Solvent-Dependent Conformation of Amylose Tris(Phenylcarbamate) as Deduced from Scattering and Viscosity Data

The z-average mean-square radius of gyration 〈S^2〉_z, the particle scattering function P(k), the second virial coefficient, and the intrinsic viscosity [η] have been determined for amylose tris(phenylcarbamate) (ATPC) in methyl acetate (MEA) at 25°C, in ethyl acetate (EA) at 33°C, and in 4-methyl-2-pentanone (MIBK) at 25°C by light and small-angle X-ray scattering and viscometry as functions of the weight-average molecular weight in a range from 2 × 10^4 to 3 × 10^6. The first two solvents attain the theta state, whereas the last one is a good solvent for the amylose derivative. Analysis of the 〈S^2〉_z, P(k), and [η] data based on the wormlike chain yields h (the contour length or helix pitch per repeating unit) = 0.37 ± 0.02 and λ^ (the Kuhn segment length) = 15 ± 2 nm in MEA, h = 0.39 ± 0.02 and λ^ = 17 ± 2 nm in EA, and h = 0.42 ± 0.02 nm and λ^ = 24 ± 2 nm in MIBK. These h values, comparable with the helix pitches (0.37–0.40 nm) per residue of amylose triesters in the crystalline state, are somewhat larger than the previously determined h of 0.33 ± 0.02 nm for ATPC in 1,4-dioxane and 2-ethoxyethanol, in which intramolecular hydrogen bonds are formed between the C[DOUBLE BOND]O and NH groups of the neighbor repeating units. The slightly extended helices of ATPC in the ketone and ester solvents are most likely due to the replacement of those hydrogen bonds by intermolecular hydrogen bonds between the NH groups of the polymer and the carbonyl groups of the solvent.This is the peer reviewed version of the following article: Taichi Fujii1, Ken Terao, Maiko Tsuda, Shinichi Kitamura, Takashi Norisuye, “Solvent-dependent conformation of amylose tris(phenylcarbamate) as deduced from scattering and viscosity data”, Biopolymers, Volume 91, Issue 9, pages 729–736, September 2009, which has been published in final form at DOI: 10.1002/bip.21219. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving

Triple minima in free energy of semiflexible polymers

We study the free energy of the worm-like-chain model, in the constant-extension ensemble, as a function of the stiffness for finite chains of length L. We find that the polymer properties obtained in this ensemble are "qualitatively" different from those obtained using constant-force ensembles. In particular we find that as we change the stiffness parameter, the polymer makes a transition from the flexible to the rigid phase and there is an intermediate regime of parameter values where the free energy has three minima and both phases are stable. This leads to interesting features in the force-extension curves.Comment: Published version, 4 pages, 5 figures, revte

Solution Properties of Amylose Tris(Phenylcarbamate) : Local Conformation and Chain Stiffness in 1,4-Dioxane and 2-Ethoxyethanol

Light and small-angle X-ray scattering, sedimentation equilibrium, viscosity, circular dichroism, and infrared absorption measurements have been made on 1,4-dioxane (DIOX) and 2-ethoxyethanol (2EE) solutions of seven amylose tris(phenylcarbamate) samples ranging in molecular weight from 2 x 10^4 to 3 x 10^6. Analyses of gyration radius, scattering function, and intrinsic viscosity data in terms of the wormlike chain model yield Kuhn segment lengths of 22 ± 2 nm and 16 ± 2nm in DIOX and 2EE, respectively, and a contour length per residue of 0.33 ± 0.02 nm in both, showing that the amylose derivative chain has high stiffness and a contour length slightly shorter than the known value 0.37-0.40 nm for amylosetriesters in the crystalline state. These results are consistent with the intramolecular hydrogen bonding between the C=0 and NH groups of the neighbor repeating units detected by infrared absorption and also with the locally regular (or helical) conformation indicated by circular dichroism

Conformational, Dimensional, and Hydrodynamic Properties of Amylose Tris(n-butylcarbamate) in Tetrahydrofuran, Methanol, and Their Mixtures

This document is the unedited Author’s version of a Submitted Work that was subsequently accepted for publication in Macromolecules, copyright © American Chemical Society after peer review. To access the final edited and published work see https://doi.org/10.1021/ma902200z

The recent distribution of lead in the Indian Ocean reflects the impact of regional emissions

Author Posting. © The Author(s), 2014. This is the author's version of the work. It is posted here by permission of National Academy of Sciences for personal use, not for redistribution. The definitive version was published in Proceedings of the National Academy of Sciences of the United States of American 111 (2014): 15328–15331, doi:10.1073/pnas.1417370111Humans have injected lead (Pb) massively into the earth surface environment in a temporally and spatially evolving pattern. A significant fraction is transported by the atmosphere into the surface ocean where we can observe its transport by ocean currents and sinking particles. This study of the Indian Ocean documents high Pb concentrations in the northern and tropical surface waters, and extremely low Pb levels in the deep water. North of 20°S, dissolved Pb concentrations decrease from 42-82 pmol/Kg in surface waters to 1.5-3.3 pmol/Kg in deep waters. South of 20°S, surface water Pb concentrations decrease from 21 pmol/Kg at 31°S to 7 pmol/Kg at 62°S. This surface Pb concentration gradient reflects a southward decrease in anthropogenic Pb emissions. The upper waters of the north and central Indian Ocean have high Pb concentrations resulting from recent regional rapid industrialization and a late phase-out of leaded gasoline, and these concentrations are now higher than currently seen in the central North Pacific and North Atlantic Oceans. The Antarctic sector of the Indian Ocean shows very low concentrations due to limited regional anthropogenic Pb emissions, high scavenging rates, and rapid vertical mixing, but Pb still occurs at higher levels than would have existed centuries ago. Penetration of Pb into the northern and central Indian Ocean thermocline waters is minimized by limited ventilation. Pb concentrations in the deep Indian Ocean are comparable to the other oceans at the same latitude, and deep waters of the central Indian Ocean match the lowest observed oceanic Pb concentrations.Y. Echegoyen thanks the Spanish Ministry of Science and Innovation for a postdoctoral MEC-Fulbright grant. MIT laboratory expenses were supported by a grant from the Singapore National Research Foundation to the SMART-CENSAM project. Sample collection was supported by grants from the Steel Foundation for Environmental Protection Technology and from Grant-in-Aid of Scientific Research, the Ministry of Education, Culture, Sports, Science, and Technology of Japan

Behaviors of dissolved and particulate Co, Ni, Cu, Zn, Cd and Pb during a mesoscale Fe enrichment experiment (SEEDS II) in the western North Pacific

During mesoscale Fe enrichment (SEEDS II) in the western North Pacific ocean, we investigated dissolved and particulate Co, Ni, Cu, Zn, Cd and Pb in seawater from both field observation and shipboard bottle incubation of a natural phytoplankton assemblage with Fea ddition. Before the Fe enrichment, strong correlations between dissolved trace metals (Ni, Zn and Cd) and PO43-, and between particulate trace metals (Ni, Zn and Cd) and chlorophyll-a were obtained, suggesting that biogeochemical cycles mainly control the distributions of Ni, Zn and Cd in the study area. Average concentrations of dissolved Co, Ni, Cu, Zn, Cd and Pb in the surface mixed layer (0–20m) were 70 pM, 4.9, 2.1, 1.6, 0.48 nM and 52 pM, respectively, and those for the particulate species were 1.7 pM, 0.052, 0.094, 0.46, 0.037 nM and 5.2 pM, respectively. After Fe enrichment, chlorophyll-a increased 3 fold (up to 3 mg/L) during developing phases of the bloom (12 days). Mesozooplankton biomass also increased. Particulate Co, Ni, Cu and Cd inside the patch increase in the concentrations, but there were no analytically significant differences between concentrations inside and outside the patch. The bottle incubation with Fe addition (1 nM) showed an increase in chlorophyll-a (8.9 mg/L) and raised the particulate fraction up to 3–45% for all the metals, accompanying changes in Si/P, Zn/P and Cd/P. These results suggest that Fe addition lead to changes in biogeochemical cycling of trace metals. The comparison between the mesoscale Fe enrichment and the bottle incubation experiment suggests that although Fe was a limiting factor for the growth of phytoplankton, the enhanced biomass of mesozooplankton also limited the growth of phytoplankton and the transformation of trace metal speciation during the mesoscale Fe enrichment. Sediment trap data and the elemental ratios taken up by phytoplankton suggest that export loss was another reason that no detectable change in the concentrations of particulate trace metals was observed during the mesoscale Fe enrichment

Applications of Mach-Zehnder Interferometry to Studies on Local Deformation of Polymers Under Photocuring

A Mach‐Zehnder interferometer (MZI) was built and modified to in situ monitor the deformation of polymers during the photocuring process. In this review, the working principle and method of operation of this MZI were explained together with the method of data analysis. As the examples for the utilization of this modified MZI, measurements of the deformation induced by photopolymerization was demonstrated for three different types of samples: homopolymer in the bulk state, miscible polymer blends and phase‐separated polymer blends. Finally, a concluding remark is provided for the usage of MZI in polymer research

Chain dimensions and hydration behavior of collagen model peptides in aqueous solution: [Glycyl-4(R)-hydroxyprolyl-4(R)-hydroxyproline]n, [Glycylprolyl-4(R)-hydroxyproline]n, and some related model peptides

Terao K., Mizuno K., Murashima M., et al. Chain dimensions and hydration behavior of collagen model peptides in aqueous solution: [Glycyl-4(R)-hydroxyprolyl-4(R)-hydroxyproline]n, [Glycylprolyl-4(R)-hydroxyproline]n, and some related model peptides. Macromolecules, 41(19), 7203-7210, September 4, 2008. Copyright © 2008, American Chemical Society. https://doi.org/10.1021/ma800790w