Dependence of the Distribution of Atomic Chain Lengths on a Vicinal Surface on External Parameters

Monte Carlo simulations of chain conformations in a restricted spherical volume at relatively high densities of segments were performed for various numbers of chains, N, and chain lengths (number of segments), L, on a tetrahedral lattice. All chains are randomly end-tethered to the surface of the sphere. A relatively uniform surface density of the tethered ends is guaranteed in our simulations. A simultaneous self-avoiding walk of all chains creates starting conformations for a subsequent equilibration. A modified algorithm similar to that of Siepmann and Frenkel is used for the equilibration of the chain conformations. In this paper, only a geometrical excluded volume effect of segments is considered. Various structural and conformational characteristics, e.g. segment densities gS(r), free end densities gF(r) as functions of the position in the sphere (a distance from the center), distributions of the tethered-to-free end distances, ρTF(rTF), etc. are calculated and their physical meaning is discussed. The model is suitable for studies of chain conformations is swollen cores of multimolecular block copolymer micelles and for interpretation of non-radiative excitation energy migration in polymeric micellar systems.

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Rotationsbarriere der Endgruppen bei Poly- methinoxonolen verschiedener Kettenlänge / Rotation Barrier of the End Groups of Polymethine Oxonols with Different Chain Lengths

Zeitschrift für Naturforschung A ◽

10.1515/zna-1976-0826 ◽

1976 ◽

Vol 31 (8) ◽

pp. 1017-1018 ◽

Cited By ~ 2

Author(s):

H. Oehling ◽

F. Baer

Keyword(s):

Nmr Spectra ◽

Rotation Barrier ◽

Free Enthalpy ◽

Temperature Dependent ◽

Restricted Rotation ◽

H Nmr ◽

Enthalpy Of Activation ◽

End Groups ◽

Electron Contribution ◽

Chain Lengths

Abstract Polymethine oxonols show temperature dependent 1H-NMR-spectra because of restricted rotation of the end groups. The dependence of the value of the corresponding free enthalpy of activation AGt on the length of the poly-methine chain can be explained by the change of the π-electron contribution to ⊿G≠.

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Steady state charge conduction through solution processed liquid crystalline lanthanide bisphthalocyanine films

Journal of Porphyrins and Phthalocyanines ◽

10.1142/s1088424619501918 ◽

2019 ◽

Vol 23 (11n12) ◽

pp. 1603-1615

Author(s):

Chandana Pal ◽

Isabelle Chambrier ◽

Andrew N. Cammidge ◽

A. K. Sharma ◽

Asim K. Ray

Keyword(s):

Metal Ions ◽

Liquid Crystalline ◽

Microscopy Study ◽

Individual Characteristics ◽

Central Metal ◽

Force Microscopy ◽

Atomic Force ◽

Double Decker ◽

Order Of Magnitude ◽

Chain Lengths

In-plane electrical characteristics of non-peripherally octyl(C[Formula: see text]H[Formula: see text]- and hexyl(C[Formula: see text]H[Formula: see text]-substituted liquid crystalline (LC) double decker lanthanide bisphthalocyanine (LnPc[Formula: see text] complexes with central metal ions lutetium (Lu), and gadolinium (Gd) have been measured in thin film formulations on interdigitated gold (Au) electrodes for the applied voltage ([Formula: see text] range of [Formula: see text]. The conduction mechanism is found to be Ohmic within the bias of [Formula: see text] while the bulk limited Poole–Frenkel mechanism is responsible for the higher bias. The compounds show individual characteristics depending on the central metal ions, substituent chain lengths and their mesophases. Values of 67.55 [Formula: see text]cm[Formula: see text] and 42.31 [Formula: see text]cm[Formula: see text] have been obtained for room temperature in-plane Ohmic conductivity of as-deposited octyl lutetium (C[Formula: see text]LuPc[Formula: see text] and hexyl gadolinium (C[Formula: see text]GdPc[Formula: see text] films, respectively while C[Formula: see text]GdPc[Formula: see text] films exhibit nearly two orders of magnitude smaller conductivity. On annealing at 80[Formula: see text]C, Ohmic conductivities of C[Formula: see text]LuPc[Formula: see text] and C[Formula: see text]GdPc[Formula: see text] are found to have increased but the conductivity of C[Formula: see text]GdPc[Formula: see text] decreased by more than one order of magnitude to 1.5 [Formula: see text]cm[Formula: see text]. For physical interpretation of the charge transport behavior of these three molecules, their UV-vis optical absorption spectra in the solution and in as-deposited and annealed solid phases and atomic force microscopy study have been performed. It is believed that both orientation and positional reorganizations are responsible, depending upon the size of the central ion and side chain length.

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Immuno-compatibility of desaminotyrosine and desaminotyrosyl tyrosine functionalized star-shaped oligo(ethylene glycol)s with different molecular weights

MRS Proceedings ◽

10.1557/opl.2015.327 ◽

2015 ◽

Vol 1718 ◽

pp. 97-102 ◽

Cited By ~ 1

Author(s):

Toralf Roch ◽

Konstanze K. Julich-Gruner ◽

Axel T. Neffe ◽

Nan Ma ◽

Andreas Lendlein

Keyword(s):

Aqueous Solution ◽

Ethylene Glycol ◽

Average Molecular Weight ◽

Molecular Weights ◽

Immunological Effects ◽

Microbial Products ◽

Low Levels ◽

Chain Lengths ◽

Immunological Evaluation

ABSTRACTPolymer-based therapeutic strategies require biomaterials with properties and functions tailored to the demands of specific applications leading to an increasing number of newly designed polymers. For the evaluation of those new materials, comprehensive biocompatibility studies including cyto-, tissue-, and immunocompatibility are essential. Recently, it could be demonstrated that star-shaped amino oligo(ethylene glycol)s (sOEG) with a number average molecular weight of 5 kDa and functionalized with the phenol-derived moieties desaminotyrosine (DAT) or desaminotyrosyl tyrosine (DATT) behave in aqueous solution like surfactants without inducing a substantial cytotoxicity, which may qualify them as solubilizer for hydrophobic drugs in aqueous solution. However, for biomedical applications the polymer solutions need to be free of immunogenic contaminations, which could result from inadequate laboratory environment or contaminated starting material. Furthermore, the materials should not induce uncontrolled or undesired immunological effects arising from material intrinsic properties. Therefore, a comprehensive immunological evaluation as perquisite for application of each biomaterial batch is required. This study investigated the immunological properties of sOEG-DAT(T) solutions, which were prepared using sOEG with number average molecular weights of 5 kDa, 10 kDa, and 20 kDa allowing analyzing the influence of the sOEG chain lengths on innate immune mechanisms. A macrophage-based assay was used to first demonstrate that all DAT(T)-sOEG solutions are free of endotoxins and other microbial contaminations such as fungal products. In the next step, the capacity of the different DAT(T)-functionalized sOEG solutions to induce cytokine secretion and generation of reactive oxygen species (ROS) was investigated using whole human blood. It was observed that low levels of the pro-inflammatory cytokines interleukin(IL)-1β and IL-6 were detected for all sOEG solutions but only when used at concentrations above 250 µg·mL-1. Furthermore, only the 20 kDa sOEG-DAT induced low amounts of ROS-producing monocytes. Conclusively, the data indicate that the materials were not contaminated with microbial products and do not induce substantial immunological adverse effectsin vitro,which is a prerequisite for future biological applications.

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The Effect of Surfactant-Modified Montmorillonite on the Cross-Linking Efficiency of Polysiloxanes

Materials ◽

10.3390/ma14102623 ◽

2021 ◽

Vol 14 (10) ◽

pp. 2623

Author(s):

Monika Wójcik-Bania ◽

Jakub Matusik

Keyword(s):

Total Pore Volume ◽

Cross Linking ◽

X Ray Diffraction ◽

X Ray ◽

Transmission Electron ◽

The Cross ◽

Chain Lengths ◽

First Time ◽

Substituent Influence ◽

Benzyl Substituent

Polymer–clay mineral composites are an important class of materials with various applications in the industry. Despite interesting properties of polysiloxanes, such matrices were rarely used in combination with clay minerals. Thus, for the first time, a systematic study was designed to investigate the cross-linking efficiency of polysiloxane networks in the presence of 2 wt % of organo-montmorillonite. Montmorillonite (Mt) was intercalated with six quaternary ammonium salts of the cation structure [(CH3)2R’NR]+, where R = C12, C14, C16, and R’ = methyl or benzyl substituent. The intercalation efficiency was examined by X-ray diffraction, CHN elemental analysis, and Fourier transform infrared (FTIR) spectroscopy. Textural studies have shown that the application of freezing in liquid nitrogen and freeze-drying after the intercalation increases the specific surface area and the total pore volume of organo-Mt. The polymer matrix was a poly(methylhydrosiloxane) cross-linked with two linear vinylsiloxanes of different siloxane chain lengths between end functional groups. X-ray diffraction and transmission electron microscopy studies have shown that the increase in d-spacing of organo-Mt and the benzyl substituent influence the degree of nanofillers’ exfoliation in the nanocomposites. The increase in the degree of organo-Mt exfoliation reduces the efficiency of hydrosilylation reaction monitored by FTIR. This was due to physical hindrance induced by exfoliated Mt particles.

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Molecular Description of Grafted Supramolecular Assemblies on Gold Surfaces: Effect of Grafting Points and Chain Lengths

ACS Omega ◽

10.1021/acsomega.0c01453 ◽

2020 ◽

Vol 5 (27) ◽

pp. 16628-16634

Author(s):

Ludovic Garnier ◽

Christine Bonal ◽

Patrice Malfreyt

Keyword(s):

Supramolecular Assemblies ◽

Gold Surfaces ◽

Chain Lengths ◽

Molecular Description

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Anaerobic 1-Alkene Metabolism by the Alkane- and Alkene-Degrading Sulfate Reducer Desulfatibacillum aliphaticivorans Strain CV2803T

Applied and Environmental Microbiology ◽

10.1128/aem.01097-07 ◽

2007 ◽

Vol 73 (24) ◽

pp. 7882-7890 ◽

Cited By ~ 25

Author(s):

Vincent Grossi ◽

Cristiana Cravo-Laureau ◽

Alain Méou ◽

Danielle Raphel ◽

Frédéric Garzino ◽

...

Keyword(s):

Fatty Acids ◽

Inorganic Carbon ◽

Direct Evidence ◽

Gas Chromatography Mass Spectrometry ◽

Sulfate Reducing ◽

Branched Fatty Acids ◽

Initial Activation ◽

Fumarate Addition ◽

Chain Lengths ◽

Methyl Branched Fatty Acids

ABSTRACT The alkane- and alkene-degrading, marine sulfate-reducing bacterium Desulfatibacillum aliphaticivorans strain CV2803T, known to oxidize n-alkanes anaerobically by fumarate addition at C-2, was investigated for its 1-alkene metabolism. The total cellular fatty acids of this strain were predominantly C-(even number) (C-even) when it was grown on C-even 1-alkenes and predominantly C-(odd number) (C-odd) when it was grown on C-odd 1-alkenes. Detailed analyses of those fatty acids by gas chromatography-mass spectrometry after 6- to 10-week incubations allowed the identification of saturated 2- and 4-ethyl-, 2- and 4-methyl-, and monounsaturated 4-methyl-branched fatty acids with chain lengths that correlated with those of the 1-alkene. The growth of D. aliphaticivorans on (per)deuterated 1-alkenes provided direct evidence of the anaerobic transformation of these alkenes into the corresponding 1-alcohols and into linear as well as 10- and 4-methyl-branched fatty acids. Experiments performed with [13C]bicarbonate indicated that the initial activation of 1-alkene by the addition of inorganic carbon does not occur. These results demonstrate that D. aliphaticivorans metabolizes 1-alkene by the oxidation of the double bond at C-1 and by the subterminal addition of organic carbon at both ends of the molecule [C-2 and C-(ω-1)]. The detection of ethyl-branched fatty acids from unlabeled 1-alkenes further suggests that carbon addition also occurs at C-3. Alkylsuccinates were not observed as potential initial intermediates in alkene metabolism. Based on our observations, the first pathways for anaerobic 1-alkene metabolism in an anaerobic bacterium are proposed. Those pathways indicate that diverse initial reactions of 1-alkene activation can occur simultaneously in the same strain of sulfate-reducing bacterium.

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PenA, a penicillin-binding protein-type thioesterase specialized for small peptide cyclization

Journal of Industrial Microbiology & Biotechnology ◽

10.1093/jimb/kuab023 ◽

2021 ◽

Author(s):

Kenichi Matsuda ◽

Kei Fujita ◽

Toshiyuki Wakimoto

Keyword(s):

Enzymatic Activity ◽

Computational Model ◽

Binding Protein ◽

Penicillin Binding Protein ◽

Small Peptide ◽

Peptide Cyclization ◽

Chain Lengths ◽

Non Ribosomal Peptides

Abstract Penicillin binding protein-type thioesterases (PBP-type TEs) are a recently identified group of peptide cyclases that catalyze head-to-tail macrolactamization of non-ribosomal peptides. PenA, a new member of this group, is involved in the biosyntheses of cyclic pentapeptides. In this study, we demonstrated the enzymatic activity of PenA in vitro, and analyzed its substrate scope with a series of synthetic substrates. A comparison of the reaction profiles between PenA and SurE, a representative PBP-type TE, showed that PenA is more specialized for small peptide cyclization. A computational model provided a possible structural rationale for the altered specificity for substrate chain lengths.

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