Crystal structures of propanediamine complexed with L and DL- glutamic acid: effect of chirality on propanediamine.

The structures of complexes of 1,3-diaminopropane With L- and DL-glutamic acid have been determined. L-Glutamic acid complex: C3H12N22+.2C5H8NO4-, M(r) = 368.4, orthorhombic. P2(1)2(1)2(1), a = 5.199 (1), b = 16.832 (1). c = 20.076 (3) angstrom, V = 1756.6 (4) angstrom3, z = 4, D(x) = 1.39 g cm-3, lambda(Mo K-alpha) = 0.7107 angstrom, mu = 1.1 cm-1, F(000) = 792. T = 296 K, R = 0.044 for 1276 observed reflections. DL-Glutamic acid complex: C3H12N22+.2C5H8NO4-, M(r) = 368.4, orthorhombic, Pna2(1), a = 15.219(2), b = 5.169 (1), c 22.457 (4) angstrom, V = 1766.6 (5) angstrom3 Z = 4, D(x) = 1.38 g cm-3, lambda(Mo K-alpha) = 0.7107 angstrom, mu = 1.1 cm F(000) = 792, T = 296 K, R = 0.056 for 993 observed reflections. The conformation of diaminopropane is all-trans in the DL complex but trans-gauche in the L complex. The main packing feature in the L complex is the arrangement of diaminopropane around dimers of antiparallel L-glutamic acid molecules. The diaminopropane in the DL complex is sandwiched between two antiparallel glutamic acid molecules of the same chirality and this forms the basic packing unit. This might be the dominant form of interaction between L-glutamic acid and diaminopropane in solution. The structures reveal the adaptability of the polyamine backbone to different environments and the probable reasons for their choice as biological cations.

Reactivity Of Pph3 Toward Ruiiruiiicl(O2car)4 - Syntheses, Molecular-Structures, And Spectroscopic And Electrochemical Properties Of Ruiiruiii(Oh2)Cl(Mecn)(O2car)4(Pph3)2 And Ruii2(Oh2)(Mecn)2(O2car)4(Pph3)2

By the reaction of Ru2Cl(O2CAr)4 (1) and PPh3 in MeCN-H2O the diruthenium(II,III) and diruthenium(II) compounds of the type Ru2(OH2)Cl(MeCN)(O2CAr)4(PPh3)2 (2) and Ru2(OH2)(MeCN)2(O2CAr)4(PPh3)2 (3) were prepared and characterized by analytical, spectral, and electrochemical data (Ar is an aryl group, C6H4-p-X; X = H, OMe, Me, Cl, NO2). The molecular structure of Ru2(OH2)Cl(MeCN)(O2CC6H4-p-OMe)4(PPh3)2 was determined by X-ray crystallography. Crystal data are as follows: triclinic, P1BAR, a = 13.538 (5) angstrom, b = 15.650 (4) angstrom, c = 18.287 (7) angstrom, alpha = 101.39 (3)-degrees, beta = 105.99 (4)-degrees, gamma = 97.94 (3)-degrees, V = 3574 angstrom 3, Z = 2. The molecule is asymmetric, and the two ruthenium centers are clearly distinguishable. The Ru(III)-Ru(II), Ru(III)-(mu-OH2), and Ru(II)-(mu-OH2) distances and the Ru-(mu-OH2)-Ru angle in [{Ru(III)Cl(eta-1-O2CC6H4-p-OMe)(PPh3)}(mu-OH2)(mu-O2CC6H4-p-OMe)2{Ru(II)(MeCN)(eta-1-O2CC6H4-p-OMe)(PPh3)}] are 3.604 (1), 2.127 (8), and 2.141 (10) angstrom and 115.2 (5)-degrees, respectively. The compounds are paramagnetic and exhibit axial EPR spectra in the polycrystalline form. An intervalence transfer (IT) transition is observed in the range 900-960 nm in chloroform in these class II type trapped mixed-valence species 2. Compound 2 displays metal-centered one-electron reduction and oxidation processes near -0.4 and +0.6 V (vs SCE), respectively in CH2Cl2-TBAP. Compound 2 is unstable in solution phase and disproportionates to (mu-aquo)diruthenium(II) and (mu-oxo)diruthenium(III) complexes. The mechanistic aspects of the core conversion are discussed. The molecular structure of a diruthenium(II) compound, Ru2(OH2)(MeCN)2(O2CC6H4-p-NO2)4(PPh3)2.1.5CH2Cl2, was obtained by X-ray crystallography. The compound crystallizes in the space group P2(1)/c with a = 23.472 (6) angstrom, b = 14.303 (3) angstrom, c = 23.256 (7) angstrom, beta = 101.69 (2)-degrees, V = 7645 angstrom 3, and Z = 4. The Ru(II)-Ru(II) and two Ru(II)-(mu-OH2) distances and the Ru(II)-(mu-OH2)-Ru(II) angle in [{(PPh3)-(MeCN)(eta-1-O2CC6H4-p-NO2)Ru}2(mu-OH2)(mu-O2CC6H4-p-NO2)2] are 3.712 (1), 2.173 (9), and 2.162 (9) angstrom and 117.8 (4)-degrees, respectively. In both diruthenium(II,III) and diruthenium(II) compounds, each metal center has three facial ligands of varying pi-acidity and the aquo bridges are strongly hydrogen bonded with the eta-1-carboxylato facial ligands. The diruthenium(II) compounds are diamagnetic and exhibit characteristic H-1 NMR spectra in CDCl3. These compounds display two metal-centered one-electron oxidations near +0.3 and +1.0 V (vs SCE) in CH2Cl2-TBAP. The overall reaction between 1 and PPh3 in MeCN-H2O through the intermediacy of 2 is of the disproportionation type. The significant role of facial as well as bridging ligands in stabilizing the core structures is observed from electrochemical studies.

Growth of Orthorhombic SnS Nanobox Structures on Seeded Substrates

Tin sulfide (SnS) nanostructures have been synthesized using a simple and low temperature chemical solution method on seeded substrates, and their structural and optical properties have been investigated. The as-grown SnS nanostructures with well-defined facets exhibited good stoichiometry between constituent elements. These nanobox structures are preferentially oriented along the 010] direction by having 100] and 001] orientations as surrounding facets and exhibited Two distinguishable optical band gaps of 1.36 and 1.9 eV. The effect of solution concentration as well as seed layer on the morphology or SnS structures has also been studied, and finally, the growth mechanism of the regular SnS nanobox structures is proposed.

An improved iterative finite element solution for pin joints

Accurate, reliable and economical methods of determining stress distributions are important for fastener joints. In the past the contact stress problems in these mechanically fastened joints using interference or push or clearance fit pins were solved using both inverse and iterative techniques. Inverse techniques were found to be most efficient, but at times inadequate in the presence of asymmetries. Iterative techniques based on the finite element method of analysis have wider applications, but they have the major drawbacks of being expensive and time-consuming. In this paper an improved finite element technique for iteration is presented to overcome these drawbacks. The improved iterative technique employs a frontal solver for elimination of variables not requiring iteration, by creation of a dummy element. This automatically results in a large reduction in computer time and in the size of the problem to be handled during iteration. Numerical results are compared with those available in the literature. The method is used to study an eccentrically located pin in a quasi-isotropic laminated plate under uniform tension.

The effect of structure on the dilute solution properties of branched polysaccharides studied with SEC and AsFlFFF

Cereal arabinoxylans, guar galactomannans, and dextrans produced by lactic acid bacteria(LAB) are a structurally diverse group of branched polysaccharides with nutritional and industrial functions. In this thesis, the effect of the chemical structure on the dilute solution properties of these polysaccharides was investigated using size-exclusion chromatography(SEC) and asymmetric flow field-flow fractionation (AsFlFFF) with multiple-detection. The chemical structures of arabinoxylans were determined, whereas galactomannan and dextran structures were studied in previous investigations. Characterization of arabinoxylans revealed differences in the chemical structures of cereal arabinoxylans. Although arabinoxylans from wheat, rye, and barley fiber contained similar amounts of arabinose side units, the substitution pattern of arabinoxylans from different cereals varied. Arabinoxylans from barley husks and commercial low-viscosity wheat arabinoxylan contained a lower number of arabinose side units. Structurally different dextrans were obtained from different LAB. The structural effects on the solution properties could be studied in detail by modifying pure wheat and rye arabinoxylans and guar galactomannan with specific enzymes. The solution characterization of arabinoxylans, enzymatically modified galactomannans, and dextrans revealed the presence of aggregates in aqueous polysaccharide solutions. In the case of arabinoxylans and dextrans, the comparison of molar mass data from aqueous and organic SEC analyses was essential in confirming aggregation, which could not be observed only from the peak or molar mass distribution shapes obtained with aqueous SEC. The AsFlFFF analyses gave further evidence of aggregation. Comparison of molar mass and intrinsic viscosity data of unmodified and partially debranched guar galactomannan, on the other hand, revealed the aggregation of native galactomannan. The arabinoxylan and galactomannan samples with low or enzymatically extensively decreased side unit content behaved similarly in aqueous solution: lower molar mass samples stayed in solution but formed large aggregates, whereas the water solubility of the higher-molar-mass samples decreased significantly. Due to the restricted solubility of galactomannans in organic solvents, only aqueous galactomannan solutions were studied. The SEC and AsFlFFF results differed for the wheat arabinoxylan and dextran samples. Column matrix effects and possible differences in the separation parameters are discussed, and a problem related to the non-established relationship between the separation parameters of the two separation techniques is highlighted. This thesis shows that complementary approaches in the solution characterization of chemically heterogeneous polysaccharides are needed to comprehensively investigate macromolecular behavior in solution. These results may also be valuable when characterizing other branched polysaccharides.

Recognition of Polycyclic Aromatic Hydrocarbons and Their Derivatives by the 1,3-Dinaphthalimide Conjugate of Calix4]arene: Emission, Absorption, Crystal Structures, and Computational Studies

Polycyclic aromatic hydrocarbons (PAHs) are environmental pollutants as well as well-known carcinogens. Therefore, it is important to develop an effective receptor for the detection and quantification of such molecules in solution. In view of this, a 1,3-dinaphthalimide derivative of calix4]arene (L) has been synthesized and characterized, and the structure has been established by single crystal XRD. In the crystal lattice, intermolecular arm-to-arm pi center dot center dot center dot pi overlap dominates and thus L becomes a promising receptor for providing interactions with the aromatic species in solution, which can be monitored by following the changes that occur in its fluorescence and absorption spectra. On the basis of the solution studies carried out with about 17 derivatives of the aromatic guest molecular systems, it may be concluded that the changes that occur in the fluorescence intensity seem to be proportional to the number of aromatic rings present and thus proportional to the extent of pi center dot center dot center dot pi interaction present between the naphthalimide moieties and the aromatic portion of the guest molecule. Though the nonaromatic portion of the guest species affects the fluorescence quenching, the trend is still based on the number of rings present in these. Four guest aldehydes are bound to L with K-ass of 2000-6000 M-1 and their minimum detection limit is in the range of 8-35 mu M. The crystal structure of a naphthaldehyde complex, L.2b, exhibits intermolecular arm-to-arm as well as arm-to-naphthaldehyde pi center dot center dot center dot pi interactions. Molecular dynamics studies of L carried out in the presence of aromatic aldehydes under vacuum as well as in acetonitrile resulted in exhibiting interactions observed in the solid state and hence the changes observed in the fluorescence and absorption spectra are attributable for such interactions. Complex formation has also been delineated through ESI MS studies. Thus L is a promising receptor that can recognize PAHs by providing spectral changes proportional to the aromatic conjugation of the guest and the extent of aromatic pi center dot center dot center dot pi interactions present between L and the guest.

Constructions of 2D-Metallamacrocycles Using Half-Sandwich Ru-2(II) Precursors: Synthesis, Molecular Structures, and Self-Selection for a Single Linkage Isomer

Coordination-driven self-assembly of oxalato-bridged half-sandwich p-cymene ruthenium complex Ru-2(mu-eta(4)-C2O4)(MeOH)(2)(eta(6)-p-cymene)(2)] (O3SCF3)(2) (1a) with several ditopic donors (L-a-L-d) in methanol affords a series of bi- and tetranuclear metallamacrocycles (2a and 3-5). Similarly, the combination of 2,5-dihydroxy-1,4-benzoquinonato (dhbq)-bridged binuclear complex Ru-2(mu-eta(4)-C6H2O4)(MeOH)(2)(eta(6)-p-cymene)(2)](O3SCF3)(2) (1b) with a flexible bidentate amide linker (L-a) in 1:1 molar ratio gave the corresponding tetranuclear complex 2b. All the macrocycles were isolated as their triflate salts in high yields and were fully characterized by various spectroscopic techniques. Finally, the molecular structures of all the assemblies were determined unambiguously by single-crystal X-diffraction analysis. Interestingly, the combination of acceptor 1a or 1b with an unsymmetrical linear ditopic donor L-a results in a self-sorted linkage isomeric (head-to-tail) macrocycle (2a or 2b) despite the possibility of formation of two different isomeric macrocycles (head-to-head or head-to-tail) due to different connectivity of the donor. Molecular structures of the complexes 2a and 2b showed tetranuclear rectangular geometry with dimensions of 5.51 angstrom x 13.29 angstrom for 2a and 7.91 angstrom x 13.46 angstrom for 2b. In both cases, two binuclear Ru-2(II) building blocks are connected by a mu-N-(4-pyridyl)isonicotinamide donor in a head-to-tail fashion. Surprisingly, the macrocycle 2a loses one counteranion and cocrystallizes with monodeprotonated 1,3,5-trihydroxybenzene via strong intermolecular pi-pi stacking and hydrogen bonding. The tweezer complex 3 showed strong fluorescence in solution, and it showed fluorescence sensing toward nitroaromatic compounds. A fluorescence study demonstrated a marked quenching of the initial fluorescence intensity of the macrocycle 3 upon gradual addition of trinitrotoluene and exhibits significant fluorescence quenching response only for nitroaromatic compounds compared to various other aromatic compounds tested.

Fast algorithm for data exchange in reconfigurable tree structures

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

Critical earthquake input power spectral density function models for engineering structures

The problem of determining optimal power spectral density models for earthquake excitation which satisfy constraints on total average power, zero crossing rate and which produce the highest response variance in a given linear system is considered. The solution to this problem is obtained using linear programming methods. The resulting solutions are shown to display a highly deterministic structure and, therefore, fail to capture the stochastic nature of the input. A modification to the definition of critical excitation is proposed which takes into account the entropy rate as a measure of uncertainty in the earthquake loads. The resulting problem is solved using calculus of variations and also within linear programming framework. Illustrative examples on specifying seismic inputs for a nuclear power plant and a tall earth dam are considered and the resulting solutions are shown to be realistic.

Synthesis and structures of oxyanion encapsulated copper(I)-dppm complexes (dppm = bis(diphenylphosphino) methane)

Copper(I)-dppm complexes encapsulating the oxyanions ClO4-, NO3-, CH3C6H4CO2-, SO42-, and WO42- have been synthesized either by reduction of the corresponding Cu(II) salts and treatment with dppm, or by treating the complex [Cu-2(dppm)(2)(dmcn)(3)](BF4)(2) (1) (dmcn = dimethyl cyanamide) with the respective anion. The isolated complexes [Cu-2(dppm)(2)(dmcn)(2)(ClO4)] (ClO4) (2), [Cu-2(dppm)(2)(dmcn)(2)(NO3)] (NO3) (3), Cu-2(dppm)(2)(NO3)(2) (4), [Cu-2(dppm)(2)(CH3C6H4CO2)(2)]dmcn.2THF (5), Cu-2(dppm)(2)(SO4) (6), and [Cu-3(dppm)(3)(Cl)(WO4)] 0.5H(2)O (7) have been characterized by IR, H-1 and P-31{H-1} NMR, UV-vis, and emission spectroscopy. The solid-state molecular structure of complexes 1, 2, 4, and 7 were determined by single-crystal X-ray diffraction. Pertinent crystal data are as follows: for 1, monoclinic P2(1)/c, a = 11.376(10) Angstrom, b = 42.503(7) Angstrom, c = 13.530(6) Angstrom, beta = 108.08(2)degrees, V = 6219(3) Angstrom(3), Z = 4; for 2, monoclinic P2(1)/c, a = 21.600(3) Angstrom, b = 12.968(3) Angstrom, c = 23.050(3) Angstrom, beta = 115.97(2)degrees, V = 5804(17) Angstrom(3), Z = 4; for 4, triclinic , a = 10.560(4) Angstrom, b = 10.553(3) Angstrom, c = 22.698(3) Angstrom, alpha = 96.08(2)degrees, beta = 96.03(2)degrees, gamma = 108.31(2)degrees, V = 2362(12) Angstrom(3), Z = 2; and for 7, orthorhombic P2(1)2(1)2(1), a = 14.407(4) Angstrom, b = 20.573(7) Angstrom, c = 24.176(6) Angstrom, V = 7166(4) Angstrom(3), Z = 4. Analyses of the crystallographic and spectroscopic data of these complexes reveal the nature of interactions between the Cu-I-dppm core and oxyanion. The anchoring of the oxyanion to the Cu-n(dppm)(n) unit is primarily through coordination to the metal, but the noncovalent C-H ... O interactions between the methylene and phenyl protons of the dppm and oxygen atoms of the oxyanion play a significant role. The solid-state emission spectra for complexes 1-6 are very similar but different from 7. In CDCl3 solution, addition of ClO4- or NO3- (as their tetrabutylammonium salts) to 1 establishes a rapid equilibrium between the anion-complexed and uncomplexed forms. The association constant values for ClO4- and NO3- have been estimated from the P-31{H-1} NMR spectra.

Active Vibration Suppression of One-dimensional Nonlinear Structures Using Optimal Dynamic Inversion

A flexible robot arm can be modeled as an Euler-Bernoulli beam which are infinite degrees of freedom (DOF) system. Proper control is needed to track the desired motion of a robotic arm. The infinite number of DOF of beams are reduced to finite number for controller implementation, which brings in error (due to their distributed nature). Therefore, to represent reality better distributed parameter systems (DPS) should be controlled using the systems partial differential equation (PDE) directly. In this paper, we propose to use a recently developed optimal dynamic inversion technique to design a controller to suppress nonlinear vibration of a beam. The method used in this paper determines control forces directly from the PDE model of the system. The formulation has better practical significance, because it leads to a closed form solution of the controller (hence avoids computational issues).

Thermodynamics and phase equilibria involving the spinel solid solution FexMg1-xCr2O4

Activities of FeCr2O4 in the spinel solid solutions Fe X Mg1−X Cr2O4 (0solution parameter Ω s =−2260 (±200) J/mol. The lattice parameter of the spinel solid solutions quenched from 1200 K was found to obey Vegard’s law. The phase relations in the FeO-MgO-Cr2O3 system have been deduced from the results obtained in this study together with other relevant thermodynamic data from the literature. The tie-lines between the solid solutions with rock salt and spinel structures represent the influence of intercrystalline ion exchange. The tie-lines are skewed toward the FeCr2O4 corner, primarily because of the higher stability of FeCr2O4 compared to MgCr2O4, with respect to their component binary oxides. The oxygen partial pressure corresponding to the two three-phase regions, Fe + Fe X Mg1−X Cr2O4 + Cr2O3 and Fe + Fe Y Mg1−Y O + Fe X Mg1−X Cr2O4, have been evaluated as a function of composition at 1200 K.

Thermodynamic activities in the Pb(Zr1−XTiX)O3 solid solution at 1373K

Although Pb(Zr1−XTiX)O3 solid solution is the cornerstone of the piezoelectric ceramics, there is no information in the literature on thermodynamic activities of the component phases in the solid solution. Using inter-crystalline ion exchange equilibria between Pb(Zr1−XTiX)O3 solid solution with cubic perovskite structure and (Zr1−YTiY)O2 solid solutions with monoclinic and tetragonal structures, activities of PbTiO3 and PbZrO3 in the perovskite solid solution have been derived at 1373 K using the modified Gibbs–Duhem integration technique of Jacob and Jeffes. Tie-lines from the cubic solid solution are skewed towards the ZrO2 corner. Activities in the zirconia-rich (Zr1−YTiY)O2 solid solutions are taken from a recent emf study. The results for the perovskite solid solution at 1373 K can be represented by a sub-regular solution model:View the MathML sourcewhere ΔGE,M is the excess Gibbs energy of mixing of the cubic solid solution and Xi represents the mole fraction of component i. There is a significant positive deviation from ideality for PbTiO3-rich compositions and mild negative deviation near the PbZrO3 corner. The cubic solid solution is intrinsically stable against composition fluctuations at temperatures down to 840 K. The results contrast sharply with the recent calorimetric data on enthalpy of mixing which signal instability of the cubic perovskite solid solution.

Structure of the Pyridine-Chloranil Complex in Solution: A Surprise from Depolarized Hyper-Rayleigh Scattering Measurements

In this article, we report the structure of a 1:1 charge transfer complex between pyridine (PYR) and chloranil (CHL) in solution (CHCl(3)) from the measurement of hyperpolarizability (beta(HRS)) and linear and circular depolarization ratios, D and D', respectively, by the hyper-Rayleigh scattering technique and state-of-the-art quantum chemical calculations. Using linearly (electric field vector along X) and circularly polarized incident light, respectively, we have measured two macroscopic depolarization ratios D = I(X,X)(2 omega)/I(X,Z)(2 omega) and D' = I(X,C)(2 omega)/I(Z,C)(2 omega) in the laboratory fixed XYZ frame by detecting the second harmonic (SH) scattered light in a polarization resolved fashion. The stabilization energy and the optical gap calculated through the MP2/cc-pVDZ method using Gaussian09 were not significantly different to distinguish between the cofacial and T-shape structures. Only when the experimentally obtained beta(HRS) and the depolarization ratios, D and D', were matched with the theoretically computed values from single and double configuration interaction (SDCI) calculations performed using the ZINDO-SCRF technique, we concluded that the room temperature equilibrium structure of the complex is cofacial. This is in sharp contrast to an earlier theoretical prediction of the T-shape structure of the complex.