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Vibrational Studies of Saccharide-Induced Lipid Film Reorganization at Aqueous/Air Interfaces
Vibrational sum frequency generation (VSFG) and surface tension experiments were used to examine the effects of aqueous phase soluble saccharides on the structure and organization of insoluble lipid monolayers adsorbed to aqueous-air interfaces. Changes in dipalmitoylphosphocholine (DPPC) chain structure as a function of aqueous phase saccharide concentration and pH are reported. Complementary differential scanning calorimetry (DSC) measurements performed on solutions containing soluble saccharides and DPPC vesicles measured the effects of the saccharides on the lipid membrane phase behavior. Here, data show that the saccharides glucosamine and glucuronic acid induce a higher degree of organization in compressed DPPC monolayers regardless of the saccharide’s charge.
The Impact of Divalent Cations on the Enrichment of Soluble Saccharides in Primary Sea Spray Aerosol
Field measurements have shown that sub-micrometer sea spray aerosol (SSA) is significantly enriched in organic material, of which a large fraction has been attributed to soluble saccharides. Existing mechanistic models of SSA production struggle to replicate the observed enhancement of soluble organic material. Here, we assess the role for divalent cation mediated co-adsorption of charged surfactants and saccharides in the enrichment of soluble organic material in SSA. Using measurements of particle supersaturated hygroscopicity, we calculate organic volume fractions for molecular mimics of SSA generated from a Marine Aerosol Reference Tank. Large enhancements in SSA organic volume fractions (X org > 0.2) were observed for 50 nm dry diameter (d p ) particles in experiments where cooperative ionic interactions were favorable (e.g., palmitic acid, Mg 2+ , and glucuronic acid) at seawater total organic carbon concentrations (<1.15 mM C) and ocean pH. Significantly smaller SSA organic volume fractions (X org < 1.5 × 10 -3 ) were derived from direct measurements of soluble saccharide concentrations in collected SSA with dry diameters <250 nm, suggesting that organic enrichment is strongly size dependent. The results presented here indicate that divalent cation mediated co-adsorption of soluble organics to insoluble surfactants at the ocean surface may contribute to the enrichment of soluble saccharides in SSA. The extent to which this mechanism explains the observed enhancement of saccharides in nascent SSA depends strongly on the concentration, speciation, and charge of surfactants and saccharides in the sea surface microlayer.
SU-E-T-130: Dosimetric Evaluation of Tissue Equivalent Gel Dosimeter Using Saccharide in Radiotherapy System
Purpose: In this study, the dose responses of the MAGIC gel with various concentrations and type of saccharide are examined to clarify the roles of mono and disaccharide in the polymerization process. Then we focused on the tissue equivalence and dose sensitivity of MAGIC gel dosimeters. Methods: The gel is composed of HPLC, 8% gelatin, 2 × 10-3 M L-ascorbic acid, 1.8 × 10-2 M hydroquinone, 8 × 10-5 M copper(II)sulfate and 9% methacrylic acid, new polymer gels are synthesized by adding glucose(monosaccharide), sucrose(disaccharide) and urea in the concentration range of 5∼35%. For irradiation of the gel, cesium-137 gamma-ray irradiator was used, radiation dose was delivered from 5∼50 Gy. MRI images of the gel were acquired by using a 3.0 T MRI system. Results: When saccharide and urea were added, the O/C, O/N and C/N ratios agreed with those of soft tissue with 1.7%. The dose-response of glucose and sucrose gel have slope-to-intercept ratio of 0.044 and 0.283 respectively. The slope-to-ratio is one important determinant of gel sensitivity. R-square values of glucose and sucrose gel dosimeters were 0.984 and 0.994 respectively. Moreover when urea were added, the slope-to-intercept ratio is 0.044 and 0.073 respectively. R-square values of mono and disaccharide gel were 0.973 and 0.989 respectively. When a saccharide is added into the MAGIC gel dosimeter, dose sensitivity is increased. However when urea were added, dose sensitivity is slightly decreased. Conclusion: In this study, it was possible to obtain the following conclusions by looking at the dose response characteristics after adding mono-, di-saccharide and urea to a MAGIC gel dosimeter. Saccharide was a tendency of increasing dose sensitivity with disaccharide. Sa.ccharide is cost effective, safe, soft tissue equivalent, and can be used under various experimental conditions, making it a suitable dosimeter for some radiotherapy applications.
Elucidate the molecular basis of ampholytic chitosan as a high-performance cryoprotectant to myosin denaturation: The importance of saccharide charges
The uses of charged poly/oligo-saccharides enable the retarding of protein denaturation against various environmental stresses during food storage and manufacturing. However, at subzero temperatures, the molecular basis of such stabilization behaviors, i.e., cryoprotections, remain less explored. Here, in this study, we introduced an ampholytic saccharide, carboxymethyl chitooligosaccharide (CMCO) that effectively inhibited the freezing-induced myosin denaturation. The in-depth cryoprotective mechanism was systematically investigated by using molecular dynamic simulation and multispectral characterizations. Results showed that CMCO may interact with myosin through hydrogen bonding and electrostatic interactions, which caused the expelling of water at protein surfaces and the reduced conformational flexibility of myosin molecules. Due to this water replacement event, both secondary and ternary structures of myosin became freezing-resistant, leading to the inhibited protein aggregations and retained functionalities, such as solubility, Ca 2+ -ATPase activity, and gelling properties. Moreover, cryoprotective behaviors of CMCO were charge-dependent. CMCO with a higher degree of carboxymethyl substitution (DS: 1.2) was inclined to bind and stabilize myosin molecules better than the low-DS (DS: 0.8) one, even though both outperformed other cryoprotective saccharides. Therefore, this investigation not only introducing a high-performance myosin cryoprotectant, but also elaborated the cryoprotective mechanism of ampholytic saccharides.
From Vibrational Spectroscopy to Force Fields and Structures of Saccharides: New Computational Algorithms and Applications
This work was undertaken with the main objective to investigate basic reactions that take place in relatively simple saccharides (mono-saccharides and cellobiose - the building block of cellulose) , in isolation and in cluster with few water molecules or with (gas-phase) clusters of few waters and ionic compounds (salt, isolated ions like H + or OH - ). Within the context of this work, different potentials were investigated; among them, were the PM3 semi empirical potential, DFT/BLYP and a new hybrid potential constructed from MP2 for the harmonic part and from adjusted Hartree-Fock anharmonic interactions (VSCF-PT2). These potentials were evaluated by comparison with experimental data from published sources and from several collaborating groups. The findings show excellent agreement between experiments and predictions with the hybrid VSCF-PT2 potential and very good agreement with predictions obtained from dynamics with dispersion corrected DFT/BLYP potential. Investigation of hydration of cellobiose, was another topic of interest. Guided by a hydration motif demonstrated by our experimental collaborators (team of Prof J.P. Simons), we demonstrated large energetic and structural differences between the two species of cellobiose: cis and trans. The later, which is dominant in solid and liquid phases, is higher in energy in the gas-phase and compared to pure water, it does not disturb as much the network of H bonds. In contrast, the cis species exhibits asymmetric hydration in cluster with up to 25 waters, indicating that it has surfactant properties. Another highlight of this research effort was the successful first time spectrometric and spectroscopic study of a gas-phase protonated sugar derivative (alpha-D-Galactopyranoside) and its interpretation by Ab Initio molecular dynamics (AIMD) simulations. The findings demonstrate the formation of a motif in which a proton bridges between two Oxygen atoms (belonging to OH groups) at the sugar; The vibrational bands involving the shared proton were strongly shifted to lower frequencies ( by about ~ 500 cm -1 for the symmetric mode, in this case). A similar motif was also observed recently by us in protonated cellobiose, indicating that this might be a common mechanism for interaction of a proton with sugars, perhaps similar to the proton wires observed in proteins. The simulations with protonated sugars also shed light on different mechanisms of interaction of a sugar with a proton, including formation of a carboxonium ion, mutarotation events, ring puckering and in the disaccharide cellobiose, the breaking of the glycosidic bond (in both forms of cis and trans). One final highlight to note in this summary, is the finding that in the monosaccharide beta-D-Galactose a hydroxyl ion abstracts a proton (forming water) in a barrierless process at room temperature, but the water remains bound to the sugar backbone, though it migrates around it; actual degradation occurs at ~500 K when water leaves the sugar. However, the study also shows that the water abstraction reaction can be reversed in the presence of 2 additional water molecules complexed with the sugar.
Effect of Saccharide and Alditol Additives on Uniaxial Tensile Behavior of Gellan Films
The uniaxial tensile behavior of gellan films containing saccharides or alditols was examined to elucidate the plasticizing effect of these additives. Five saccharides as well as two alditols were used. The films were tested after removal of water as far as possible. The tensile modulus decreased as the content of the additives increased, suggesting apparent plasticizing effect of the additives. The plasticizing effect was discussed referring the glass transition temperature instead of the melting point of the additives, assuming the additives were in the “supercooled” liquid state even below the melting point. Since some additives showed similar values of tensile modulus regardless of whether the additive was in the solid state or in the liquid state, a blending law of the moduli was proposed to explain the apparent plasticizing effect. On the other hand, it was found that xylitol and two monosaccharides glucose and fructose acted as true plasticizers. The effective factor was attributed to the solubility of these additives to the gellan matrix. A relationship between the profile of the stress–strain curve and the plasticizing effect was also proposed.
Kinetic Studies of Acid Hydrolysis of Food Waste-Derived Saccharides
Starch saccharified glucose from food waste can be an important precursor for renewable chemicals and fuels. Despite numerous studies on hydrolysis of biomass, detailed kinetic studies and associated models of hydrolysis are lacking. We investigated the kinetics of glycosidic bond scission of malto-oligosaccharides in lithium bromide acidified molten salt hydrate (AMSH) medium and estimated rate parameters from experimental data. Our data support the hypothesis that the terminal, nonreducing bonds hydrolyze faster than the interior and terminal-reducing C–O bonds. Next, we extended the model to simulate the hydrolysis of linear and cyclic saccharides of varying degree of polymerization and of potato starch. We characterize starch using X-ray diffraction (XRD) and light scattering methods. The model is in excellent agreement with the experimentally determined concentrations of glucose and other oligosaccharides. Finally, the chain length of saccharides is found to be directly related to their hydrolysis rate constant, but inversely proportional to the glucose formation rate constant
One-bond 13 C– 13 C spin-coupling constants in saccharides: a comparison of experimental and calculated values by density functional theory using solid-state 13 C NMR and X-ray crystallography
Methyl aldohexopyranosides were 13 C-labeled at contiguous carbons, crystallized, and studied by single-crystal X-ray crystallography and solid-state 13 C nuclear magnetic resonance (NMR) spectroscopy to examine the degree to which density functional theory (DFT) can calculate one-bond 13C–13C spin-coupling constants ( 1 J CC ) in saccharides with sufficient accuracy to permit their use in MA'AT analysis, a newly-reported hybrid DFT/NMR method that provides probability distributions of molecular torsion angles in solution (Zhang et al., J. Phys. Chem. B, 2017, 121, 3042–3058; Meredith et al., J. Chem. Inf. Model., 2022, 62, 3135–3141). Experimental 1 J CC values in crystalline samples of the doubly 13 C-labeled compounds were measured by solid-state 13 C NMR and compared to those calculated from five different DFT models: (1) 1 J CC values calculated from single structures identical to those observed in crystalline samples by X-ray crystallography (all atom refinement); (2) 1 J CC values calculated from the single structures in (1) but after Hirshfeld atom refinement (HAR); (3) 1 J CC values calculated from the single structures in (1) after DFT-optimization of hydrogen atoms only; and (4 and 5) 1 J CC values calculated in rotamers of torsion angle θ 2 (C1–C2–O2–O2H) or ω(C4–C5–C6–O6) from which either specific or generalized parameterized equations were obtained and used to calculate 1 J CC values in the specific θ 2 or ω rotamers observed in crystalline samples. Good qualitative agreement was observed between calculated 1 J CC values and those measured by solid-state 13 C NMR regardless of the DFT model, but in no cases were calculated 1 J CC values quantitative, differing (over-estimated) on average by 4–5% from experimental values. These findings, and those reported recently from solution NMR studies (Tetrault et al., J. Phys. Chem. B 2022, 126, 9506–9515), indicate that improvements in DFT calculations are needed before calculated 1 J CC values can be used directly as reliable constraints in MA'AT analyses of saccharides in solution.
Incorporation of measured photosynthetic rate in a mathematical model for calculation of non-structural saccharide concentration
A simple mathematical model for calculating the concentration of mobile carbon skeletons in the shoot of soya bean plants [Glycine max (L.) Merrill cv. Ransom] was built to examine the suitability of measured net photosynthetic rates (PN) for calculation of saccharide flux into the plant. The results suggest that either measurement of instantaneous PN overestimated saccharide influx or respiration rates utilized in the model were underestimated. If neither of these is the case, end-product inhibition of photosynthesis or waste respiration through the alternative pathway should be included in modelling of CH2O influx or efflux; and even if either of these is the case, the model output at a low coefficient of leaf activity indicates that PN still may be controlled by either end-product inhibition or alternative respiration.
Efficient process for producing saccharides and ethanol from a biomass feedstock
Described herein is a process for producing saccharides and ethanol from biomass feedstock that includes (a) producing an enzyme composition by culturing a fungal strain(s) in the presence of a lignocellulosic medium, (b) using the enzyme composition to saccharify the biomass feedstock, and (c) fermenting the saccharified biomass feedstock to produce ethanol. The process is scalable and, in certain aspects, is capable of being deployed on farms, thereby allowing local production of saccharides and ethanol and resulting in a reduction of energy and other costs for farm operators. Optional steps to improve the biomass-to-fuel conversion efficiency are also contemplated, as are uses for byproducts of the process described herein.
Enzymes that cleave non-glycosidic ether bonds between lignins or derivatives thereof and saccharides
The patent application relates to isolated polypeptides that specifically cleave non-glycosidic ether bonds between lignins or derivatives thereof and saccharides, and to cDNAs encoding the polypeptides. The patent application also relates to nucleic acid constructs, expression vectors and host cells comprising the cDNAs, as well as methods of producing and using the isolated polypeptides for treating pulp and biomass to increase soluble saccharide yield and enrich lignin fractions.
Efficient process for producing saccharides and ethanol from a biomass feedstock
Described herein is a process for producing saccharides and ethanol from biomass feedstock that includes (a) producing an enzyme composition by culturing a fungal strain(s) in the presence of a lignocellulosic medium, (b) using the enzyme composition to saccharify the biomass feedstock, and (c) fermenting the saccharified biomass feedstock to produce ethanol. The process is scalable and, in certain aspects, is capable of being deployed on farms, thereby allowing local production of saccharides and ethanol and resulting in a reduction of energy and other costs for farm operators. Optional steps to improve the biomass-to-fuel conversion efficiency are also contemplated, as are uses for byproducts of the process described herein.
Two-bond 13 C– 13 C spin-coupling constants in saccharides: dependencies on exocyclic hydroxyl group conformation
Seven doubly 13 C-labeled isotopomers of methyl β-D-glucopyranoside, methyl β-D-xylopyranoside, methyl β-D-galactopyranoside, methyl β-D-galactopyranosyl-(1→4)-β-D-glucopyranoside and methyl β-D-galactopyranosyl-(1→4)-β-D-xylopyranoside were prepared, crystallized, and studied by single-crystal X-ray crystallography and solid-state 13 C NMR spectroscopy to determine experimentally the dependence of 2 J C1,C3 values in aldopyranosyl rings on the C1–C2–O2–H torsion angle, θ 2 , involving the C2 carbon of the C1–C2–C3 coupling pathway. Using X-ray crystal structures to determine θ 2 in crystalline samples and by selecting compounds that exhibit a relatively wide range of θ 2 values in the crystalline state, 2 J C1,C3 values measured in crystalline samples were plotted against θ 2 and the resulting plot compared to that obtained from density functional theory (DFT) calculations. For θ 2 values ranging from ~90° to ~240°, very good agreement was observed between the experimental and theoretical plots, providing strong validation of DFT-calculated spin-coupling dependencies on exocyclic C–O bond conformation involving the central carbon of geminal C–C–C coupling pathways. we report that these findings provide new experimental evidence supporting the use of 2 J CCC values as non-conventional spin-coupling constraints in MA'AT conformational modeling of saccharides in solution, and the use of NMR spin-couplings not involving coupled hydroxyl hydrogens as indirect probes of C–O bond conformation. Solvomorphism was observed in crystalline βGal-(1→4)-βGlcOCH 3 wherein the previously-reported methanol solvate form was found to spontaneously convert to a monohydrate upon air-drying, leading to small but discernible conformational changes in, and a new crystalline form of, this disaccharide.
Saccharide analysis of onion outer epidermal walls
Abstract Background Epidermal cell walls have special structural and biological roles in the life of the plant. Typically they are multi-ply structures encrusted with waxes and cutin which protect the plant from dehydration and pathogen attack. These characteristics may also reduce chemical and enzymatic deconstruction of the wall for sugar analysis and conversion to biofuels. We have assessed the saccharide composition of the outer epidermal wall of onion scales with different analytical methods. This wall is a particularly useful model for cell wall imaging and mechanics. Results Epidermal walls were depolymerized by acidic methanolysis combined with 2M trifluoracetic acid hydrolysis and the resultant sugars were analyzed by high-performance anion-exchange chromatography with pulsed amperometric detection (HPAEC-PAD). Total sugar yields based on wall dry weight were low (53%). Removal of waxes with chloroform increased the sugar yields to 73% and enzymatic digestion did not improve these yields. Analysis by gas chromatography/mass spectrometry (GC/MS) of per- O -trimethylsilyl (TMS) derivatives of the sugar methyl glycosides produced by acidic methanolysis gave a high yield for galacturonic acid (GalA) but glucose (Glc) was severely reduced. In a complementary fashion, GC/MS analysis of methyl alditols produced by permethylation gave substantial yields for glucose and other neutral sugars, but GalA was severely reduced. Analysis of the walls by 13 C solid-state NMR confirmed and extended these results and revealed 15% lipid content after chloroform extraction (potentially cutin and unextractable waxes). Conclusions Although exact values vary with the analytical method, our best estimate is that polysaccharide in the outer epidermal wall of onion scales is comprised of homogalacturonan (~ 50%), cellulose (~ 20%), galactan (~ 10%), xyloglucan (~ 10%) and smaller amounts of other polysaccharides. Low yields of specific monosaccharides by some methods may be exaggerated in epidermal walls impregnated with waxes and cutin and call for cautious interpretation of the results.
Changes in active-site geometry on X-ray photoreduction of a lytic polysaccharide monooxygenase active-site copper and saccharide binding
The recently discovered lytic polysaccharide monooxygenases (LPMOs) are Cu-containing enzymes capable of degrading polysaccharide substrates oxidatively. The generally accepted first step in the LPMO reaction is the reduction of the active-site metal ion from Cu 2+ to Cu + . Here we have used a systematic diffraction data collection method to monitor structural changes in two AA9 LPMOs, one from Lentinus similis (LsAA9_A) and one from Thermoascus aurantiacus (TaAA9_A), as the active-site Cu is photoreduced in the X-ray beam. For LsAA9_A, the protein produced in two different recombinant systems was crystallized to probe the effect of post-translational modifications and different crystallization conditions on the active site and metal photoreduction. We can recommend that crystallographic studies of AA9 LPMOs wishing to address the Cu 2+ form use a total X-ray dose below 3 × 10 4 Gy, while the Cu + form can be attained using 1 × 10 6 Gy. In all cases, we observe the transition from a hexacoordinated Cu site with two solvent-facing ligands to a T-shaped geometry with no exogenous ligands, and a clear increase of the θ 2 parameter and a decrease of the θ 3 parameter by averages of 9.2° and 8.4°, respectively, but also a slight increase in θ T . Thus, the θ 2 and θ 3 parameters are helpful diagnostics for the oxidation state of the metal in a His-brace protein. On binding of cello-oligosaccharides to LsAA9_A, regardless of the production source, the θ T parameter increases, making the Cu site less planar, while the active-site Tyr—Cu distance decreases reproducibly for the Cu 2+ form. Thus, the θ T increase found on copper reduction may bring LsAA9_A closer to an oligosaccharide-bound state and contribute to the observed higher affinity of reduced LsAA9_A for cellulosic substrates.
OCEANFILMS-2: Representing coadsorption of saccharides in marine films and potential impacts on modeled marine aerosol chemistry
Here we show that the addition of chemical interactions of soluble polysaccharides with a surfactant monolayer improves agreement of modeled sea spray chemistry with observed marine aerosol chemistry. In particular, the fraction of hydroxyl functional groups in modeled sea spray organic matter is increased, improving agreement with FTIR observations of marine aerosol composition. The overall organic fraction of submicron sea spray also increases, allowing organic mass fractions in the range 0.5 – 0.7 for submicron sea spray particles over highly active phytoplankton blooms. We show results from Sum Frequency Generation (SFG) experiments that support the modeling approach, by demonstrating that soluble polysaccharides can strongly adsorb to a lipid monolayer via columbic interactions under appropriate conditions.
Photocatalytic production of hydrogen from methanol and saccharides using carbon nanotube-TiO2 catalysts
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