Self-assembly of a designed amyloid peptide containing the functional thienylalanine unit

The self-assembly of a peptide based on a sequence from the amyloid beta peptide but incorporating the non-natural amino acid beta-2-thienylalanine (2-Thi) has been investigated in aqueous and methanol solutions. The peptide AAKLVFF was used as a design motif, replacing the phenylalanine residues (F) with 2-Thi units to yield (2-Thi)(2-Thi)VLKAA. The 2-Thi residues are expected to confer interesting electronic properties due to charge delocalization and pi-stacking. The peptide is shown to form beta-sheet-rich amyloid fibrils with a twisted morphology, in both water and methanol solutions at sufficiently high concentration. The formation of a self-assembling hydrogel is observed at high concentration. Detailed molecular modeling using molecular dynamics methods was performed using NOE constraints provided by 2D-NMR experiments. The conformational and charge properties of 2-Thi were modeled using quantum mechanical methods, and found to be similar to those previously reported for the beta-3-thienylalanine analogue. The molecular dynamics simulations reveal well-defined folded structures (turn-like) in dilute aqueous solution, driven by self-assembly of the hydrophobic aromatic units, with charged lysine groups exposed to water.

Fulvalene cyclopentadienyl titanium and zirconium(III) and -(IV) complexes. X-Ray crystal structure of [{Ti(η5-C5H5) Cl}2 (μ-O)(μ-η5-η5-C10H8)]

The reaction of the fulvalene titanium(III) hydride [{Ti(η5-C5H5)(μ-H)}2(μ-η5-η5-C10H8)] (1) with chlorine leads to [{Ti(η5-C5H5)(μ-Cl)}2(μ-η5-η5-C10H8)] (3) and [{Ti(η5-C5H5)Cl2}2(μ-η5-η5-C10H8)] (4). The reaction of 3 with azobenzene, in wet toluene, gives [{Ti(η5-C5H5)Cl}2(μ-O)(μ-η5-η5-C10H8)] (5) and 1,2-diphenyl hydrazine. The alkylation of 4 and the analogous zirconium complex [{Zr(η5-C5H55)Cl2}2(μ-η5-η5-C10H8)] (2) with LiCH2SiMe3 or LiCH3 permits isolation of the tetraalkyl derivatives [{M(η5-C5H5)(CH2SiMe3)2}2(μ-η5-η5-C10H8)] (M  Ti (6); Zr (8)) and [{Ti(η5-C5H5)(CH3)2}2(μ-η5-η5C10H8)] (7). All the new fulvalene compounds were characterized by IR, and 1H and 13C NMR spectroscope, and mass spectra and 5 by X-ray diffraction. The structure of 5 is very similar to that of the comparable TiIV compound [{Ti(η5-C5H5)2Cl}2(μ-O)] except for the smaller TiOTi angle (159.4° against 173.81°) and a significant deviation from linearity.

Metalloporphyrin anion sensors: the effect of the metal centre on the anion binding properties of amide-functionalised and tetraphenyl metalloporphyrins

This article describes the synthesis and anion binding properties of a series of ‘picket fence’ metalloporphyrin complexes, within which the metal centre is systematically varied. The porphyrin structure contains four amide bonds and is the same for each metal. The anion binding properties of these receptors are further contrasted with those of their tetraphenylporphyrin congeners to elucidate both the effect of the metal centre and the influence of the amide groups on the anion recognition process. Anion binding was demonstrated using UV/visible and 1H NMR spectroscopies, electrochemistry and luminescence. The metal centre was found to be highly influential in the strength and selectivity of binding; for example, the cadmium and mercury complexes exhibited far greater affinities for anions than the zinc complexes in competitive solvents such as DMSO. The amide functionalities were found to enhance the anion binding process.

Synthesis of thiolated and acrylated nanoparticles using thiol-ene click chemistry: towards novel mucoadhesive materials for drug delivery

Thiol- and acrylate-functionalized nanoparticles have been synthesized from pentaerythritol tetrakis(3-mercapto-propionate) and pentaerythritol tetraacrylate using thiol-ene click chemistry. Using Raman and 1H NMR spectroscopy as well as Ellman's assay, it was demonstrated that excess pentaerythritol tetraacrylate in the feed mixture led to nanoparticles with free acrylate groups on their surface, whereas nanoparticles with thiolated surfaces could be synthesized using feed mixtures with excess pentaerythritol tetrakis(3-mercapto-propionate). The possibility of fluorescent labelling of thiolated nanoparticles has been demonstrated through their reaction with fluorescein-5-maleimide. The thiolated nanoparticles were found to be mucoadhesive and exhibited retention on mucosal surface of porcine urinary bladder.

Synthesis of novel hyperbranched polymers featuring oxazoline linear units and their application in fast-drying solvent-borne coating formulations

Novel acid-terminated hyperbranched polymers (HBPs) containing adipic acid and oxazoline monomers derived from oleic and linoleic acid have been synthesized via a bulk polymerization procedure. Branching was achieved as a consequence of an acid-catalyzed opening of the oxazoline ring to produce a trifunctional monomer in situ which delivered branching levels of >45% as determined by 1H and 13C NMR spectroscopy. The HBPs were soluble in common solvents, such as CHCl3, acetone, tetrahydrofuran, dimethylformamide, and dimethyl sulfoxide and were further functionalized by addition of citronellol to afford white-spirit soluble materials that could be used in coating formulations. During end group modification, a reduction in branching levels of the HBPs (down to 12–24%) was observed, predominantly on account of oxazoline ring reformation and trans-esterification processes under the reaction conditions used. In comparison to commercial alkyd resin paint coatings, formulations of the citronellol-functionalized hyperbranched materials blended with a commercial alkyd resin exhibited dramatic decreases of the blend viscosity when the HBP content was increased. The curing characteristics of the HBP/alkyd blend formulations were studied by dynamic mechanical analysis which revealed that the new coatings cured more quickly and produced tougher materials than otherwise identical coatings prepared from only the commercial alkyd resins.

Bunodosine 391: An Analgesic Acylamino Acid from the Venom of the Sea Anemone Bunodosoma cangicum

A new acylamino acid, bunodosine 391 (BDS 391), was isolated from the venom of the sea anemone Bunodosoma cangicum. The structure was elucidated by spectroscopic analyses (2D NMR, ESIMS/MS) and verified by its synthesis. Intraplantar injection of BDS 391 into the hind paw of a rat induced a potent analgesic effect. This effect was not altered by naloxone (an opioid receptor antagonist), but was completely reversed by methysergide (a serotonin receptor antagonist), indicating that the effect is mediated by activation of serotonin receptors:

Evaluation of a bounded high order upwind scheme for 3D incompressible free surface flow computations

fit the context of normalized variable formulation (NVF) of Leonard and total variation diminishing (TVD) constraints of Harten. this paper presents an extension of it previous work by the authors for solving unsteady incompressible flow problems. The main contributions of the paper are threefold. First, it presents the results of the development and implementation of a bounded high order upwind adaptative QUICKEST scheme in the 3D robust code (Freeflow), for the numerical solution of the full incompressible Navier-Stokes equations. Second, it reports numerical simulation results for 1D hock tube problem, 2D impinging jet and 2D/3D broken clam flows. Furthermore, these results are compared with existing analytical and experimental data. And third, it presents the application of the numerical method for solving 3D free surface flow problems. (C) 2007 IMACS. Published by Elsevier B.V. All rights reserved,

Synthesis and structural characterization of a new polymeric zinc(II) complex with thiophene-2-carboxylic acid

A new polymeric zinc(II) complex with thiophene-2-carboxylic acid (-tpc) of composition [Zn2(C20H12O8S4)]n was obtained and structurally characterized by X-ray diffraction, thermal analysis, nuclear magnetic resonance (NMR), and infrared spectroscopies. Upfield shift in the 1H-NMR spectrum is explained by the crystalline structure, which shows the thiophene rings overlapping each other in parallel pairs. The compound crystallizes in the monoclinic system, space group P21/c, with a = 9.7074(4) angstrom, b = 13.5227(3) angstrom, c = 18.9735(7) angstrom, = 95.797(10)degrees, and Z = 4. Three -tpc groups bridge between two Zn(II) ions through oxygens and the fourth one bridges between one of these ions and the third one, symmetry related by a twofold screw axis. This arrangement gives rise to infinite chains along the crystallographic a direction. The metal atoms display an approximate tetrahedral configuration. The complex is insoluble in water, ethanol, and acetone, but soluble in dimethyl sulfoxide.

Withanolides from Aureliana fasciculata var. fasciculata

In the first phytochemical study of the Aureliana genus (Solanaceae), two new withanolides, 1 and 2, together with two known sterols, were isolated from the MeOH extract of the leaves of Aureliana fasciculata var. fasciculata. The structures were established as (4S,22R)-16 alpha-acetoxy-5 beta,6 beta-epoxy-4 beta,17 alpha-dihydroxy-1-oxowitha-2,24-dienolide (aurelianolide A) and (4S,22R)-16 alpha-acetoxy-4 beta,17 alpha-dihydroxy-1-oxowitha-2,5,24-trienolide (aurelianolide B). The new compounds possessed the unusual 16 alpha,17 alpha-dioxygenated group and were fully characterized by spectroscopic techniques, including (1)H- and (13)C-NMR (DEPT), as well as 2D-NMR (HMBC, HMQC, (1)H, (1)H-COSY, NOESY) experiments, and HR-MS.

Synthesis and structure of new oligomethylene-bridged double ladders. How far can the layers be separated?

The synthesis of the α,ω-bis[dichloro(trimethylsilylmethyl)stannyl]alkanes, (Me₃SiCH₂)C1₂Sn(CH₂)_nSnCl₂(CH₂SiMe₃) (13, n=5; 14, n=6; 15, n=7; 16, n=8; 17, n=10; 18, n=12) and the corresponding oligomethylene-bridged diorganotin oxides [(Me₃SiCH₂)(O)Sn(CH₂)_nSn(O)(CH₂SiMe₃)]_m (19, n=5; 20, n=6; 21, n=7; 22, n=8; 23, n=10; 24; n=12) is reported. The reaction of the diorganodichlorostannanes 13–18 with the corresponding diorganotin oxides 19–24 provided the spacer-bridged tetraorganodistannoxanes {[(Me₃SiCH₂)ClSn(CH₂)_nSnCl(CH₂SiMe₃)]O}₄ (25, n=5; 26, n=6; 27, n=7; 28, n=8; 29, n=10; 30, n=12). Compounds 13–30 have been identified by elemental analyses and multinuclear NMR spectroscopy. Compounds 25, 27, 29 and 30 have also been characterised by single crystal X-ray diffraction analysis and electrospray mass spectrometry. For the latter the essential double ladder motif is maintained for all n in the solid state, but subtle changes in alignment of the ladder planes occur. Separation between the two layers of the double ladder ranges from approx. 8.7  Å (for 25, n=5) to approx. 15 Å (for 30, n=12). In solution there is some dissociation of the double ladders into the corresponding dimers. The degree of dissociation is favoured by increasing oligomethylene chain length n.

Evaluation of selective growth in a Fe-2.8% Si single crystal using Rodrigues-Frank space

A Fe-2.8%Si single crystal was scratched in order to randomise the texture in the neighbourhood of the notch. Annealing resulted in recrystallization and grain growth starting from the deformed zone. Misorientations between the single crystal matrix and the grown grains were gathered and were studied in order to investigate the possibility for selective growth based on a specific misorientation. However, instead of studying the misorientation angle or axis profiles separately in a 1D or 2D projection a full misorientation analysis was carried out in the 3-dimensional Rodrigues-Frank misorientation space, which offers an unambiguous interpretation of the data because no features are hidden or masked by a projection. It is concluded that the selective growth phenomenon following the <110>26.5deg misorientation relationship is strongly supported by the gathered orientation data, after appropriately normalizing these data with respect to a random misorientation distribution.

Acylmethyl(aryl)tellurium(IV,II) derivatives : intramolecular secondary bonding and steric rigidity

Electrophilic substitution of acylmethanes (methyl ketones), RCOCH3 (R = i-Pr, 1; Et, 2; Me, 3) with aryltellurium trichlorides, ArTeCl3 (Ar = 1-C10H7, Np, A; 2,4,6-Me3C6H2, Mes, B; 4-MeOC6H4, Anisyl, C) under mild conditions affords the corresponding acylmethyl(aryl)tellurium dichlorides (RCOCH2)ArTeCl2. Reduction of the dichlorides, gives tellurides, (i-PrCOCH2)ArTe, 1A–1C, which give the corresponding dihalides, (i-PrCOCH2)ArTeX2 (X = Cl, 1Aa–1Ca; Br, 1Ab–1Cb; I, 1Ac–1Cc) when reacted in situ with SO2Cl2, Br2 or I2. The unsymmetric tellurides are labile towards disproportionation and attempts to obtain them lead to the isolation of Ar2Te2 except in the case of (i-PrCOCH2)MesTe ( 1B), which represents an interesting example of a kinetically stable aryl(alkyl)telluride. All the dihalomesityltellurium(IV) derivatives show separate 1H and 13C NMR signals for the ortho methyls irrespective of the sizes of R and X ligands. The telluride, 1B with free rotation about Te–C(mesityl) bond shows, like the unsymmetric diorganotellurium(IV) dihalides, only one 125Te NMR signal. The 1,4-chelating behavior of the acyl ligand among diorganotellurium(IV) compounds is inferred from the X-ray diffraction data for 1Aa, 1Ac, 1Ba, 1Bb, 1Ca and 1Cc which are indicative of the presence of intramolecular TeO secondary bonding interactions (SBIs) at least in the solid state. As a consequence, steric repulsion in case of the mesityltellurium(IV) derivatives, 1Ba and 1Bb, reaches the threshold so as to cause loss of two-fold rotational symmetry of the mesityl group about the Te–C(mesityl) bond axis. Intermolecular C–HO H-bonding interactions appears to stabilize such an orientation of the aryl ligand at least in the solid state.

Studies of hypervalent organotin complexes and organotin clusters

(119)Sn, (31)P and (13)C variable temperature NMR spectroscopies have been used to examine the effective coordination spheres in solution of a series of hypervalent organotin(IV) dithiolate compounds RnSnXm(S-S)4-n-m where R = Ph, Me, nBu, tBu; X = Cl, Br; (S-S) = S2CNR'2, S2COR', S2P(OR')2 (R' = Me, Et, iPr) and n = 1, 2, 3; m = 0,1,2. Stereochemical nonrigidity is a common phenomenon found for these hypervalent compounds. On the basis of heteronuclear NMR data and X-ray crystallographic data, dynamic behaviors of these hypervalent compounds have been established. The system of hypervalent organotin(IV) fluoride complexes has also been investigated by variable temperature heteronuclear NMR techniques. A series of monomeric pentacoordinate complexes [RnSnC1mF5-n-m]-(R = Ph, Me, nBu, tBu; n = 2, 3; m - 0, 1, 2, 3) and dimeric complexes [(Me3SnX)F(Me3SnX')]- (X = F, Cl; X' = F, Cl) and hexacoordinate complexes [RnSnClmF6-n.m]2- (R = Ph, Me, nBu; n = 1, 2; m = (X 1, 2, 3,4) are identified in solution. The fluoride is of higer affinite to tin than the chloride. The stereochemistry and dynamic behavior of these complexes in solution has been studied. Fluoride ion may induce phenyl group disproportionation of phenyhin(IV) compounds. It is also found that in pentacoordinate diorganotin complexes, such as [Ph2SnCl2F]- and [Ph2SnClF2]- fluorine can be less apicophilic than chlorine. Studies of stereochemistry and dynamic behavior of bi-functional Lewis acid bis(haloorganosiannes) have also been carried out. The bis(haloorganostannes) exhibit strong chelate ability towards halide, with high selectivity on fluoride, forming heterocyclic chelating rings, the stability of which depend on the ring size. In further exploration of the Lewis acidity of organotin(IV) halides, complexation of organotin(IV) halides with bis(tertiary phosphinc) ligands has been studied by 119Sn and 31P NMR spectroscopy and X-ray crystallography. The phenyl group disproportionation is often observed in the complexation reaction. Furthermore, organotin(IV) clusters such as [(RSn)12O14(OH)6]Cl2-2H2O (R = iPr, nBu) have been successfully prepared by base hydrolysis of RSnCl3. These clusters contain 12 tin atoms in one molecule and the cores of the clusters are dications. Other organotin clusters such as [nBuSn(O)O2CCH3]6 and [(nBuSn(OH)O2PPh2)3][O2PPh2) are readily formed by reaction of the 12-tin-atom cluster with an appropriate acid. The reactivity of and interconversion between organotin(FV) clusters have also been studied.

Protic ionic liquids based on the dimeric and oligomeric anions: [(AcO)xHx−1]−

We describe a fluidity and conductivity study as a function of composition in N-methylpyrrolidine–acetic acid mixtures. The simple 1:1 acid–base mixture appears to form an ionic liquid, but its degree of ionicity is quite low and such liquids are better thought of as poorly dissociated mixtures of acid and base. The composition consisting of 3 moles acetic acid and 1 mole N-methylpyrrolidine is shown to form the highest ionicity mixture in this binary due to the presence of oligomeric anionic species [(AcO)_xH_x−1]− stabilised by hydrogen bonds. These oligomeric species, being weaker bases than the acetate anion, shift the proton transfer equilibrium towards formation of ionic species, thus generating a higher degree of ionicity than is present at the 1:1 composition. A Walden plot analysis, thermogravimetric behaviour and proton NMR data, as well as ab initio calculations of the oligomeric species, all support this conclusion.

A unified 2D-3D video scene change detection framework for mobile camera platforms

In this paper, we present a novel scene change detection algorithm for mobile camera platforms. Our approach integrates sparse 3D scene background modelling and dense 2D image background modelling into a unified framework. The 3D scene background modelling identifies inconsistent clusters over time in a set of 3D cloud points as the scene changes. The 2D image background modelling further confirms the scene changes by finding inconsistent appearances in a set of aligned images using the classical MRF background subtraction technique. We evaluate the performance of our proposed system on a number of challenging video datasets obtained from a camera placed on a moving vehicle and the experiments show that our proposed method outperforms previous works in scene change detection, which suggested the feasibility of our approach.