Diffusion on a self-assembled monolayer: molecular modeling of a bound + mobile lubricant

The diffusion of tricresyl phosphate molecules on an octadecyltrichlorosilane self-assembled monolayer (SAM) was characterized using molecular dynamics simulations. The simulations predict that when placed on the top of a close-packed SAM, the molecules remain mobile on the surface with an isotropic diffusion activation energy of approximately 9 kJ/mol. In contrast, an anisotropic barrier that results from chain tilt within the SAM is predicted for diffusion into a defect created by reducing the alkane chain length within a cylinderical region of the surface. Once in the defect, the molecules become trapped by embedding part of the molecule into the side of the SAM.     

The polymorphism of poly(vinylidene fluoride). I. The effect of head-to-head structure

The phenomenon of polymorphism in poly(vinylidene fluoride) has been observed recently by several authors. It has also been reported that high-resolution NMR measurements demonstrate the presence in this polymer of head-to-head linkages, resulting from the “backward” addition of from 5-6% of the monomer units. Since the van der Waals radii of fluorine (1.35 Å) and hydrogen (1.1-1.2 Å) are similar, the cocrystallization in a polymer chain of units that differ only by the substitution of fluorine atoms for hydrogen atoms is not unexpected. The two polymorphic forms of poly(vinylidene fluoride), examined in this investigation, have different chain conformations. Chains in phase I have a planar zigzag conformation, while chains in phase II are assumed to exhibit a 2₁ helical conformation. The incorporation into the polymer chain of small amounts of tetrafluoroethylene or trifluoroethylene comonomer favored the crystallization of phase I. This is in accord with the relative abilities, deduced from consideration of atomic size, of these comonomers to cocrystallize with vinylidene fluoride units in the two indicated chain conformations of the polymer. Since tetrafluoroethylene units are present in the head-to-head structure in the homopolymer, it can be concluded that the elimination of the head-to-head structure will eliminate or restrict crystallization in phase I.     

Isomerism due to the rotation of an alkyl side-chain attached to a heterocyclic ring: Crystal and molecular structure of two forms of 6-nitro-2,4-bis(1′,1′,2′-trichloropropyl)-1,3-benzdioxin

Compound I crystallizes in the space groupP2₁/c withZ=4,a=5.889(5),b=30.755(10),c=10.815(3) Å,=92.95(6)°. Compound II crystallizes in the space groupP2₁/n withZ=4,a=10.235(2),b=10.144(1),c=18.346(2) Å,=92.00(1)°. The structures were solved by direct methods and refined by full-matrix least squares, from room-temperature data obtained with an Enraf-Nonius CAD4 diffractometer, to conventionalR factors of 0.041 for I and 0.048 for II.In both isomers the dioxin ring has an approximate envelope conformation with a pseudoequatorial –CC1₂·CHCl·CH₃ group in the 2-position and a pseudoaxial –CCl₂·CHCl·CH₃ group in the 4-position. The molecular structures of I and II differ in that the group at the 2-position is rotated by about 120° in one isomer relative to its position in the other. Both compounds have packing patterns with a wave motif. In II there are interactions of the –NO₂ group with other atoms both between molecules in the same wave and also between molecules in adjacent waves. In I the interactions of the –NO₂ group with other atoms are in the same wave only with adjacent waves being packed together by van der Waals forces alone.     

The N,N-diacetylaminobenzene group in the structure of 6-methyl-8-N,N-diacetylamino-2,4-bis(trichloromethyl)-1,3-benzdioxin

Crystals of 6-methyl-8-N,N-diacetylamino-2,4-bis(trichloromethyl)-1,3-benzdioxin are triclinic, P¯1,Z=2,a=9.586(3),b=9.914(2),c=12.308(5) Å,=67.19(3),=71.95(3), =74.14(2)°. The structure was solved by direct methods, from data collected at room temperature on an Enraf-Nonius CAD4 difFractometer, and refined by least squares to a finalR value of 0.039 using 3038 reflections. The heterocyclic ring has an envelope conformation. Of thecis-CCl₃ groups one CC1₃ group is pseudoequatorial while the –(C_Ar·C)CCl₃ group is pseudoaxial. (C_Ar)O-C 1.405(4); (C_Ar·O)C-O 1.387(4) Å; C_Ar-C(C_ax)-0 112.3(3); C(C_ax)-O-C(C_eq) 116.1(2)°; (C_Ar)O-C-O-C(C_Ar)58.2(3)°. The configuration of the diacetylamino group (DAA) issyn-anti. The -systems of the DAA and of the aromatic ring are approximately orthogonal, the deviations from orthogonality probably being caused by an intermolecular bifurcated hydrogen bond, each such interaction involving two molecules only, between thesyn O(=C) of the DAA and both hydrogen atoms bonded to the heterocyclic ring in a molecule of the enantiomer. The geometry of the DAA-benzene fragment is compared with those found in the other three published X-ray structures containing this group.     

Crystal and molecular structure of 6-nitro-1,3-benzdioxin: Comparison with the molecular structures of the 2,4-bis(dichloromethyl) and 2,4-bis(trichloromethyl) derivatives

6-Nitro-1,3-benzdioxin is orthorhombic,Pbca,a=7.278(4),b=19.292(3),c=10.978(1) Å,Z=8. The structure was solved by direct methods from data collected at room temperature on an Enraf-Nonius CAD4 diffractometer and refined by least squares to a finalR value of 0.041 using 725 reflections. Some parameters associated with the heterocycle are torsion angle (C_Ar)O-C-O-C(C_Ar) 69.1(4)°; bond lengths C_Ar-O 1.362(3), (C_Ar)O-C 1.434(5), (C_Ar.O)C-O 1.377(5), O-C(C_Ar) 1.431(5), C-C_Ar 1.501(5) Å; bond angles C_Ar-O-C 113.5(3), O-C-O 111.5(3), C-O-C(C_Ar) 110.3(3), O-C-C_Ar 109.9(3)°;H_axH_ax 2.52(5) Å.     

Structure of the α-(allcis) form of 2,4,6-tris(trichloromethyl)-1-oxa-3,5-dithian

The higher-melting (mp 236°C)-isomer of dithioparachloral, i.e.,-2,4,6-tris(trichloromethyl)-1-oxa-3,5-dithian, is orthorhombic,Pnma,a=9.983(2),b=15.318(2),c=10.416(2) Å,V=1592.81 ų,Z=4. The structure was solved by direct methods, from data collected at room temperature on an Enraf-Nonius CAD4 diffractometer, and refined by least-squares to a finalR value of 0.040 using 1017 reflections. The molecule is in the chair conformation with all threecis-CCl₃ groups located pseudoequatorially. Endocyclic parameters are: torsion angles (deg) C-O-C-S 75.1(3), O-C-S-C –63.2(3), C-S-C-S 62.4(3); angles (deg) C-O-C 111.9(2), O-C-S 112.6(3), C-S-C 94.8(2), S-C-S 113.2(1); bond lengths (Å) O-C 1.426(5), C-S 1.824(4), S-C 1.818(3) (quoted in cyclic order).     

Structure and conformation of 6,8-dinitro-2,4-bis(trichloromethyl)-1,3-benzdioxin: X-ray crystallographic determination

6,8-dinitro-2,4-bis(trichloromethyl)-1,3-benzdioxin is monoclinic,P2₁/c,Z=4,a=12.348(2),b=11.575(3),c=12.183(4) Å,=107.48(2)°. The structure was solved by direct methods, from data collected at room temperature on an Enraf-Nonius CAD4 diffractometer, and refined by least-squares to a finalR value of 0.032 using 2192 reflections. The heterocyclic ring is an envelope structure, the dihedral angle between the plane of the aromatic ring and that containing five of the atoms of the heterocycle being 4.98(6)°. One -CCl₃ group is pseudoequatorial while the (Ar-C)CCl₃ group is pseudoaxial. C-C_eq 1.526(3) Å; C-C_ax 1.537(3) Å; C-C(C_ax)-O 112.4(2)°; C(C_ax)-O-C(C_eq) 115.2(2)°.     

Synthesis and Magnetic Properties of Novel Azamacrocyclic LnIII,CuII, FeIII,and SrII Complexes and Conformational Analysis of the Ligands

Hexaalkoxy‐substituted azamacrocyclic metal complexes 1 · MX_n [MX_n = FeCl₃, CuCl₂, SrCl₂, Ln(NO₃)₃; Ln = La, Pr, Eu, Ho, Er] with various chain lengths were prepared by a convergent approach using 1,2‐bisalkoxy‐4,5‐diamines 3 and 4‐alkoxy‐pyridine‐2,6‐dicarbaldehydes 4 as key building blocks for template‐assisted cyclocondensation. Metal complexes 1 · MX_n were considered as potential metallomesogens. However, differential scanning calorimetry and optical polarizing microscopy of 1 · MX_n did not reveal any mesomorphism. The magnetic susceptibility shows deviation from Curie‐like behavior. Due to ligand field effects the effective magnetic moments are a function of the temperature. In order to obtain structural informations on the free ligand 1 , which is synthetically not accessible, theoretical calculations were carried out. For the free azamacrocycle 2a and the free hexamethoxy‐substituted azamacrocycle 1a the IR spectra were computed at the level of density functional theory. A planar and a saddle‐shaped conformation was considered. The IR spectra and especially the dependence of the C=N vibration on the structural parameters and the charge distribution are discussed.     

Discontinuously propagating waves in the bathoferroin-catalyzed Belousov-Zhabotinsky reaction incorporated into a microemulsion

Three new types of discontinuously propagating waves are reported in the bathoferroin-catalyzed Belousov-Zhabotinsky (BZ) reaction dispersed in water-in-oil Aerosol OT microemulsion. Jumping waves (JWs) are typically observed at or above room temperature and develop from the familiar trigger waves. Bubble waves (BWs) typically emerge from trigger or JWs at similar temperatures, while rotating waves (RWs) evolve from JW at higher temperatures (>40 degrees C). All these waves propagate discontinuously in a saltatory fashion. Other characteristic features include a discontinuous front for BW consisting of small concentric waves (bubbles) and lateral rotation of annular RWs. All three types of waves, as well as segmented but continuously propagating waves, can coexist. A simple model that is able to describe both jumping and segmented waves is described.     

The development of an immobilized enzyme reactor containing glyceraldehyde-3-phosphate dehydrogenase from Trypanosoma cruzi: the effect of species' specific differences on the immobilization

Glyceraldehyde-3-phosphate dehydrogenase (GAPDH) plays an important role in the life cycle of the Trypanosoma cruzi, and an immobilized enzyme reactor (IMER) has been developed for use in the on-line screening for GAPDH inhibitors. An IMER containing human GAPDH has been previously reported; however, these conditions produced a T. cruzi GAPDH-IMER with poor activity and stability. The factors affecting the stability of the human and T. cruzi GAPDHs in the immobilization process and the influence of pH and buffer type on the stability and activity of the IMERs have been investigated. The resulting T. cruzi GAPDH-IMER was coupled to an analytical octyl column, which was used to achieve chromatographic separation of NAD(+) from NADH. The production of NADH stimulated by d-glyceraldehyde-3-phosphate was used to investigate the activity and kinetic parameters of the immobilized T. cruzi GAPDH. The Michaelis-Menten constant (K(m)) values determined for d-glyceraldehyde-3-phosphate and NAD(+) were K(m) = 0.5 +/- 0.05 mM and 0.648 +/- 0.08 mM, respectively, which were consistent with the values obtained using the non-immobilized enzyme.