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At least 649 records · Page 36

Elongated galactan side chains mediate cellulose–pectin interactions in engineered Arabidopsis secondary cell walls

SUMMARY The plant secondary cell wall is a thickened matrix of polysaccharides and lignin deposited at the cessation of growth in some cells. It forms the majority of carbon in lignocellulosic biomass, and it is an abundant and renewable source for forage, fiber, materials, fuels, and bioproducts. The complex structure and arrangement of the cell wall polymers mean that the carbon is difficult to access in an economical and sustainable way. One solution is to alter the cell wall polymer structure so that it is more suited to downstream processing. However, it remains difficult to predict what the effects of this engineering will be on the assembly, architecture, and properties of the cell wall. Here, we make use of Arabidopsis plants expressing a suite of genes to increase pectic galactan chain length in the secondary cell wall. Using multi‐dimensional solid‐state nuclear magnetic resonance, we show that increasing galactan chain length enhances pectin–cellulose spatial contacts and increases cellulose crystallinity. We also found that the increased galactan content leads to fewer spatial contacts of cellulose with xyloglucan and the backbone of pectin. Hence, we propose that the elongated galactan side chains compete with xyloglucan and the pectic backbone for cellulose interactions. Due to the galactan topology, this may result in comparatively weak interactions and disrupt the cell wall architecture. Therefore, introduction of this strategy into trees or other bioenergy crops would benefit from cell‐specific expression strategies to avoid negative effects on plant growth.

59 BASIC BIOLOGICAL SCIENCES↗

Solution structure of telomere binding domain of AtTRB2 derived from Arabidopsis thaliana

Highlights: • We have determined solution structure of Myb domain of AtTRB2. • The Myb domain of AtTRB2 is located in the N-terminal region. • The Myb domain of AtTRB2 binds to plant telomeric DNA without fourth helix. • Helix 2 and 3 of the Myb domain of AtTRB2 are involved in DNA recognition. • AtTRB2 is a novel protein distinguished from other known plant TBP. - Abstract: Telomere homeostasis is regulated by telomere-associated proteins, and the Myb domain is well conserved for telomere binding. AtTRB2 is a member of the SMH (Single-Myb-Histone)-like family in Arabidopsis thaliana, having an N-terminal Myb domain, which is responsible for DNA binding. The Myb domain of AtTRB2 contains three α-helices and loops for DNA binding, which is unusual given that other plant telomere-binding proteins have an additional fourth helix that is essential for DNA binding. To understand the structural role for telomeric DNA binding of AtTRB2, we determined the solution structure of the Myb domain of AtTRB2 (AtTRB2{sub 1–64}) using nuclear magnetic resonance (NMR) spectroscopy. In addition, the inter-molecular interaction between AtTRB2{sub 1–64} and telomeric DNA has been characterized by the electrophoretic mobility shift assay (EMSA) and NMR titration analyses for both plant (TTTAGGG)n and human (TTAGGG)n telomere sequences. Data revealed that Trp28, Arg29, and Val47 residues located in Helix 2 and Helix 3 are crucial for DNA binding, which are well conserved among other plant telomere binding proteins. We concluded that although AtTRB2 is devoid of the additional fourth helix in the Myb-extension domain, it is able to bind to plant telomeric repeat sequences as well as human telomeric repeat sequences.

60 APPLIED LIFE SCIENCES↗

Determination of residual monomers resulting from the chemical polymerization process of dental materials

The residual monomer present in post-polymerized dental materials encourages premature degradation of the reconstructed tooth. That is why the residual monomer should be quantified in a simple, fast, accurate and reproducible manner. In our work we propose such an approach for accurate determination of the residual monomer in dental materials which is based on low-field nuclear magnetic resonance (NMR) relaxometry. The results of the NMR approach are compared with those of the high performance liquid chromatography (HPLC) technique. The samples under study contain the main monomers (2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]propane and triethylene glycol dimethacrylate) constituting the liquid phase of most dental materials and an initiator. Two samples were analyzed with different ratios of chemical initiation systems: N,N-dimethyl-p-toluide: benzoyl peroxide (1:2 and 0.7:1.2). The results obtained by both techniques highlight that by reducing the initiator the polymerization process slows down and the amount of residual monomer reduces. This prevents the premature degradation of the dental fillings and consequently the reduction of the biomaterial resistance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Experimental tests of a 263 GHz gyrotron for spectroscopic applications and diagnostics of various media

A 263 GHz continuous-wave (CW) gyrotron was developed at the IAP RAS for future applications as a microwave power source in Dynamic Nuclear Polarization / Nuclear magnetic resonance (DNP/NMR) spectrometers. A new experimental facility with a computerized control was built to test this and subsequent gyrotrons. We obtained the maximum CW power up to 1 kW in the 15 kV/0.4 A operation regime. The power about 10 W, which is sufficient for many spectroscopic applications, was realized in the low current 14 kV/0.02 A regime. The possibility of frequency tuning by variation of the coolant temperature about 4 MHz/1 °C was demonstrated. The spectral width of the gyrotron radiation was about 10{sup −6}.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

{sup 1}H and {sup 19}F spin-lattice relaxation and CH{sub 3} or CF{sub 3} reorientation in molecular solids containing both H and F atoms

The dynamics of methyl (CH{sub 3}) and fluoromethyl (CF{sub 3}) groups in organic molecular (van der Waals) solids can be exploited to survey their local environments. We report solid state {sup 1}H and {sup 19}F spin-lattice relaxation experiments in polycrystalline 3-trifluoromethoxycinnamic acid, along with an X-ray diffraction determination of the molecular and crystal structure, to investigate the intramolecular and intermolecular interactions that determine the properties that characterize the CF{sub 3} reorientation. The molecule is of no particular interest; it simply provides a motionless backbone (on the nuclear magnetic resonance (NMR) time scale) to investigate CF{sub 3} reorientation occurring on the NMR time scale. The effects of {sup 19}F–{sup 19}F and {sup 19}F–{sup 1}H spin-spin dipolar interactions on the complicated nonexponential NMR relaxation provide independent inputs into determining a model for CF{sub 3} reorientation. As such, these experiments provide much more information than when only one spin species (usually {sup 1}H) is present. In Sec. IV, which can be read immediately after the Introduction without reading the rest of the paper, we compare the barrier to CH{sub 3} and CF{sub 3} reorientation in seven organic solids and separate this barrier into intramolecular and intermolecular components.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Microstructural and bulk property changes in hardened cement paste during the first drying process

This paper reports the microstructural changes and resultant bulk physical property changes in hardened cement paste (hcp) during the first desorption process. The microstructural changes and solid-phase changes were evaluated by water vapor sorption, nitrogen sorption, ultrasonic velocity, and {sup 29}Si and {sup 27}Al nuclear magnetic resonance. Strength, Young's modulus, and drying shrinkage were also examined. The first drying process increased the volume of macropores and decreased the volume of mesopores and interlayer spaces. Furthermore, in the first drying process globule clusters were interconnected. During the first desorption, the strength increased for samples cured at 100% to 90% RH, decreased for 90% to 40% RH, and increased again for 40% to 11% RH. This behavior is explained by both microstructural changes in hcp and C–S–H globule densification. The drying shrinkage strains during rapid drying and slow drying were compared and the effects of the microstructural changes and evaporation were separated.

36 MATERIALS SCIENCE↗

Structure-topology-property correlations of sodium phosphosilicate glasses

In this work, we investigate the correlations among structure, topology, and properties in a series of sodium phosphosilicate glasses with [SiO{sub 2}]/[SiO{sub 2} + P{sub 2}O{sub 5}] ranging from 0 to 1. The network structure is characterized by {sup 29}Si and {sup 31}P magic-angle spinning nuclear magnetic resonance and Raman spectroscopy. The results show the formation of six-fold coordinated silicon species in phosphorous-rich glasses. Based on the structural data, we propose a formation mechanism of the six-fold coordinated silicon, which is used to develop a quantitative structural model for predicting the speciation of the network forming units as a function of chemical composition. The structural model is then used to establish a temperature-dependent constraint description of phosphosilicate glass topology that enables prediction of glass transition temperature, liquid fragility, and indentation hardness. The topological constraint model provides insight into structural origin of the mixed network former effect in phosphosilicate glasses.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Obtaining aluminas from the thermal decomposition of their different precursors: An {sup 27}Al MAS NMR and X-ray powder diffraction studies

Graphical abstract: - Highlights: • We synthesized three precursors of alumina from different methods. • The calcination of the precursors generated several alumina polymorphs. • XRD and NMR were used for structural investigation of the polymorphs. • The synthesis route determines the structural and textural properties of the solids. - Abstract: A commercial sample of Boehmite was used as precursor of alumina polymorphs. For comparison, three other precursors were synthesized from different methods. Particularly, the use of excess of urea promoted a very crystalline form of basic aluminum carbonate. The characteristics of the four precursors were investigated by thermal, vibrational and X-ray powder diffraction (XRD) analysis. Additionally, the nuclear magnetic resonance, with magic angle spinning ({sup 27}Al MAS NMR), was used to verify the coordination of aluminum cations. Each precursor was calcined at various temperatures generating alumina polymorphs, which were structurally analyzed by XRD and {sup 27}Al MAS NMR. Due to interest in catalysis supports, special attention was given to the γ-Al{sub 2}O{sub 3} phase, which in addition to structural investigation was subjected to textural analysis. The results showed that, from different synthesis procedures and common route of calcination, one can obtain materials with the same composition but with different structural and textural properties, which in turn can significantly influence the performance of a supported catalyst.

36 MATERIALS SCIENCE↗

Investigation of miscibility of p(3hydroxybutyrate-co-3hydroxyhexanoate) and epoxidized natural rubber blends

Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate [P(3HB-co-3HHx)] produced by C. necator PHB{sup −}4 harboring phaC{sub cs} from crude palm kernel oil with 21 mol% of 3-hydroxyhexanoate and epoxidized natural rubber with 25 mol% of epoxy content (ENR-25) were used to study the miscibility of the blends by attenuated total reflection-Fourier transform infrared (ATR-FTIR) and differential scanning calorimetry (DSC). The polymers used were purified and the blends were prepared by solution casting method. Nuclear magnetic resonance (NMR) spectra confirm the purity and molecular structures of P(3HB-co-3HHx) and ENR-25. FTIR spectra for different compositions of P(3HB-co-3HHx) and ENR-25 blends show absorbance change of the absorbance bands but with no significant shifting of the absorbance bands as the P(3HB-co-3HHx) content decreases, which shows that there is no intermolecular interaction between the parent polymer blends. On top of that, there are two T{sub g}s present for the blends and both remain constant for different compositions which corresponds to the T{sub g}s of the parent polymers. This indicates that the blends are immiscible.

36 MATERIALS SCIENCE↗

The influence of silanized nano-SiO{sub 2} on the hydration of cement paste: NMR investigations

It is known that by adding a small amount of nanoparticles to the cement-based materials a strong influence on the workability, strength and durability is obtained. These characteristics of the material are fundamentally determined by the hydration process taking place after mixing the cement grains with water. In the present study the influence introduced by the addition of nano-silica with silanized surfaces on the hydration process was investigated using low-field nuclear magnetic resonance (NMR) relaxometry. The cement samples were prepared using gray cement at a water-to-cement ratio of 0.4 and a 5% addition of nanosilica. The surface of the nanoparticles was modified using a coating of Silane A174. The cement pastes were monitored during their standard curing time of 28 days. It was established that, by using unmodified nanosilica particles, an acceleration of the hydration process takes place as compared with the pure cement paste. On the other side, by adding silanized nanoparticles, the dormancy stage significantly extends and the hydration process is slower. This slowing down process could enhance the mechanical strength of cement based materials as a result of a better compaction of the hydrated samples.

36 MATERIALS SCIENCE↗

Synthesis, Vibrational Spectra, and DFT Simulations of 3-bromo-2-methyl-5-(4-nitrophenyl)thiophene

A new thiophene derivative, 3-bromo-2-methyl-5-(4-nitrophenyl)thiophene (2), was synthesized through the Suzuki coupling reaction of 4-bromo-5-methylthiophen-2-ylboronic acid (1) and 4-iodonitrobenzene, and its structure was confirmed by nuclear magnetic resonance (NMR), low and high resolution mass spectrometry (HRMS), Fourier transform infrared spectroscopy (FT-IR), and X-ray investigations of the crystal structure. The FT-IR spectra (4000–400 cm{sup –1}), Raman spectra (4000–100 cm{sup –1}), and theoretical vibrational frequencies of this new substance were investigated. Its theoretically established geometric parameters and calculated vibrational frequencies are in good agreement with the reported experimental data. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies and other related parameters of the compound were calculated. The ionization potentials given by the B3LYP and HF (Hartree–Fock) methods for this new compound are –0.30456 and –0.30501 eV, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Comparative experimental investigation on the actuation mechanisms of ionic polymer–metal composites with different backbones and water contents

Water-based ionic polymer–metal composites (IPMCs) exhibit complex deformation properties, especially when the water content changes. To explore the general actuation mechanisms, both Nafion and Flemion membranes are used as the polymer backbones. IPMC deformation includes three stages: fast anode deformation, relaxation deformation, and slow anode deformation, which is mainly dependent on the water content and the backbone. When the water content decreases from 21 to 14 wt. %, Nafion–IPMC exhibits a large negative relaxation deformation, zero deformation, a positive relaxation deformation, and a positive steady deformation without relaxation in sequence. Despite the slow anode deformation, Flemion–IPMC also shows a slight relaxation deformation, which disappears when the water content is less than 13 wt. %. The different water states are investigated at different water contents using nuclear magnetic resonance spectroscopy. The free water, which decreases rapidly at the beginning through evaporation, is proven to be critical for relaxation deformation. For the backbone, indirect evidence from the steady current response is correlated with the slow anode deformation of Flemion-IPMC. The latter is explained by the secondary dissociation of the weak acid group –COOH. Finally, we thoroughly explain not only the three deformations by swelling but also their evolvement with decreasing water content. A fitting model is also presented based on a multi-diffusion equation to reveal the deformation processes more clearly, the results from which are in good agreement with the experimental results.

36 MATERIALS SCIENCE↗

Interfaces in polymer nanocomposites – An NMR study

Nuclear Magnetic Resonance (NMR) is applied for the investigation of polymer nanocomposites. Solid-state NMR is applied to study the modification steps to compatibilize layered double hydroxides with non-polar polymers. {sup 1}H relaxation NMR gives insight on the polymer dynamics over a wide range of correlation times. For the polymer chain dynamics the transverse relaxation time T{sub 2} is most suited. In this presentation we report on two applications of T{sub 2} measurements under external mechanical stress. In a low-field system relaxation NMR studies are performed in-situ under uniaxial stress. High-temperature experiments in a Couette cell permit the investigation of the polymer dynamics in the melt under shear flow.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Structure, Molecular Modification, and Anti-radiation Activity of Melanin from Lachnum YM156 on Ultraviolet B-Induced Injury in Mice

The purpose of this study was to examine the protective effects of intracellular homogeneous melanin produced by Lachnum YM156 (LIM) against ultraviolet B (UVB) induced damage in mice. The possible structural formula of the LIM was concluded based on elemental analysis, ultraviolet–visible spectroscopy (UV–Vis), Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), and mass spectrometry (MS). The LIM was modified by arginine to improve its water solubility and biological activities. LIM and ALIM show significant anti-radiation activity in which LIM and ALIM protect the skin under UV radiation. Results indicate that activities of anti-oxidant enzymes in skin were improved after treatment of LIM or ALIM. In addition, LIM and ALIM inhibited over expression of the pro-inflammatory cytokines, including interleukin (IL)-1α, IL-1β, and IL-6 and tumor necrosis factor-α (TNF-α). The protection ability of ALIM was higher than that of LIM at the same dose. Thus, applied LIM and ALIM may be a promising radiation-protective agent.

60 APPLIED LIFE SCIENCES↗

Structural Characterization of Lignins from Willow Bark and Wood

Understanding the chemical structure of lignin in willow bark is an indispensable step to design how to separate its fiber bundles. The whole cell wall and enzyme lignin preparations sequentially isolated from ball-milled bark, inner bark, and wood were comparatively investigated by nuclear magnetic resonance (NMR) spectroscopy and three classical degradative methods, i.e., alkaline nitrobenzene oxidation, derivatization followed by reductive cleavage, and analytical thioacidolysis. All results demonstrated that the guaiacyl (G) units were predominant in the willow bark lignin over syringyl (S) and minor p-hydroxyphenyl (H) units. Moreover, the monomer yields and S/G ratio rose progressively from bark to inner bark and wood, indicating that lignin may be more condensed in bark than in other tissues. Additionally, major interunit linkage substructures (β-aryl ethers, phenylcoumarans, and resinols) together with cinnamyl alcohol end groups were relatively quantitated by two-dimensional NMR spectroscopy. Bark and inner bark were rich in pectins and proteins, which were present in large quantities and also in the enzyme lignin preparations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis and antitumor activity of cyclic octapeptide, samoamide A, and its derivatives

Using 2-chloro-trityl chloride resin as a solid phase carrier, a linear peptide was synthesized by Fmoc solid phase synthesis followed by liquid phase cyclization. After separation and purification by high-performance liquid chromatography (HPLC), cyclic octapeptide samoamide A was prepared. The synthesis yield was 54.5%. The structure of cyclic octapeptide samoamide A was characterized by electrospray ionization–mass spectrometry (ESI-MS) and nuclear magnetic resonance (NMR) spectrometry. The biological activity was evaluated by the CCK-8 assay and DPP4 enzyme activity inhibition assay. This compound exhibited high antitumor activity. Using samoamide A as a lead compound, eight cyclic octapeptide samoamide A derivatives (a, b, c, d, e, f, g, and h) were designed and synthesized using the alanine scanning method. The molecular weight and chemical structure of these derivatives were verified by ESI-MS and NMR, and the antitumor activity of the derivatives was analyzed. The antitumor activity of compound f was similar to that of samoamide A, and its replacement site is the non-active site of samoamide A, providing a theoretical basis for further modification and transformation of samoamide A.

60 APPLIED LIFE SCIENCES↗

Thermal and Physiochemical Characterization of Lignin Extracted from Wheat Straw by Organosolv Process

The purified lignin extracted from wheat straw by organosolv process was characterized for the existence of lignin subunits, functional groups and physical and thermal behaviours. Presence of carboxyl, hydroxyl, methoxyl groups and C–C, C–O, C=O linkages were conducted by Fourier Transform Infrared (FT-IR). By {sup 1}H-NMR (Nuclear Magnetic Resonance Spectroscopy) presence of aromatic protons, phenolic hydroxyls, carboxylic acids, and aldehydes were established. Moreover, {sup 13}C-NMR spectra have disclosed the presence of condensed and uncondensed aliphatic and aromatic aryls and ethers. The existence of syringyl and guaiacyl units also were confirmed with both FTIR and NMR spectroscopies. Furthermore, the results from Thermal Gravimetric Analysis (TGA) showed the weight of extracted lignin is changed in temperatures between 180 and 670 °C by devolatization, formation and condensation of different chemicals. Also, the Differential Scanning Calorimetry (DSC) graph displayed a glass transition temperature of 105 °C for extracted lignin. As a result, the extracted lignin with high purity can be a suitable candidate for carrying out value-added products.

36 MATERIALS SCIENCE↗

Recycling of waste automotive laminated glass and valorization of polyvinyl butyral through mechanochemical separation

Due to strong binding, optical clarity, adhesion to many surfaces, toughness and flexibility polyvinyl butyral (PVB) resin films are commonly used in the automotive and architectural application as a protective interlayer in the laminated glass. Worldwide million tons of PVB waste generated from end-of-life automotive associated with various environmental issues. Stringent environmental directive, higher land cost eliminates land filling option, needs a study, we have developed a mechanochemical separation process to separate PVB resins from glass and characterized the separated PVB through various techniques, i.e., scanning electron microscope (SEM), energy-dispersive X-ray spectroscopy (EDS), infrared spectroscopy (IR) and nuclear magnetic resonance spectroscopy (NMR). Commercial nonionic surfactants D201 used for the mechanochemical separation purpose. Through parameter optimization following conditions are considered to be the optimum condition; 30 vol% D201, stirring speed of 400 rpm, 35 °C temperature, operation time 1 h, and dilute D201 volume to waste automotive laminated glass weight ratio of ≈25. The technology developed in our laboratory is sustainable, environmentally friendly, techno-economical feasible process, capable of mass production (recycling). - Highlights: • Waste automotive laminated glass and polyvinyl butyral mechanochemically separated. • An economical total recovery and environment-friendly process has been developed. • It is a global problem rather than regional environmental issue has been addressed. • Without using hazardous chemical wastes are being converted to a wealth.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗