te local electronic structures for three different systems of materials. The first example concerns the In Sn S system. We show that Li insertion in In16Sn4S32 leads to changes of the Sn oxidation states from Sn(IV) to Sn(II). The second example concerns materials of the Tl Sb S system. We show that variations of the 121Sb Mössbauer isomer shift and surface of the first peak of the X-ray absorption spectra at the Sb LIII edge can be linearly correlated because of the main influence of the Sb 5s electrons. This is explained by changes in the local environment of the Sb atoms. The last example concerns the crystalline phases of the Tl Sn Te system. The formal oxidation numbers of the Te atoms are determined from 125Te Mössbauer spectroscopy and X-ray photoelectron spectroscopy. They are related to the different types of bonds involving the Te atoms in the Tl Sn Te compounds.

  2. Solid state NMR of biopolymers and synthetic polymers

    Jelinski, Lynn W. [Cornell Univ., Geneva, NY (United States)


    Solid state NMR has been invaluable in evaluating the structure, phase separation, and dynamics of polymers. Because polymers are generally used in the solid state, solid state NMR is especially powerful because it provides information about the materials in their native state. This review gives a general overview of solid state NMR, concentrating on solid state {sup 13} C and {sup 2} H NMR. It then focuses on two examples: the biopolymer spider silka and the engineering material polyurethane. It illustrates how solid state NMR can provide new information about synthetic and bio-polymers. (author) 11 refs., 5 figs., 3 tabs.

  3. Studies in semiconducting metal oxides in conjunction with silicon for solid state gas sensors. Progress report, April 1, 1977-September 30,1979

    Jordan, A.G.; Advani, G.N.


    A fundamental investigation of SnO/sub 2/ and ZnO thin films with emphasis on their use in solid state gas detection is discussed. Methods of thin film preparation, described here, include the chemical vapor deposition (CVD) technique for SnO/sub 2/ films and the radio frequency sputtering technique for SnO/sub 2/ and ZnO films. The use of Auger electron spectroscopy, (AES), transmission electron microscopy, (TEM) and x ray diffractometry, (XRD) in the analysis of these films is reported. Careful selection of the most useful films are made by applying these techniques to the films prepared here. The electrical stability and gas sensitivity response of rf sputtered films are studied. Information regarding the mechanisms involved in gas detection are also presented. Some preliminary device structures using these films along with well-established techniques for planar processing are also reported.

  4. Radon diffusion studies in some building materials using solid state nuclear track detectors

    Singh, S; Singh, B; Singh, J


    LR-115 plastic track detector has been used to study radon diffusion through some building materials, viz. cement, soil, marble chips, sand and lime as well as air. Diffusion constant and diffusion length is calculated for all these materials.

  5. Solid state compatibility studies with tablet excipients using non thermal methods.

    Liltorp, Karin; Larsen, Trine Gorm; Willumsen, Birgitte; Holm, René


    Compatibility between two new active pharmaceutical ingredients (API) and several pharmaceutical excipients used in solid formulations has been investigated by FT-IR and HPLC following storage under two different conditions. Compatibility was investigated by storage at isothermal stress conditions for (i) 3days and subsequently analysed by FT-IR and (ii) 12weeks of storage and analysis by HPLC. For the majority of the examined excipients a large degradation measured by HPLC after 12weeks storage was also detected by FT-IR following storage at isothermal stress conditions for 3days, i.e. there was a general agreement between the results obtained by the two protocols. Further, the FT-IR method showed clear incompatibility with three excipients where no degradation products were detected by HPLC, but where a significant decrease in the API quantified by the HPLC assay, was observed. The accelerated method thus showed a clear advantage: incompatibility found after 12weeks using HPLC was seen after 3days with FT-IR. Furthermore, FT-IR provides an insight into structural changes not seen with HPLC. This is exemplified by the desalting of a hydrogen bromide salt of one of the two compounds, which might lead to changes of the intrinsic dissolution rate and potentially affect the bioavailability of the API.

  6. Probing local structures of siliceous zeolite frameworks by solid-state NMR and first-principles calculations of 29Si-O-29Si scalar couplings.

    Cadars, Sylvian; Brouwer, Darren H; Chmelka, Bradley F


    Subtle structural details of siliceous zeolites are probed by using two-bond scalar (J) coupling constants to characterize covalently bonded 29Si-O-29Si site pairs and local framework order. Solid-state two-dimensional (2D) 29Si{29Si} NMR measurements and first-principles calculations of 2J(29Si-O-29Si) couplings shed insights on both the local structures of siliceous zeolites Sigma-2 and ZSM-12, as well as the sensitivity of J couplings for detailed characterization analyses. DFT calculations on a model linear silicate dimer show that 2J(Si-O-Si) couplings have complicated multiple angular dependencies that make semi-empirical treatments impractical, but which are amenable to cluster approaches for accurate J-coupling calculations in zeolites. DFT calculations of 2J(29Si-O-29Si) couplings of the siliceous zeolite Sigma-2, whose framework structure is known to high accuracy from single-crystal X-ray diffraction studies, yield excellent agreement between calculated and experimentally measured 2J(Si-O-Si) couplings. For the siliceous zeolite ZSM-12, calculated 2J(29Si-O-29Si) couplings based on less-certain powder X-ray diffraction analyses deviate significantly from experimental values, while a refined structure based on 29Si chemical-shift-tensor analyses shows substantially improved agreement. 29Si J-coupling interactions can be used as sensitive probes of local structures of zeolitic frameworks and offer new opportunities for refining and solving complicated structures, in combination with complementary scattering, modeling, and other nuclear spin interactions.

  7. A.c. conductivity and dielectric study of LiNiPO4 synthesized by solid-state method

    M Ben Bechir; A Ben Rhaiem; K Guidara


    LiNiPO4 compound was prepared by the conventional solid-state reaction. The sample was characterized by X-ray powder diffraction, infrared, Raman analysis spectroscopy and electrical impedance spectroscopy. The compound crystallizes in the orthorhombic system, space group with = 10.0252(7) Å, = 5.8569(5) Å and = 4.6758(4) Å. Vibrational analysis was used to identify the presence of PO$^{3-}_{4}$ group in this compound. The complex impedance has been measured in the temperature and frequency ranges 654–716 K and 242 Hz–5 MHz, respectively. The ' and '' vs frequency plots are well-fitted to an equivalent circuit consisting of series of combination of grains and grain boundary elements. Dielectric data were analysed using complex electrical modulus * for the sample at various temperatures. The modulus plots are characterized by the presence of two peaks thermally activated. The frequency dependence of the conductivity is interpreted in terms of equation: _a.c.() = [g/(1 + 22) + (∞22/1 + 22) + An]. The near values of activation energies obtained from the analysis of ", conductivity data and equivalent circuit confirms that the transport is through ion hopping mechanism dominated by the motion of Li+ in the structure of the investigated material.

  8. Applications of electron density studies in molecular and solid state science

    Overgaard, Jacob


    The present dissertation contains the distillate of my scientific output in the field of experimental and theoretical electron density studies roughly over the last decade and a little more, since earning my PhD-degree in 2001. There are several reasons that I have chosen to write my dissertation...

  9. Application of solid state NMR for the study of surface bound species and fossil fuels

    Althaus, Stacey [Iowa State Univ., Ames, IA (United States)


    In this study, stimulated echo with pulsed field gradients was used to measure the diffusion of two different solvents, water and hexane, in AP-MSN-2.7 and AP-MSN-3.7. The resulting data were then fit using two different methods. Based on these fits, the diffusion of hexane in AP-MSN-2.7 was shown to be slower than in the larger pores. This agrees well with our studies of catalytic activity, which show an increase in the reaction rate with the increase in pore size. Thus, both substrate inhibition and diffusion played a role in the decreased efficiency of the APMSN with small pore sizes.

  10. Formulation studies on stability of solid-state proteases for detergent applications

    Ay, Suzan Biran; Jensen, Anker Degn; Kiil, Søren;


    Enzymes are one of the most important components in the laundry detergents. They effectively contribute to the washing process by decreasing energy and water consumption, reducing environmental load of detergent products, leaving non-toxic water effluents and providing fabric care. Ensuring proper...... that, the inactivation was caused by single-oxidation of the enzyme at Met222 residue. Formulation studies revealed that, having an anti-oxidative property,Na2S2O3 had a better activity-preservation effect compared to Na2CO3, retaining 80% and 60% residual activity, respectively. In addition, mixing...

  11. An experimental and theoretical NMR study of NH-benzimidazoles in solution and in the solid state: proton transfer and tautomerism

    Carla I. Nieto


    Full Text Available This paper reports the 1H, 13C and 15N NMR experimental study of five benzimidazoles in solution and in the solid state (13C and 15N CPMAS NMR as well as the theoretically calculated (GIAO/DFT chemical shifts. We have assigned unambiguously the "tautomeric positions" (C3a/C7a, C4/C7 and C5/C6 of NH-benzimidazoles that, in some solvents and in the solid state, appear different (blocked tautomerism. In the case of 1H-benzimidazole itself we have measured the prototropic rate in HMPA-d18.

  12. Real-time plasmon spectroscopy study of the solid-state oxidation and Kirkendall void formation in copper nanoparticles.

    Susman, Mariano D; Feldman, Yishai; Bendikov, Tatyana A; Vaskevich, Alexander; Rubinstein, Israel


    Oxidation and corrosion reactions have a major effect on the application of non-noble metals. Kinetic information and simple theoretical models are often insufficient for describing such processes in metals at the nanoscale, particularly in cases involving formation of internal voids (nano Kirkendall effect, NKE) during oxidation. Here we study the kinetics of solid-state oxidation of chemically-grown copper nanoparticles (NPs) by in situ localized surface plasmon resonance (LSPR) spectroscopy during isothermal annealing in the range 110-170 °C. We show that LSPR spectroscopy is highly effective in kinetic studies of such systems, enabling convenient in situ real-time measurements during oxidation. Change of the LSPR spectra throughout the oxidation follows a common pattern, observed for different temperatures, NP sizes and substrates. The well-defined initial Cu NP surface plasmon (SP) band red-shifts continuously with oxidation, while the extinction intensity initially increases to reach a maximum value at a characteristic oxidation time τ, after which the SP intensity continuously drops. The characteristic time τ is used as a scaling parameter for the kinetic analysis. Evolution of the SP wavelength and extinction intensity during oxidation at different temperatures follows the same kinetics when the oxidation time is normalized to τ, thus pointing to a general oxidation mechanism. The characteristic time τ is used to estimate the activation energy of the process, determined to be 144 ± 6 kJ mol(-1), similar to previously reported values for high-temperature Cu thermal oxidation. The central role of the NKE in the solid-state oxidation process is revealed by electron microscopy, while formation of Cu2O as the major oxidation product is established by X-ray diffraction, XPS, and electrochemical measurements. The results indicate a transition of the oxidation mechanism from a Valensi-Carter (VC) to NKE mechanism with the degree of oxidation. To interpret the

  13. Study of ion diffusional motion in ionic liquid-based polymer electrolytes by simultaneous solid state NMR and DTA.

    Rajput, Dushyant Singh; Yamada, Koji; Sekhon, S S


    Polymer electrolytes containing ionic liquid (IL), 2-methyl-1,3-dipropylimidazolium dihydrogenphosphate (MDPImH2PO4) have been studied by (1)H solid state NMR and differential thermal analysis (DTA) simultaneously by using a specially designed probe. To the best of our knowledge, this is the first report of its kind for IL based polymer electrolytes. The variation of NMR line width with temperature for the IL and polymer electrolytes shows line narrowing at the glass transition and melting temperature. The onset of long-range ion diffusional motion also takes place at these temperatures and is accompanied by a sudden increase in ionic conductivity value by 2-3 orders of magnitude. The presence of amorphous and crystalline phases in IL-based polymer electrolytes has been observed from X-ray diffraction (XRD) studies, and the amorphous phase is the high conducting phase in these polymer electrolytes. The IL-based polymer electrolytes have been observed to be thermally stable up to 200 °C. The results obtained from ion transport studies have also been supported by Fourier transform infrared (FTIR), XRD, and cyclic voltammetry (CV) studies.

  14. Solid-state (13)C NMR and synchrotron SAXS/WAXS studies of uniaxially-oriented polyethylene.

    Afeworki, Mobae; Brant, Pat; Lustiger, Arnold; Norman, Alexander


    We report solid-state (13)C NMR and synchrotron wide-and small-angle X-ray scattering experiments (WAXS, SAXS) on metallocene linear low density polyethylene films (e.g., Exceed™ 1018 mLLDPE; nominally 1MI, 0.918 density ethylene-hexene metallocene copolymer) as a function of uniaxial draw ratio, λ. Combined, these experiments provide an unambiguous, quantitative molecular view of the orientation of both the crystalline and amorphous phases in the samples as a function of draw. Together with previously reported differential scanning calorimetry (DSC), gas transport measurements, transmission electron microscopy (TEM), optical birefringence, small angle X-ray scattering (SAXS) as well as other characterization techniques, this study of the state of orientation in both phases provides insight concerning the development of unusually high barrier properties of the most oriented samples (λ=10). In this work, static (non-spinning) solid-state NMR measurements indicate that in the drawn Exceed(TM) films both the crystalline and amorphous regions are highly oriented. In particular, chemical shift data show the amorphous phase is comprised increasingly of so-called "taut tie chains" (or tie chains under any state of tautness) in the mLLDPE with increasing draw ratio - the resonance lines associated with the amorphous phase shift to where the crystalline peaks are observed. In the sample with highest total draw (λ=10), virtually all of the chains in the non-crystalline region have responded and aligned in the machine (draw) direction. Both monoclinic and orthorhombic crystalline peaks are observed in high-resolution, solid-state magic-angle spinning (MAS) NMR measurements of the oriented PE films. The orientation is comparable to that obtained for ultra-high molecular weight HDPE fibers described as "ultra-oriented" in the literature. Furthermore, the presence of a monoclinic peak in cold-drawn samples suggests that there is an appreciable internal stress associated

  15. A solid state nuclear magnetic resonance study of industrial inorganic pigments

    Dajda, N


    Nuclear magnetic resonance has been used to look at a number of colourful ceramic pigment systems, most of which are sold commercially in large quantities. Doped zircon (ZrSiO sub 4) pigments were examined using sup 1 sup 9 F, sup 2 sup 3 Na, sup 2 sup 9 Si, sup 5 sup 1 V and sup 9 sup 1 Zr NMR. In these systems, paramagnetic species are incorporated into the sample in small quantities creating the colourful pigment. The impurity dopants in the systems studied either dope directly into lattice sites in the zircon, or form an extra chemical phase. NMR was able to distinguish between these two doping mechanisms in a number of doped zircon pigments. Most spectra showed effects which were due to the magnetic influence of paramagnetic colouring species, and the strength of the interaction depended on the magnetic moment of the ion containing the unpaired electron. In the case of vanadium doped zircon, the moment was small enough that it allowed extra contact shifted peaks to be resolved in the spectra which indica...

  16. Solid state 1H NMR studies of cell wall materials of potatoes

    Tang, Huiru; Belton, Peter S.; Ng, Annie; Waldron, Keith W.; Ryden, Peter


    Cell wall materials from potatoes ( Solanum tuberosum) prepared by two different methods have been studied using NMR proton relaxation times. Spin lattice relaxation in both the rotating and laboratory frames as well as transverse relaxation have been measured over a range of temperatures and hydration levels. It was observed that the sample prepared using a DMSO extraction showed anomalous behaviour of spin lattice relaxation in the laboratory frame probably due to residual solvent in the sample. Spin lattice relaxation in the laboratory frame is the result of hydroxymethyl rotation and another unidentified high frequency motion. In the rotating frame relaxation is adequately explained by hydroxymethyl rotation alone. In neither experiment is methyl group rotation observed, calculation suggests that this is due to the low density of methyl groups in the sample. Non-freezing water in potato cell walls, α-cellulose and pectin was found about 0.2, 0.04 and 0.18 g per gram dry matter, indicating preferable hydration of pectin compared to cellulose. The effects of hydration are most noticeable in the measurements that reflect low frequency motions, particularly transverse relaxation, where both second moments and the relative intensity of signals arising from immobile material are reduced by hydration.

  17. Solid-State Nuclear Magnetic Resonance Investigation of the Structural Topology and Lipid Interactions of a Viral Fusion Protein Chimera Containing the Fusion Peptide and Transmembrane Domain.

    Yao, Hongwei; Lee, Myungwoon; Liao, Shu-Yu; Hong, Mei


    The fusion peptide (FP) and transmembrane domain (TMD) of viral fusion proteins play important roles during virus-cell membrane fusion, by inducing membrane curvature and transient dehydration. The structure of the water-soluble ectodomain of viral fusion proteins has been extensively studied crystallographically, but the structures of the FP and TMD bound to phospholipid membranes are not well understood. We recently investigated the conformations and lipid interactions of the separate FP and TMD peptides of parainfluenza virus 5 (PIV5) fusion protein F using solid-state nuclear magnetic resonance. These studies provide structural information about the two domains when they are spatially well separated in the fusion process. To investigate how these two domains are structured relative to each other in the postfusion state, when the ectodomain forms a six-helix bundle that is thought to force the FP and TMD together in the membrane, we have now expressed and purified a chimera of the FP and TMD, connected by a Gly-Lys linker, and measured the chemical shifts and interdomain contacts of the protein in several lipid membranes. The FP-TMD chimera exhibits α-helical chemical shifts in all the membranes examined and does not cause strong curvature of lamellar membranes or membranes with negative spontaneous curvature. These properties differ qualitatively from those of the separate peptides, indicating that the FP and TMD interact with each other in the lipid membrane. However, no (13)C-(13)C cross peaks are observed in two-dimensional correlation spectra, suggesting that the two helices are not tightly associated. These results suggest that the ectodomain six-helix bundle does not propagate into the membrane to the two hydrophobic termini. However, the loosely associated FP and TMD helices are found to generate significant negative Gaussian curvature to membranes that possess spontaneous positive curvature, consistent with the notion that the FP-TMD assembly may

  18. Solid-state NMR and Membrane Proteins

    Opella, Stanley J.


    The native environment for a membrane protein is a phospholipid bilayer. Because the protein is immobilized on NMR timescales by the interactions within a bilayer membrane, solid-state NMR methods are essential to obtain high-resolution spectra. Approaches have been developed for both unoriented and oriented samples, however, they all rest on the foundation of the most fundamental aspects solid-state NMR, and the chemical shift and homo- and hetero-nuclear dipole-dipole interactions. Solid-state NMR has advanced sufficiently to enable the structures of membrane proteins to be determined under near-native conditions in phospholipid bilayers. PMID:25681966




    Full Text Available Coconut fat could be an important source of bioactive compounds with a large applicability in industry. In this study it was realized the enzymatic hydrolysis of coconut fat with different yeast strains of Yarrowia lipolytica. The aim of this study was to optimize the hydrolysis conditions and determination of Yarrowia lipolytica specificity on coconut fat as substrate. The hydrolysis was performed by yeast strains cultivated on stationary solid state conditions on spirit blue agar medium supplemented with 3% coconut fat, at 25°C and 4°C, and at values of water activity of 0.98, 0.96 and 0.93. The substrate hydrolysis index was recorded every 24 hours, during of 240 hours of stationary cultivation. The most active lipolytic yeast was strain coded S5 which produce a high level of extracellular lipase with high coconut hydrolyze activity at 25°C and two water activities 0.98 and 0.96, in the shortest time (24 – 72 hours. In the presence of 3% NaCl in media, the strains coded S9, S5 and S4 were the most active from all tested strains at 25°C and 4°C. At low temperatures and in presence of 10.1% NaCl all tested yeasts had no lipolytic activity.

  20. The study of ultrasonic irradiation effects on solid state powders of HTc superconductor YBa2Cu3O7-x

    Kargar, Mahboubeh; Khoshnevisan, Bahram


    In this paper, an ultrasound assisted solid state synthesis method for high-temperature (HTc) YBa2Cu3O7-x (YBCO) superconductor nanostructures with different morphologies is presented. Here, the routine heat treatment of the powder mixture of as-prepared precursors is followed by the ultrasound irradiation inside various alcoholic solutions. Not only the influence of the ultrasound irradiation intensity and duration but also the influence of different solvents such as ethanol, methanol and 1-butanol with various vapor pressures and so various destruction powers were also studied on the morphology and particle size of the products. The various morphologies were studied by scanning electron microscope (SEM) which not only have been affected by intensity and type of alcoholic solvent but also sonication time and ultrasound power have significant role as well. Formation of the YBCO superconducting phase was examined by using Rietveld refinement of X-ray diffraction (XRD) which indicates the crystalline preferred growth in c-axis orientation in crystal. Magnetic susceptibility measurements showed the ultrasound waves had no important effect on the onset critical temperature of the prepared nanorods (about 91.64 K) which is compared with the bulk samples (Tc ˜ 92K).

  1. Characterization of phosphate sequestration by a lanthanum modified bentonite clay: A solid- state NMR, EXAFS and PXRD study

    Dithmer, Line; Lipton, Andrew S.; Reitzel, Kasper; Warner, Terence E.; Lundberg, Daniel; Nielsen, Ulla Gro


    Phosphate (P) sequestration by a lanthanum (La) exchanged bentonite (a clay mineral), which is extensively used in chemical lake restoration, was investigated on the molecular level using a combination of 31P and 139La solid state NMR spectroscopy (SSNMR), extended X-ray absorption spectroscopy (EX-AFS) and powder X-ray diffraction (PXRD) in combination with sorption studies. 31P SSNMR show that all phosphate is immobilized as rhabdophane, LaPO4·xH2O, which is further supported by 139La SSNMR and EXAFS; whereas PXRD results are ambiguous with respect to rhabdophane and monazite (LaPO4). Adsorption studies show that, at humic acids (HA) concentrations above ca. 250 μM the binding capacity is only 50 % of the theoretical value or even less. No other lanthanum or phosphate phases are detected by SSNMR and EXAFS indicating the effect of HA is kinetic. Moreover, 31P SSNMR shows that rhabdophane formed upon P sequestration is in close proximity to the clay matrix.

  2. Variability of cork from Portuguese Quercus suber studied by solid-state (13)C-NMR and FTIR spectroscopies.

    Lopes, M H; Barros, A S; Pascoal Neto, C; Rutledge, D; Delgadillo, I; Gil, A M


    A new approach is presented for the study of the variability of Portuguese reproduction cork using solid-state (13)C-NMR spectroscopy and photoacoustic (PAS) FTIR (FTIR-PAS) spectroscopy combined with chemometrics. Cork samples were collected from 12 different geographical sites, and their (13)C-cross-polarization with magic angle spinning (CP/MAS) and FTIR spectra were registered. A large spectral variability among the cork samples was detected by principal component analysis and found to relate to the suberin and carbohydrate contents. This variability was independent of the sample geographical origin but significantly dependent on the cork quality, thus enabling the distinction of cork samples according to the latter property. The suberin content of the cork samples was predicted using multivariate regression models based on the (13)C-NMR and FTIR spectra of the samples as reported previously. Finally, the relationship between the variability of the (13)C-CP/MAS spectra with that of the FTIR-PAS spectra was studied by outer product analysis. This type of multivariate analysis enabled a clear correlation to be established between the peaks assigned to suberin and carbohydrate in the FTIR spectrum and those appearing in the (13)C-CP/MAS spectra.

  3. Study on All-Solid-State Chloride Sensor Based on Tin Oxide/Indium Tin Oxide Glass

    Cheng, Jui-Fu; Chou, Jung-Chuan; Sun, Tai-Ping; Hsiung, Shen-Kan; Kao, Hui-Ling


    An all-solid-state chloride electrode based on a tin oxide (SnO2)/indium tin oxide (ITO) glass was developed in this study. The sensing membrane of the electrode was prepared by mixing poly(vinyl chloride) (PVC), bis(2-ethylhexyl) sebacate (DOS), [4,5-dimethy-l-3,6-bis(dodecyloxy)-1,2-phenylene] bis(mercury chloride) (ETH9033), and tridodecylmethyl ammonium chloride (TDDMACl). The mixed solution was mixed with tetrahydrofuran (THF), and then dropped on the sensing window of SnO2/ITO glass. According to the experimental results, the optimal weight ratio were PVC:DOS:ETH9033:TDDMACl=33:66:2:5. At this optimum weight ratio, the sensitivity was 54 mV/dec while the range of linear concentrations of NaCl solutions was between 10-4 and 1 M. The lower detection limit of the sensor reached 8×10-5 M and the response time was less than 1 s. The selectivity coefficient was consistent with the theory of Hofmeister lipophilicity. The lifetime was over 60 days and the repeatability was over 50 times. Moreover, the chloride ion sensor was successfully applied to detecting chloride ions in rinsing solutions for contact lenses, and the experimental results revealed that the correlation coefficient was 0.99.

  4. First-principles study of intercalation of alkali ions in FeSe for solid-state batteries

    Jiang, Zhiqiang; Gu, Xiao; Wang, Linxia; Huang, Li


    Electrochemical properties of alkali ions (Li+, Na+, and K+) intercalating into FeSe have been studied based on first-principles calculations within density functional theory. The intercalation sites of lithium ions are found to be different from sodium and potassium ions due to the small ionic radius of lithium. Calculations of minimum energy path on the diffusions of Li+, Na+, and K+ in FeSe show that the activation energies for those alkali ions increase with their ionic radii. Lithium ions have a rather smaller diffusion barrier of about 0.20 eV, which leads to a bigger diffusion coefficient of about 6.3 ×10-6cm2 /s . We also show that FeSe has a flat discharging stage at about 1.0 V with lithium ions. These results indicate that XFe2Se2 (X = Li, Na, K) may be potential electrochemical active materials, especially for solid-state electrolyte and supercapacitors.

  5. Adiabatic fast passage application in solid state NMR study of cross relaxation and molecular dynamics in heteronuclear systems

    Baranowski, M.; Woźniak-Braszak, A.; Jurga, K.


    The paper presents the benefits of using fast adiabatic passage for the study of molecular dynamics in the solid state heteronuclear systems in the laboratory frame. A homemade pulse spectrometer operating at the frequency of 30.2 MHz and 28.411 MHz for protons and fluorines, respectively, has been enhanced with microcontroller direct digital synthesizer DDS controller [1-4]. This work briefly describes how to construct a low-cost and easy-to-assemble adiabatic extension set for homemade and commercial spectrometers based on recently very popular Arduino shields. The described set was designed for fast adiabatic generation. Timing and synchronization problems are discussed. The cross-relaxation experiments with different initial states of the two spin systems have been performed. Contrary to our previous work [5] where the steady-state NOE experiments were conducted now proton spins 1H are polarized in the magnetic field B0 while fluorine spins 19F are perturbed by selective saturation for a short time and then the system is allowed to evolve for a period in the absence of a saturating field. The adiabatic passage application leads to a reversal of magnetization of fluorine spins and increases the amplitude of the signal.

  6. Cross-linked carbon network with hierarchical porous structure for high performance solid-state electrochemical capacitor

    Cheng, Yongliang; Huang, Liang; Xiao, Xu; Yao, Bin; Hu, Zhimi; Li, Tianqi; Liu, Kang; Zhou, Jun


    The development of portable electronics strongly requires flexible, lightweight, and inexpensive energy-storage devices with high power density, long cycling stability, and high reliability. In this work, we prepare a flexible solid-state electrochemical capacitor using cross-linked hierarchical porous carbon network as electrode material via electrospinning and carbonization process. This device can reversibly deliver a maximum energy density of 10.18 W h/kg with excellent cycling stability which achieves 95% capacitance retention after 20000 charge/discharge cycles. Moreover, it also demonstrates outstanding mechanical flexibility and excellent capacitance retention even when the device is repeatedly bended 10000 cycles under 90°. All of these results suggest its promising perspective in flexible energy storage device.

  7. Solid state 13C NMR studies of methane dehydroaromatization reaction on Mo/HZSM-5 and W/HZSM-5 catalysts.

    Yang, Jun; Ma, Ding; Deng, Feng; Luo, Qing; Zhang, Mingjin; Bao, Xinhe; Ye, Chaohui


    Methane dehydroaromatization on Mo/HZSM-5 and W/HZSM-5 catalysts was studied by solid state 13C NMR spectroscopy, both variation of the state of transition metal component and products such as ethane, benzene, ethene adsorbed on or in zeolite were observed after high temperature (900-1000 K) reaction.

  8. Fluorine segregation in crystalline materials: structural control and solid-state [2+2] cycloaddition in CF(3)-substituted tetrathiafulvalene derivatives.

    Jeannin, Olivier; Fourmigué, Marc


    The well-known influence of long perfluorinated chains on the structures and stability of amphiphilic molecules in liquid crystalline mesophases or mesoscopic micellar arrangements is evaluated here in the realm of crystalline materials based on rigid aromatic molecules bearing only a limited number of CF(3) moieties. Tetrathiafulvalene (TTF) derivatives bearing one or two CF(3) groups, that is, (Z)- and (E)-(CF(3))(2)TTF ((Z)-1, (E)-1), EDT-TTF-CF(3) (2), and EDT-TTF(CF(3))(2) (3) (EDT=ethylenedithio) are prepared from the 1,3-dipolar reaction of methyl 4,4,4-trifluorotetrolate with ethylenetrithiocarbonate. The structures of neutral (Z)-1, (E)-1, 2, and 3 as indicated by single-crystal X-ray diffraction measurements reveal the recurrent formation of layered structures with a strong segregation of the fluorinated moieties and formation of fluorous bilayers, attributed to the amphiphilic character of those TTF derivatives upon CF(3) functionalization, and without need for longer C(n)F(2n+1) (n>1) perfluorinated chains. The short intermolecular distance between outer C==C double bonds observed in the layered structure of (E)-1 allows a solid-state [2+2] photocyclization with formation of chiral dyads incorporating the characteristic cyclobutane ring. These dyads containing two dihydrotetrathiafulvalene moieties facing each other exhibit reversible oxidation to the mixed-valence radical cation state and organize in the solid-state into the same layered structures with fluorous bilayers.

  9. Variations of structures and solid-state conductivity of isomeric silver(I) coordination polymers having linear and V-shaped thiophene-centered ditriazole ligands

    Hu, Bin [State Key Laboratory of Coordination Chemistry, Nanjing National Laboratory of Microstructures, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093 (China); School of Environmental and Chemical Engineering, Nanchang Hangkong University, Nanchang, 330063 (China); Geng, Jiao; Zhang, Lie [State Key Laboratory of Coordination Chemistry, Nanjing National Laboratory of Microstructures, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093 (China); Huang, Wei, E-mail: [State Key Laboratory of Coordination Chemistry, Nanjing National Laboratory of Microstructures, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093 (China)


    A pair of new linear and V-shaped acceptor–donor–acceptor (A−D−A) thiophene-centered ditriazole structural isomers, i.e., 2,5-di(1H-1,2,4-triazol-1-yl)thiophene (L{sup 1}) and 3,4-di(1H-1,2,4-triazol-1-yl)thiophene (L{sup 2}), has been synthesized and characterized. They are used as μ{sub 2}-bridging ligands to prepare a pair of silver(I) coordination polymers formulated as [Ag(L{sup 1})(NO{sub 3})]{sub n} (1) and [Ag(L{sup 2})(NO{sub 3})]{sub n} (2), which are also structural isomers at the supramolecular level. X-ray single-crystal diffraction analyses for 1 and 2 reveal that they exhibit the same one-dimensional (1D) coordination polymers but different structural architectures because of the distinguishable shape and configuration of isomeric ligands (L{sup 1} and L{sup 2}) and the alterations of the coordination numbers. More interestingly, compared with the free ligands, 1D silver(I) polymeric isomers 1 and 2 show significant enhancement of solid-state conductivity to different extents (1.42×10{sup 4} and 2.17×10{sup 3} times), where 6.96 times' enhancement of solid-state conductivity from 1 to 2 has been observed. The formation of Ag–N coordinative bonds and the configurational discrepancy of L{sup 1} and L{sup 2} are believed to play important roles in facilitating the electron transport between molecules, which can also be supported by Density Function Theory calculations of their band gaps. - Graphical abstract: A pair of linear and V-shaped isomeric thiophene-centered ditriazole ligands (L{sup 1}) and L{sup 2} are used to prepare a pair of silver(I) polymeric isomers (1 and 2), where significant enhancement of solid-state conductivity to different extents are observed originating from the distinguishable shape and configuration of isomeric ligands. - Highlights: • A pair of linear and V-shaped thiophene-centered ditriazole structural isomers is prepared. • They are used as µ{sub 2}-bridging ligands to prepare a pair of silver

  10. Influences of the non-covalent interaction strength on reaching high solid-state order and device performance of a low bandgap polymer with axisymmetrical structural units.

    Jheng, Jyun-Fong; Lai, Yu-Ying; Wu, Jhong-Sian; Chao, Yi-Hsiang; Wang, Chien-Lung; Hsu, Chain-Shu


    A high organic field-effect transistor mobility (0.29 cm(2) V(-1) s(-1) ) and bulk-heterojunction polymer solar cell performance (PCE of 6.82%) have been achieved in a low bandgap alternating copolymer consisting of axisymmetrical structural units, 5,6-difluorobenzo-2,1,3-thiadiazole. Introducing the fluorine substituents enhanced intermolecular interaction and improved the solid-state order, which consequently resulted in the highest device performances among the 2,1,3-thiadiazole-quarterthiophene based alternating copolymers.

  11. Pharmaceutical Applications of Relaxation Filter-Selective Signal Excitation Methods for ¹⁹F Solid-State Nuclear Magnetic Resonance: Case Study With Atorvastatin in Dosage Formulation.

    Asada, Mamiko Nasu; Nemoto, Takayuki; Mimura, Hisashi


    We recently developed several new relaxation filter-selective signal excitation (RFS) methods for (13)C solid-state nuclear magnetic resonance (NMR) that allow (13)C signal extraction of the target components from pharmaceuticals. These methods were successful in not only qualification but also quantitation over the wide range of 5% to 100%. Here, we aimed to improve the sensitivity of these methods and initially applied them to (19)F solid-state NMR, on the basis that the fluorine atom is one of the most sensitive NMR-active nuclei. For testing, we selected atorvastatin calcium (ATC), an antilipid BCS class II drug that inhibits 3-hydroxy-3-methylglutaryl-coenzyme A reductase and is marketed in crystalline and amorphous forms. Tablets were obtained from 2 generic drug suppliers, and the ATC content occurred mainly as an amorphous form. Using the RFS method with (19)F solid-state NMR, we succeeded in qualifying trace amounts (less than 0.5% w/w level) of crystalline phase (Form I) of ATC in the tablets. RFS methods with (19)F solid-state NMR are practical and time efficient and can contribute not only to the study of pharmaceutical drugs, including those with small amounts of a highly potent active ingredient within a formulated product, but also to the study of fluoropolymers in material sciences. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

  12. Characterization of phosphate sequestration by a lanthanum modified bentonite clay: A solid-state NMR, EXAFS and PXRD study

    Dithmer, Line; Lipton, Andrew S; Reitzel, Kasper;


    Phosphate (Pi) sequestration by a lanthanum (La) exchanged clay mineral (La-Bentonite), which is extensively used in chemical lake restoration, was investigated on the molecular level using a combination of 31P and 139La solid state NMR spectroscopy (SSNMR), extended X-ray absorption spectroscopy...

  13. Characterization of phosphate sequestration by a lanthanum modified bentonite clay: A solid-state NMR, EXAFS and PXRD study

    Dithmer, Line; Lipton, Andrew S; Reitzel, Kasper


    Phosphate (Pi) sequestration by a lanthanum (La) exchanged clay mineral (La-Bentonite), which is extensively used in chemical lake restoration, was investigated on the molecular level using a combination of 31P and 139La solid state NMR spectroscopy (SSNMR), extended X-ray absorption spectroscopy...... formed upon Pi sequestration is in close proximity to the clay matrix....

  14. Advanced solid-state NMR spectroscopy of natural organic matter.

    Mao, Jingdong; Cao, Xiaoyan; Olk, Dan C; Chu, Wenying; Schmidt-Rohr, Klaus


    Solid-state NMR is essential for the characterization of natural organic matter (NOM) and is gaining importance in geosciences and environmental sciences. This review is intended to highlight advanced solid-state NMR techniques, especially a systematic approach to NOM characterization, and their applications to the study of NOM. We discuss some basics of how to acquire high-quality and quantitative solid-state (13)C NMR spectra, and address some common technical mistakes that lead to unreliable spectra of NOM. The identification of specific functional groups in NOM, primarily based on (13)C spectral-editing techniques, is described and the theoretical background of some recently-developed spectral-editing techniques is provided. Applications of solid-state NMR to investigating nitrogen (N) in NOM are described, focusing on limitations of the widely used (15)N CP/MAS experiment and the potential of improved advanced NMR techniques for characterizing N forms in NOM. Then techniques used for identifying proximities, heterogeneities and domains are reviewed, and some examples provided. In addition, NMR techniques for studying segmental dynamics in NOM are reviewed. We also briefly discuss applications of solid-state NMR to NOM from various sources, including soil organic matter, aquatic organic matter, organic matter in atmospheric particulate matter, carbonaceous meteoritic organic matter, and fossil fuels. Finally, examples of NMR-based structural models and an outlook are provided. Copyright © 2016 Elsevier B.V. All rights reserved.

  15. Solid state physics

    Burns, Gerald


    The objective of Solid State Physics is to introduce college seniors and first-year graduate students in physics, electrical engineering, materials science, chemistry, and related areas to this diverse and fascinating field. I have attempted to present this complex subject matter in a coherent, integrated manner, emphasizing fundamental scientific ideas to give the student a strong understanding and ""feel"" for the physics and the orders of magnitude involved. The subject is varied, covering many important, sophisticated, and practical areas, which, at first, may appear unrelated but which ar

  16. Solid State Research.


    Diadiuk, M.C. Plonko. and D.L. Hovey (to be published in AppI . Phys. Lett., January 1985). 3. CA-f. Cox. III (unpublished). 4. D. Yap and L.M. Johnson... AppI . Opt. 23. 2991 (1984). 5. L.M. Johnson and D. Yap. AppI . Opt. 23. 2988 (1984). 6. Solid State Research Report. Lincoln Laboratory, M.I.T. (1983...drift current. 21. A. Carenco, L. Menegaux, and N.T. Lenh, Appi . Phys. Lett. 40, 653 (1982). 22. F.J. Leonberger, J.P. Donnelly, and C.O. Bozler

  17. β-Sheet Nanocrystalline Domains Formed from Phosphorylated Serine-Rich Motifs in Caddisfly Larval Silk: A Solid State NMR and XRD Study

    Addison, J. Bennett; Ashton, Nicholas N.; Weber, Warner S.; Stewart, Russell J.; Holland, Gregory P.; Yarger, Jeffery L.


    Adhesive silks spun by aquatic caddisfly (order Trichoptera) larvae are used to build both intricate protective shelters and food harvesting nets underwater. In this study, we use 13C and 31P solid-state Nuclear Magnetic Resonance (NMR) and Wide Angle X-ray Diffraction (WAXD) as tools to elucidate molecular protein structure of caddisfly larval silk from the species Hesperophylax consimilis. Caddisfly larval silk is a fibroin protein based biopolymer containing mostly repetitive amino acid motifs. NMR and X-ray results provide strong supporting evidence for a structural model in which phosphorylated serine repeats (pSX)4 complex with divalent cations Ca2+ and Mg2+ to form rigid nanocrystalline β-sheet structures in caddisfly silk. 13C NMR data suggests that both phosphorylated serine and neighboring valine residues exist in a β-sheet secondary structure conformation while glycine and leucine residues common in GGX repeats likely reside in random coil conformations. Additionally, 31P chemical shift anisotropy (CSA) analysis indicates that the phosphates on phosphoserine residues are doubly ionized, and are charge-stabilized by divalent cations. Positively charged arginine side chains also likely play a role in charge stabilization. Finally, WAXD results finds that the silk is at least 7–8% crystalline, with β-sheet inter-plane spacings of 3.7 and 4.5 Å. PMID:23452243

  18. Combining oximes with azides to create a novel 1-D [NaCo(III)(2)] system: synthesis, structure and solid-state NMR.

    Pathmalingam, Thushan; Habib, Fatemah; Widdifield, Cory M; Loiseau, Francis; Burchell, Tara J; Gorelsky, Serge I; Beauchemin, André M; Bryce, David L; Murugesu, Muralee


    The synthesis and structure of a novel complex with the formula [NaCo(III)(2)(dmo)(2)(mu-N(3))(3)(N(3))(2)](infinity), , are reported. Complex was synthesized from the reaction of 1-(dimethylamino)propan-2-one oxime (Hdmo), CoCl(2).6H(2)O, and NaN(3) in MeOH. It crystallizes in the monoclinic space group C2/c. The molecular structure consists of one Na(I) and two Co(III) ions bridged by two oxime ligands, two end-to-end azide and three end-on azide anions. The units are linked, forming a 1-D chain. This complex was characterized by UV-Vis spectroscopy where the data confirm the presence of low-spin Co(III) ions. Solid-state (23)Na NMR experiments indicate the presence of one magnetically unique site in the repeating unit, that sample purity in the bulk powdered form is high, and that it possesses microcrystalline order. Solid-state (59)Co NMR experiments at ultra-high field (B(0) = 21.1 T) are in agreement with the structure obtained through X-ray crystallography where the Co(III) ions are coordinated to five nitrogen atoms as well as an oxygen atom.

  19. The Target of β-Expansin EXPB1 in Maize Cell Walls from Binding and Solid-State NMR Studies.

    Wang, Tuo; Chen, Yuning; Tabuchi, Akira; Cosgrove, Daniel J; Hong, Mei


    The wall-loosening actions of β-expansins are known primarily from studies of EXPB1 extracted from maize (Zea mays) pollen. EXPB1 selectively loosens cell walls (CWs) of grasses, but its specific binding target is unknown. We characterized EXPB1 binding to sequentially extracted maize CWs, finding that the protein primarily binds glucuronoarabinoxylan (GAX), the major matrix polysaccharide in grass CWs. This binding is strongly reduced by salts, indicating that it is predominantly electrostatic in nature. For direct molecular evidence of EXPB1 binding, we conducted solid-state nuclear magnetic resonance experiments using paramagnetic relaxation enhancement (PRE), which is sensitive to distances between unpaired electrons and nuclei. By mixing (13)C-enriched maize CWs with EXPB1 functionalized with a Mn(2+) tag, we measured Mn(2+)-induced PRE Strong (1)H and (13)C PREs were observed for the carboxyls of GAX, followed by more moderate PREs for carboxyl groups in homogalacturonan and rhamnogalacturonan-I, indicating that EXPB1 preferentially binds GAX In contrast, no PRE was observed for cellulose, indicating very weak interaction of EXPB1 with cellulose. Dynamics experiments show that EXPB1 changes GAX mobility in a complex manner: the rigid fraction of GAX became more rigid upon EXPB1 binding while the dynamic fraction became more mobile. Combining these data with previous results, we propose that EXPB1 loosens grass CWs by disrupting noncovalent junctions between highly substituted GAX and GAX of low substitution, which binds cellulose. This study provides molecular evidence of β-expansin's target in grass CWs and demonstrates a new strategy for investigating ligand binding for proteins that are difficult to express heterologously.

  20. Optimization of fermentation parameters to study the behavior of selected lactic cultures on soy solid state fermentation.

    Rodríguez de Olmos, A; Bru, E; Garro, M S


    The use of solid fermentation substrate (SSF) has been appreciated by the demand for natural and healthy products. Lactic acid bacteria and bifidobacteria play a leading role in the production of novel functional foods and their behavior is practically unknown in these systems. Soy is an excellent substrate for the production of functional foods for their low cost and nutritional value. The aim of this work was to optimize different parameters involved in solid state fermentation (SSF) using selected lactic cultures to improve soybean substrate as a possible strategy for the elaboration of new soy food with enhanced functional and nutritional properties. Soy flour and selected lactic cultures were used under different conditions to optimize the soy SSF. The measured responses were bacterial growth, free amino acids and β-glucosidase activity, which were analyzed by applying response surface methodology. Based on the proposed statistical model, different fermentation conditions were raised by varying the moisture content (50-80%) of the soy substrate and temperature of incubation (31-43°C). The effect of inoculum amount was also investigated. These studies demonstrated the ability of selected strains (Lactobacillus paracasei subsp. paracasei and Bifidobacterium longum) to grow with strain-dependent behavior on the SSF system. β-Glucosidase activity was evident in both strains and L. paracasei subsp. paracasei was able to increase the free amino acids at the end of fermentation under assayed conditions. The used statistical model has allowed the optimization of fermentation parameters on soy SSF by selected lactic strains. Besides, the possibility to work with lower initial bacterial amounts to obtain results with significant technological impact was demonstrated.

  1. Direct observation of cell wall structure in living plant tissues by solid-state C NMR spectroscopy.

    Jarvis, M C; Apperley, D C


    Solid-state (13)C nuclear magnetic resonance (NMR) spectra of the following intact plant tissues were recorded by the crosspolarization magic-angle spinning technique: celery (Apium graveolens L.) collenchyma; carob bean (Ceratonia siliqua L.), fenugreek (Trigonella foenum-graecum L.), and nasturtium (Tropaeolum majus L.) endosperm; and lupin (Lupinus polyphyllus Lindl.) seed cotyledons. All these tissues had thickened cell walls which allowed them to withstand the centrifugal forces of magic angle spinning and which, except in the case of lupin seeds, dominated the NMR spectra. The celery collenchyma cell walls gave spectra typical of dicot primary cell walls. The carob bean and fenugreek seed spectra were dominated by resonances from galactomannans, which showed little sign of crystalline order. Resonances from beta(1,4')-d galactan were visible in the lupin seed spectrum, but there was much interference from protein. The nasturtium seed spectrum was largely derived from a xyloglucan, in which the conformation of the glucan core chain appeared to be intermediate between the solution form and solid forms of cellulose.

  2. Elucidating connectivity and metal-binding structures of unlabeled paramagnetic complexes by 13C and 1H solid-state NMR under fast magic angle spinning.

    Wickramasinghe, Nalinda P; Shaibat, Medhat A; Ishii, Yoshitaka


    Characterizing paramagnetic complexes in solids is an essential step toward understanding their molecular functions. However, methodologies to characterize chemical and electronic structures of paramagnetic systems at the molecular level have been notably limited, particularly for noncrystalline solids. We present an approach to obtain connectivities of chemical groups and metal-binding structures for unlabeled paramagnetic complexes by 13C and 1H high-resolution solid-state NMR (SSNMR) using very fast magic angle spinning (VFMAS, spinning speed >or=20 kHz). It is experimentally shown for unlabeled Cu(II)(Ala-Thr) that 2D 13C/1H correlation SSNMR under VFMAS provides the connectivity of chemical groups and assignments for the characterization of unlabeled paramagnetic systems in solids. We demonstrate that on the basis of the assignments provided by the VFMAS approach multiple 13C-metal distances can be simultaneously elucidated by a combination of measurements of 13C anisotropic hyperfine shifts and 13C T1 relaxation due to hyperfine interactions for this peptide-Cu(II) complex. It is also shown that an analysis of 1H anisotropic hyperfine shifts allows for the determination of electron-spin states in Fe(III)-chloroprotoporphyin-IX in solid states.

  3. Highly-efficient gating of solid-state nanochannels by DNA supersandwich structure containing ATP aptamers: a nanofluidic IMPLICATION logic device.

    Jiang, Yanan; Liu, Nannan; Guo, Wei; Xia, Fan; Jiang, Lei


    Integrating biological components into artificial devices establishes an interface to understand and imitate the superior functionalities of the living systems. One challenge in developing biohybrid nanosystems mimicking the gating function of the biological ion channels is to enhance the gating efficiency of the man-made systems. Herein, we demonstrate a DNA supersandwich and ATP gated nanofluidic device that exhibits high ON-OFF ratios (up to 10(6)) and a perfect electric seal at its closed state (~GΩ). The ON-OFF ratio is distinctly higher than existing chemically modified nanofluidic gating systems. The gigaohm seal is comparable with that required in ion channel electrophysiological recording and some lipid bilayer-coated nanopore sensors. The gating function is implemented by self-assembling DNA supersandwich structures into solid-state nanochannels (open-to-closed) and their disassembly through ATP-DNA binding interactions (closed-to-open). On the basis of the reversible and all-or-none electrochemical switching properties, we further achieve the IMPLICATION logic operations within the nanofluidic structures. The present biohybrid nanofluidic device translates molecular events into electrical signals and indicates a built-in signal amplification mechanism for future nanofluidic biosensing and modular DNA computing on solid-state substrates.

  4. La(Ni,Fe)O3 Stability in the Presence of Cr Species - solid-state Reactivity Study

    Stodolny, M.K.; van Berkel, Frans P.; Boukamp, Bernard A.


    The solid-state reactivity between La(Ni0.6Fe0.4)O3 (LNF) and Cr2O3 in the IT-SOFC operating temperature range of 600-800 ºC has been investigated using XRD analysis. Because LNF material can be used as a cathode, as a current collecting layer and/or an interconnect coating, a thorough investigation

  5. La(Ni,Fe)O3 Stability in the Presence of Cr Species - solid-state Reactivity Study

    Stodolny, Maciej K.; Berkel, van Frans P.; Boukamp, Bernard A.


    The solid-state reactivity between La(Ni0.6Fe0.4)O3 (LNF) and Cr2O3 in the IT-SOFC operating temperature range of 600-800 ºC has been investigated using XRD analysis. Because LNF material can be used as a cathode, as a current collecting layer and/or an interconnect coating, a thorough investigation

  6. The Oxford solid state basics

    Simon, Steven H


    The study of solids is one of the richest, most exciting, and most successful branches of physics. While the subject of solid state physics is often viewed as dry and tedious this new book presents the topic instead as an exciting exposition of fundamental principles and great intellectual breakthroughs. Beginning with a discussion of how the study of heat capacity of solids ushered in the quantum revolution, the author presents the key ideas of the field while emphasizing the deepunderlying concepts. The book begins with a discussion of the Einstein/Debye model of specific heat, and the Drude

  7. Chemical structures of coal lithotypes before and after CO2 adsorption as investigated by advanced solid-state 13C nuclear magnetic resonance spectroscopy

    Cao, X.; Mastalerz, Maria; Chappell, M.A.; Miller, L.F.; Li, Y.; Mao, J.


    Four lithotypes (vitrain, bright clarain, clarain, and fusain) of a high volatile bituminous Springfield Coal from the Illinois Basin were characterized using advanced solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. The NMR techniques included quantitative direct polarization/magic angle spinning (DP/MAS), cross polarization/total sideband suppression (CP/TOSS), dipolar dephasing, CHn selection, and recoupled C-H long-range dipolar dephasing techniques. The lithotypes that experienced high-pressure CO2 adsorption isotherm analysis were also analyzed to determine possible changes in coal structure as a result of CO2 saturation at high pressure and subsequent evacuation. The main carbon functionalities present in original vitrain, bright clarain, clarain and fusain were aromatic carbons (65.9%-86.1%), nonpolar alkyl groups (9.0%-28.9%), and aromatic C-O carbons (4.1%-9.5%). Among these lithotypes, aromaticity increased in the order of clarain, bright clarain, vitrain, and fusain, whereas the fraction of alkyl carbons decreased in the same order. Fusain was distinct from other three lithotypes in respect to its highest aromatic composition (86.1%) and remarkably small fraction of alkyl carbons (11.0%). The aromatic cluster size in fusain was larger than that in bright clarain. The lithotypes studied responded differently to high pressure CO2 saturation. After exposure to high pressure CO2, vitrain and fusain showed a decrease in aromaticity but an increase in the fraction of alkyl carbons, whereas bright clarain and clarain displayed an increase in aromaticity but a decrease in the fraction of alkyl carbons. Aromatic fused-rings were larger for bright clarain but smaller for fusain in the post-CO2 adsorption samples compared to the original lithotypes. These observations suggested chemical CO2-coal interactions at high pressure and the selectivity of lithotypes in response to CO2 adsorption. ?? 2011 Elsevier B.V.

  8. New structural information on a humic acid from two-dimensional 1H-13C correlation solid-state nuclear magnetic resonance.

    Mao, J D; Xing, B; Schmidt-Rohr, K


    New information on the chemical structure of a peat humic acid has been obtained using a series of two-dimensional 1H-13C heteronuclear correlation solid-state NMR (HETCOR) experiments with different contact times and with spectral editing by dipolar dephasing and 13C transverse relaxation filtering. Carbon-bonded methyl groups (C-CH3) are found to be near both aliphatic and O-alkyl but not aromatic groups. The spectra prove that most OCH3 groups are connected directly with the aromatic rings, as is typical in lignin. As a result, about one-third of the aromatic C-O groups is not phenolic C-OH but C-OCH3. Both protonated and unprotonated anomeric O-C-O carbons are identified in the one- and two-dimensional spectra. COO groups are found predominantly in OCHn-COO environments, but some are also bonded to aromatic rings and aliphatic groups. All models of humic acids in the literature lack at least some of the features observed here. Compositional heterogeneity was studied by introducing 1H spin diffusion into the HETCOR experiment. Comparison with data for a synthetic polymer, polycarbonate, indicates that the separation between O-alkyl and aromatic groups in the humic acid is less than 1.5 nm. However, transverse 13C relaxation filtering under 1H decoupling reveals heterogeneity on a nanometer scale, with the slow-relaxing component being rich in lignin-like aromatic-C-O-CH3 moieties and poor in COO groups.

  9. Hydrogen bridges of polycyclic aromatic systems with O-H···O bonds--a gas-phase vs. solid-state Car-Parrinello study.

    Panek, Jarosław J; Jezierska, Aneta


    The current study belongs to a series of investigations of polycyclic aromatic compounds containing intramolecular hydrogen bonds. Close proximity of the coupled aromatic system and hydrogen bridges gives rise to resonance-assisted hydrogen bonding phenomena. Substituted naphthols are ideally suited for this kind of investigation. The parent compound, 1-hydroxy-8-methoxy-3-methylnaphthalene, and its derivative, 1-bromo-5-hydroxy-4-isopropoxy-7-methylnaphthalene, both with known crystal structure, are investigated. Car-Parrinello molecular dynamics (CPMD) is chosen as a theoretical background for this study. Gas phase and solid state simulations are carried out. The effect of Grimme's dispersion corrections is also included. The report presents time evolution of structural parameters, spectroscopic signatures based on the CPMD simulations, and comparison with available experimental data. We show that the proton transfer phenomena do not occur within the simulations, which is consistent with evaluation based on the acidity of the donor and acceptor sites. The effects of the substitution in the aromatic system and change of the environment (gas vs. condensed phase) are of similar magnitude.

  10. A novel Zn(4)O-based triazolyl benzoate MOF: synthesis, crystal structure, adsorption properties and solid state 13C NMR investigations.

    Lincke, Jörg; Lässig, Daniel; Stein, Karolin; Moellmer, Jens; Kuttatheyil, Anusree Viswanath; Reichenbach, Christian; Moeller, Andreas; Staudt, Reiner; Kalies, Grit; Bertmer, Marko; Krautscheid, Harald


    The newly synthesized Zn(4)O-based MOF (3)(∞)[Zn(4)(μ(4)-O){(Metrz-pba)(2)mPh}(3)]·8 DMF (1·8 DMF) of rare tungsten carbide (acs) topology exhibits a porosity of 43% and remarkably high thermal stability up to 430 °C. Single crystal X-ray structure analyses could be performed using as-synthesized as well as desolvated crystals. Besides the solvothermal synthesis of single crystals a scalable synthesis of microcrystalline material of the MOF is reported. Combined TG-MS and solid state NMR measurements reveal the presence of mobile DMF molecules in the pore system of the framework. Adsorption measurements confirm that the pore structure is fully accessible for nitrogen molecules at 77 K. The adsorptive pore volume of 0.41 cm(3) g(-1) correlates well with the pore volume of 0.43 cm(3) g(-1) estimated from the single crystal structure.

  11. An Integrated Approach for Structural Characterization of Complex Solid State Electrolytes: The Case of Lithium Lanthanum Titanate

    Cheng, Yongqiang [ORNL; Bi, [ORNL; Huq, Ashfia [ORNL; Feygenson, Mikhail [ORNL; Bridges, Craig A [ORNL; Paranthaman, Mariappan Parans [ORNL; Sumpter, Bobby G [ORNL


    Neutron scattering and first principles simulation are integrated to reveal the atomic-level to nanoscale structure of lithium lanthanum titanate (LLTO), a representative solid electrolyte material with applications in Li-ion batteries. The integrated approach solves the hierarchical local structure of LLTO in detail, including the coupled chemical order and topological distortion, as well as their correlation length scale and the spatial modulation with coherent boundaries. Ab initio molecular dynamics simulations are used to map out the distribution of the mobile ions and identify the migration pathway. Overall, this integrated approach provides a powerful means for detailed study of materials with complex local chemical and topological environment.

  12. Solid-State Synthesis of Polyaniline/Single-Walled Carbon Nanotubes: A Comparative Study with Polyaniline/Multi-Walled Carbon Nanotubes

    Adalet Rahman


    Full Text Available The polyaniline/single-walled carbon nanotubes (PANI/SWNTs composites with a content of SWNTs varying from 8 wt% to 32 wt% were synthesized using a solid-state synthesis method. The structure and morphology of the samples were characterized by fourier transform infrared (FTIR spectra, ultraviolet-visible (UV-vis absorption spectra, X-ray diffraction (XRD and transmission electron microscopy (TEM. The electrochemical performances of the composites were investigated by galvanostatic charge–discharge and cycling stability measurements. The structure and properties of PANI/SWNTs were compared with those of PANI/multi-walled carbon nanotubes (PANI/MWNTs prepared under the same polymerization conditions. The results from FTIR and UV-vis spectra showed that the composites with SWNTs displayed a higher oxidation and doping degree than pure PANI, which is similar to that of PANI/MWNTs. The morphological studies revealed that PANI/SWNTs did not display any rod-like and granular-like features, which appeared in PANI/MWNTs. The galvanostatic charge–discharge measurements indicated that the specific capacitance of PANI/SWNTs is not higher than that of PANI/MWNTs, but the PANI/SWNTs exhibited higher cycling stability and more stable electrochemical behavior in neutral and alkaline electrolytes than PANI/MWNTs.

  13. BOOK REVIEW: Solid State Physics: An Introduction

    Jakoby, Bernhard


    There's a wealth of excellent textbooks on solid state physics. The author of the present book is well aware of this fact and does not attempt to write just another one. Rather, he has provided a very compact introduction to solid state physics for third-year students. As we are faced with the continuous appearance interdisciplinary fields and associated study curricula in natural and engineering sciences (biophysics, mechatronics, etc), a compact text in solid state physics would be appreciated by students of these disciplines as well. The book features 11 chapters where each is provided with supplementary discussion questions and problems. The first chapters deal with a review of chemical bonding mechanisms, crystal structures and mechanical properties of solids, which are brief but by no means superficial. The following, somewhat more detailed chapter on thermal properties of lattices includes a nice introduction to phonons. The foundations of solid state electronics are treated in the next three chapters. Here the author first discusses the classical treatment of electronic behaviour in metals (Drude model) and continues with a quantum-theoretical approach starting with the free-electron model and leading to the band structures in conductive solids. The next chapter is devoted to semiconductors and ends with a brief but, with respect to the topical scope, adequate discussion of semiconductor devices. The classical topics of magnetic and dielectric behaviour are treated in the sequel. The book closes with a chapter on superconductivity and a brief chapter covering the modern topics of quantum confinement and aspects of nanoscale physics. In my opinion, the author has succeeded in creating a very concise yet not superficial textbook. The account presented often probes subjects deep enough to lay the basis for a thorough understanding, preparing the reader for more specialized textbooks. For instance, I think that this book may serve as an excellent first

  14. Development of Solid State NMR Methods for the Structural Characterization of Membrane Proteins: Applications to Understand Multiple Sclerosis

    Cosman, M; Tran, A T; Ulloa, J; Maxwell, R S


    Multiple sclerosis (MS) is a relapsing-remitting disorder of the central nervous system that results in the loss of the myelin sheaths insulating nerve fibers (axons). Strong evidence suggests that MS is an autoimmune disease mediated by T-cell and antibody responses against myelin antigens. Myelin oligodendrocyte glycoprotein (MOG) is a 26 kD to 28 kD an integral membrane protein of the central nervous system implicated as a target for autoaggressive antibodies in MS. To date, the conformation of MOG in association with the myelin membrane is unknown and the exact nature of the interactions between this protein and disease-inducing immune responses have not been determined. Since membrane associated proteins are typically characterized by decreased correlation times, solution state NMR methodologies are often impracticable. Membrane proteins are also often difficult to crystallize for X-ray diffraction studies, Consequently, there is an urgent need to develop new structure characterization tools for this important class of biomolecules. The research described here overviews the initial stages of our effort to develop an integrated, NMR based approach to structural studies of MOG over the many structural domains it is postulated to posses. The structural knowledge gained about this important MS antigen in its native environment will contribute significantly to our understanding of its function in vivo. This project will also aid in the development of therapeutics to inhibit the antigedantibody interaction and thus prevent demyelination in MS patients.

  15. Synthesis and structural characterization of some Pb(B$^{'}_{1/3}$Nb2/3)O3 type materials by two-stage solid-state route

    Mukul Pastor; P K Bajpai; R N P Choudhary


    Two-stage columbite solid state reaction route has been used for the preparation of Pb (B$^{'}_{1/3}$Nb2/3)O3 materials (B′ = Mg, Ni and Cd). The columbite precursor phase was structurally characterized using diffraction data. MgNb2O6, NiNb2O6 and CdNb2O6 show orthorhombic structures i.e. pure columbite phase. Final phase materials get stabilized in mixed phase. The diffraction pattern shows that it is a mixture of cubic pyrochlore and perovskite phase. Percentage of perovskite phase was calculated using the band intensities of (110) perovskite and (222) pyrochlore peaks. The calculated percentages show the dominant perovskite phase. Possible reasons for mixed phase are discussed.

  16. A solid-state trimerisation of a diene diacid affords a bicyclobutyl: reactant structure from X-ray powder data and product separation and structure determination via co-crystallisation.

    Atkinson, Manza B J; Halasz, Ivan; Bučar, Dejan-Krešimir; Dinnebier, Robert E; Mariappan, S V Santhana; Sokolov, Anatoliy N; MacGillivray, Leonard R


    A bicyclobutyl that bears six carboxylic acid groups results from a trimerisation of a diene diacid in the solid state. Powder X-ray diffraction and a co-crystallisation are used to solve the structure of the diene and elucidate the stereochemistry of the bicyclobutyl, respectively.

  17. Ultrathin two-dimensional inorganic materials: new opportunities for solid state nanochemistry.

    Sun, Yongfu; Gao, Shan; Lei, Fengcai; Xiao, Chong; Xie, Yi


    CONSPECTUS: The ultimate goal of solid state chemistry is to gain a clear correlation between atomic, defect, and electronic structure and intrinsic properties of solid state materials. Solid materials can generally be classified as amorphous, quasicrystalline, and crystalline based on their atomic arrangement, in which crystalline materials can be further divided into single crystals, microcrystals, and nanocrystals. Conventional solid state chemistry mainly focuses on studying single crystals and microcrystals, while recently nanocrystals have become a hot research topic in the field of solid state chemistry. As more and more nanocrystalline materials have been artificially fabricated, the solid state chemistry for studying those nanosolids has become a new subdiscipline: solid state nanochemistry. However, solid state nanochemistry, usually called "nanochemistry" for short, primarily studies the microstructures and macroscopic properties of a nanomaterial's aggregation states. Due to abundant microstructures in the aggregation states, it is only possible to build a simple but imprecise correlation between the microscopic morphology and the macroscopic properties of the nanostructures. Notably, atomically thin two-dimensional inorganic materials provide an ideal platform to establish clear structure-property relationships in the field of solid state nanochemistry, thanks to their homogeneous dispersion without the assistance of a capping ligand. In addition, their atomic structures including coordination number, bond length, and disorder degree of the examined atoms can be clearly disclosed by X-ray absorption fine structure spectroscopy. Also, their more exposed interior atoms would inevitably induce the formation of various defects, which would have a non-negligible effect on their physicochemical properties. Based on the obtained atomic and defect structural characteristics, density-functional calculations are performed to study their electronic structures

  18. Modeling solid-state precipitation

    Nebylov, AlexanderKozeschnik, Ernst


    Over recent decades, modeling and simulation of solid-state precipitation has attracted increased attention in academia and industry due to their important contributions in designing properties of advanced structural materials and in increasing productivity and decreasing costs for expensive alloying. In particular, precipitation of second phases is an important means for controlling the mechanical-technological properties of structural materials. However, profound physical modeling of precipitation is not a trivial task. This book introduces you to the classical methods of precipitation modeling and to recently-developed advanced, computationally-efficient techniques. If you're a research professional, academic, or student, you'll learn: nucleation theory, precipitate growth, calculation of interfacial energies. advanced techniques for technologically relevant multicomponent systems and complex thermo-mechanical treatments. numerical approaches using evolution equations and discrete particle size distribu...

  19. Position sensitive solid state detectors

    Schnatterly, S.E.; Husk, D.


    Solid state detectors have been used for years as high quantum efficiency detectors for visible light. In this paper the use of PDA and CCD, solid state detectors, in the X-ray region will be discussed. In particular examples of data in the soft X-ray region are presented. Finally the use of phosphor coatings to enhance the sensitivity of solid state detectors is described.

  20. Physics of Nanostructured Solid State Devices

    Bandyopadhyay, Supriyo


    Physics of Nanostructured Solid State Devices introduces readers to theories and concepts such as semi-classical and quantum mechanical descriptions of electron transport, methods for calculations of band structures in solids with applications in calculation of optical constants, and other advanced concepts.  The information presented here will equip readers with the necessary tools to carry out cutting edge research in modern solid state nanodevices. This book also: Covers sophisticated models of charge transport including the drift-diffusion model, Boltzmann transport model and various quantum transport models Discusses the essential elements of quantum mechanics necessary for an understanding of nanostructured solid state devices Presents band structure calculation methods based on time-independent perturbation theory Discusses theory of optical transitions and optical devices employing quantum-confined structures such as quantum wells,wires and dots Elucidates quantum mechanics of electrons in a magneti...

  1. Fine refinement of solid-state molecular structures of Leu- and Met-enkephalins by NMR crystallography.

    Pawlak, Tomasz; Potrzebowski, Marek J


    This paper presents a methodology that allows the fine refinement of the crystal and molecular structure for compounds for which the data deposited in the crystallographic bases are of poor quality. Such species belong to the group of samples with molecular disorder. In the Cambridge Crystallographic Data Center (CCDC), there are approximately 22,000 deposited structures with an R-factor over 10. The powerful methodology we present employs crystal data for Leu-enkephalin (two crystallographic forms) with R-factor values of 14.0 and 8.9 and for Met-enkephalin (one form) with an R-factor of 10.5. NMR crystallography was employed in testing the X-ray data and the quality of the structure refinement. The GIPAW (gauge invariant projector augmented wave) method was used to optimize the coordinates of the enkephalins and to compute NMR parameters. As we reveal, this complementary approach makes it possible to generate a reasonable set of new coordinates that better correlate to real samples. This methodology is general and can be employed in the study of each compound possessing magnetically active nuclei.

  2. Solid state chemistry an introduction

    Smart, Lesley E


    ""Smart and Moore are engaging writers, providing clear explanations for concepts in solid-state chemistry from the atomic/molecular perspective. The fourth edition is a welcome addition to my bookshelves. … What I like most about Solid State Chemistry is that it gives simple clear descriptions for a large number of interesting materials and correspondingly clear explanations of their applications. Solid State Chemistry could be used for a solid state textbook at the third or fourth year undergraduate level, especially for chemistry programs. It is also a useful resource for beginning graduate

  3. Thermal aging of interfacial polymer chains in ethylene-propylene-diene terpolymer/aluminum hydroxide composites: solid-state NMR study.

    Gabrielle, Brice; Lorthioir, Cédric; Lauprêtre, Françoise


    The possible influence of micrometric-size filler particles on the thermo-oxidative degradation behavior of the polymer chains at polymer/filler interfaces is still an open question. In this study, a cross-linked ethylene-propylene-diene (EPDM) terpolymer filled by aluminum trihydrate (ATH) particles is investigated using (1)H solid-state NMR. The time evolution of the EPDM network microstructure under thermal aging at 80 °C is monitored as a function of the exposure time and compared to that of an unfilled EPDM network displaying a similar initial structure. While nearly no variations of the topology are observed on the neat EPDM network over 5 days at 80 °C, a significant amount of chain scission phenomena are evidenced in EPDM/ATH. A specific surface effect induced by ATH on the thermodegradative properties of the polymer chains located in their vicinity is thus pointed out. Close to the filler particles, a higher amount of chain scissions are detected, and the characteristic length scale related to these interfacial regions displaying a significant thermo-oxidation process is determined as a function of the aging time.

  4. Dielectric and magnetic studies of BaTi0.5Fe0.5O3 ceramic materials, synthesized by solid state sintering

    Samuvel, K.; Ramachandran, K.


    A comparative study of the surface morphology, dielectric and magnetic properties of the BaTi0.5Fe0.5O3 (BTFO) ceramics materials. This has been carried out by synthesizing the samples in different routes. BTFO samples have shown single phased 12R type hexagonal structure with R 3m ‾ , P4mm space group. Interfacial effects on the dielectric properties of the samples have been understood by Cole-Cole plots in complex impedance and modulus formalism. It has been identified that huge dielectric constant (103-106) at lower frequencies is largely contributed by the heterogeneous electronic microstructure at the interfaces of grains. Modulus formalism has identified the effects of both grain and grain boundary microstructure on the dielectric properties, particularly in chemical routed samples. The order of grain boundary resistivity suggests the semiconductor/insulator class of the material. The grain boundary resistivity of the mechanical alloyed samples is remarkably lower than the solid state and chemical routed samples. Few samples have of the samples have exhibited signature of ferromagnetism at the room temperature.

  5. Dielectric and magnetic studies of BaTi0.5Fe0.5O3 ceramic materials, synthesized by solid state sintering.

    Samuvel, K; Ramachandran, K


    A comparative study of the surface morphology, dielectric and magnetic properties of the BaTi0.5Fe0.5O3 (BTFO) ceramics materials. This has been carried out by synthesizing the samples in different routes. BTFO samples have shown single phased 12R type hexagonal structure with R3m, P4mm space group. Interfacial effects on the dielectric properties of the samples have been understood by Cole-Cole plots in complex impedance and modulus formalism. It has been identified that huge dielectric constant (10(3)-10(6)) at lower frequencies is largely contributed by the heterogeneous electronic microstructure at the interfaces of grains. Modulus formalism has identified the effects of both grain and grain boundary microstructure on the dielectric properties, particularly in chemical routed samples. The order of grain boundary resistivity suggests the semiconductor/insulator class of the material. The grain boundary resistivity of the mechanical alloyed samples is remarkably lower than the solid state and chemical routed samples. Few samples have of the samples have exhibited signature of ferromagnetism at the room temperature.

  6. A Solid State Pyranometer

    Dumitrescu Anca Laura


    Full Text Available The construction of a solid state device-based pyranometer designated to broadband irradiance measurements is presented in this paper. The device is built on the physical basis that the temperature difference between two bodies of identical shape and external surface area, identically exposed to the incident radiation, but having different absorption and heat transfer coefficients (e.g. one body is painted white and the other is painted black, is proportional to the incident irradiance. This proportionality may be put in evidence if the two bodies consisting of identical arrays of correspondingly painted semiconductor diodes, due to the thermal behaviour of their p-n junction. It is theoretically predicted and experimentally confirmed that the voltage drop across a diode passed through a constant forward current linearly decreases with the temperature of the junction. In other words, a signal proportional to the irradiance of the light source may be obtained via conventional analog electronics. The calibration of the apparatus, as performed by means of a professional device (LP PYRA 03, indicates a good linearity.

  7. Solid State Ultracapacitor

    Rolin, Terry D.


    NASA analyzes, tests, packages, and fabricates electrical, electronic, and electromechanical (EEE) parts used in space vehicles. One area that NASA wishes to advance is energy storage and delivery. Currently, space vehicles use rechargeable batteries that utilize silver zinc or lithium ion electrochemical processes. These current state-of-the-art rechargeable batteries cannot be rapidly charged, contain harmful chemicals, and suffer from early wear-out mechanisms. A solid state ultracapacitor is an EEE part that offers significant advantages over current electrochemical and electrolytic devices. The objective of this research is to develop an internal barrier layer ultracapacitor (IBLC) using novel dielectric materials as a battery replacement with a focus on these advantages: longer life, lower mass-toweight ratio, rapid charging, on-demand pulse power, improved on-pad standby time without maintenance, and environmental friendliness. The approach is unique in two areas. A deposition technique is used that has been shown to produce a more uniformly coated nanoparticle than sol-gel, which has resulted in colossal permittivities. These particles are then distributed in an ink formulation developed at NASA Marshall Space Flight Center (MSFC) and deposited utilizing a 3D aerosol jet technique. This additive manufacturing technique controls layer thickness, resulting in extremely large capacitance and energy density.

  8. Crystal structure and terahertz spectroscopy of α,α,α‧,α‧-tetrabromo-p-xylene modeled using solid-state density functional theory

    Pellizzeri, Steven; Smith, Tiffany M.; Delaney, Sean P.; Korter, Timothy M.; Zubieta, Jon


    The previously unknown crystal structure of α,α,α‧,α‧-tetrabromo-p-xylene has been determined using single-crystal X-ray diffraction, and it was discovered that the molecular packing primarily involves electrostatic interactions between neighboring molecules. Due to the unusual nature of the packing in this system, the vibrational motions were investigated. The low energy lattice and molecular vibrations unique to molecular crystals were measured in the terahertz (THz) region (10-100 cm-1). These vibrational motions were then reproduced using solid-state density functional theory (DFT) as implemented in CRYSTAL09, and it was found that the majority of the motions in this region involve either whole molecular translation or molecular scissoring.

  9. Terahertz spectroscopy and solid-state density functional theory calculations of structural isomers: Nicotinic acid, isonicotinic acid and 2-picolinic acid

    Ding, Ling; Fan, Wen-Hui; Chen, Xu; Chen, Ze-You; Song, Chao


    We report, for the first time to our knowledge, the terahertz (THz) spectra of isonicotinic acid and 2-picolinic acid. The distinct THz spectral differences among these two isomers and nicotinic acid have also been observed, indicating that the THz vibrational modes are highly sensitive to the structural differences even in similar molecular crystals. Besides, solid-state density functional theory calculations reveal better qualitative agreement with the measured absorption features, which are related to the molecular vibrations of nicotinic acid and isonicotinic acid. As for 2-picolinic acid, the calculation based on the primitive cell reproduces the absorption features at 1.46, 1.82 and 2.46 THz originating from intermolecular vibrations. These results suggest that THz spectra can identify the complex intermolecular interactions even in similar molecular crystals, which shows potential applications in identifying isomers in food and pharmaceutical production.

  10. (31)P Solid-State NMR study of the chemical setting process of a dual-paste injectable brushite cements.

    Legrand, A P; Sfihi, H; Lequeux, N; Lemaître, J


    The composition and evolution of a brushite-type calcium phosphate cement was investigated by Solid-State NMR and X-ray during the setting process. The cement is obtained by mixing beta-tricalcium phosphate [Ca(3)(PO(4))(2), beta-TCP] and monocalcium phosphate monohydrate [Ca(H(2)PO(4))(2).H(2)O, MCPM] in presence of water, with formation of dicalcium phosphate dihydrate or brushite [CaHPO(2).2H(2)O, DCPD]. Analysis of the initial beta-TCP paste has shown the presence of beta-calcium pyrophosphate [Ca(2)P(2)O(7), beta-CPy] and that of the initial MCPM a mixture of MCPM and dicalcium phosphate [CaHPO(4), DCP]. Follow-up of the chemical composition by (31)P Solid-State NMR enables to show that the chemical setting process appeared to reach an end after 20 min. The constant composition observed at the end of the process was similarly determined.

  11. Cation ion specifically induces a conformational change in trans-dehydroandrosterone - a solid-state NMR study.

    Wang, Darong; Chen, Meiman; Chein, Rong-Jie; Ching, Wei-Min; Hung, Chen-Hsiung; Tzou, Der-Lii M


    In this work, we demonstrated that calcium (Ca(+2)) is able to induce a conformational change in trans-dehydroandrosterone (DHEA). To this respect, solid-state NMR spectroscopy was applied to a series of DHEA molecules that were incubated with Ca(+2) under different concentrations. The high-resolution (13)C NMR spectra of the DHEA/Ca(+2) mixtures exhibited two distinct sets of signals; one was attributed to DHEA in the free form, and the second set was due to the DHEA/Ca(+2) complex. Based on chemical shift isotropy and anisotropy analyses, we postulated that Ca(+2) might have associated with the oxygen attached to C17 via a lone-pair of electrons, which induced a conformational change in DHEA. Apart from Ca(+2), we also incubated DHEA with magnesium (Mg(+2)) to determine whether Mg(+2) was able to interact with DHEA in a similar manner to Ca(+2). We found that Mg(+2) was able to induce a conformational change in DHEA deviated from that of Ca(+2). These solid-state NMR observations indicate that DHEA is able to interact with cations, such as Mg(+2) and Ca(+2), with specificity.

  12. Study of cross - relaxation and molecular dynamics in the solid 3-(trifluoromethyl) benzoic acid by solid state NMR off - resonance.

    Woźniak-Braszak, Aneta


    Molecular dynamics of the solid 3-(trifluoromethyl) benzoic acid containing proton (1)H and fluorine (19)F nuclei was explored by the solid-state NMR off - resonance technique. Contrary to the previous experiments the proton nuclei system I relaxed in the off - resonance effective field B→e while fluorine nuclei system S was saturated for short time in comparison to the relaxation time T1I. New cross - relaxation solid - state NMR off - resonance experiments were conducted on a homebuilt pulse spectrometer operating at the on-resonance frequency of 30.2MHz, at the off - resonance frequency varied between 30.2 and 30.6MHz for protons and at the frequency of 28.411MHz for fluorines, respectively. Based on the experimental data the dispersions of the proton off - resonance spin - lattice relaxation rate ρρ(I), the fluorine off - resonance spin - lattice relaxation rate ρρ(S) and the cross - relaxation rate σρ in the rotating frame were determined. Copyright © 2016 Elsevier Inc. All rights reserved.

  13. Cationic copper (I) complexes with bulky 1,4-diaza-1,3-butadiene ligands - Synthesis, solid state structure and catalysis

    Anga, Srinivas; Kottalanka, Ravi K.; Pal, Tigmansu; Panda, Tarun K.


    We report the full characterization of two glyoxal-based ligands N,N bis(diphenylmethyl)-1,4-diaza-1,3-butadiene ligand (DADPh2, 1) and more bulky N,N bis(triphenylmethyl)-1,4-diaza-1,3-butadiene ligand (DADPh3, 2) by the condensation reaction of glyoxal and diphenylmethanamine and triphenyl-methanamine respectively. The copper (I) complex of composition [Cu(DADPh2)2]PF6 (3) having two neutral bidentate N,N bis(diphenyl-methyl)-1,4-diaza-1,3-butadiene ligand was prepared by the reaction of [Cu(CH3CN)4]PF6 and 1 in 1:2 ratio in dichloromethane. In a similar reaction with N,N bis(triphenylmethyl)-1,4-diaza-1,3-butadiene ligand (2) and [Cu(CH3CN)4]PF6 in dichloromethane yielded corresponding heteroleptic copper (I) complex [Cu(DADPh3)(CH3CN)2]PF6 (4). Another copper (I) complex [Cu(DADPh2)(PPh3)]PF6 (5) can also be obtained by the one pot reaction involving ligand 1, [Cu(CH3CN)4]PF6 and triphenylphosphine. Solid state structures of all the five compounds were established by single crystal X-ray diffraction analysis. The solid state structures of the copper complexes 3-5 reveal a distorted tetrahedral geometry around the copper (I) centers. The copper complexes 3-5 were tested as catalysts for the coupling reaction of o-iodophenol and phenyl acetylene and it was observed that complex 4 exhibits the highest catalytic activity.

  14. Structural, thermal, magnetic and optical characterization of undoped nanocrystalline ZnS prepared by solid state reaction

    Faita, F.L., E-mail: [Departamento de Física, Universidade Federal de Santa Catarina, Campus Trindade, 88040-900 Florianópolis, SC (Brazil); Ersching, K. [Instituto Federal de Educação, Ciência e Tecnologia Catarinense – Campus Camboriú, 88340-000 Camboriú, SC (Brazil); Poffo, C.M. [Departamento de Física, Universidade Federal do Amazonas, 3000 Japiim, 69077000 Manaus, AM (Brazil); Benetti, L.C. [Departamento de Física, Universidade Federal de Santa Catarina, Campus Trindade, 88040-900 Florianópolis, SC (Brazil); Trichês, D.M.; Souza, S.M. [Departamento de Física, Universidade Federal do Amazonas, 3000 Japiim, 69077000 Manaus, AM (Brazil); Viegas, A.D.C.; Lima, J.C. de [Departamento de Física, Universidade Federal de Santa Catarina, Campus Trindade, 88040-900 Florianópolis, SC (Brazil)


    Highlights: • Nanocrystalline zinc blende and wurtzite ZnS phases produced by mechanical alloying. • Sulfur and/or zinc vacancies in the ZnS as-milled. • Magnetic and semiconductor behavior for the as-milled ZnS-10h. • Irreversible demagnetization and Curie temperature above room temperature. • Structural stability after annealing and aged of the ZnS-10h sample. -- Abstract: Nanocrystalline zinc blende and wurtzite ZnS phases with sulfur and/or zinc vacancies were obtained from a mechanically alloyed Zn{sub 50}S{sub 50} powder mixture. Structural, thermal, magnetic, optical and photoacoustic studies were carried out using X-ray diffraction, transmission electron microscopy, differential scanning calorimetry, vibrating sample magnetometer, UV–Vis absorption, photoluminescence and photoacoustic spectroscopy techniques. The cubic zinc blende (ZnS{sup ZB}) and hexagonal wurtzite (ZnS{sup WZ}) phases were nucleated in 3 h of milling and remained until 10 h when the milling process was stopped. The coexistence of these two phases was confirmed by high resolution transmission electron microscopy. X-ray diffraction measurements attested the structural stability of the sample milled for 10 h and aged for eighteen months and of the sample milled 10 h and annealed at 300 °C and 600 °C. Differential scanning calorimetry measurements showed the unreacted sulfur in molecular form (rings and/or chains). Magnetic behavior was observed for as-milled sample and Curie temperature was estimated at 430 °C. Moreover, an irreversible behavior of magnetic properties was observed and correlated with changes on the structural vacancies densities. The UV–Vis absorption spectra and McLean analysis showed an optical band gap around 3.4 eV and 3.9 for ZnS{sup ZB} and ZnS{sup WZ} phases, respectively. The sample milled for 10 h showed low blue photoemission intensity centered at 470 nm and thermal diffusivity around 0.02 cm{sup 2}/s.

  15. Solid-State Neutron Detector Device

    Bensaoula, Abdelhak (Inventor); Starikov, David (Inventor); Pillai, Rajeev (Inventor)


    The structure and methods of fabricating a high efficiency compact solid state neutron detector based on III-Nitride semiconductor structures deposited on a substrate. The operation of the device is based on absorption of neutrons, which results in generation of free carriers.

  16. Solid State Reactor Final Report

    Mays, G.T.


    The Solid State Reactor (SSR) is an advanced reactor concept designed to take advantage of Oak Ridge National Laboratory's (ORNL's) recently developed graphite foam that has enhanced heat transfer characteristics and excellent high-temperature mechanical properties, to provide an inherently safe, self-regulated, source of heat for power and other potential applications. This work was funded by the U.S. Department of Energy's Nuclear Energy Research Initiative (NERI) program (Project No. 99-064) from August 1999 through September 30, 2002. The initial concept of utilizing the graphite foam as a basis for developing an advanced reactor concept envisioned that a suite of reactor configurations and power levels could be developed for several different applications. The initial focus was looking at the reactor as a heat source that was scalable, independent of any heat removal/power conversion process. These applications might include conventional power generation, isotope production and destruction (actinides), and hydrogen production. Having conducted the initial research on the graphite foam and having performed the scoping parametric analyses from neutronics and thermal-hydraulic perspectives, it was necessary to focus on a particular application that would (1) demonstrate the viability of the overall concept and (2) require a reasonably structured design analysis process that would synthesize those important parameters that influence the concept the most as part of a feasible, working reactor system. Thus, the application targeted for this concept was supplying power for remote/harsh environments and a design that was easily deployable, simplistic from an operational standpoint, and utilized the new graphite foam. Specifically, a 500-kW(t) reactor concept was pursued that is naturally load following, inherently safe, optimized via neutronic studies to achieve near-zero reactivity change with burnup, and proliferation resistant. These four major areas

  17. Radio Frequency Solid State Amplifiers

    Jacob, J


    Solid state amplifiers are being increasingly used instead of electronic vacuum tubes to feed accelerating cavities with radio frequency power in the 100 kW range. Power is obtained from the combination of hundreds of transistor amplifier modules. This paper summarizes a one hour lecture on solid state amplifiers for accelerator applications.

  18. Ionic conduction in the solid state

    P Padma Kumar; S Yashonath


    Solid state ionic conductors are important from an industrial viewpoint. A variety of such conductors have been found. In order to understand the reasons for high ionic conductivity in these solids, there have been a number of experimental, theoretical and computational studies in the literature. We provide here a survey of these investigations with focus on what is known and elaborate on issues that still remain unresolved. Conductivity depends on a number of factors such as presence of interstitial sites, ion size, temperature, crystal structure etc. We discuss the recent results from atomistic computer simulations on the dependence of conductivity in NASICONs as a function of composition, temperature, phase change and cation among others. A new potential for modelling of NASICON structure that has been proposed is also discussed.

  19. Solid State Lighting Program (Falcon)

    Meeks, Steven


    Over the past two years, KLA-Tencor and partners successfully developed and deployed software and hardware tools that increase product yield for High Brightness LED (HBLED) manufacturing and reduce product development and factory ramp times. This report summarizes our development effort and details of how the results of the Solid State Light Program (Falcon) have started to help HBLED manufacturers optimize process control by enabling them to flag and correct identified killer defect conditions at any point of origin in the process manufacturing flow. This constitutes a quantum leap in yield management over current practice. Current practice consists of die dispositioning which is just rejection of bad die at end of process based upon probe tests, loosely assisted by optical in-line monitoring for gross process deficiencies. For the first time, and as a result of our Solid State Lighting Program, our LED manufacturing partners have obtained the software and hardware tools that optimize individual process steps to control killer defects at the point in the processes where they originate. Products developed during our two year program enable optimized inspection strategies for many product lines to minimize cost and maximize yield. The Solid State Lighting Program was structured in three phases: i) the development of advanced imaging modes that achieve clear separation between LED defect types, improves signal to noise and scan rates, and minimizes nuisance defects for both front end and back end inspection tools, ii) the creation of defect source analysis (DSA) software that connect the defect maps from back-end and front-end HBLED manufacturing tools to permit the automatic overlay and traceability of defects between tools and process steps, suppress nuisance defects, and identify the origin of killer defects with process step and conditions, and iii) working with partners (Philips Lumileds) on product wafers, obtain a detailed statistical correlation of automated

  20. High-resolution structure of the Shigella type-III secretion needle by solid-state NMR and cryo-electron microscopy

    Demers, Jean-Philippe; Habenstein, Birgit; Loquet, Antoine; Kumar Vasa, Suresh; Giller, Karin; Becker, Stefan; Baker, David; Lange, Adam; Sgourakis, Nikolaos G.


    We introduce a general hybrid approach for determining the structures of supramolecular assemblies. Cryo-electron microscopy (cryo-EM) data define the overall envelope of the assembly and rigid-body orientation of the subunits while solid-state nuclear magnetic resonance (ssNMR) chemical shifts and distance constraints define the local secondary structure, protein fold and inter-subunit interactions. Finally, Rosetta structure calculations provide a general framework to integrate the different sources of structural information. Combining a 7.7-Å cryo-EM density map and 996 ssNMR distance constraints, the structure of the type-III secretion system needle of Shigella flexneri is determined to a precision of 0.4 Å. The calculated structures are cross-validated using an independent data set of 691 ssNMR constraints and scanning transmission electron microscopy measurements. The hybrid model resolves the conformation of the non-conserved N terminus, which occupies a protrusion in the cryo-EM density, and reveals conserved pore residues forming a continuous pattern of electrostatic interactions, thereby suggesting a mechanism for effector protein translocation.

  1. Acid-base interactions and secondary structures of poly-L-lysine probed by 15N and 13C solid state NMR and Ab initio model calculations.

    Dos, Alexandra; Schimming, Volkmar; Tosoni, Sergio; Limbach, Hans-Heinrich


    The interactions of the 15N-labeled amino groups of dry solid poly-L-lysine (PLL) with various halogen and oxygen acids HX and the relation to the secondary structure have been studied using solid-state 15N and 13C CPMAS NMR spectroscopy (CP = cross polarization and MAS = magic angle spinning). For comparison, 15N NMR spectra of an aqueous solution of PLL were measured as a function of pH. In order to understand the effects of protonation and hydration on the 15N chemical shifts of the amino groups, DFT and chemical shielding calculations were performed on isolated methylamine-acid complexes and on periodic halide clusters of the type (CH3NH3(+)X(-))n. The combined experimental and computational results reveal low-field shifts of the amino nitrogens upon interaction with the oxygen acids HX = HF, H2SO4, CH3COOH, (CH3)2POOH, H3PO4, HNO3, and internal carbamic acid formed by reaction of the amino groups with gaseous CO2. Evidence is obtained that only hydrogen-bonded species of the type (Lys-NH2***H-X)n are formed in the absence of water. 15N chemical shifts are maximum when H is located in the hydrogen bond center and then decrease again upon full protonation, as found for aqueous solution at low pH. By contrast, halogen acids interact in a different way. They form internal salts of the type (Lys-NH3(+)X(-))n via the interaction of many acid-base pairs. This salt formation is possible only in the beta-sheet conformation. By contrast, the formation of hydrogen-bonded complexes can occur both in beta-sheet domains as well as in alpha-helical domains. The 15N chemical shifts of the protonated ammonium groups increase when the size of the interacting halogen anions is increased from chloride to iodide and when the number of the interacting anions is increased. Thus, the observed high-field 15N shift of ammonium groups upon hydration is the consequence of replacing interacting halogen atoms by oxygen atoms.

  2. Studies on solid state synthesis and the oxygenation property of cobalt(II) Schiff base (vanilline polyamine)complexes

    XIAO Furong; CHEN Lu; WANG Jide; WU Ronglan; YUE Fan; LI Jing


    Three new cobalt complexes were synthesized by solid-state reaction at room temperature and the resultant Co complexes reacted with two equivalent oxygen molecules at room temperature to produce the oxygenated complexes 2H2O (L3=N, N'-bis(4-hydroxyl-3-methoxy-benzyltetraethylenepentamine).The oxygenated complexes were characterized by elemental analysis,IR (Infrared),1H-NMR (Nuclear Magnetic Resonance),and UV-Vis (Ultraviolet Visual) spectrometry,and TG/DTA (Thermogravimetry/Differential Thermal Analysis) analysis,and molar conductance.The coordinated oxygen contents in the oxygenated complexes were also determined by weight method.It was supposed that only one O2 molecule coordinated to the Co ion forming a superoxo type oxygenated complex.

  3. A Comparative Study of Temperature Optimal Control in a Solid State Fermentation Process for Edible Mushroom Growing

    K. J. Gurubel


    Full Text Available In this paper, optimal control strategies for temperature trajectory determination in order to maximize thermophilic bacteria in a fed-batch solid-state fermentation reactor are proposed. This process is modeled by nonlinear differential equations, which has been previously validated experimentally with scale reactor temperature profiles. The dynamic input aeration rate of the reactor is determined to increase microorganisms growth of a selective substrate for edible mushroom cultivation. In industrial practice, the process is comprised of three thermal stages with constant input air flow and three types of microorganisms in a 150-hour lapse. Scytalidium thermophilum and actinobacteria are desired in order to obtain a final biomass composition with acceptable microorganisms concentration. The Steepest Descent gradient algorithm in continuous time and the Gradient Projection algorithm in discrete-time are used for the process optimal control. A comparison of simulation results in the presence of disturbances is presented, where the resulting temperature trajectories exhibit similar tendencies as industrial data.

  4. Molecular interactions between green tea catechins and cheese fat studied by solid-state nuclear magnetic resonance spectroscopy.

    Rashidinejad, Ali; Birch, Edward J; Hindmarsh, Jason; Everett, David W


    Molecular integrations between green tea catechins and milk fat globules in a cheese matrix were investigated using solid-state magic angle spinning nuclear magnetic resonance spectroscopy. Full-fat cheeses were manufactured containing free catechin or free green tea extract (GTE), and liposomal encapsulated catechin or liposomal encapsulated GTE. Molecular mobility of the carbon species in the cheeses was measured by a wide-line separation technique. The (1)H evolution frequency profile of the (13)C peak at 16ppm obtained for the control cheese and cheeses containing encapsulated polyphenols (catechin or GTE) were similar, however, the spectrum was narrower for cheeses containing free polyphenols. Differences in spectral width indicates changes in the molecular mobility of --CH3- or -C-C-PO4- species through hydrophobic and/or cation-π associations between green tea catechins and cheese fat components. However, the similar spectral profile suggests that encapsulation protects cheese fat from interaction with catechins.

  5. Study of Microwave Solid State Power Amplifier′s CAD%微波固态功放CAD研究



    A network synthesis method of microwave solid state power amplifier impedance matching circuit is introduced in this paper. A new idea of realizing matching circuit using precise microstrip line model is proposed to solve this problem, computer numerical arithmetic is used and Matlab language is selected. A simulation is done using EESOF simulation software and the result is satisfied.%介绍了微波固态功放阻抗匹配电路的网络综合方法,提出用精确的微带线模型实现匹配电路的新思路。选用Matlab语言,用计算机数值算法求解。用EESOF仿真软件对上述计算结果进行仿真,获得了令人满意的结果。


    Prafulla Chetri; Neelotpal Sen Sarma; Narendra Nath Dass


    An attempt has been made in the present work to prepare poly(vinyl borate), PVBO and its calcium derivative by homogeneous esterification of PVA with boric acid in non-aqueous medium in the presence of a catalyst ethyl nitrate dimethyl sulfoxide. The compounds were characterized by IR and 1H-NMR spectra. Conductivities were determined from 30℃ to 90℃ in solid state within a frequency range of 42 Hz to 100 kHz. The compounds so formed showed ionic conductivity and their conductivities were dependent on frequencies used. It is found that the addition of Ca2+ ion increases the ionic conductivity of PVBO appreciably. The conductivity of PVBO-Ca increases rapidly after 50℃. The total ionic transport number and activation energy of the copolymers were also determined.

  7. Analytical challenges of determining composition and structure in small volumes with applications to semiconductor technology, nanostructures and solid state science

    Ma, Zhiyong; Kuhn, Markus; Johnson, David C.


    Determining the structure and composition of small volumes is vital to the ability to understand and control nanoscale properties and critical for advancing both fundamental science and applications, such as semiconductor device manufacturing. While metrology of nanoscale materials (nanoparticles, nanocomposites) and nanoscale semiconductor structures is challenging, both basic research and cutting edge technology benefit from new and enhanced analytical techniques. This focus issue contains articles describing approaches to overcome the challenges in obtaining statistically significant atomic-scale quantification of structure and composition in a variety of materials and devices using electron microscopy and atom probe tomography.

  8. Three-dimensional skeleton networks of graphene wrapped polyaniline nanofibers: an excellent structure for high-performance flexible solid-state supercapacitors

    Hu, Nantao; Zhang, Liling; Yang, Chao; Zhao, Jian; Yang, Zhi; Wei, Hao; Liao, Hanbin; Feng, Zhenxing; Fisher, Adrian; Zhang, Yafei; Xu, Zhichuan J.


    Thin, robust, lightweight, and flexible supercapacitors (SCs) have aroused growing attentions nowadays due to the rapid development of flexible electronics. Graphene-polyaniline (PANI) hybrids are attractive candidates for high performance SCs. In order to utilize them in real devices, it is necessary to improve the capacitance and the structure stability of PANI. Here we report a hierarchical three-dimensional structure, in which all of PANI nanofibers (NFs) are tightly wrapped inside reduced graphene oxide (rGO) nanosheet skeletons, for high-performance flexible SCs. The as-fabricated film electrodes with this unique structure showed a highest gravimetric specific capacitance of 921 F/g and volumetric capacitance of 391 F/cm3. The assembled solid-state SCs gave a high specific capacitance of 211 F/g (1 A/g), a high area capacitance of 0.9 F/cm2, and a competitive volumetric capacitance of 25.6 F/cm3. The SCs also exhibited outstanding rate capability (~75% retention at 20 A/g) as well as excellent cycling stability (100% retention at 10 A/g for 2000 cycles). Additionally, no structural failure and loss of performance were observed under the bending state. This structure design paves a new avenue for engineering rGO/PANI or other similar hybrids for high performance flexible energy storage devices.

  9. Adsorption-desorption induced structural changes of Cu-MOF evidenced by solid state NMR and EPR spectroscopy.

    Jiang, Yijiao; Huang, Jun; Kasumaj, Besnik; Jeschke, Gunnar; Hunger, Michael; Mallat, Tamas; Baiker, Alfons


    Adsorption-desorption induced structural changes of Cu(bpy)(H(2)O)(2)(BF(4)),(bpy) (bpy = 4,4'-bipyridine) [Cu-MOF] have been evidenced by combined NMR and EPR spectroscopy. Upon adsorption of probe molecules even at a few mbar, EPR spectra show that they are activated to form complexes at Cu(II) sites, which results in a change of the Cu-MOF's structure as indicated by a high-field shift of the (11)B MAS NMR. After desorption, both EPR and (11)B MAS NMR spectra evidenced that the structure of the Cu-MOF reversibly shifted to the original state. This observation indicates that MOFs can undergo structural changes during processes where adsorption-desorption steps are involved such as gas storage, separation, and catalysis.

  10. Nanographite Films for Solid State Electronic Applications

    Sergey G. Lebedev


    Full Text Available The structure and properties of nanographite films useful for applications in solid state devices are described. The possibility to use low conducting state of nanographite film for detecting radiation in the segmented solid state detectors is considered. Other interesting phenomena include the field effect conductivity switching which can be used in contactless current limiters and circuit breakers, the rf-to-dc conversion which can be utilized in microwave and photo detectors, and light emitting subsequent to the conductivity switching with possible application as light sources. The possible underlying gears of the mentioned effects are discussed.

  11. Three novel photoisomeric compounds of the 4-acyl pyrazolone derivants: Crystal structures and substituent effects on photo-isomerism in solid state


    Three new photoisomeric compounds: 1,3-diphenyl-4-benzal-5-pyrazolone 4-methylthiosemicarbazone (DPBP-MTSC), 1,3-diphenyl-4-(4′-methylbenzal)-5-pyrazolone 4-methylthiosemicarbazone (DP4MBP- MTSC), and 1,3-diphenyl-4-(4′-bromobenzal)-5-pyrazolone 4-methylthiosemicarbazone (DP4BrBP-MTSC) were synthesized by direct condensation of pyrazolones and 4-methylthiosemicarbazone. Their struc- tures were confirmed using 1H NMR, IR, elemental analyses, and X-ray crystallographic analyses. The photoisomeric properties in the solid state were studied under UV light irradiation and the photo- isomerization phenomena were interpreted by the double proton-transfer mechanism. Moreover, the effects of different substituent groups at the 4-position of the benzal in the three compounds on the photoisomeric properties were discussed.

  12. A Solid-State 11B NMR and Computational Study of Boron Electric Field Gradient and Chemical Shift Tensors in Boronic Acids and Boronic Esters


    The results of a solid-state 11B NMR study of a series of 10 boronic acids and boronic esters with aromatic substituents are reported. Boron-11 electric field gradient (EFG) and chemical shift (CS) tensors obtained from analyses of spectra acquired in magnetic fields of 9.4 and 21.1 T are demonstrated to be useful for gaining insight into the molecular and electronic structure about the boron nucleus. Data collected at 21.1 T clearly show the effects of chemical shift anisotropy (CSA), with tensor spans (Ω) on the order of 10−40 ppm. Signal enhancements of up to 2.95 were achieved with a DFS-modified QCPMG pulse sequence. To understand the relationship between the measured tensors and the local structure better, calculations of the 11B EFG and magnetic shielding tensors for these compounds were conducted. The best agreement was found between experimental results and those obtained from GGA revPBE DFT calculations. A positive correlation was found between Ω and the dihedral angle (ϕCCBO), which describes the orientation of the boronic acid/ester functional group relative to an aromatic system bound to boron. The small boron CSA is discussed in terms of paramagnetic shielding contributions as well as diamagnetic shielding contributions. Although there is a region of overlap, both Ω and the 11B quadrupolar coupling constants tend to be larger for boronic acids than for the esters. We conclude that the span is generally the most characteristic boron NMR parameter of the molecular and electronic environment for boronic acids and esters, and show that the values result from a delicate interplay of several competing factors, including hydrogen bonding, the value of ϕCCBO, and the electron-donating or withdrawing substituents bound to the aromatic ring. PMID:20337440

  13. Solid-state structures of (R sub 3 P) sub 2 PtX sub 2 complexes as determined by a combination of sup 13 C( sup 1 H) and sup 31 P( sup 1 H) NMR spectroscopy

    Rahn, J.A.; Nelson, J.H. (Univ. of Nevada, Reno (USA)); Baltusis, L. (Varian Instrument Div., Palo Alto, CA (USA))


    Cross-polarization, combined with magic-angle spinning, has been employed to obtain high-resolution solid-state {sup 13}C and {sup 31}P NMR spectra of a series of 31 (R{sub 3}P){sub 2}PtX{sub 2} complexes. These data together with spectra obtained in solution were used to compare the solid-state structures with those in solution. It was found that most of these complexes, which have regular square-planar structures in solution, are distorted in the solid state. The extent of the solid-state distortion is a function of the bulk of the coordinated ligands and increases as the ligand size increases. The solid-state distortions appear to result from intramolecular steric effects for cis-(R{sub 3}P){sub 2}PtX{sub 2} and probably from intermolecular crystal packing forces for trans-(R{sub 3}P){sub 2}PtX{sub 2}. 37 refs., 6 figs., 3 tabs.

  14. Solid state structure by X-ray and 13C CP/MAS NMR of new 5-[2-(N,N-dimethylamino)ethoxy]-4,7-dimethylcoumarins

    Ostrowska, Kinga; Maciejewska, Dorota; Dobrzycki, Łukasz; Socha, Pawel


    5-[2-(N,N-dimethylamino)ethoxy]-4,7-dimethylcoumarin (1) and 6-acetyl-5-[2-(N,N-dimethylamino)ethoxy]-4,7-dimethylcoumarin (2), structurally related, were synthesized using both conventional and microwave-assisted approach. An impact of acetyl groups on the molecular structure of coumarin derivatives has been examined. Crystals of 2 were investigated using single crystal and powder X-ray diffraction techniques. Compound 2 crystallizes forming two polymorphs (denoted as 2_1 and 2_2), both belonging to P21/c space group. Both polymorphs are comparably stable and can be formed simultaneously during crystallization process. The solid state structure was also analysed using the fully resolved 13C CP/MAS NMR. The double signals with the intensity ratio of about 1:1 which were observed in the 13C CP/MAS NMR spectrum of compound 1 must arise due to the presence of two conformers of 1. In contrast, NMR spectrum recorded for powder mixture of two polymorphs of compound 2 displays no signal splitting. This is related to structural similarities of molecules in both polymorphs.

  15. Crystal and molecular structures of alkali oxalates: first proof of a staggered oxalate anion in the solid state.

    Dinnebier, Robert E; Vensky, Sascha; Panthöfer, Martin; Jansen, Martin


    The molecular and crystal structures of solvent-free potassium, rubidium, and cesium oxalates have been determined ab initio from high-resolution synchrotron and X-ray laboratory powder patterns. In the case of potassium oxalate K(2)C(2)O(4) (a = 10.91176(7) A, b = 6.11592(4) A, c = 3.44003(2) A, orthorhombic, Pbam, Z = 2), the oxalate anion is planar, whereas in cesium oxalate Cs(2)C(2)O(4) (a = 6.62146(5) A, b = 11.00379(9) A, c = 8.61253(7) A, beta = 97.1388(4) degrees, monoclinic, P2(1)/c, Z = 4) it exhibits a staggered conformation. For rubidium oxalate at room temperature, two polymorphs exist, one (beta-Rb(2)C(2)O(4)) isotypic to potassium oxalate (a = 11.28797(7) A, b = 6.29475(4) A, c = 3.62210(2) A, orthorhombic, Pbam, Z = 2) and the other (alpha-Rb(2)C(2)O(4)) isotypic to cesium oxalate (a = 6.3276(1) A, b = 10.4548(2) A, c = 8.2174(2) A, beta = 98.016(1) degrees, monoclinic, P2(1)/c, Z = 4). The potassium oxalate structure can be deduced from the AlB(2) type, and the cesium oxalate structure from the Hg(99)As type, respectively. The relation between the two types of crystal structures and the reason for the different conformations of the oxalate anion are discussed.

  16. Solid state sciences committee forum

    Smith, Philip


    The 1991 SSSC Forum was conducted under the auspices of the Board on Physics and Astronomy's Solid State Sciences Committee (SSSC) and cosponsored with the National Materials Advisory Board (NMAB). The Forum was the culmination of a year-long dissemination effort following up the NCR study Materials Science and Engineering for the 1990s that was released in September of 1989 and successfully brought together experts and policy makers in the field of advanced materials processing to discuss issues pertinent to the field. Support for the Forum was provided by the Air Force office of Scientific Research (AFOSR), the Department of Energy (DOE), the National Science Foundation (NSF), and the office of Naval Research (ONR).

  17. Solid-State Random Lasers

    Noginov, Mikhail A


    Random lasers are the simplest sources of stimulated emission without cavity, with the feedback provided by scattering in a gain medium. First proposed in the late 60’s, random lasers have grown to a large research field. This book reviews the history and the state of the art of random lasers, provides an outline of the basic models describing their behavior, and describes the recent advances in the field. The major focus of the book is on solid-state random lasers. However, it also briefly describes random lasers based on liquid dyes with scatterers. The chapters of the book are almost independent of each other. So, the scientists or engineers interested in any particular aspect of random lasers can read directly the relevant section. Researchers entering the field of random lasers will find in the book an overview of the field of study. Scientists working in the field can use the book as a reference source.

  18. Solid-state dynamics of uranyl polyoxometalates.

    Alam, Todd M; Liao, Zuolei; Zakharov, Lev N; Nyman, May


    Understanding fundamental uranyl polyoxometalate (POM) chemistry in solution and the solid state is the first step to defining its future role in the development of new actinide materials and separation processes that are vital to every step of the nuclear fuel cycle. Many solid-state geometries of uranyl POMs have been described, but we are only beginning to understand their chemical behavior, which thus far includes the role of templates in their self-assembly, and the dynamics of encapsulated species in solution. This study provides unprecedented detail into the exchange dynamics of the encapsulated species in the solid state through Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR) spectroscopy. Although it was previously recognized that capsule-like molybdate and uranyl POMs exchange encapsulated species when dissolved in water, analogous exchange in the solid state has not been documented, or even considered. Here, we observe the extremely high rate of transport of Li(+) and aqua species across the uranyl shell in the solid state, a process that is affected by both temperature and pore blocking by larger species. These results highlight the untapped potential of emergent f-block element materials and vesicle-like POMs. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. The high-temperature modification of ScRuSi - Structure, 29Si and 45Sc solid state NMR spectroscopy

    Hoffmann, Rolf-Dieter; Rodewald, Ute Ch.; Haverkamp, Sandra; Benndorf, Christopher; Eckert, Hellmut; Heying, Birgit; Pöttgen, Rainer


    A polycrystalline sample of the TiNiSi type low-temperature (LT) modification of ScRuSi was synthesized by arc-melting. Longer annealing in a sealed silica tube (6 weeks at 1270 K) followed by quenching led to the high-temperature (HT) phase. HT-ScRuSi adopts the ZrNiAl structure type: P 6 bar 2 m , a = 688.27(9), c = 336.72(5) pm, wR2 = 0.0861, 260 F2 values, 14 variables. The striking structural building units are regular, tricapped trigonal prisms Si1@Ru3Sc6 and Si2@Ru6Sc3. Both polymorphs have been characterized by 29Si and 45Sc MAS-NMR spectroscopy. The local scandium environments in the two polymorphs are easily distinguished by their electric field gradient tensor values, in agreement with theoretically calculated values.

  20. Room temperature synthesis and solid-state structure of Ni 2P 2O 6·12H 2O

    Haag, J. M.; LeBret, G. C.; Cleary, D. A.; Twamley, B.


    The synthesis and crystal structure of Ni 2P 2O 6·12H 2O are reported. The compound was synthesized from aqueous solutions of nickel chloride and sodium hypodiphosphate at room temperature. The space group is orthorhombic, Pnnm. Unit cell dimensions are a=11.2418(5) Å, b=18.5245(8) Å, and c=7.3188(3) Å, Z=4. The product is unstable with respect to dehydration above room temperature.

  1. Radioactive isotopes in solid-state physics

    Deicher, M


    Radioactive atoms have been used in solid-state physics and in material science for many decades. Besides their classical application as tracer for diffusion studies, nuclear techniques such as M\\"ossbauer spectroscopy, perturbed angular correlation, $\\beta$-NMR, and emission channelling have used nuclear properties (via hyperfine interactions or emitted particles) to gain microscopical information on the structural and dynamical properties of solids. During the last decade, the availability of many different radioactive isotopes as a clean ion beam at ISOL facilities such as ISOLDE at CERN has triggered a new era involving methods sensitive for the optical and electronic properties of solids, especially in the field of semiconductor physics. Extremely sensitive spectroscopic techniques like deep-level transient spectroscopy (DLTS), photoluminescence (PL), and Hall effect have gained a new quality by using radioactive isotopes. Because of their decay the chemical origin of an observed electronic and optical b...

  2. Chrystal structure properties of Al-doped Li{sub 4}Ti{sub 5}O{sub 12} synthesized by solid state reaction method

    Sandi, Dianisa Khoirum, E-mail:; Suryana, Risa, E-mail: [Department of Physics, Faculty of Mathematics and Natural Sciences, Sebelas Maret University (Indonesia); Priyono, Slamet, E-mail: [Physics Research Center (P2F)-LIPI, Puspiptek Area, Serpong, Tangerang (Indonesia)


    This research aim is to analyze the effect of Aluminum (Al) doping in the structural properties of Al-doped Li{sub 4}Ti{sub 5}O{sub 12} as anode in lithium ion battery. Al-doped Li{sub 4}Ti{sub 5}O{sub 12} powders were synthesized by solid state reaction method. LiOH.H{sub 2}O, TiO{sub 2}, and Al{sub 2}O{sub 3} were raw materials. These materials were milled for 15 h, calcined at temperature of 750{sup o}C and sintered at temperature of 800{sup o}C. Mole percentage of doping Al (x) was varied at x=0; x=0.025; and x =0.05. Al-doped Li{sub 4}Ti{sub 5}O{sub 12} powders were synthesized by solid state reaction method. X-ray diffraction was employed to determine the structure of Li{sub 4}Ti{sub 5}O{sub 12}. The PDXL software was performed on the x-ray diffraction data to estimate the phase percentage, the lattice parameter, the unit cell volume, and the crystal density. Al-doped Li{sub 4}Ti{sub 5}O{sub 12} has cubic crystal structure. Al-doping at x=0 and x=0.025 does not change the phase as Li{sub 4}Ti{sub 5}O{sub 12} while at x=0.050 the phase changes to the LiTiAlO{sub 4}. The diffraction patterns show that the angle shifted to the right as the increase of x which indicated that Al substitute Ti site. Percentage of Li{sub 4}Ti{sub 5}O{sub 12} phase at x=0 and x=0.025 was 97.8% and 96.8%, respectively. However, the lattice parameters, the unit cell volume, and the crystal density does not change significantly at x=0; x=0.025; and x=0.050. Based on the percentage of Li{sub 4}Ti{sub 5}O{sub 12} phase, the Al-doped Li at x=0 and x=0.025 is promising as a lithium battery anode.

  3. Preliminary Analysis of a Fully Solid State Magnetocaloric Refrigeration

    Abdelaziz, Omar [ORNL


    Magnetocaloric refrigeration is an alternative refrigeration technology with significant potential energy savings compared to conventional vapor compression refrigeration technology. Most of the reported active magnetic regenerator (AMR) systems that operate based on the magnetocaloric effect use heat transfer fluid to exchange heat, which results in complicated mechanical subsystems and components such as rotating valves and hydraulic pumps. In this paper, we propose an alternative mechanism for heat transfer between the AMR and the heat source/sink. High-conductivity moving rods/sheets (e.g. copper, brass, iron, graphite, aluminum or composite structures from these) are utilized instead of heat transfer fluid significantly enhancing the heat transfer rate hence cooling/heating capacity. A one-dimensional model is developed to study the solid state AMR. In this model, the heat exchange between the solid-solid interfaces is modeled via a contact conductance, which depends on the interface apparent pressure, material hardness, thermal conductivity, surface roughness, surface slope between the interfaces, and material filled in the gap between the interfaces. Due to the tremendous impact of the heat exchange on the AMR cycle performance, a sensitivity analysis is conducted employing a response surface method, in which the apparent pressure, effective surface roughness and grease thermal conductivity are the uncertainty factors. COP and refrigeration capacity are presented as the response in the sensitivity analysis to reveal the important factors influencing the fully solid state AMR and optimize the solid state AMR efficiency. The performances of fully solid state AMR and traditional AMR are also compared and discussed in present work. The results of this study will provide general guidelines for designing high performance solid state AMR systems.

  4. Intermolecular interactions in the solid state structures of neutral and N-protonated 5-alkoxymethyl-8-hydroxyquinolines

    Schulze, Mathias M.; Böhme, Uwe; Schwarzer, Anke; Weber, Edwin


    A series of five different alkoxymethyl substituted derivatives of 8-hydroxyquinoline was synthesised both in protonated (1a-1e) and neutral (2a-2e) form. The alkoxymethyl groups are MeO (1a, 2a), EtO (1b, 2b), n-PrO (1c, 2c), iso-PrO (1d, 2d), n-BuO (1e, 2e). The compounds were characterised by single crystal X-ray diffraction and spectroscopic methods. Hirshfeld surface analysis was performed to analyse the crystal packing quantitatively. Topological analysis of the electron density distribution delivers information about the strength of the hydrogen bonds. The overall results reveal a main difference between the charged (1a-1d) and uncharged (2a-2e) compounds in the orientation of the hydroxyl group resulting in a different cyclic dimer formation. In both cases the structures are dominated by hydrogen bonding (1a-1d: Osbnd H⋯Cl, Nsbnd H⋯Cl and 2a-2e: Osbnd H⋯N). Furthermore, all crystal structures show π involved interactions though taking only a minor part in the packing of the molecules.

  5. DFT calculations of quadrupolar solid-state NMR properties: Some examples in solid-state inorganic chemistry.

    Cuny, Jerome; Messaoudi, Sabri; Alonzo, Veronique; Furet, Eric; Halet, Jean-François; Le Fur, Eric; Ashbrook, Sharon E; Pickard, Chris J; Gautier, Regis; Le Polles, Laurent


    This article presents results of first-principles calculations of quadrupolar parameters measured by solid-state nuclear magnetic measurement (NMR) spectroscopy. Different computational methods based on density functional theory were used to calculate the quadrupolar parameters. Through a series of illustrations from different areas of solid state inorganic chemistry, it is shown how quadrupolar solid-state NMR properties can be tackled by a theoretical approach and can yield structural information.

  6. Fabrication of supramolecular frameworks by tuning the binding site of a tripodal ligand with 10 metal ions: Interplay of covalent and non-covalent interactions in solid-state structure

    Debajyoti Ghoshal; Tapas Kumar Maji


    Two new coordination polymers of Zn(II) and Cd(II) have been synthesized using 2,4,6-tri(4-pyridyl)-1,3,5-triazine (tpt), where it acts as a bi-bridging ligand. The compounds are characterized by IR spectroscopy, elemental analysis and single crystal X-ray diffraction studies. Compound [Zn(tpt)(NO3)2(H2O)2] (1) and [Cd(tpt)(NO3)2(H2O)2] (2) are isomorphous and show 1D coordination structure with almost octahedral metal center, which is extended to supramolecular 3D structure by cooperative weak interactions, like H-bonding, - and C-H…O interactions. Both the compounds reveal interplay of covalent and non-covalent interactions for fabricating supramolecular solid-state architecture.

  7. Structure analyses using X-ray photoelectron spectroscopy and X-ray absorption near edge structure for amorphous MS3 (M: Ti, Mo) electrodes in all-solid-state lithium batteries

    Matsuyama, Takuya; Deguchi, Minako; Mitsuhara, Kei; Ohta, Toshiaki; Mori, Takuya; Orikasa, Yuki; Uchimoto, Yoshiharu; Kowada, Yoshiyuki; Hayashi, Akitoshi; Tatsumisago, Masahiro


    Electronic structure changes of sulfurs in amorphous TiS3 and MoS3 for positive electrodes of all-solid-state lithium batteries are examined by X-ray photoelectron spectroscopy (XPS) and the X-ray absorption near edge structure (XANES). The all-solid-state cell with amorphous TiS3 electrode shows the reversible capacity of about 510 mAh g-1 for 10 cycles with sulfur-redox in amorphous TiS3 during charge-discharge process. On the other hand, the cell with amorphous MoS3 shows the 1st reversible capacity of about 720 mAh g-1. The obtained capacity is based on the redox of both sulfur and molybdenum in amorphous MoS3. The irreversible capacity of about 50 mAh g-1 is observed at the 1st cycle, which is attributed to the irreversible electronic structure change of sulfur during the 1st cycle. The electronic structure of sulfur in amorphous MoS3 after the 10th charge is similar to that after the 1st charge. Therefore, the all-solid-state cell with amorphous MoS3 electrode shows relatively good cyclability after the 1st cycle.

  8. Cation size effects in mixed-ion metaphosphate glasses: structural characterization by multinuclear solid state NMR spectroscopy.

    Schneider, J; Tsuchida, J; Eckert, H


    Metaphosphate glasses with two monovalent species A(1-x)B(x)PO3 (0 ≤x≤ 1) show mixed-ion effects (MIE) in the dc conductivities and glass transition temperatures, which are strongly dependent on the cation size mismatch between the two mobile species. In the present contribution, mixed-ion metaphosphate glasses based on the cation combinations Cs-Li, Rb-Li, and Cs-Ag, exhibiting particularly large size mismatches, are analyzed by (31)P, (87)Rb, (109)Ag and (133)Cs NMR to determine possible correlations between this mismatch and some of the structural properties critical to the development of the MIE: the local environments around the mobile species and their spatial distribution relative to each other. The results are compared with those obtained in the Na-Ag metaphosphate series, which serves as a reference system, with minimized cation mismatch MIE. The local coordination environments of the Ag(+), Rb(+) and Cs(+) ions follow analogous compositional trends as previously observed in Na-based mixed-ion metaphosphate glasses: for a given cation species A, the average A-O distance shows an expansion/compression when this cation is replaced by a second species B with smaller/bigger ionic radius, respectively. This compositional differentiation of the structural sites for the mobile species may contribute to the MIE. Concerning the relative spatial distribution of the mobile ions, results from (7)Li-(133)Cs (SEDOR) experiments indicate a random mixture of Cs and Li in Cs-Li metaphosphate glasses. While this result is in agreement with one of the fundamental hypotheses of the models proposed to describe the MIE, it is at variance with the observation of various partial cation segregation phenomena observed in Na-based mixed alkali glasses. This result suggests that cation size mismatch is not the decisive parameter in determining segregation or non-statistical mixing of cations in the glass. In the Cs-Ag and Na-Ag glasses, (109)Ag spin-echo NMR reveals a progressive

  9. A coordination chemistry study of hydrated and solvated cationic vanadium ions in oxidation states +III, +IV, and +V in solution and solid state

    Krakowiak, Joanna; Lundberg, Daniel; Persson, Ingmar


    The coordination chemistry of hydrated and solvated vanadium(III), oxovanadium(IV), and dioxovanadium(V) ions in the oxygen donor solvents water, dimethylsulfoxide (dmso) and N,N′-dimethylpropyleneurea (dmpu) has been studied in solution by EXAFS and large angle X-ray scattering (LAXS) and in solid state by single crystal X-ray diffraction and EXAFS. The hydrated vanadium(III) ion has a regular octahedral configuration with a mean V-O bond distance of 1.99 Å. In the hydrated and dimethylsulfo...

  10. A 1H, 13C and 15N NMR study in solution and in the solid state of six N-substituted pyrazoles and indazoles.

    Claramunt, Rosa M; Santa María, M Dolores; Sanz, Dionisia; Alkorta, Ibon; Elguero, José


    Three N-substituted pyrazoles and three N-substituted indazoles [1-(4-nitrophenyl)-3,5-dimethylpyrazole (1), 1-(2,4-dinitrophenyl)-3,5-dimethylpyrazole (2), 1-tosyl-pyrazole (3), 1-p-chlorobenzoylindazole (4), 1-tosylinda-zole (5) and 2-(2-hydroxy-2-phenylethyl)-indazole (6)] have been studied by NMR spectroscopy in solution (1H, 13C, 15N) and in the solid state (13C, 15N). The chemical shifts have been compared with GIAO/DFT calculated absolute shieldings. Some discrepancies have been analyzed.

  11. Study of hydrogen in coals, polymers, oxides, and muscle water by nuclear magnetic resonance; extension of solid-state high-resolution techniques. [Hydrogen molybdenum bronze

    Ryan, L.M.


    Nuclear magnetic resonance (NMR) spectroscopy has been an important analytical and physical research tool for several decades. One area of NMR which has undergone considerable development in recent years is high resolution NMR of solids. In particular, high resolution solid state /sup 13/C NMR spectra exhibiting features similar to those observed in liquids are currently achievable using sophisticated pulse techniques. The work described in this thesis develops analogous methods for high resolution /sup 1/H NMR of rigid solids. Applications include characterization of hydrogen aromaticities in fossil fuels, and studies of hydrogen in oxides and bound water in muscle.

  12. Anhydrate to hydrate solid-state transformations of carbamazepine and nitrofurantoin in biorelevant media studied in situ using time-resolved synchrotron X-ray diffraction.

    Boetker, Johan P; Rantanen, Jukka; Arnfast, Lærke; Doreth, Maria; Raijada, Dhara; Loebmann, Korbinian; Madsen, Cecilie; Khan, Jamal; Rades, Thomas; Müllertz, Anette; Hawley, Adrian; Thomas, Diana; Boyd, Ben J


    Transformation of the solid-state form of a drug compound in the lumen of the gastrointestinal tract may alter the drug bioavailability and in extreme cases result in patient fatalities. The solution-mediated anhydrate-to-hydrate phase transformation was examined using an in vitro model with different biorelevant media, simulated fasted and fed state intestinal fluids containing bile salt and dioleoylphosphatidylcholine (DOPC) micelles, DOPC/sodium dodecyl sulfate (SDS) mixture, bile salt solution and water. Two anhydrate compounds (carbamazepine, CBZ and nitrofurantoin, NF) with different overall transformation time into hydrate form were used as model compounds. The transformations were monitored using direct structural information from time-resolved synchrotron X-ray diffraction. The kinetics of these transformations were estimated using multivariate data analysis (principal component analysis, PCA) and compared to those for nitrofurantoin (NF). The study showed that the solution-mediated phase transformation of CBZ anhydrate was remarkably faster in the DOPC/SDS medium compared to transformation in all the other aqueous dispersion media. The conversion time for CBZ anhydrate in water was shorter than for DOPC/SDS but still faster than the conversion seen in fed and fasted state micellar media. The conversion of CBZ anhydrate to hydrate was the slowest in the solution containing bile salt alone. In contrast, the solution-mediated phase transformations of NF did only show limited kinetic dependence on the dispersion media used, indicating the complexity of the nucleation process. Furthermore, when the CBZ and NF material was compacted into tablets the transformation times were remarkably slower. Results suggest that variations in the composition of the contents of the stomach/gut may affect the recrystallization kinetics, especially when investigating compounds with relatively fast overall transformation time, such as CBZ.

  13. Structural characterization of bismuth rare earth tungstates obtained by fast microwave-assisted solid-state synthesis

    Rocha, G.N.; Melo, L.F.L. [Grupo de Química de Materiais Avançados (GQMAT), Departamento de Química Analítica e Físico-Química, Universidade Federal do Ceará – UFC, Campus do Pici, CP 12100, CEP 60451-970 Fortaleza – CE (Brazil); Castro, M.C.; Ayala, A.P. [Departamento de Física, Universidade Federal do Ceará (Brazil); Menezes, A.S. de [Departamento de Física – CCET, Universidade Federal do Maranhão, Campus do Bacanga, 65085-580 São Luís, MA (Brazil); Fechine, P.B.A., E-mail: [Grupo de Química de Materiais Avançados (GQMAT), Departamento de Química Analítica e Físico-Química, Universidade Federal do Ceará – UFC, Campus do Pici, CP 12100, CEP 60451-970 Fortaleza – CE (Brazil)


    A new synthetic route was used to obtain bismuth rare earth tungstates: BiREWO{sub 6}, where RE = Y, Gd and Nd. These materials were obtained by microwave radiation in air at 900–1100 °C for 10 min, depend on the rare earth composition in the ceramic. Structural characterization was performed by X-ray powder diffraction, Infrared and Raman spectroscopy. It was observed that all samples are isostructural materials with monoclinic phase with space group A12/m1 and member of the Aurivillius family, as Bi{sub 2}WO{sub 6} ferroelectric phase. It was observed moderated values for dielectric measurements (14<ε{sub r}{sup ′}>19 and 0.018 < tg δ > 0.079) at microwaves frequencies, which can be used as Dielectric Resonator Antenna or for size reduction of the electric device. - Highlights: ► New synthetic route to obtain bismuth rare earth tungstates by microwave radiation. ► Vibration spectroscopy was based in Group Theory and observed in FTIR and Raman. ► BiGdWO{sub 6} presented simultaneously higher ε{sub r}{sup ′} and smaller tg δ values at microwaves frequencies. ► The samples can be used as a DRA or for size reduction of the electric device.

  14. Theoretical investigation of electronic structure and charge transport property of 9,10-distyrylanthracene (DSA) derivatives with high solid-state luminescent efficiency.

    Wang, Lijuan; Xu, Bin; Zhang, Jibo; Dong, Yujie; Wen, Shanpeng; Zhang, Houyu; Tian, Wenjing


    The electronic structure and charge transport property of 9,10-distyrylanthracene (DSA) and its derivatives with high solid-state luminescent efficiency were investigated by using density functional theory (DFT). The impact of substituents on the optimized structure, reorganization energy, ionization potential (IP) and electronic affinity (EA), frontier orbitals, crystal packing, transfer integrals and charge mobility were explored based on Marcus theory. It was found that the hole mobility of DSA was 0.21 cm(2) V(-1) s(-1) while the electron mobility was 0.026 cm(2) V(-1) s(-1), which were relatively high due to the low reorganization energies and high transfer integrals. The calculated results showed that the charge transport property of these compounds can be significantly tuned via introducing different substituents to DSA. When one electron-withdrawing group (cyano group) was introduced into DSA, DSA-CN exhibited hole mobility of 0.14 cm(2) V(-1) s(-1) which was on the same order of that of DSA. However, the electron mobility of DSA-CN decreased to 8.14 × 10(-4) cm(2) V(-1) s(-1) due to the relatively large reorganization energy and disadvantageous transfer integral. The effect of electron-donating substituents was investigated by introducing methoxy group and tertiary butyl into DSA. DSA-OCH(3) and DSA-TBU showed much lower charge mobility than DSA resulting from the steric hindrance of substituents. On the other hand, both of them exhibited balanced transport properties (for DSA-OCH(3), the hole and electron mobility was 0.0026 and 0.0027 cm(2) V(-1) s(-1); for DSA-TBU, the hole and electron mobility was 0.045 and 0.012 cm(2) V(-1) s(-1)) because of their similar transfer integrals for both hole and electron. DSA and its derivatives were supposed to be one of the most excellent emissive materials for organic electroluminescent applications because of their high charge mobility and high solid-state luminescent efficiency.

  15. Poly(ethylene oxide) irradiated in the solid state, melt and aqueous solution—a DSC and WAXD study

    Jurkin, Tanja; Pucić, Irina


    Interactions of the aggregate state of poly(ethylene oxide), PEO, and γ-irradiation conditions (total dose, atmosphere) on its thermal and crystalline properties were investigated by DSC and WAXD taking into account sample molecular mass and form. In PEO irradiated in the solid state and in the presence of oxygen, chain scission dominated over concurrent crosslinking up to 200 kGy, particularly in PEO powders, due to a large surface being in contact with air. In solid samples the degree of crystallinity and crystallite size increased with the dose up to 50 kGy, probably not just due to partial crystallization upon degradation of amorphous phase, but to recrystallization of broken tie molecules. The least changes in crystallinity and phase transformation temperatures occurred in solid films. A substantial decrease in crystallinity and transformation temperatures without the initial crystallinity increase was achieved in samples that were amorphous on irradiation, at temperatures above the PEO melting temperature and in aqueous solutions. Radiation crosslinking of the PEO aqueous solution in an inert atmosphere is the most suitable way to obtain a lower degree of crystallinity and phase transformation temperatures while preserving mechanical properties.

  16. Static solid-state (14)N NMR and computational studies of nitrogen EFG tensors in some crystalline amino acids.

    O'Dell, Luke A; Schurko, Robert W


    The recently reported direct enhancement of integer spin magnetization (DEISM) methodology for signal enhancement in solid-state NMR of integer spins has been used to obtain static (14)N powder patterns from alpha-glycine, L-leucine and L-proline in relatively short experimental times at 9.4 T, allowing accurate determination of the quadrupolar parameters. Proton decoupling and deuteration of the nitrogen sites were used to reduce the (1)H-(14)N dipolar contribution to the transverse relaxation time allowing more echoes to be acquired per scan. In addition, ab initio calculations using molecular clusters (Gaussian 03) and the full crystal lattice (CASTEP) have been employed to confirm these results, to obtain the orientation of the electric field gradient (EFG) tensors in the molecular frame, and also to correctly assign the two sets of parameters for L-leucine. The (14)N EFG tensor is shown to be highly sensitive to the surrounding environment, particularly to nearby hydrogen bonding.

  17. Recrystallized S-layer protein of a probiotic Propionibacterium: structural and nanomechanical changes upon temperature or pH shifts probed by solid-state NMR and AFM.

    de sa Peixoto, Paulo; Roiland, Claire; Thomas, Daniel; Briard-Bion, Valérie; Le Guellec, Rozenn; Parayre, Sandrine; Deutsch, Stéphanie-Marie; Jan, Gwénaël; Guyomarc'h, Fanny


    Surface protein layers (S layers) are common constituents of the bacterial cell wall and originate from the assembly of strain-dependent surface layer proteins (Slps). These proteins are thought to play important roles in the bacteria's biology and to have very promising technological applications as biomaterials or as part of cell-host cross-talk in probiotic mechanism. The SlpA from Propionibacterium freudenreichii PFCIRM 118 strain was isolated and recrystallized to investigate organization and assembly of the protein using atomic force microscopy and solid-state (1)H and (13)C-nuclear magnetic resonance. SlpA was found to form hexagonal p1 monolayer lattices where the protein exhibited high proportions of disordered regions and of bound water. The lattice structure was maintained, but softened, upon mild heating or acidification, probably in relation with the increasing mobilities of the disordered protein regions. These results gave structural insights on the mobile protein regions exposed by S layer films, upon physiologically relevant changes of their environmental conditions.

  18. Structural, optical, and magnetic properties of polycrystalline Co-doped TiO{sub 2} synthesized by solid-state method

    Bouaine, Abdelhamid, E-mail: [Laboratoire d' Etude des Materiaux (LEM), Departement de Physique, Faculte des Sciences Exactes et des Sciences de la Nature et de la vie, Universite de Jijel, cite Oued-Aissa, B.P 98, Jijel 18000 (Algeria); Institut de Physique et Chimie des Materiaux de Strasbourg (IPCMS), UMR 7504 CNRS - UdS, 23 rue du Loess, B.P. 43, 67034 Strasbourg Cedex 2 (France); Schmerber, G.; Ihiawakrim, D.; Derory, A. [Institut de Physique et Chimie des Materiaux de Strasbourg (IPCMS), UMR 7504 CNRS - UdS, 23 rue du Loess, B.P. 43, 67034 Strasbourg Cedex 2 (France)


    Highlights: Black-Right-Pointing-Pointer Influence of Co doping on the TiO{sub 2} tetragonal structure. Black-Right-Pointing-Pointer Decrease of the energy band gap after doping with Co atoms. Black-Right-Pointing-Pointer Appearance of ferromagnetism in Co-doped TiO{sub 2} diluted magnetic semiconductors. - Abstract: We have used a solid-state method to synthesize polycrystalline Co-doped TiO{sub 2} diluted magnetic semiconductors (DMSs) with Co concentrations of 0, and 0.5 at.%. X-ray diffraction patterns reveal that Co doped TiO{sub 2} crystallizes in the rutile tetragonal structure with no additional peaks. Transmission electron microscopy (TEM) did not indicate the presence of magnetic parasitic phases and confirmed that Co ions are uniformly distributed inside the samples. Optical absorbance measurements showed an energy band gap which decreases after doping with the Co atoms into the TiO{sub 2} matrix. Magnetization measurements revealed a paramagnetic behavior for the as-prepared Co-doped TiO{sub 2} and a ferromagnetic behavior for the same samples after annealed under a mixture of H{sub 2}/N{sub 2} atmosphere.

  19. Solid-state 13C and 1H spin diffusion NMR analyses of the microfibril structure for bacterial cellulose.

    Masuda, Kenji; Adachi, Masayuki; Hirai, Asako; Yamamoto, Hiroyuki; Kaji, Hironori; Horii, Fumitaka


    To obtain further information about the cause for the rather large splitting of the C4 resonance line into the downfield (C4D) and upfield (C4U) lines in CP/MAS 13C NMR spectra for native cellulose, 13C and 1H spin diffusion measurements have been conducted by using different types of bacterial cellulose samples. In 13C spin diffusion measurements, the C4D resonance line is selectively inverted by the Dante pi pulse sequence and the 13C spin diffusion is allowed to proceed from the C4D carbons to other carbons including the C4U carbons with use of the 13C4-enriched bacterial cellulose sample. The analysis based on the simple spin diffusion theory for the process experimentally observed reveals that the C4U carbons may be located at distances less than about 1 nm from the C4D carbons. In 1H spin diffusion measurements, poly(vinyl alcohol) (PVA) films in which ribbon assemblies of bacterial cellulose are dispersed are employed and the 1H spin diffusion process is examined from the water-swollen PVA continuous phase to the dispersed ribbon assemblies by the 13C detection through the 1H-13C CP technique. As a result, it is found that the C4D and C4U carbons are almost equally subjected to the 1H spin diffusion from the PVA phase, indicating that the C4U carbons are not localized in some limited area, e.g. in the surfacial region, but are distributed in the whole area in the microfibrils. These experimental results suggest that the C4U carbons may exist as structural defects probably due to conformational irregularity associated with disordered hydrogen bonding of the CH(2)OH groups in the microfibrils.

  20. Solid-state laser engineering

    Koechner, Walter


    Solid-State Laser Engineering, written from an industrial perspective, discusses in detail the characteristics, design, construction, and performance of solid-state lasers. Emphasis is placed on engineering and practical considerations; phenomenological aspects using models are preferred to abstract mathematical derivations. This new edition has extensively been updated to account for recent developments in the areas of diode-laser pumping, laser materials, and nonlinear crystals. Walter Koechner received a doctorate in Electrical Engineering from the University of Technology in Vienna, Austria, in 1965. He has published numerous papers in the fields of solid-state physics, optics, and lasers. Dr. Koechner is founder and president of Fibertek, Inc., a research firm specializing in the design, development, and production of advanced solid-state lasers, optical radars, and remote-sensing systems.

  1. Solid-state laser engineering

    Koechner, Walter


    Solid-State Laser Engineering, written from an industrial perspective, discusses in detail the characteristics, design, construction, and performance of solid-state lasers. Emphasis is placed on engineering and practical considerations; phenomenological aspects using models are preferred to abstract mathematical derivations. This new edition has extensively been updated to account for recent developments in the areas of diode-laser pumping, mode locking, ultrashort-pulse generation etc. Walter Koechner received a doctorate in Electrical Engineering from the University of Technology in Vienna, Austria, in 1965. He has published numerous papers in the fields of solid-state physics, optics, and lasers. Dr. Koechner is founder and president of Fibertek, Inc., a research firm specializing in the design, development, and production of advanced solid-state lasers, optical radars, and remote-sensing systems.

  2. Solid State Photovoltaic Research Branch


    This report summarizes the progress of the Solid State Photovoltaic Research Branch of the Solar Energy Research Institute (SERI) from October 1, 1988, through September 30,l 1989. Six technical sections of the report cover these main areas of SERIs in-house research: Semiconductor Crystal Growth, Amorphous Silicon Research, Polycrystalline Thin Films, III-V High-Efficiency Photovoltaic Cells, Solid-State Theory, and Laser Raman and Luminescence Spectroscopy. Sections have been indexed separately for inclusion on the data base.

  3. Solid-state laser engineering

    Koechner, Walter


    Solid-State Laser Engineering is written from an industrial perspective and discusses in detail the characteristics, design, construction and practical problems of solid-state lasers. Emphasis is placed on engineering and practical considerations, with a phenomenological treatment using modelsbeing preferred to abstract mathematical derivations. This new edition has been updated and revised to include important developments, concepts and technologies that have emerged since the publication of the first edition.

  4. A chelate-stabilized ruthenium(sigma-pyrrolato) complex: resolving ambiguities in nuclearity and coordination geometry through 1H PGSE and 31P solid-state NMR studies.

    Foucault, Heather M; Bryce, David L; Fogg, Deryn E


    Reaction of RuCl2(PPh3)3 with LiNN' (NN' = 2-[(2,6-diisopropylphenyl)imino]pyrrolide) affords a single product, with the empirical formula RuCl[(2,6-iPr2C6H3)N=CHC4H3N](PPh3)2. We identify this species as a sigma-pyrrolato complex, [Ru(NN')(PPh3)2]2(mu-Cl)2 (3b), rather than mononuclear RuCl(NN')(PPh3)2 (3a), on the basis of detailed 1D and 2D NMR characterization in solution and in the solid state. Retention of the chelating, sigma-bound iminopyrrolato unit within 3b, despite the presence of labile (dative) chloride and PPh3 donors, indicates that the chelate effect is sufficient to inhibit sigma --> pi isomerization of 3b to a piano-stool, pi-pyrrolato structure. 2D COSY, SECSY, and J-resolved solid-state 31P NMR experiments confirm that the PPh3 ligands on each metal center are magnetically and crystallographically inequivalent, and 31P CP/MAS NMR experiments reveal the largest 99Ru-31P spin-spin coupling constant (1J(99Ru,31P) = 244 +/- 20 Hz) yet measured. Finally, 31P dipolar-chemical shift spectroscopy is applied to determine benchmark phosphorus chemical shift tensors for phosphine ligands in hexacoordinate ruthenium complexes.

  5. Ultrasonic methods in solid state physics

    Truell, John; Elbaum, Charles


    Ultrasonic Methods in Solid State Physics is devoted to studies of energy loss and velocity of ultrasonic waves which have a bearing on present-day problems in solid-state physics. The discussion is particularly concerned with the type of investigation that can be carried out in the megacycle range of frequencies from a few megacycles to kilomegacycles; it deals almost entirely with short-duration pulse methods rather than with standing-wave methods. The book opens with a chapter on a classical treatment of wave propagation in solids. This is followed by separate chapters on methods and techni

  6. Hilbert space structure of a solid state quantum computer two-electron states of a double quantum dot artificial molecule

    Hu, X; Hu, Xuedong


    We study theoretically a double quantum dot hydrogen molecule in the GaAs conduction band as the basic elementary gate for a quantum computer with the electron spins in the dots serving as qubits. Such a two-dot system provides the necessary two-qubit entanglement required for quantum computation. We determine the excitation spectrum of two horizontally coupled quantum dots with two confined electrons, and study its dependence on an external magnetic field. In particular, we focus on the splitting of the lowest singlet and triplet states, the double occupation probability of the lowest states, and the relative energy scales of these states. We point out that at zero magnetic field it is difficult to have both a vanishing double occupation probability for a small error rate and a sizable exchange coupling for fast gating. On the other hand, finite magnetic fields may provide finite exchange coupling for quantum computer operations with small errors. We critically discuss the applicability of the envelope funct...

  7. Structural investigation of α-LaZr2F11 by coupling X-ray powder diffraction, 19F solid state NMR and DFT calculations

    Martineau, Charlotte; Legein, Christophe; Body, Monique; Péron, Olivier; Boulard, Brigitte; Fayon, Franck


    α-LaZr2F11 has been synthesized by solid state reaction. Its crystal structure has been refined from X-ray powder diffraction data (space group no. 72 Ibam, a=7.785(1) Å, b=10.086(1) Å and c=11.102(1) Å). α-LaZr2F11 contains one La, one Zr and four F inequivalent crystallographic sites. F3 and F4 are shared between one ZrF73- polyhedron and one LaF85- polyhedron, while F1 and F2 bridge two ZrF73- polyhedra. 19F 1D MAS NMR spectra of α-LaZr2F11 are in agreement with the proposed structural model. Assignment of the 19F resonances to the corresponding crystallographic sites has been performed on the basis of both their relative intensities and their correlation patterns in a 19F 2D dipolar-based double-quantum recoupling MAS NMR spectrum. DFT calculations of the 19F chemical shielding tensors have been performed using the GIPAW method implemented in the NMR-CASTEP code, for the experimental structure and two PBE-DFT geometry optimized structures of α-LaZr2F11 (atomic position optimization and full geometry optimization with rescaling of the unit cell volume to the experimental value). Computations were done with and without using a modified La pseudopotential allowing the treatment of the 4f localized empty orbitals of La3+. A relatively nice agreement between the experimental 19F isotropic and anisotropic chemical shifts and the values calculated for the proposed structural model is obtained.

  8. Development of the plastic solid-dye cell for tunable solid-state dye lasers and study on its optical properties

    Ko, Do Kyeong; Lee, Jong Min; Cha, Byung Heon; Jung, E. C.; Kim, Hyun Su; Lim, Gwon


    we have fabricated solid-state dyes with PMMA and sol-gel materials. We developed single longitudianl mode solid-state dye laser with the linewidth of less than 500MHz. We have constructed a self-seeded laser and observed the increase of the output power because of self-seeding effect. We investigated the operating characteristics of the dualwave laser oscillator and DFDL with solid-state dyes. And we have constructed the 3-color solid-state dye laser oscillator and amplifier system and observed 3-color operation. We also improved the laser oscliiator with disk-type solid-state dye cell which can be translated and rotated with the help of the two stepping motors. With the help of computer control, we could constantly changed the illuminated area of the dye cell and, therefore, were able to achieve long time operation and to use almost the entire region of the solid-state dye cell.

  9. Solid state synthesis, structural, physicochemical and optical properties of an inter-molecular compound: 2-hydroxy-1, 2-diphenylethanone-4-nitro-o-phenylenediamine system

    Rai, U. S.; Singh, Manjeet; Rai, R. N.


    The phase diagram of 2-hydroxy-1, 2-diphenylethanone (HDPE)-4-nitro-o-phenylenediamine (NOPDA) system, determined by the thaw-melt method, gives two eutectics E1 (m p = 66.0 °C) and E2 (m p = 155.0 °C) with 0.30 and 0.55 mol fractions of NOPDA, respectively, and an 1:1 inter-molecular compound (IMC) (m p 162.0 °C). This IMC was synthesized by adopting the green synthetic method of solid state reaction. While its formation and structure were confirmed by the X-ray diffraction and spectroscopic methods, the ORTEP view gives mode of crystal packing, C‒H…O, C‒H…N, π-π stacking and the inter-molecular hydrogen bonding in the compound. The single crystal of the IMC shows 53% transmission and emits significantly higher dual fluorescence, and the band gap was computed to be 3.04 eV. The values of solubility of the IMC, measured in the temperature range 304-322 K, satisfy the mole fraction (X) and temperature equation: Xeq= 5.1324 × 10-7 e 0.01356T.

  10. Structural tungsten-imido chemistry: the gas-phase structure of W(NBut)2(NHBut)2 and the solid-state structures of novel heterobimetallic W/N/M (M = Rh, Pd, Zn) species.

    Choujaa, Hamid; Cosham, Samuel D; Johnson, Andrew L; Kafka, Graeme R; Mahon, Mary F; Masters, Sarah L; Molloy, Kieran C; Rankin, David W H; Robertson, Heather E; Wann, Derek A


    The gas-phase (electron diffraction) and solid-state (X-ray) structures of W(NBut)2(NHBut)2 (1) have been determined. In the gas phase, 1 adopts both C1 and C2 conformations in a 69:31 ratio. The solid-state structure is disordered over two equal sites, both showing approximate C2 conformation as in the gas phase; the imido and amido centers are, however, clearly distinguished. Compound 1 has been used to synthesize novel heterobimetallic derivatives W(NBut)4[Rh(COD)]2 (3) and W(NBut)4[Pd(eta3-C3H5)]2 (4) via the dilithiated intermediate Li2[W(NBut)4] (2). In both cases, the [W(NBut)4] moiety bridges the two organometallic fragments. Reaction of 1 with Me2Zn has produced [Me(tBuN)W(mu-NBut)2ZnMe(NH2But)] (5). The structures of 3, 4, and 5 have been determined. Thermal decomposition of 4 under an autogenerated pressure at 700 degrees C has formed the hitherto uncharacterized bimetallic alloy WPd2.

  11. Applied solid state science advances in materials and device research

    Wolfe, Raymond


    Applied Solid State Science: Advances in Materials and Device Research, Volume 4 covers articles on single crystal compound semiconductors and complex polycrystalline materials. The book discusses narrow gap semiconductors and solid state batteries. The text then describes the advantages of hot-pressed microcrystalline compacts of oxygen-octahedra ferroelectrics over single crystal materials, as well as heterostructure junction lasers. Solid state physicists, materials scientists, electrical engineers, and graduate students studying the subjects being discussed will find the book invaluable.

  12. Chemical and nanometer-scale structure of kerogen and its change during thermal maturation investigated by advanced solid-state 13C NMR spectroscopy

    Mao, J.; Fang, X.; Lan, Y.; Schimmelmann, A.; Mastalerz, Maria; Xu, L.; Schmidt-Rohr, K.


    We have used advanced and quantitative solid-state nuclear magnetic resonance (NMR) techniques to investigate structural changes in a series of type II kerogen samples from the New Albany Shale across a range of maturity (vitrinite reflectance R0 from 0.29% to 1.27%). Specific functional groups such as CH3, CH2, alkyl CH, aromatic CH, aromatic C-O, and other nonprotonated aromatics, as well as "oil prone" and "gas prone" carbons, have been quantified by 13C NMR; atomic H/C and O/C ratios calculated from the NMR data agree with elemental analysis. Relationships between NMR structural parameters and vitrinite reflectance, a proxy for thermal maturity, were evaluated. The aromatic cluster size is probed in terms of the fraction of aromatic carbons that are protonated (???30%) and the average distance of aromatic C from the nearest protons in long-range H-C dephasing, both of which do not increase much with maturation, in spite of a great increase in aromaticity. The aromatic clusters in the most mature sample consist of ???30 carbons, and of ???20 carbons in the least mature samples. Proof of many links between alkyl chains and aromatic rings is provided by short-range and long-range 1H-13C correlation NMR. The alkyl segments provide most H in the samples; even at a carbon aromaticity of 83%, the fraction of aromatic H is only 38%. While aromaticity increases with thermal maturity, most other NMR structural parameters, including the aromatic C-O fractions, decrease. Aromaticity is confirmed as an excellent NMR structural parameter for assessing thermal maturity. In this series of samples, thermal maturation mostly increases aromaticity by reducing the length of the alkyl chains attached to the aromatic cores, not by pronounced growth of the size of the fused aromatic ring clusters. ?? 2010 Elsevier Ltd. All rights reserved.

  13. Solid state reaction studies in Fe{sub 3}O{sub 4}–TiO{sub 2} system by diffusion couple method

    Ren, Zhongshan [State Key Laboratory of Advanced Metallurgy, University of Science and Technology Beijing, Beijing 100083 (China); School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing 100083 (China); Hu, Xiaojun, E-mail: [State Key Laboratory of Advanced Metallurgy, University of Science and Technology Beijing, Beijing 100083 (China); School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing 100083 (China); Xue, Xiangxin [School of Materials and Metallurgy, Northeastern University, Shenyang 110006 (China); Chou, Kuochih [State Key Laboratory of Advanced Metallurgy, University of Science and Technology Beijing, Beijing 100083 (China); School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing 100083 (China)


    Highlights: •The solid state reactions of Fe2O3-TiO2 system was studied by the diffusion couple method. •Different products were formed by diffusion, and the FeTiO3 was more stable phase. •The inter-diffusion coefficients and diffusion activation energy were estimated. -- Abstract: The solid state reactions in Fe{sub 3}O{sub 4}–TiO{sub 2} system has been studied by diffusion couple experiments at 1323–1473 K, in which the oxygen partial pressure was controlled by the CO–CO{sub 2} gas mixture. The XRD analysis was used to confirm the phases of the inter-compound, and the concentration profiles were determined by electron probe microanalysis (EPMA). Based on the concentration profile of Ti, the inter-diffusion coefficients in Fe{sub 3}O{sub 4} phase, which were both temperature and concentration of Ti ions dependent, were calculated by the modified Boltzmann–Matano method. According to the relation between the thickness of diffusion layer and temperature, the diffusion coefficient of the Fe{sub 3}O{sub 4}–TiO{sub 2} system was obtained. According to the Arrhenius equation, the estimated diffusion activation energy was about 282.1 ± 18.8 kJ mol{sup −1}.

  14. A solid-state nuclear magnetic resonance study of post-plasma reactions in organosilicone microwave plasma-enhanced chemical vapor deposition (PECVD) coatings.

    Hall, Colin J; Ponnusamy, Thirunavukkarasu; Murphy, Peter J; Lindberg, Mats; Antzutkin, Oleg N; Griesser, Hans J


    Plasma-polymerized organosilicone coatings can be used to impart abrasion resistance and barrier properties to plastic substrates such as polycarbonate. Coating rates suitable for industrial-scale deposition, up to 100 nm/s, can be achieved through the use of microwave plasma-enhanced chemical vapor deposition (PECVD), with optimal process vapors such as tetramethyldisiloxane (TMDSO) and oxygen. However, it has been found that under certain deposition conditions, such coatings are subject to post-plasma changes; crazing or cracking can occur anytime from days to months after deposition. To understand the cause of the crazing and its dependence on processing plasma parameters, the effects of post-plasma reactions on the chemical bonding structure of coatings deposited with varying TMDSO-to-O2 ratios was studied with (29)Si and (13)C solid-state magic angle spinning nuclear magnetic resonance (MAS NMR) using both single-pulse and cross-polarization techniques. The coatings showed complex chemical compositions significantly altered from the parent monomer. (29)Si MAS NMR spectra revealed four main groups of resonance lines, which correspond to four siloxane moieties (i.e., mono (M), di (D), tri (T), and quaternary (Q)) and how they are bound to oxygen. Quantitative measurements showed that the ratio of TMDSO to oxygen could shift the chemical structure of the coating from 39% to 55% in Q-type bonds and from 28% to 16% for D-type bonds. Post-plasma reactions were found to produce changes in relative intensities of (29)Si resonance lines. The NMR data were complemented by Fourier transform infrared (FTIR) spectroscopy. Together, these techniques have shown that the bonding environment of Si is drastically altered by varying the TMDSO-to-O2 ratio during PECVD, and that post-plasma reactions increase the cross-link density of the silicon-oxygen network. It appears that Si-H and Si-OH chemical groups are the most susceptible to post-plasma reactions. Coatings produced at a

  15. Solid-State 13C NMR Spectroscopy Applied to the Study of Carbon Blacks and Carbon Deposits Obtained by Plasma Pyrolysis of Natural Gas

    Jair C. C. Freitas


    Full Text Available Solid-state 13C nuclear magnetic resonance (NMR spectroscopy was used in this work to analyze the physical and chemical properties of plasma blacks and carbon deposits produced by thermal cracking of natural gas using different types of plasma reactors. In a typical configuration with a double-chamber reactor, N2 or Ar was injected as plasma working gas in the first chamber and natural gas was injected in the second chamber, inside the arc column. The solid residue was collected at different points throughout the plasma apparatus and analyzed by 13C solid-state NMR spectroscopy, using either cross polarization (CP or direct polarization (DP, combined with magic angle spinning (MAS. The 13C CP/MAS NMR spectra of a number of plasma blacks produced in the N2 plasma reactor showed two resonance bands, broadly identified as associated with aromatic and aliphatic groups, with indication of the presence of oxygen- and nitrogen-containing groups in the aliphatic region of the spectrum. In contrast to DP experiments, only a small fraction of 13C nuclei in the plasma blacks are effectively cross-polarized from nearby 1H nuclei and are thus observed in spectra recorded with CP. 13C NMR spectra are thus useful to distinguish between different types of carbon species in plasma blacks and allow a selective study of groups spatially close to hydrogen in the material.

  16. Studies on Magnetometry and Samples used for an Experimental Search on the Electric Dipole Moment of the Electron using Solid-State Techniques

    Kim, Young Jin; Huffer, Craig; Karcz, Maciej; Liu, Chen-Yu; Reddy, Goverdhan


    A discovery of a permanent electric dipole moment of the electron (eEDM) at the current sensitivity level will imply new sources of CP violation beyond the standard model of particle physics. We are attempting to improve the experimental limit of the eEDM using a new technique employing solid-state systems at low temperatures. The experiment requires a system with a large magnetic response and the application of sensitive SQUID magnetometry. In this talk, I will present results in characterizing the magnetic properties of our solid-state sample, polycrystalline Gadolinium Gallium Garnet (GGG), and discuss preliminary results of systematic studies on our SQUID detectors. In our current setup, SQUID sensors record a non-zero change in magnetic flux with no GGG samples. This non-zero signals indicate sources of systematic effects which mimic EDM signals. We identified that several sources are responsible for producing systematic errors: the eddy current and the transient current. The dominant effect due to the eddy current can be reduced by using electrode material with a high resistivity, such as graphite..

  17. Miniature all-solid-state heterostructure nanowire Li-ion batteries as a tool for engineering and structural diagnostics of nanoscale electrochemical processes.

    Oleshko, Vladimir P; Lam, Thomas; Ruzmetov, Dmitry; Haney, Paul; Lezec, Henri J; Davydov, Albert V; Krylyuk, Sergiy; Cumings, John; Talin, A Alec


    Complex interfacial phenomena and phase transformations that govern the operation of Li-ion batteries require detailed nanoscale 3D structural and compositional characterization that can be directly related to their capacity and electrical transport properties. For this purpose, we have designed model miniature all solid-state radial heterostructure Li-ion batteries composed of LiCoO2 cathode, LiPON electrolyte and amorphous Si anode shells, which were deposited around metallized high-aspect-ratio Si nanowires as a scaffolding core. Such diagnostic batteries, the smallest, complete secondary Li-ion batteries realized to date, were specifically designed for in situ electrical testing in a field-emission scanning electron microscope and/or transmission electron microscope. The results of electrochemical testing were described in detail in a previous publication (Nano Lett., 2012, 12, 505-511). The model Li-ion batteries allow analysis of the correlations between electrochemical properties and their structural evolution during cycling in various imaging, diffraction and spectroscopic modes down to the atomic level. Employing multimode analytical scanning/transmission electron microscopy imaging coupled with correlative multivariate statistical analysis and tomography, we have analyzed and quantified the 3D morphological and structural arrangement of the batteries, including textured platelet-like LiCoO2 nanocrystallites, buried electrode-electrolyte interfaces and hidden internal defects to clarify effects of scaling on a battery's electrochemical performance. Characterization of the nanoscale interfacial processes using model heterostructure nanowire-based Li-ion batteries provides useful guidelines for engineering of prospective nano-sized building blocks in future electrochemical energy storage systems.

  18. Structural color-tunable mesoporous bragg stack layers based on graft copolymer self-assembly for high-efficiency solid-state dye-sensitized solar cells

    Lee, Chang Soo; Park, Jung Tae; Kim, Jong Hak


    We present a facile fabrication route for structural color-tunable mesoporous Bragg stack (BS) layers based on the self-assembly of a cost-effective graft copolymer. The mesoporous BS layers are prepared through the alternating deposition of organized mesoporous-TiO2 (OM-TiO2) and -SiO2 (OM-SiO2) films on the non-conducting side of the counter electrode in dye-sensitized solar cells (DSSCs). The OM layers with controlled porosity, pore size, and refractive index are templated with amphiphilic graft copolymers consisting of poly(vinyl chloride) backbones and poly(oxyethylene methacrylate) side chains, i.e., PVC-g-POEM. The morphology and properties of the structural color-tunable mesoporous BS-functionalized electrodes are characterized using energy filtered transmission electron microscopy (EF-TEM), field emission-scanning electron microscopy (FE-SEM), spectroscopic ellipsometry, and reflectance spectroscopy. The solid-state DSSCs (ssDSSCs) based on a structural color-tunable mesoporous BS counter electrode with a single-component solid electrolyte show an energy conversion efficiency (η) of 7.1%, which is much greater than that of conventional nanocrystalline TiO2-based cells and one of the highest values for N719 dye-based ssDSSCs. The enhancement of η is due to the enhancement of current density (Jsc), attributed to the improved light harvesting properties without considerable decrease in fill factor (FF) or open-circuit voltage (Voc), as confirmed by incident photon-to-electron conversion efficiency (IPCE) and electrochemical impedance spectroscopy (EIS).

  19. Ce11Ge3.73(2)In6.27: Solid-state synthesis, crystal structure and site-preference

    Jeon, Beom-Yong; Nam, Gnu; Lee, Dong Woo; Min Ok, Kang; You, Tae-Soo


    A novel intermetallic compound of Ce11Ge3.73(2)In6.27 has been synthesized through the high-temperature solid-state reaction using Nb-ampoules. A batch of well grown block-/short bar-shaped single-crystals has been obtained, and the crystal structure of the title compound has been characterized by single-crystal X-ray diffraction analyses. Ce11Ge3.73(2)In6.27 adopts the Ho11Ge10-type structure belonging to the tetragonal space group I4/mmm (Z=4, Pearson symbol tI84) with nine crystallographically unique atomic positions in the asymmetric unit. The lattice parameters are a=12.0163(1) Å and c=16.5396(2) Å. The overall crystal structure can simply be depicted as an assembly of three different types of co-facial cationic polyhedra centered by anions, which is further enclosed by the three-dimensional (3-D) cage-like anionic framework. The extra amount of In is observed in one of three isolated anionic sites resulting in introducing the Ge/In-mixed site at the Wyckoff 4e site. This unique site-preference of In substitution for Ge at the 4e site has been enlightened via the atomic size-aspect which was fully supported and rationalized by the site- and bond-energies analyses using tight-binding linear muffin-tin orbital (TB-LMTO) calculations. Energy-dispersive X-ray spectroscopy (EDS), density of states (DOS), crystal orbital Hamilton population (COHP), and electron localization function (ELF) analyses for the title compound are also presented. Magnetic susceptibility measurement proves that an antiferromagnetic ordering of Ce atoms at a low temperature with a paramagnetic Curie temperature of -23.2 K.

  20. A coordination chemistry study of hydrated and solvated cationic vanadium ions in oxidation states +III, +IV, and +V in solution and solid state.

    Krakowiak, Joanna; Lundberg, Daniel; Persson, Ingmar


    The coordination chemistry of hydrated and solvated vanadium(III), oxovanadium(IV), and dioxovanadium(V) ions in the oxygen-donor solvents water, dimethyl sulfoxide (DMSO), and N,N'-dimethylpropyleneurea (DMPU) has been studied in solution by extended X-ray absorption fine structure (EXAFS) and large-angle X-ray scattering (LAXS) and in the solid state by single-crystal X-ray diffraction and EXAFS. The hydrated vanadium(III) ion has a regular octahedral configuration with a mean V-O bond distance of 1.99 Å. In the hydrated and DMSO-solvated oxovanadium(IV) ions, vanadium binds strongly to an oxo group at ca. 1.6 Å. The solvent molecule trans to the oxo group is very weakly bound, at ca. 2.2 Å, while the remaining four solvent molecules, with a mean V-O bond distance of 2.0 Å, form a plane slightly below the vanadium atom; the mean O═V-O(perp) bond angle is ca. 98°. In the DMPU-solvated oxovanadium(IV) ion, the space-demanding properties of the DMPU molecule leave no solvent molecule in the trans position to the oxo group, which reduces the coordination number to 5. The O═V-O bond angle is consequently much larger, 107°, and the mean V═O and V-O bond distances decrease to 1.58 and 1.97 Å, respectively. The hydrated and DMSO-solvated dioxovanadium(V) ions display a very distorted octahedral configuration with the oxo groups in the cis position with a mean V═O bond distance of 1.6 Å and a O═V═O bond angle of ca. 105°. The solvent molecules trans to the oxo groups are weakly bound, at ca. 2.2 Å, while the remaining two have bond distances of 2.02 Å. The experimental studies of the coordination chemistry of hydrated and solvated vanadium(III,IV,V) ions are complemented by summarizing previously reported crystal structures to yield a comprehensive description of the coordination chemistry of vanadium with oxygen-donor ligands.

  1. Syntheses and solid state structures of zinc (II) complexes with Bi-dentate -(Aryl)imino-acenapthenone (Ar-BIAO) ligands

    Srinivas Anga; Supriya Rej; Kishor Naktode; Tigmansu Pal; Tarun K Panda


    We have synthesized five zinc complexes of molecular formulae [ZnCl2(2,6-dimethylphenyl-BIAO)]2 (1a), [ZnBr2(2,6-dimethylphenyl-BIAO)]2 (1b), [ZnI2(2,6-dimethylphenyl-BIAO)]2(1c), [ZnBr2(mes-BIAO)]2(2b) and [ZnBr2(dipp-BIAO)] (3b) with rigid unsymmetrical iminoacenaphthenone ligands, (2,6-dimethylphenyl-BIAO) (1), (mesityl-BIAO) (2) and (2,6-diisopropylphenyl-BIAO) (3). The zinc complex 1a was prepared by the reaction of ZnCl2 and neutral (mesityl-BIAO) (1). However, complexes 1b, 2b and 3b were obtained by the treatment of ZnBr2 and neutral ligands 1-3 respectively in 1:1 molar ratio in dichloromethane at ambient temperature. In a similar reaction of ZnI2 with (2,6-dimethylphenyl-BIAO) (1) in dichloromethane the corresponding iodo-complex 1c was obtained in good yield. All the zinc (II) complexes are characterized by FT-IR, 1H and 13C{1H} NMR spectroscopic techniques. The solid state structures of the complexes 1a, 1b, 1c, 2b and 3b are confirmed by single crystal X-ray diffraction analysis. The molecular structures of complexes 1a, 1b, 1c and 2b reveal the dimeric nature of the complexes and subsequently the centre atom zinc is penta-coordinated to adopt distorted trigonal bipyramidal geometry around it. In contrast, the complex 3b is in monomeric in nature due to bulkier size of the ligand and zinc ion is tetra coordinated to adopt distorted tetrahedral geometry.

  2. Residue-specific structures and membrane locations of pH-low insertion peptide by solid-state nuclear magnetic resonance

    Shu, Nicolas S.; Chung, Michael S.; Yao, Lan; An, Ming; Qiang, Wei


    The pH-low insertion peptide (pHLIP) binds to a membrane at pH 7.4 unstructured but folds across the bilayer as a transmembrane helix at pH∼6. Despite their promising applications as imaging probes and drug carriers that target cancer cells for cytoplasmic cargo delivery, the mechanism of pH modulation on pHLIP-membrane interactions has not been completely understood. Here, we show the first study on membrane-associated pHLIP using solid-state NMR spectroscopy. Data on residue-specific conformation and membrane location describe pHLIP in various surface-bound and membrane-inserted states at pH 7.4, 6.4 and 5.3. The critical membrane-adsorbed state is more complex than previously envisioned. At pH 6.4, for the major unstructured population, the peptide sinks deeper into the membrane in a state II′ that is distinct from the adsorbed state II observed at pH 7.4, which may enable pHLIP to sense slight change in acidity even before insertion. PMID:26195283

  3. Solid state oxygen sensor

    Garzon, F.H.; Brosha, E.L.


    A potentiometric oxygen sensor is formed having a logarithmic response to a differential oxygen concentration while operating as a Nernstian-type sensor. Very thin films of mixed conducting oxide materials form electrode services while permitting diffusional oxygen access to the interface between the zirconia electrolyte and the electrode. Diffusion of oxygen through the mixed oxide is not rate-limiting. Metal electrodes are not used so that morphological changes in the electrode structure do not occur during extended operation at elevated temperatures. 6 figs.

  4. Solid-state proton conductors

    Remick, R.J.; Jewulski, J.; Osif, T.


    Work on this project is divided into three tasks. In the first, a comprehensive literature review was performed for the purpose of collecting data on solid proton conductors. The data was then analyzed with the goal of correlating physical and chemical characteristics with protonic conductivity in order to gain a better understanding of the phenomenon. In the second task, the results of the correlation study were used to choose an electrolyte system in which to work and to aid in the formulation of new candidate proton conductors. Under the third task, a universal test stand was constructed which can measure both electronic and protonic conductivity and which can be converted to use as a solid state fuel cell test stand. Samples of doped SrCe{sub 0.95}Yb{sub 0.05}O{sub 3} have been coated with palladium electrodes and the mechanism responsible for ionic conductivity through this material is currently under study. 6 refs., 1 fig.

  5. Coordination-Site Exchange and Solid-State *O1*O3C NMR Studies of Bis(oxalato)dioxovanadate(V) Ion

    Schaumburg, Kjeld; Lee, Man-Ho


    Coordination-site exchange, *O1*O3 C NMR, solid state *O1*O3C NMR, Bis(oxalato)dioxovanadate(V) ion......Coordination-site exchange, *O1*O3 C NMR, solid state *O1*O3C NMR, Bis(oxalato)dioxovanadate(V) ion...

  6. Nanoscale solid-state cooling: a review

    Ziabari, Amirkoushyar; Zebarjadi, Mona; Vashaee, Daryoosh; Shakouri, Ali


    The recent developments in nanoscale solid-state cooling are reviewed. This includes both theoretical and experimental studies of different physical concepts, as well as nanostructured material design and device configurations. We primarily focus on thermoelectric, thermionic and thermo-magnetic coolers. Particular emphasis is given to the concepts based on metal-semiconductor superlattices, graded materials, non-equilibrium thermoelectric devices, Thomson coolers, and photon assisted Peltier coolers as promising methods for efficient solid-state cooling. Thermomagnetic effects such as magneto-Peltier and Nernst-Ettingshausen cooling are briefly described and recent advances and future trends in these areas are reviewed. The ongoing progress in solid-state cooling concepts such as spin-calorimetrics, electrocalorics, non-equilibrium/nonlinear Peltier devices, superconducting junctions and two-dimensional materials are also elucidated and practical achievements are reviewed. We explain the thermoreflectance thermal imaging microscopy and the transient Harman method as two unique techniques developed for characterization of thermoelectric microrefrigerators. The future prospects for solid-state cooling are briefly summarized.

  7. Nanoscale solid-state cooling: a review.

    Ziabari, Amirkoushyar; Zebarjadi, Mona; Vashaee, Daryoosh; Shakouri, Ali


    The recent developments in nanoscale solid-state cooling are reviewed. This includes both theoretical and experimental studies of different physical concepts, as well as nanostructured material design and device configurations. We primarily focus on thermoelectric, thermionic and thermo-magnetic coolers. Particular emphasis is given to the concepts based on metal-semiconductor superlattices, graded materials, non-equilibrium thermoelectric devices, Thomson coolers, and photon assisted Peltier coolers as promising methods for efficient solid-state cooling. Thermomagnetic effects such as magneto-Peltier and Nernst-Ettingshausen cooling are briefly described and recent advances and future trends in these areas are reviewed. The ongoing progress in solid-state cooling concepts such as spin-calorimetrics, electrocalorics, non-equilibrium/nonlinear Peltier devices, superconducting junctions and two-dimensional materials are also elucidated and practical achievements are reviewed. We explain the thermoreflectance thermal imaging microscopy and the transient Harman method as two unique techniques developed for characterization of thermoelectric microrefrigerators. The future prospects for solid-state cooling are briefly summarized.

  8. Organic solid-state lasers

    Forget, Sébastien


    Organic lasers are broadly tunable coherent sources, potentially compact, convenient and manufactured at low-costs. Appeared in the mid 60’s as solid-state alternatives for liquid dye lasers, they recently gained a new dimension after the demonstration of organic semiconductor lasers in the 90's. More recently, new perspectives appeared at the nanoscale, with organic polariton and surface plasmon lasers. After a brief reminder to laser physics, a first chapter exposes what makes organic solid-state organic lasers specific. The laser architectures used in organic lasers are then reviewed, with a state-of-the-art review of the performances of devices with regard to output power, threshold, lifetime, beam quality etc. A survey of the recent trends in the field is given, highlighting the latest developments with a special focus on the challenges remaining for achieving direct electrical pumping of organic semiconductor lasers. A last chapter covers the applications of organic solid-state lasers.

  9. Solid-State Laser Engineering

    Koechner, Walter


    Written from an industrial perspective, Solid-State Laser Engineering discusses in detail the characteristics, design, construction, and performance of solid-state lasers. Emphasis is placed on engineering and practical considerations; phenomenological aspects using models are preferred to abstract mathematical derivations. Since its first edition almost 30 years ago this book has become the standard in the field of solid-state lasers for scientists,engineers and graduate students. This new edition has been extensively revised and updated to account for recent developments in the areas of diode-laser pumping, laser materials and nonlinear crystals. Completely new sections have been added dealing with frequency control, the theory of mode-locking, femto second lasers, high efficiency harmonic generation, passive and acousto-optic Q-switching, semiconductor saturable absorber mirrors (SESAM) and peridically poled nonlinear crystals.

  10. An innovative method for the non-destructive identification of photodegradation products in solid state: 1H-14N NMR-NQR and DFT/QTAIM study of photodegradation of nifedipine (anti-hypertensive) to nitrosonifedipine (potential anti-oxidative).

    Latosińska, J N; Latosińska, M; Seliger, J; Zagar, V


    Stability of the antihypertensive drug nifedipine (NIF) has been studied experimentally in solid state by (1)H-(14)N NMR-NQR double resonance (NQDR) and theoretically by the Density Functional Theory (DFT). Photodegradation of NIF to its metabolite in vivo nitrosonifedipine, NO-NIF (antioxidative agent) upon long term daylight exposure was detected and the changes in the molecular structure of NIF were analysed. The photoconversion of NIF to NO-NIF in solid was found to be accompanied with the electron density redistribution at nitrogen sites (NH to N and NO(2) to NO) and proved to be successfully detected with identification of photoproducts by (1)H-(14)N NQDR and DFT methods. The increase in the e(2)qQ/h and η describing EFG tendency towards non-spherical symmetry was significantly greater upon the reduction of NO(2) site than upon hydrogen abstraction from NH site. The level of sensitivity of detection of the photodegradation product was about 1% of the original sample. The Quantum Theory of Atoms in Molecules (QTAIM) analysis has been found useful in predicting photoreactive sites in the molecules and finding the explanation of differences in reactivity between parent NIF and its photoproduct NO-NIF. Using NIF as a model, this study demonstrates the suitability of NQDR supported by DFT for non-destructive determination of the photodegradation products in solid state.

  11. Introduction to solid state electronics

    Wang, FFY


    This textbook is specifically tailored for undergraduate engineering courses offered in the junior year, providing a thorough understanding of solid state electronics without relying on the prerequisites of quantum mechanics. In contrast to most solid state electronics texts currently available, with their generalized treatments of the same topics, this is the first text to focus exclusively and in meaningful detail on introductory material. The original text has already been in use for 10 years. In this new edition, additional problems have been added at the end of most chapters. These proble

  12. Solid-state lithium battery

    Ihlefeld, Jon; Clem, Paul G; Edney, Cynthia; Ingersoll, David; Nagasubramanian, Ganesan; Fenton, Kyle Ross


    The present invention is directed to a higher power, thin film lithium-ion electrolyte on a metallic substrate, enabling mass-produced solid-state lithium batteries. High-temperature thermodynamic equilibrium processing enables co-firing of oxides and base metals, providing a means to integrate the crystalline, lithium-stable, fast lithium-ion conductor lanthanum lithium tantalate (La.sub.1/3-xLi.sub.3xTaO.sub.3) directly with a thin metal foil current collector appropriate for a lithium-free solid-state battery.

  13. Solid state electrolyte systems

    Pederson, L.R.; Armstrong, B.L.; Armstrong, T.R. [Pacific Northwest Lab., Richland, WA (United States)] [and others


    Lanthanum gallates are a new family of solid electrolytes that exhibit high ionic conductivity and are stable to high temperatures. Compositions have been developed that are as much as a factor of two more conductive than yttria-stabilized zirconia at a given temperature, through partial replacement of lanthanum by calcium, strontium, and/or barium and through partial replacement of gallium by magnesium. Oxide powders were prepared using combustion synthesis techniques developed in this laboratory; these were sintered to >95% of theoretical density and consisted of a single crystalline phase. Electrical conductivities, electron and ion transference numbers, thermal expansion, and phase behavior were evaluated as a function of temperature and oxygen partial pressure. A key advantage of the use of lanthanum gallate electrolytes in solid oxide fuel cells is that the temperature of operation may be lowered to perhaps 800 C, yet provide approximately the same power density as zirconia-based cells operating at 1000 C. Ceramic electrolytes that conduct both oxygen ions and electrons are potentially useful to passively separate pure oxygen from an air source at low cost. In such materials, an oxygen ion flux in one direction is charge-compensated by an opposing electron flux. The authors have examined a wide range of mixed ion and electron conducting perovskite ceramics in the system La{sub 1{minus}x}M{sub x}Co{sub 1{minus}y{minus}z}Fe{sub y}N{sub z}O{sub 3{minus}{delta}}, where M = Sr, Ca, and Ba, and N = Pr, Mn, Ni, Cu, Ti, and Al, as well as mixed conducting brownmillerite ceramics, and have characterized oxygen permeation behavior, defect chemistry, structural and phase stability, and performance as cathodes.

  14. Solid State Research


    Development ; Electro optic Tuning of a Ti:Al2O3 Laser; Er:YAG Laser Development ; Laser Frequency Conversion; Tracer Gas Studies for OMVPE Reactor...Contents: High-Speed Photoconductive Switches Fabricated on Ti Doped Semi-insulating InP; Diode Lasers with Cylindrical Mirror Facets; Ti:Al2O3 Laser

  15. Sulfato-bridged ECE-pincer palladium(II) complexes: structures in the solid-state and in solution, and catalytic properties

    Kruithof, C.A.; Berger, A.; Dijkstra, H.P.; Soulimani, F.; Visser, T.; Lutz, M.; Spek, A.L.; Klein Gebbink, R.J.M.; van Koten, G.


    ECE-pincer sulfato palladium complexes (pincer = [C(6)H(3)(CH(2)E)(2)-2,6](-); E = SPh (), SMe (), S(t)Bu (), NMe(2) ()) were synthesized and characterized. In the solid-state (X-ray determinations) and exist as neutral ECE-pincer palladium sulfato complexes with a mu(2)-O,O' bridging sulfato ligand

  16. Fundamental Studies and Development of III-N Visible LEDs for High-Power Solid-State Lighting Applications

    Dupuis, Russell


    The goal of this program is to understand in a fundamental way the impact of strain, defects, polarization, and Stokes loss in relation to unique device structures upon the internal quantum efficiency (IQE) and efficiency droop (ED) of III-nitride (III-N) light-emitting diodes (LEDs) and to employ this understanding in the design and growth of high-efficiency LEDs capable of highly-reliable, high-current, high-power operation. This knowledge will be the basis for our advanced device epitaxial designs that lead to improved device performance. The primary approach we will employ is to exploit new scientific and engineering knowledge generated through the application of a set of unique advanced growth and characterization tools to develop new concepts in strain-, polarization-, and carrier dynamics-engineered and low-defect materials and device designs having reduced dislocations and improved carrier collection followed by efficient photon generation. We studied the effects of crystalline defect, polarizations, hole transport, electron-spillover, electron blocking layer, underlying layer below the multiplequantum- well active region, and developed high-efficiency and efficiency-droop-mitigated blue LEDs with a new LED epitaxial structures. We believe new LEDs developed in this program will make a breakthrough in the development of high-efficiency high-power visible III-N LEDs from violet to green spectral region.

  17. Production of phytase under solid-state fermentation using Rhizopus oryzae: novel strain improvement approach and studies on purification and characterization.

    Rani, Richa; Ghosh, Sanjoy


    Present study introduces linseed oil cake as a novel substrate for phytase production by Rhizopus oryzae. Statistical approach was employed to optimize various medium components under solid state fermentation (SSF). An overall 8.41-fold increase in phytase production was achieved at the optimum concentrations (w/w, mannitol, 2.05%; ammonium sulfate, 2.84% and phosphate, 0.38%). Further enhancement by 59% was observed due to a novel strain improvement approach. Purified phytase (∼34 kDa) showed optimal temperature of 45 °C, dual pH optima at 1.5 and 5.5 and possesses high catalytic efficiency (2.38×10(6) M(-1) s(-1)). Characterization study demonstrates the phytase as highly thermostable and resistant to proteolysis, heavy metal ions, etc. Furthermore, an improved HPLC method was introduced to confirm the ability of phytase to degrade phytic acid completely and was found to be an efficient method.

  18. Specific 13C labeling of leucine, valine and isoleucine methyl groups for unambiguous detection of long-range restraints in protein solid-state NMR studies.

    Fasshuber, Hannes Klaus; Demers, Jean-Philippe; Chevelkov, Veniamin; Giller, Karin; Becker, Stefan; Lange, Adam


    Here we present an isotopic labeling strategy to easily obtain unambiguous long-range distance restraints in protein solid-state NMR studies. The method is based on the inclusion of two biosynthetic precursors in the bacterial growth medium, α-ketoisovalerate and α-ketobutyrate, leading to the production of leucine, valine and isoleucine residues that are exclusively (13)C labeled on methyl groups. The resulting spectral simplification facilitates the collection of distance restraints, the verification of carbon chemical shift assignments and the measurement of methyl group dynamics. This approach is demonstrated on the type-three secretion system needle of Shigella flexneri, where 49 methyl-methyl and methyl-nitrogen distance restraints including 10 unambiguous long-range distance restraints could be collected. By combining this labeling scheme with ultra-fast MAS and proton detection, the assignment of methyl proton chemical shifts was achieved.

  19. A case study of real-time monitoring of solid-state phase transformations in acoustically levitated particles using near infrared and Raman spectroscopy

    Rehder, Sönke; Wu, Jian-Xiong; Laackmann, Julian


    . The recrystallisation kinetic parameters were estimated from the recrystallisation profiles. While the empirical recrystallisation rate constant determined by NIR and Raman spectroscopy were comparable, the lag time for recrystallisation was significantly lower with Raman spectroscopy as compared to NIRS......The objective of this study was to monitor the amorphous-to-crystalline solid-state phase transformation kinetics of the model drug ibuprofen with spectroscopic methods during acoustic levitation. Chemical and physical information was obtained by real-time near infrared (NIRS) and Raman...... spectroscopy measurements. The recrystallisation kinetic parameters (overall recrystallisation rate constant ß and the time needed to reach 50% of the equilibrated level t(50)), were determined using a multivariate curve resolution approach. The acoustic levitation device coupled with non-invasive spectroscopy...

  20. Specific 13C labeling of leucine, valine and isoleucine methyl groups for unambiguous detection of long-range restraints in protein solid-state NMR studies

    Fasshuber, Hannes Klaus; Demers, Jean-Philippe; Chevelkov, Veniamin; Giller, Karin; Becker, Stefan; Lange, Adam


    Here we present an isotopic labeling strategy to easily obtain unambiguous long-range distance restraints in protein solid-state NMR studies. The method is based on the inclusion of two biosynthetic precursors in the bacterial growth medium, α-ketoisovalerate and α-ketobutyrate, leading to the production of leucine, valine and isoleucine residues that are exclusively 13C labeled on methyl groups. The resulting spectral simplification facilitates the collection of distance restraints, the verification of carbon chemical shift assignments and the measurement of methyl group dynamics. This approach is demonstrated on the type-three secretion system needle of Shigella flexneri, where 49 methyl-methyl and methyl-nitrogen distance restraints including 10 unambiguous long-range distance restraints could be collected. By combining this labeling scheme with ultra-fast MAS and proton detection, the assignment of methyl proton chemical shifts was achieved.

  1. (13)C and (19)F solid-state NMR and X-ray crystallographic study of halogen-bonded frameworks featuring nitrogen-containing heterocycles.

    Szell, Patrick M J; Gabriel, Shaina A; Gill, Russell D D; Wan, Shirley Y H; Gabidullin, Bulat; Bryce, David L


    Halogen bonding is a noncovalent interaction between the electrophilic region of a halogen (σ-hole) and an electron donor. We report a crystallographic and structural analysis of halogen-bonded compounds by applying a combined X-ray diffraction (XRD) and solid-state nuclear magnetic resonance (SSNMR) approach. Single-crystal XRD was first used to characterize the halogen-bonded cocrystals formed between two fluorinated halogen-bond donors (1,4-diiodotetrafluorobenzene and 1,3,5-trifluoro-2,4,6-triiodobenzene) and several nitrogen-containing heterocycles (acridine, 1,10-phenanthroline, 2,3,5,6-tetramethylpyrazine, and hexamethylenetetramine). New structures are reported for the following three cocrystals, all in the P21/c space group: acridine-1,3,5-trifluoro-2,4,6-triiodobenzene (1/1), C6F3I3·C13H9N, 1,10-phenanthroline-1,3,5-trifluoro-2,4,6-triiodobenzene (1/1), C6F3I3·C12H8N2, and 2,3,5,6-tetramethylpyrazine-1,3,5-trifluoro-2,4,6-triiodobenzene (1/1), C6F3I3·C8H12N2. (13)C and (19)F solid-state magic-angle spinning (MAS) NMR is shown to be a convenient method to characterize the structural features of the halogen-bond donor and acceptor, with chemical shifts attributable to cocrystal formation observed in the spectra of both nuclides. Cross polarization (CP) from (19)F to (13)C results in improved spectral sensitivity in characterizing the perfluorinated halogen-bond donor when compared to conventional (1)H CP. Gauge-including projector-augmented wave density functional theory (GIPAW DFT) calculations of magnetic shielding constants, along with optimization of the XRD structures, provide a final set of structures in best agreement with the experimental (13)C and (19)F chemical shifts. Data for carbons bonded to iodine remain outliers due to well-known relativistic effects.

  2. -Phenoxo--pseudohalide and -pseudohalide dinuclear, tetranuclear and one-dimensional complexes: magneto-structural correlation and interesting type of solid state isomerism

    Sujit Sasmal; Sasankasekhar Mohanta


    Five Schiff base ligands have been utilized to explore metallo-pseudohalide (azide or cyanate) systems. These ligands are the 1:1 condensation products of 3-methoxysalicylaldehyde with ethanolamine (H2L1)/1-(2-aminoethyl)-piperidine (HL2)/ 4-(2-aminoethyl)-morpholine (HL3) or salicylaldehyde with 1-(2-aminoethyl)-piperidine (HL4)/4-(2-aminoethyl)-morpholine (HL5). The derived complexes are as follows: Four heterobridged -phenoxo-1,1-azide/cyanate dinickel(II) compounds of composition [Ni$^{\\text{II}}_{2}$ (HL1)3(1,1-N3)]$\\cdot$3H2O (1), [Ni$^{\\text{II}}_{2}$ (L2)2(1,1-N3)(N3)(H2O)]·CH3CH2OH (2), [Ni$^{\\text{II}}_{2}$ (L3)2-(1,1-N3)(CH3CN)(H2O)](ClO4)·H2O·CH3CN (3) and [Ni$^{\\text{II}}_{2}$ (HL1)3(1,1-NCO)]·2H2O (4); Two 1,3-azide bridged tetranickel(II) compounds [{NiII(L4)(1,3-N3)(H2O)}4] (5) and [{NiII(L5)(1,3-N3)(H2O)}4] (6); Two 1,3-azide/cyanate one-dimensional compounds [CuIIL5(1,3-NCO)]·2H2O (7) and [CuIIL5(1,3-N3)]·2H2O (8). Except compound 5 which shows overall antiferromagnetic coupling, other compounds exhibit overall ferromagnetic interaction. Syntheses, crystal structures, magnetic properties, density functional theoretical (DFT) calculations and experimental/theoretical magneto-structural correlations have been carried out which have revealed some interesting observations on composition/topology, magneto-structural correlations and solid state isomerism. The results have been already published. The present report deals with a review of the salient and interesting features of these works.

  3. Solid State Physics Principles and Modern Applications

    Quinn, John J


    Intended for a two semester advanced undergraduate or graduate course in Solid State Physics, this treatment offers modern coverage of the theory and related experiments, including the group theoretical approach to band structures, Moessbauer recoil free fraction, semi-classical electron theory, magnetoconductivity, electron self-energy and Landau theory of Fermi liquid, and both quantum and fractional quantum Hall effects. Integrated throughout are developments from the newest semiconductor devices, e.g. space charge layers, quantum wells and superlattices. The first half includes all material usually covered in the introductory course, but in greater depth than most introductory textbooks. The second half includes most of the important developments in solid-state researches of the past half century, addressing e.g. optical and electronic properties such as collective bulk and surface modes and spectral function of a quasiparticle, which is a basic concept for understanding LEED intensities, X ray fine struc...

  4. SPS solid state antenna power combiner

    Fitzsimmons, G. W.


    A concept for a solar power satellite antenna power combiner which utilizes solid state dc-rf converters is described. To avoid the power combining losses associated with circuit hybrids it is proposed that the power from multiple solid state amplifiers be combined by direct coupling of each amplifier's output to the radiating antenna structure. The selected power-combining antenna consists of a printed (metalized) microstrip circuit on a ceramic type dielectric substrate which is backed by a shallow lightweight aluminum cavity which sums the power of four microwave sources. The antenna behaves like two one-half wavelength slot-line antennas coupled together via their common cavity structure. A significant feature of the antenna configuration selected is that the radiated energy is summed to yield a single radiated output phase which represents the average insertion phase of the four power amplifiers. This energy may be sampled and, by comparison with the input signal, one can phase error correct to maintain the insertion phase of all solid state power combining modules at exactly the same value. This insures that the insertion phase of each SPS power combining antenna module is identical. An experiment verification program is described.

  5. In situ quantitative study of microstructural evolution at the interface of Sn3.0Ag0.5Cu/Cu solder joint during solid state aging

    Li, Hailong [State Key Laboratory of Advanced Welding and Joining, Harbin Institute of Technology, Harbin 150001 (China); An, Rong, E-mail: [Key Laboratory of Micro-systems and Micro-structures Manufacturing, Harbin Institute of Technology, Ministry of Education, Harbin 150080 (China); Wang, Chunqing; Jiang, Zhi [State Key Laboratory of Advanced Welding and Joining, Harbin Institute of Technology, Harbin 150001 (China)


    Highlights: • Cu dissolution during reflowing was mainly occurred under the gaps between scallops. • Though IMC growth was diffusion-controlled, consumption of Cu substrate was not. • Growth of Cu{sub 3}Sn layer in Sn3.0Ag0.5Cu/Cu solder joint was on the both sides. • Ag and Cu lead to a thinner Cu{sub 3}Sn layer due to inhibit the diffusion of Sn into Cu. - Abstract: In situ microstructural evolution at the interface of Sn3.0Ag0.5Cu/Cu solder joint during solid state aging was quantitatively studied by nanoindentation. The morphology of Cu{sub 6}Sn{sub 5} gradually altered from scallop type to layer type. Though the growth of IMCs was diffusion-controlled, the consumption of Cu substrate was not linear with the square root of aging time. At the initial stage of solid state aging, the Cu atoms essential to the growth of IMCs were mainly from the supersaturated solder matrix. When the Cu atoms from supersaturated solder matrix were exhausted, the Cu atoms for the growth of IMCs were primarily from the Cu substrate. In addition, the IMCs formed at this state were principally used to fill up the gaps between scallops. After the gaps disappeared, the consumption of Cu substrate slowed down. Furthermore, the growth of Cu{sub 3}Sn layer in Sn3.0Ag0.5Cu/Cu solder joint was on the both sides with layer type. Since the Sn atoms were inhibited to diffuse into the Cu substrate by the alloying elements of Ag and Cu, the thickness of Cu{sub 3}Sn layer in SnAgCu/Cu solder joint was much thinner than that in pure Sn/Cu solder joint.

  6. Solid-state characterization of the HIV protease inhibitor

    Kim, Y A


    The LB71350, (3S, 4R)-Epoxy-(5S)-[[N-(1-methylethoxy) carbonyl]-3-(methylsulfonyl)-L-valinyl]amin= o]-N-[2-methyl-(1R)-[(phenyl)carbonyl]propyl-6-phenylhexanamide, is a novel HIV protease inhibitor. Its equilibrium solubility at room temperature was less than 40 mu g/mL. It was speculated that the low aqueous solubility might be due to the high crystalline lattice energy resulting from intermolecular hydrogen bonds. The present study was carried out to learn the solid-state characteristics of LB71350 using analytical methods such as NMR, FT-IR and XRD. sup 1 sup 3 C Solid-state NMR, solution NMR, and FT-IR spectra of the various solid forms of LB71350 were used to identify the conformation and structure of the solid forms. The chemical shifts of sup 1 sup 3 C solid-state NMR spectra suggest that the crystalline form might have 3 intermolecular hydrogen bondings between monomers.

  7. Interfacial study of NiTi–Ti{sub 3}SiC{sub 2} solid state diffusion bonded joints

    Kothalkar, A. [Department of Materials Science and Engineering, Texas A and M University, College Station, TX 77843 (United States); Cerit, A. [Department of Industrial Design Engineering, Erciyes University, Kayseri (Turkey); Proust, G. [School of Civil Engineering, University of Sydney, Sydney, NSW 2006 (Australia); Basu, S. [Agilent Technologies, Chandler, AZ (United States); Radovic, M., E-mail: [Department of Materials Science and Engineering, Texas A and M University, College Station, TX 77843 (United States); Karaman, I., E-mail: [Department of Materials Science and Engineering, Texas A and M University, College Station, TX 77843 (United States)


    The interfaces between the stress-assisted diffusion bonded Ti{sub 3}SiC{sub 2} and equiatomic NiTi, two distinct material systems that show pseudoelasticity were studied. The interfaces were formed in the 800–1000 °C temperature range, for 1, 5 and 10 h under flowing argon. Bonding was observed in all the cases considered, except at 800 °C after 1 h. Morphology and reaction phases in the interface were characterized using scanning electron microscopy, elemental micro probe analysis and electron backscatter diffraction analysis. The interfacial structure formed between NiTi and Ti{sub 3}SiC{sub 2} layers consists of NiTi/Ti{sub 2}Ni/Ti{sub 5}Si{sub 3}/NiTiSi/Ti{sub 3}SiC{sub 2}. Diffusion of Si into NiTi from Ti{sub 3}SiC{sub 2}, and Ni from NiTi into reaction zone was found to be responsible for the formation of reaction layers in the interface and thus for bonding at these conditions. The overall reaction layer thickness grows following the parabolic kinetic law. Nano-indentation and Vickers micro hardness tests were carried out to investigate the mechanical properties of the interface. Nano-indentation showed that the elastic moduli of the phases in the interface are close to that of Ti{sub 3}SiC{sub 2} while their hardness is higher than that of both Ti{sub 3}SiC{sub 2} and NiTi. Artificially formed cracks through microindents were observed to be branched and propagated into Ti{sub 3}SiC{sub 2} phase indicating good resistance against delamination.

  8. Solid state conformational classification of eight-membered rings

    Pérez, J.; García, L.; Kessler, M.


    A statistical classification of the solid state conformation in the title complexes using data retrieved from the Cambridge Structural Database (CSD) has been made. Phosphate and phosphinate complexes show a chair conformation preferably. In phosphonate complexes, the most frequent conformations...

  9. New in situ solid-state NMR strategies for exploring materials formation and adsorption processes: prospects in heterogenous catalysis

    Harris, Kenneth David Maclean


    Solid-state NMR spectroscopy is a powerful technique for studying structural and dynamic properties of solids and has considerable potential to be exploited for in situ studies of chemical processes. However, adapting solid-state NMR techniques and instrumentation for in situ applications are often associated with technical challenges, and for this reason, the opportunities remain underexploited. This paper highlights two experimental strategies that we have developed in recent years for in s...

  10. Structure elucidation of the unprecedented asymmetric bis-chelate complex [Pd(1,3-bis(di(o-methoxy-m-methylphenyl)phosphino)propane)2] 2+ in the solid state and in solution

    Mooibroek, T. J.; Lutz, M.; Spek, A.L.; Bouwman, E.


    Complexes of the type [Pd(ligand)2](anion)2 were prepared with a series of bidentate di(o-methoxyphenyl)phosphine ligands with increasing steric bulk on the meta position of the phenyl groups: m-H (L1); m-MeO (L2); and m-Me (L3). The solid-state structure of [Pd(L2)2](OTs)2 revealed that the two lig

  11. Molecular-Level Control of Ciclopirox Olamine Release from Poly(ethylene oxide)-Based Mucoadhesive Buccal Films: Exploration of Structure-Property Relationships with Solid-State NMR.

    Urbanova, Martina; Gajdosova, Marketa; Steinhart, Miloš; Vetchy, David; Brus, Jiri


    Mucoadhesive buccal films (MBFs) provide an innovative way to facilitate the efficient site-specific delivery of active compounds while simultaneously separating the lesions from the environment of the oral cavity. The structural diversity of these complex multicomponent and mostly multiphase systems as well as an experimental strategy for their structural characterization at molecular scale with atomic resolution were demonstrated using MBFs of ciclopirox olamine (CPX) in a poly(ethylene oxide) (PEO) matrix as a case study. A detailed description of each component of the CPX/PEO films was followed by an analysis of the relationships between each component and the physicochemical properties of the MBFs. Two distinct MBFs were identified by solid-state NMR spectroscopy: (i) at low API (active pharmaceutical ingredient) loading, a nanoheterogeneous solid solution of CPX molecularly dispersed in an amorphous PEO matrix was created; and (ii) at high API loading, a pseudoco-crystalline system containing CPX-2-aminoethanol nanocrystals incorporated into the interlamellar space of a crystalline PEO matrix was revealed. These structural differences were found to be closely related to the mechanical and physicochemical properties of the prepared MBFs. At low API loading, the polymer chains of PEO provided sufficient quantities of binding sites to stabilize the CPX that was molecularly dispersed in the highly amorphous semiflexible polymer matrix. Consequently, the resulting MBFs were soft, with low tensile strength, plasticity, and swelling index, supporting rapid drug release. At high CPX content, however, the active compounds and the polymer chains simultaneously cocrystallized, leaving the CPX to form nanocrystals grown directly inside the spherulites of PEO. Interfacial polymer-drug interactions were thus responsible not only for the considerably enhanced plasticity of the system but also for the exclusive crystallization of CPX in the thermodynamically most stable

  12. Solid-state NMR studies of Al-doped and Al{sub 2}O{sub 3}-coated LiCoO{sub 2}

    Lee, Youngil; Kim, Dongmin; Lee, Hyeyeoun [Dongbu Advanced Research Inst., Daejeon (Korea). Chemical Analysis Team; Woo, Ae Ja [Ewha Womans Univ., Seoul (Korea); Han, Kyoo Seung [Chungnam National Univ., Daejeon (Korea). Dept. of Fine Chemicals Engineering and Chemistry; Ryu, D. [Electronics and Telecommunications Research Inst., Daejeon (Korea); Sohn, Daewon [Hanyang Univ., Seoul (Korea). Dept. of Chemistry


    As a cathode material for commercial lithium rechargeable battery, Al-doped and Al{sub 2}O{sub 3}-coated LiCoO{sub 2} were structurally characterized and compared by using solid-state {sup 7}Li and {sup 27}Al magic angle spinning (MAS) NMR. The structural states of lithium and aluminum in those samples were successfully identified by calculation of NMR spectra. {sup 7}Li MAS NMR spectra of samples had shown similar features having more than three lithium sites, which were determined as quadrupole coupling constant with the same asymmetric parameter ({eta} = 0.1); C{sub Q} = 1.10 MHz for octahedral site, and C{sub Q} 2.97 MHz and C{sub Q} = 3.83 MHz for shoulders. {sup 27}Al MAS NMR spectra of samples, however, showed significant difference in two observed aluminum sites. In the simulation of NMR spectrum for Al{sub 2}O{sub 3}-coated LiCoO{sub 2}, the values of C{sub Q} and {eta} were obtained; 4.45 MHz and {eta} = 0.86 for tetrahedral site and 4.31 MHz and {eta} = 0.81 for octahedral.

  13. Solid-state membrane module

    Gordon, John Howard; Taylor, Dale M.


    Solid-state membrane modules comprising at least one membrane unit, where the membrane unit has a dense mixed conducting oxide layer, and at least one conduit or manifold wherein the conduit or manifold comprises a dense layer and at least one of a porous layer and a slotted layer contiguous with the dense layer. The solid-state membrane modules may be used to carry out a variety of processes including the separating of any ionizable component from a feedstream wherein such ionizable component is capable of being transported through a dense mixed conducting oxide layer of the membrane units making up the membrane modules. For ease of construction, the membrane units may be planar.

  14. Advances in Solid State Physics

    Haug, Rolf


    The present volume 46 of Advances in Solid State Physics contains the written versions of selected invited lectures from the spring meeting of the Arbeitskreis Festkörperphysik of the Deutsche Physikalische Gesellschaft which was held from 27 to 31 March 2006 in Dresden, Germany. Many topical talks given at the numerous symposia are included. Most of these were organized collaboratively by several of the divisions of the Arbeitskreis. The topis range from zero-dimensional physics in quantum dots, molecules and nanoparticles over one-dimensional physics in nanowires and 1d systems to more applied subjects like optoelectronics and materials science in thin films. The contributions span the whole width of solid-state physics from truly basic science to applications.

  15. Advances in Solid State Physics

    Kramer, B


    The present volume 45 of Advances in Solid-State Physics contains the written versions of selected invited lectures from the spring meeting of the Arbeitskreis Festkörperphysik of the Deutsche Physikalische Gesellschaft in the World Year of Physics 2005, the Einstein Year, which was held from 4 - 11 March 2005 in Berlin, Germany. Many topical talks given at the numerous symposia are included. Most of these were organized collaboratively by several of the divisions of the Arbeitskreis. The book presents, to some extent, the status of the field of solid-state physics in 2005 not only in Germany but also internationally. It is ''nanoscience'', namely the physics of quantum dots and wires, electrical transport, optical properties, spin transport in nanostructures, and magnetism on the nanoscale, that is of central interest to the physics community. Also, soft matter and biological systems are covered.

  16. Solid-state laser engineering

    Koechner, Walter


    This book is written from an industrial perspective and provides a detailed discussion of solid-state lasers, their characteristics, design and construction. Emphasis is placed on engineering and practical considerations. The book is aimed mainly at the practicing scientist or engineer who is interested in the design or use of solid-state lasers, but the comprehensive treatment of the subject will make the work useful also to students of laser physics who seek to supplement their theoretical knowledge with engineering information. In order to present the subject as clearly as possible, phenomenological descriptions using models have been used rather than abstract mathematical descriptions. This results in a simplified presentation. The descriptions are enhanced by the inclusion of numerical and technical data, tables and graphs. This new edition has been updated and revised to take account of important new developments, concepts, and technologies that have emerged since the publication of the first and second...

  17. Solid-State Nuclear Power

    George, Jeffrey A.


    A strategy for "Solid-State" Nuclear Power is proposed to guide development of technologies and systems into the second 50 years of nuclear spaceflight. The strategy emphasizes a simple and highly integrated system architecture with few moving parts or fluid loops; the leverage of modern advances in materials, manufacturing, semiconductors, microelectromechanical and nanotechnology devices; and the targeted advancement of high temperature nuclear fuels, materials and static power conversion to enable high performance from simple system topologies.

  18. Advances in Solid State Physics

    Haug, Rolf


    The present volume 47 of the Advances in Solid State Physics contains the written version of a large number of the invited talks of the 2007 Spring Meeting of the Arbeitskreis Festkörperphysik which was held in Regensburg, Germany, from March 26 to 30, 2007 in conjunction with the 71st Annual Meeting of the Deutsche Physikalische Gesellschaft.It gives an overview of the present status of solid state physics where low-dimensional systems such as quantum dots and quantum wires are dominating. The importance of magnetic materials is reflected by the large number of contributions in the part dealing with ferromagnetic films and particles. One of the most exciting achievements of the last couple of years is the successful application of electrical contacts to and the investigation of single layers of graphene. This exciting physics is covered in Part IV of this book. Terahertz physics is another rapidly moving field which is presented here by five contributions. Achievements in solid state physics are only rarely...

  19. Spectroscopic studies of composite obtained from solid state reaction between a mononuclear vanadium(IV) complex and kaolinite; Estudo espectroscopico de composito obtido da reacao no estado solido entre um complexo mononuclear de vanadio(IV) e caulinita

    Rezende, Edivaltris I.P. de; Mangrich, Antonio S.; Mangoni, Ana P. [Departamento de Quimica, Universidade Federal do Parana (UFPR), Curitiba, PR (Brazil); Scarpellini, Marciela; Casellato, Annelise; Fernandez, Tatiana L. [Departamento de Quimica Inorganica, Instituto de Quimica, Universidade Federal do Rio de Janeiro, RJ (Brazil)


    The use of probes, such as paramagnetic species diluted in diamagnetic materials in EPR spectroscopy, and mathematical tools such, as the Kubelka-Munk function in DRUV-VIS spectroscopy are strategies in the analysis of complex mixtures of solid materials. The results obtained here show that the solid state reaction between the complex, [VO(acac)(BMIMAPY)] [ClO{sub 4}], BMIMAPY = [(bis(1-methylimidazole-2-yl)methyl)(2-(pyridyl-2-yl)ethyl) amine] and acac = acetilacetonate, with kaolinite turns possible to obtain anisotropic EPR spectrum of the complex with a reasonable level of resolution. The study by DRUV-VIS using the method of second derivative mode of the Kubelka-Munk function revealed new complex structural arrangements, a solid hitherto unknown. (author)

  20. The influence of the stereochemistry of alanine residue on the solid state conformation and crystal packing of opioid peptides containing D-Ala or L-Ala in message domain--XRD and NMR study.

    Trzeciak-Karlikowska, Katarzyna; Bujacz, Anna; Ciesielski, Włodzimierz; Bujacz, Grzegorz D; Potrzebowski, Marek J


    In this work, an X-ray diffraction (XRD) and solid state NMR study of two tetrapeptides with different stereochemistry of alanine residue is presented using Tyr-(D-Ala)-Phe-Gly (1), an N-terminal sequence of opioid peptide dermorphin, and its biologically inactive analog Tyr-(L-Ala)-Phe-Gly (2). Single-crystal XRD proved that 1 crystallized under different conditions from exclusively one structure: a monoclinic crystal with P2(1) space group. In contrast, 2 very easily formed at least three crystallographic modifications, 2a (monoclinic P2(1)), 2b (orthorhombic P2(1)2(1)2) and 2c (tetragonal P4(1)2(1)2). Solid-state NMR spectroscopy was employed to investigate the structure and molecular dynamics of 1, 2a, and 2b. By employing different NMR experiments (dipolar dephasing and PILGRIM) and an analysis of the (13)C principal elements of the chemical shift tensor (CST), it was proven that the main skeleton of tetrapeptides is rigid, whereas significant differences in the molecular motion of the aromatic residues were observed. Comparing current data with those of previous studies (J. Phys. Chem. B2004, 108, 4535-4545 and Cryst. Growth Des. 2009, 9, 4050-4059), it can be assumed that an important preorganization mechanism anticipating the formation of peptide crystals containing D-Ala in sequence is the intramolecular CH-π interaction, which occurs for the amino acid with D stereochemistry. This effect may be responsible for the formation of only one crystallographic form of D-Ala peptides.

  1. Solid-state NMR spectroscopic trends for supramolecular assemblies and protein aggregates.

    Linser, Rasmus


    Solid-state NMR is able to generate structural data on sample preparations that are explicitly non-crystalline. In particular, for amyloid fibril samples, which can comprise significant degrees of sample disorder, solid-state NMR has been used very successfully. But also solid-state NMR studies of other supramolecular assemblies that have resisted assessment by more standard methods are being performed with increasing ease and biological impact, many of which are briefly reviewed here. New technical trends with respect to structure calculation, protein dynamics and smaller sample amounts have reshaped the field of solid-state NMR recently. In particular, proton-detected approaches based on fast Magic-Angle Spinning (MAS) were demonstrated for crystalline systems initially. Currently, such approaches are being expanded to the above-mentioned non-crystalline targets, the characterization of which can now be pursued with sample amounts on the order of a milligram. In this Trends article, I am giving a brief overview about achievements of the last years as well as the directions that the field has been heading into and delineate some satisfactory perspectives for solid-state NMR's future striving. Copyright © 2017 Elsevier Inc. All rights reserved.

  2. Solid state reactions of nitrogenous heterocyclic compounds (Ⅱ)——Solid state reactions of indole with carbonyl compounds

    李晓陆; 王永梅; 杜大明; 文忠; 熊国祥; 孟继本


    Solid state Michael addition reaction of indole with α,β-unsaturaled carbonyl compounds was carried out,by which a series of compounds containing three different heterocyclic groups binding to one carbon atom were obtained.In the presence of Lewis acid,indole could undergo the solid state condensation reaction with aromatic ketones and aldehydes or quinones.The solid state reaction showed higher selectivity and yield than solution reaction The structures of products were identified by IR,1H NMR,MS,elemental analysis and X-ray crystal analysis.The reaction mechanism was also proposed.

  3. Synthesis and structure of ruthenium(IV) complexes featuring N-heterocyclic ligands with an N-H group as the hydrogen-bond donor: hydrogen interactions in solution and in the solid state.

    Díez, Josefina; Gimeno, José; Merino, Isabel; Rubio, Eduardo; Suárez, Francisco J


    The synthesis and characterization of novel ruthenium(IV) complexes [Ru(η(3):η(3)-C(10)H(16))Cl(2)L] [L = 3-methylpyrazole (2b), 3,5-dimethylpyrazole (2c), 3-methyl-5-phenylpyrazole (2d), 2-(1H-pyrazol-5-yl)phenol (2e), 6-azauracile (3), and 1H-indazol-3-ol (4)] are reported. Complex 2e is converted to the chelated complex [Ru(η(3):η(3)-C(10)H(16))Cl(κ(2)-N,O-2-(1H-pyrazol-3-yl)phenoxy)] (5) by treatment with an excess of NaOH. All of the ligands feature N-H, O-H, or C═O as the potential hydrogen-bonding group. The structures of complexes 2a-2c, 2e, 3, and 5 in the solid state have been determined by X-ray diffraction. Complexes 2a-2c and 3, which contain the pyrazole N-H group, exhibit intra- and intermolecular hydrogen bonds with chloride ligands [N-H···Cl distances (Å): intramolecular, 2.30-2.78; intermolecular, 2.59-2.77]. Complexes 2e and 3 bearing respectively O-H and C═O groups also feature N-H···O interactions [intramolecular (2e), 2.27 Å; intermolecular (3), 2.00 Å]. Chelated complex 5, lacking the O-H group, only shows an intramolecular N-H···Cl hydrogen bonding of 2.42 Å. The structure of complex 3, which turns out to be a dimer in the solid state through a double intermolecular N-H···O hydrogen bonding, has also been investigated in solution (CD(2)Cl(2)) by NMR diffusion studies. Diffusion-ordered spectroscopy experiments reveal an equilibrium between monomer and dimer species in solution whose extension depends on the temperature, concentration, and coordinating properties of the solvent. Preliminary catalytic studies show that complex 3 is highly active in the redox isomerization of the allylic alcohols in an aqueous medium under very mild reaction conditions (35 °C) and in the absence of a base.

  4. Solid-state NMR studies of a diverged microsomal amino-proximate delta12 desaturase peptide reveal causes of stability in bilayer: tyrosine anchoring and arginine snorkeling.

    Gibbons, William J; Karp, Ethan S; Cellar, Nick A; Minto, Robert E; Lorigan, Gary A


    This study reports the solid-state NMR spectroscopic characterization of the amino-proximate transmembrane domain (TM-A) of a diverged microsomal delta12-desaturase (CREP-1) in a phospholipid bilayer. A series of TM-A peptides were synthesized with 2H-labeled side chains (Ala-53, -56, and -63, Leu-62, Val-50), and their dynamic properties were studied in 1,2-dimyristoyl-sn-glycero-3-phosphatidylcholine (DMPC) bilayers at various temperatures. At 6 mol % peptide to lipid, 31P NMR spectra indicated that the peptides did not significantly disrupt the phospholipid bilayer in the L(alpha) phase. The 2H NMR spectra from Ala-53 and Ala-56 samples revealed broad Pake patterns with quadrupolar splittings of 16.9 kHz and 13.3 kHz, respectively, indicating restricted motion confined within the hydrocarbon core of the phospholipid bilayer. Conversely, the deuterated Ala-63 sample revealed a peak centered at 0 kHz with a linewidth of 1.9 kHz, indicating increased side-chain motion and solvent exposure relative to the spectra of the other Ala residues. Val-50 and Leu-62 showed Pake patterns, with quadrupolar splittings of 3.5 kHz and 3.7 kHz, respectively, intermediate to Ala-53/Ala-56 and Ala-63. This indicates partial motional averaging and supports a model with the Val and Leu residues embedded inside the lipid bilayer. Solid-state NMR spectroscopy performed on the 2H-labeled Ala-56 TM-A peptide incorporated into magnetically aligned phospholipid bilayers indicated that the peptide is tilted 8 degrees with respect to the membrane normal of the lipid bilayer. Snorkeling and anchoring interactions of Arg-44 and Tyr-60, respectively, with the polar region or polar hydrophobic interface of the lipid bilayer are suggested as control elements for insertional depth and orientation of the helix in the lipid matrix. Thus, this study defines the location of key residues in TM-A with respect to the lipid bilayer, describes the conformation of TM-A in a biomembrane mimic, presents a

  5. Preparation of solid-state samples of a transition metal coordination compound for synchrotron radiation photoemission studies

    Crotti, C; Celestino, T; Fontana, S


    The aim of this research was to identify a sample preparation method suitable for the study of transition metal complexes by photoemission spectroscopy with synchrotron radiation as the X-ray source, even in the case where the compound is not evaporable. Solid-phase samples of W(CO) sub 4 (dppe) [dppe=1,2-bis(diphenylphosphino)ethane] were prepared according to different methods and their synchrotron radiation XPS spectra measured. The spectra acquired from samples prepared by spin coating show core level peaks only slightly broader than the spectrum recorded from UHV evaporated samples. Moreover, for these samples the reproducibility of the binding energy values is excellent. The dependence of the spin coating technique on parameters such as solvent and solution concentration, spinning speed and support material was studied. The same preparation method also allowed the acquisition of valence band spectra, the main peaks of which were clearly resolved. The results suggest that use of the spin coating techniqu...

  6. Nature and structure of aluminum surface sites grafted on silica from a combination of high-field aluminum-27 solid-state NMR spectroscopy and first-principles calculations

    Kerber, Rachel Nathaniel


    The determination of the nature and structure of surface sites after chemical modification of large surface area oxides such as silica is a key point for many applications and challenging from a spectroscopic point of view. This has been, for instance, a long-standing problem for silica reacted with alkylaluminum compounds, a system typically studied as a model for a supported methylaluminoxane and aluminum cocatalyst. While 27Al solid-state NMR spectroscopy would be a method of choice, it has been difficult to apply this technique because of large quadrupolar broadenings. Here, from a combined use of the highest stable field NMR instruments (17.6, 20.0, and 23.5 T) and ultrafast magic angle spinning (>60 kHz), high-quality spectra were obtained, allowing isotropic chemical shifts, quadrupolar couplings, and asymmetric parameters to be extracted. Combined with first-principles calculations, these NMR signatures were then assigned to actual structures of surface aluminum sites. For silica (here SBA-15) reacted with triethylaluminum, the surface sites are in fact mainly dinuclear Al species, grafted on the silica surface via either two terminal or two bridging siloxy ligands. Tetrahedral sites, resulting from the incorporation of Al inside the silica matrix, are also seen as minor species. No evidence for putative tri-coordinated Al atoms has been found. © 2012 American Chemical Society.

  7. Structure and electrochemical properties of Li(Ni0.5Mn0.5)1-xTixO2 prepared by one-step solid state reaction

    CAO Si-hai; WANG Zhi-xing; LI Xin-hai; GUO Hua-jun; PENG Wen-jie; YIN Zhou-lan


    The layered compound Li(Ni0.5Mn0.5)1-xTixO2 powders were prepared with Ni(OH)2, MnCO3, Li2CO3 and TiO2 by one-step solid state reaction. The effect of doping Ti on the structure and electrochemical properties was studied. The XRD results indicate that the powders with 0≤x≤0.05 have good layered structure and trace of impurity appears in the samples with x≥0.1. The SEM photographs show that the particle size distributes homogeneously and the sample with x=0.15 has larger particle size than other samples. The charge-discharge tests show that Li(Ni0.5Mn0.5)0.95Ti0.05O2 synthesized at 800 ℃ for 36 h exhibits good electrochemical properties. It firstly delivers 173 mA.h/g and maintains 90% of the initial discharge capacity after 30 cycles. The cyclic voltammetry and differential capacity vs voltage curves show that the major oxidation and reduction peaks are around 3.95 V and 3.75 V, respectively, assigned to Ni2+/Ni4+ oxidation-reduction process. A weak peak around 4.5 V is found during the oxidation process in the first cycle, which can be regarded as the main reason of the large drop of discharge capacity in the initial cycle.

  8. A study of indoor radon levels in rural dwellings of Ezine (Canakkale, Turkey) using solid-state nuclear track detectors.

    Orgün, Y; Altinsoy, N; Sahin, S Y; Ataksor, B; Celebi, N


    Indoor radon activity level and radon effective dose (ED) rate have been carried out in the rural dwellings of Ezine (Canakkale) during the summer season using Radosys-2000, a complete set suitable to radon concentration measurements with CR-39 plastic alpha track detectors. The range of radon concentration varied between 9 and 300 Bq m(-3), with an average of 67.9 (39.9 SD) Bq m(-3). Assuming an indoor occupancy factor of 0.8 and 0.4 for the equilibrium factor of radon indoors, it has been found that the 222Rn ED rate in the dwellings studied ranges from 0.4 to 5.2 mSv y(-1), with an average value of 1.7 (1.0) mSv y(-1). There is a possibility that low radon concentrations exist indoors during the summer season in the study area because of relatively high ventilation rates in the dwellings. A winter survey will be needed for future estimation of the annual ED.


    JIA Mingchun; SHEN Lianfang; QIAN Baogong; ZHANG Baozhen; YAO Shuren


    The 13C T1s of -CH3 side group in PPU/P(St-co-AA), AB-crosslinked polymers (i. e.ABCP) was studied by using high resolution solid state NMR. The rotation motion of -CH3 side group in PPU was analyzed by means of the average spectral density functions of internal rotation. The results showed that the rotation of the -CH3 side group is related closely to the compatibility between the two components. The compatibility was studied by analyzing the proton spin-lattice relaxation in rotating frame, spin-spin relaxation and spin-diffusion. The results showed that the hydrogen bonds between the components play a major role in determining the compatibility. Through spin diffusion studying, the soft phase domain size was calculated. By studying proton spin-spin relaxation, the content of each component in each phase and that of each phase in the samples can be obtained. The result shows that the content of interphase is related closely to the compatibility.

  10. Nanoprobes, nanostructured materials and solid state materials

    Yin, Houping


    Novel templates have been developed to prepare nanostructured porous materials through nonsurfactant templated pathway. And new applications of these materials, such as drug delivery and molecular imprinting, have been explored. The relationship between template content and pore structure has been investigated. The composition and pore structures were studied in detail using IR, TGA, SEM, TEM, BET and XRD. The obtained mesoporous materials have tunable diameters in the range of 2--12 nm. Due to the many advantages of this nonsurfactant templated pathway, such as environment friendly and biocompatibility, controlled release of antibiotics in the nanoporous materials were studied. The in vitro release properties were found to depend on the silica structures which were well tuned by varying the template content. A controlled long-term release pattern of vancomycin was achieved when the template content was 30 wt% or lower. Nanoscale electrochemical probes with dimensions as small as 50 nm in diameter and 1--2 mum in length were fabricated using electron beam deposition on the apex of conventional micron size electrodes. The electroactive region was limited to the extreme tip of the nanoprobe by coating with an insulating polymer and re-opening of the coating at the extreme tip. The novel nanoelectrodes thus prepared were employed to probe neurons in mouse brain slice and the results suggest that the nanoprobes were capable of recording neuronal excitatory postsynaptic potential signals. Interesting solid state chemistry was found in oxygenated iron phthalocyanine. Their Mossbauer spectra show the formation of four oxygenated species apart from the unoxygenated parent compound. The oxygen-bridged compounds formed in the solid matrix bear no resemblance to the one formed by solution chemistry. Tentative assignment of species has been made with the help of Mossbauer and IR spectroscopy. An effort to modify aniline trimer for potential nanoelectronics applications and to

  11. Neglect of Solid State Chemistry Scored

    Chemical and Engineering News, 1974


    At a recent symposium concerning the teaching of solid state chemistry in the classroom, many educators indicated that important areas of solid state chemistry were being neglected in college curricula. (RH)

  12. A randomized controlled study for the treatment of acne vulgaris using high-intensity 414 nm solid state diode arrays.

    Ash, Caerwyn; Harrison, Anna; Drew, Samantha; Whittall, Rebecca


    The treatment of acne vulgaris poses a challenge to the dermatologist, and the disease causes emotional anxiety for the patient. The treatment of acne vulgaris may be well-suited to home-use applications, where sufferers may be too embarrassed to seek medical treatment. This randomized controlled study is designed to quantify the effectiveness of using a blue light device in a therapy combined with proprietary creams, in the investigation of a self-treatment regimen. A total of 41 adults with mild-to-moderate facial inflammatory acne were recruited. The subjects were randomly assigned to combination blue light therapy (n = 26) or control (n = 15). Photography was used for qualitative assessment of lesion counts, at weeks 1, 2, 4, 8, and 12. All subjects in the treatment cohort achieved a reduction in their inflammatory lesion counts after 12 weeks. The mean inflammatory lesion counts reduced by 50.02% in the treatment cohort, and increased by 2.45% in the control cohort. The reduction in inflammatory lesions was typically observable at week-3, and maximal between weeks 8 and 12. The treatment is free of pain and side-effects. The blue light device offers a valuable alternative to antibiotics and potentially irritating topical treatments. Blue light phototherapy, using a narrow-band LED light source, appears to be a safe and effective additional therapy for mild to moderate acne.

  13. Enthalpy of sublimation in the study of the solid state of organic compounds. Application to erythritol and threitol.

    Lopes Jesus, A J; Tomé, Luciana I N; Eusébio, M Ermelinda; Redinha, J S


    The enthalpies of sublimation of erythritol and L-threitol have been determined at 298.15 K by calorimetry. The values obtained for the two diastereomers differ from one another by 17 kJ mol(-1). An interpretation of these results is based on the decomposition of this thermodynamic property in a term coming from the intermolecular interactions of the molecules in the crystal (delta(int)H degrees) and another one related with the conformational change of the molecules on going from the crystal lattice to the most stable forms in the gas phase (delta(conf)H degrees). This last term was calculated from the values of the enthalpy of the molecules in the gas state and of the enthalpy of the isolated molecules with the crystal conformation. Both quantities were obtained by density functional theory (DFT) calculations at the B3LYP/6-311G++(d,p) level of theory. The results obtained in this study show that the most important contribution to the differences observed in the enthalpy of sublimation are the differences in the enthalpy of conformational change (13 kJ mol(-1)) rather than different intermolecular forces exhibited in the solid phase. This is explained by the lower enthalpy of threitol in the gas phase relative to erythritol, which is attributed to the higher strength of the intramolecular hydrogen bonds in the former. The comparison of the calculated infrared spectra obtained for the two compounds in the gas phase supports this interpretation.

  14. Comprehensive Study of All-Solid-State Z-Scheme Photocatalytic Systems of ZnO/Pt/CdZnS

    Isimjan, Tayirjan Taylor


    We have investigated a Z-scheme based on a ZnO/Pt/CdZnS photocatalyst, active in the presence of a complex medium composed of acetic acid and benzyl alcohol, the effects of which on the catalyst stability and performance are studied. Transmission electron microscopy images showed uniformly dispersed sub-nanometer Pt particles. Inductively coupled plasma and X-ray photoelectron spectroscopy analyses suggested that Pt is sandwiched between ZnO and CdZnS. An apparent quantum yield (AQY) of 34% was obtained over the [ZnO]4/1 wt %Pt/CdZnS system at 360 nm, 2.5-fold higher than that of 1%Pt/CdZnS (14%). Furthermore, an AQY of 16% was observed using [ZnO]4/1 wt %Pt/CdZnS, which was comparable to that of 1 wt %Pt/CdZnS (10%) at 460 nm. On the basis of these results, we proposed a charge transfer mechanism, which was confirmed through femtosecond transient absorption spectroscopy. Finally, we identified the two main factors that affected the stability of the catalyst, which were the sacrificial reagent and the acidic pH.

  15. An Overview on Studying 222Rn Exhalation Rates using Passive Technique Solid-State Nuclear Track Detectors

    Mohamed Abd-Elzaher


    Full Text Available Problem statement: Uranium is a radiotoxic element found in trace quantities in alomost all natural accurring materials like soil, rock. Radon an inert radioactive gas whose predecessor in uranium, is emitted from soil beneath the house and from building materials. Accurate knowledge of exhalation rate plays an important role in characterization of the radon source strength in some building materials and soil. It is a useful quantity to compare the relative importance of different sample of building materials and soil. Approach: This study provides an overview of measurements of radon exhalation rates for selected samples in Egypt were carried out using passive measuring techniques were measured by Can Technique using LR-115 type II plastic track detectors. Results: The radon concentration varies from 2.44-29 k Bq m-3 and the corresponding values of surface exhalation rates from 4.16-26.24 Bq m-2. h the radium content 226Ra results in all samples under test in increasing order of magnitude. From the results it can be noticed that The lowest value of 226Ra is 7 Bq kg-1 in Sand sample, while the highest value is 85 Bq kg-1 Ordinary Cement. Conclusion: All the values of radium content in all samples under test were found to be quite lower than the permissible value of 370 Bq kg-1 recommended by Organization for Economic Cooperation and Development."

  16. Surface acidity and solid-state compatibility of excipients with an acid-sensitive API: case study of atorvastatin calcium.

    Govindarajan, Ramprakash; Landis, Margaret; Hancock, Bruno; Gatlin, Larry A; Suryanarayanan, Raj; Shalaev, Evgenyi Y


    The objectives of this study were to measure the apparent surface acidity of common excipients and to correlate the acidity with the chemical stability of an acid-sensitive active pharmaceutical ingredient (API) in binary API-excipient powder mixtures. The acidity of 26 solid excipients was determined by two methods, (i) by measuring the pH of their suspensions or solutions and (ii) the pH equivalent (pHeq) measured via ionization of probe molecules deposited on the surface of the excipients. The chemical stability of an API, atorvastatin calcium (AC), in mixtures with the excipients was evaluated by monitoring the appearance of an acid-induced degradant, atorvastatin lactone, under accelerated storage conditions. The extent of lactone formation in AC-excipient mixtures was presented as a function of either solution/suspension pH or pHeq. No lactone formation was observed in mixtures with excipients having pHeq > 6, while the lactone levels were pronounced (> 0.6% after 6 weeks at 50°C/20% RH) with excipients exhibiting pHeq 6, 3-6, and API, were identified based on pHeq measurements. The incompatibility prediction was confirmed in the chemical stability tests using AC as an example of an acid-sensitive API.

  17. Solid state proton conductors properties and applications in fuel cells

    Knauth, Philippe


    Proton conduction can be found in many different solid materials, from organic polymers at room temperature to inorganic oxides at high temperature. Solid state proton conductors are of central interest for many technological innovations, including hydrogen and humidity sensors, membranes for water electrolyzers and, most importantly, for high-efficiency electrochemical energy conversion in fuel cells. Focusing on fundamentals and physico-chemical properties of solid state proton conductors, topics covered include: Morphology and Structure of Solid Acids Diffusion in Soli

  18. Niobium Carbide Synthesis from Niobium Oxide: Study of the Synthesis Conditions, Kinetics, and Solid-State Transformation Mechanism

    Teixeira da Silva, V. L. S.; Schmal, M.; Oyama, S. T.


    The carburization of B-niobium oxide (B-Nb2O5) to niobium carbide (NbC) in 20% (v/v) CH4/H2was studied at temperature-programmed conditions. The reaction required high temperatures, greater than 1370 K, and variations of heating rate (0.04-0.17 K s-1) and molar space velocity (400-1600 h-1) had only a minor effect on the product specific surface area (Sg). In the course of the transformationSgincreased from 1 m2g-1to about 20 m2g-1, and scanning electron microscopy showed the development of macropores of about 100 nm. The progress of the reaction was followed by mass spectroscopic analysis of the gaseous products, which identified two distinct stages. X-ray diffraction analysis of reaction intermediates showed that in the first stage B-Nb2O5was reduced to NbO2, and in the second stage NbO2was simultaneously reduced and carburized to NbC. The first reduction occurred by a nucleation mechanism with an activation energy of 100 kJ mol-1. Independent experiments with NbO indicated that it was not involved in the reaction pathway. However, X-ray photoelectron spectroscopy revealed the presence of an oxycarbide phase which was probably the intermediate in the final transformation. Overall the reaction took place by the following steps:[formula]The oxycarbide phase transformed rapidly to the product NbC and was not observable as a bulk phase by XRD.

  19. Studies of the Active Sites for Methane Dehydroaromatization Using Ultrahigh-Field Solid-State Mo95 NMR Spectroscopy

    Hu, Jian Z.; Kwak, Ja Hun; Wang, Yong; Peden, Charles HF; Zheng, Heng; Ma, Ding; Bao, Xinhe


    Abstract It is found that the spin-lattice relaxation time, T1, corresponding to the surface exchanged molybdenum species in Mo/HZSM-5 catalysts is short, i.e., less than about 100ms at 21.1 T while the value of T1 for the crystallite MoO3 molecules is longer, i.e., about 30 s. Such a difference, more than two orders in magnitude, is utilized to differentiate the exchanged Mo species from the agglomerate MoO3 in Mo/HZSM-5 catalyst. An approximately linear correlation between the amount of exchanged species and the aromatics formation rate is obtained. This result significantly strengthens our prior conclusion that the exchanged Mo species are the active centers for the methane dehydroaromatization reaction on Mo/HZSM-5 catalysts (J. Am. Chem. Soc. 2008, 130, 3722-3723). Our results also suggest that one exchanged Mo atom anchors on two ion exchange sites and the exchanged Mo species on catalysts are possibly monomeric. Analyzing the linshapes obtained from both the 95Mo MAS and the static spectra indicates that the exchanged sites are heterogeneous, resulting in a significantly broadened MAS spectrum and essentially a featureless but nearly symmetric static lineshape for the exchanged Mo species. Furthermore, for crystallite MoO3 powder sample, the parameters related to the electric-field-gradient (EFG) tensor, the chemical shift anisotropy (CSA) and the three Euler angles required to align the CSA principal axis system with the quadrupolar principal axis system are determined by analyzing both the 95Mo MAS and the static spectra obtained at ultra-high field of 21.1 T. The new results obtained from this study on crystallite MoO3 powders should help to clarify some of the contradictions in prior literature reports from other groups. Key words: 95Mo NMR, MAS, relaxation, surface exchanged species, HZSM-5, electric-field-gradient (EFG), chemical shift anisotropy (CSA), active centers.

  20. A study of transition-metal organometallic complexes combining 35Cl solid-state NMR spectroscopy and 35Cl NQR spectroscopy and first-principles DFT calculations.

    Johnston, Karen E; O'Keefe, Christopher A; Gauvin, Régis M; Trébosc, Julien; Delevoye, Laurent; Amoureux, Jean-Paul; Popoff, Nicolas; Taoufik, Mostafa; Oudatchin, Konstantin; Schurko, Robert W


    A series of transition-metal organometallic complexes with commonly occurring metal-chlorine bonding motifs were characterized using (35)Cl solid-state NMR (SSNMR) spectroscopy, (35)Cl nuclear quadrupole resonance (NQR) spectroscopy, and first-principles density functional theory (DFT) calculations of NMR interaction tensors. Static (35)Cl ultra-wideline NMR spectra were acquired in a piecewise manner at standard (9.4 T) and high (21.1 T) magnetic field strengths using the WURST-QCPMG pulse sequence. The (35)Cl electric field gradient (EFG) and chemical shielding (CS) tensor parameters were readily extracted from analytical simulations of the spectra; in particular, the quadrupolar parameters are shown to be very sensitive to structural differences, and can easily differentiate between chlorine atoms in bridging and terminal bonding environments. (35)Cl NQR spectra were acquired for many of the complexes, which aided in resolving structurally similar, yet crystallographically distinct and magnetically inequivalent chlorine sites, and with the interpretation and assignment of (35)Cl SSNMR spectra. (35)Cl EFG tensors obtained from first-principles DFT calculations are consistently in good agreement with experiment, highlighting the importance of using a combined approach of theoretical and experimental methods for structural characterization. Finally, a preliminary example of a (35)Cl SSNMR spectrum of a transition-metal species (TiCl4) diluted and supported on non-porous silica is presented. The combination of (35)Cl SSNMR and (35)Cl NQR spectroscopy and DFT calculations is shown to be a promising and simple methodology for the characterization of all manner of chlorine-containing transition-metal complexes, in pure, impure bulk and supported forms.