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Solid electrolytes may be the answer to overcome many obstacles in developing the next generation of renewable batteries. A novel composite solid electrolyte (CSE) composed of a poly(vinylidene fluoride) (PVDF) base with an active nanofiber filler of aluminum-doped garnet Li ceramic, Li salt lithium bis-(trifluoromethanesulfonyl)imide (LiTFSI), Li fluoride (LiF) stabilizing additive, and plasticizer sulfolane was fabricated. In a Li|CSE|LFP cell with this CSE, a high capacity of 168 mAh g-1 with a retention of 98% after 200 cycles was obtained, representing the best performance to date of a solid electrolyte with a PVDF base and a garnet inorganic filler. In a Li metal cell with Si and Li, it yielded a discharge capacity of 2867 mAh g-1 and was cycled 60 times at a current density of 100 mAh g-1, a significant step forward in utilizing a solid electrolyte of any kind with the desirable Si anode. In producing this CSE, the components and fabrication process were chosen to have a lower cost and improved safety and environmental impact compared with the current state-of-the-art Li-ion battery.

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Fluorinated carbon (CFx) cathodes possess the highest theoretical energy density among lithium primary batteries. However, achieving reversibility in CFx remains a significant challenge. This work employs a high-voltage sulfolane electrolyte and achieves a highly reversible CFx cathodes in lithium-ion batteries (LIBs) via fine modification of the C-F bond character. The improved reversibility of CFx originates from the semi-ionic CFx phase, with a superior bond length and weaker bond energy than a covalent bond. This characteristic significantly mitigates the challenges encountered during the charging process. We screen and identify the fluorinated graphene CF1.12 as a suitable cathode, providing an appropriate fluorine content and sufficient semi-ionic C-F bonds for rechargeable LIBs. This fluorinated graphene CF1.12 exhibits an initial discharge specific capacity of 814 mAh g-1 and a reversible discharge specific capacity of 350 mAh g-1. This work provides a new clue for chemical bond regulation studies and provides insights into stimulating reversibility of primary-cell cathodes.

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Liquid-phase dehydration of glycerol to acrolein was investigated with solid acid catalysts, including H-ZSM-5, H3PO4-modified H-ZSM-5, H3PW12O40·14H2O and Cs2.5H0.5PW12O40, in the presence of sulfolane ((CH2)4SO2) as a dispersing agent under atmospheric pressure N2 in a batch reactor. High weak-acidity H-ZSM-5, high temperatures and high-boiling-point sulfolane improved the activity and selectivity for the production of acrolein through suppressing the formation of polymers and coke and promoting the diffusion of glycerol and products. Brønsted acid sites were soundly demonstrated to be responsible for dehydration of glycerol to acrolein by infrared spectroscopy of pyridine adsorption. Brønsted weak acid sites favored the selectivity to acrolein. Combined catalytic and temperature-programmed desorption of ammonia studies revealed that the selectivity to acrolein increased as the weak-acidity increased over the ZSM-5-based catalysts. The ZSM-5-based catalysts produced a higher selectivity to acrolein, while the heteropolyacids resulted in a higher selectivity to polymers and coke.

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To evaluate the effectiveness of biostimulation in remediating soil-free groundwater and groundwater with soil, experiments were conducted using soil and groundwater samples that were contaminated with sulfolane. The main objective was to characterize the differences in sulfolane removal efficiency and biotoxicity between in situ soil-free groundwater and groundwater with soil and different concentrations of dissolved oxygen (1 mg/L and 5 mg/L) and various nutrient salts (in situ and spiked). Optimizing the nutrient salt conditions improved the removal efficiency of sulfolane by 1.8-6.5 that under in situ nutrient salt conditions. Controlling the dissolved oxygen concentration enhanced the efficiency of removal of sulfolane by 1.5-4.5 times over that at the simulated in situ dissolved oxygen concentration, suggesting that the degradation of sulfolane by indigenous microorganisms requires nutrient salts more than it requires dissolved oxygen. Biotoxicity data showed that the luminescence inhibition of Aliivibrio fischeri by sulfolane was lower in the biostimulated samples than in the pre-treated samples. Biostimulation reduced the biotoxicity of the treated samples by 42-51%, revealing that it was effective in removing sulfolane and reducing biotoxicity. Microbial community analysis showed that the biostimulation did not change the dominant species in the original in situ community, and increased the proportion of sulfolane-degraders. The outcome of this study can be used to set parameters for the remediation of groundwater that is contaminated by sulfolane in oil refineries.

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Some previous studies have found the synergistic effect of mixed anions in dual-ion batteries (DIBs). In this work, both lithium tetrafluoroborate (LiBF4 ) and lithium difluoro(oxalato)borate (LiDFOB) were dissolved in sulfolane (SL) solvent, and the resultant solutions were applied for DIBs. The storage behavior of mixed anions in natural graphite positive electrodes was investigated. In-situ X-ray diffraction measurements revealed both anions could participate in the formation of graphite intercalation compounds. Their evolution followed with the decreasing tendency of discharge capacities as the content of LiDFOB increased in solutions. The exchange of anions was discussed.

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Freeze-casting (ice templating) is generally used to prepare super-macroporous materials. However, water solubility limits the application of freeze-casting in hydrophobic material fabrication. In the present work, inexpensive and low-toxic sulfolane was used as a novel crystallization-induced porogen (sulfolane crystal templating) to prepare super-macroporous hydrophobic monoliths (cryogels) with tunable polarity. The phase transition of sulfolane consisted of reversible processes in the liquid, semi-crystalline, and crystalline states. Because of the density change during phase transition, liquid sulfolane experienced a 16.4% volume shrinkage per unit mass. Thus, the cryogels obtained using the conventional freezing method contained obvious hollow-shaped defects. Furthermore, a novel route of pre-cooling, pre-crystallization, crystal growth, freezing, and thawing (PPCFT) was employed to prepare cryogels with defect-free macroscopic morphology and uniform pore structure. The as-obtained cryogels were composed of a super-macroporous structures and interconnected channels, and their porosity ranged between 85 and 97%. Moreover, the cryogels manifested good hydrophobicity (contact angle = 120-130°) and had absorption capacities greater than 10 g g-1 for oils and organic liquids. The maximum absorption capacities of the resultant cryogels in dichloromethane, ethyl acetate, and liquid paraffin were 60.3, 35.8, and 15.2 g g-1, respectively. Moreover, sulfolane could conveniently dissolve hydrophobic and hydrophilic monomers to generate amphiphilic cryogels (contact angle = 130-0°). Therefore, sulfolane crystal templating is a potential fabrication method for super-macroporous hydrophobic materials with tunable polarity.

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The development of post-lithium current sources, such as sodium-ion batteries with improved energy characteristics and an increased level of safety, is one of the key issues of modern energy. It requires the search and study of materials (including electrolytes) for these devices. Polyelectrolytes with unipolar cationic conductivity based on Nafion® membranes are promising. In this work, the effect of swelling conditions of the Nafion® 115 membrane in Na+-form with mixtures of aprotic solvents such as ethylene carbonate and sulfolane on its physicochemical and electrotransport properties was studied. Nafion-Na+ membranes were swollen in a mixture of solvents at temperatures of 40, 60, and 80 °C. The results were obtained using methods of impedance spectroscopy, simultaneous thermal analysis, and IR spectroscopy. The best conductivity was observed for a membrane swelling at 80 °C in a mixture with a mass fraction of ethylene carbonate of 0.5, which reaches 10-4 S cm-1 at 30 °C and retains rather high values down to -60 °C (10-6 S cm-1). Thus, it is possible to expand the operating temperature range of a sodium battery by varying the composition of the polymer electrolyte and the conditions for its preparation.

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For patients with myelofibrosis, allogeneic hematopoietic stem cell transplantation (allo-HSCT) remains the only curative treatment to date. Busulfan-based conditioning regimens are commonly used, although high inter-individual variability (IIV) in busulfan drug exposure makes individual dose selection challenging. Since data regarding the IIV in patients with myelofibrosis are sparse, this study aimed to develop a population pharmacokinetic (PopPK) model of busulfan and its metabolite sulfolane in patients with myelofibrosis. The influence of patient-specific covariates on the pharmacokinetics of drug and metabolite was assessed using non-linear mixed effects modeling in NONMEM®. We obtained 523 plasma concentrations of busulfan and its metabolite sulfolane from 37 patients with myelofibrosis. The final model showed a population clearance (CL) and volume of distribution (Vd) of 0.217 L/h/kg and 0.82 L/kg for busulfan and 0.021 L/h/kg and 0.65 L/kg for its metabolite. Total body weight (TBW) and a single-nucleotide polymorphism of glutathione-S-transferase A1 (GSTA1 SNP) displayed a significant impact on volume of distribution and metabolite clearance, respectively. This is the first PopPK-model developed to describe busulfan's pharmacokinetics in patients with myelofibrosis. Incorporating its metabolite sulfolane into the model not only allowed the characterization of the covariate relationship between GSTA1 and the clearance of the metabolite but also improved the understanding of busulfan's metabolic pathway.

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The Li-O2 battery should operate effectively/safely in an open O2 environment for practical applications, but not trapped in sealed/closed atmosphere. However, the typical use of volatile and flammable electrolyte restricts Li-O2 battery to be able to be running in open O2 environment. We report herein, for the first time, a highly electrochemical reversible Li-O2 battery operated in an open O2 environment, i.e., under the condition of keeping O2 flowing continuously based on a nonvolatile and nonflammable sulfolane (TMS) solvent. The electrochemical irreversibility of Li2O2/O2 conversion and incompatibility between Li metal anodes and electrolyte have been addressed via dissolving LiNO3 in concentrated TMS electrolyte. The tuned electrolyte not only enables a stable solid electrolyte interphase (SEI) with conformal inorganic components (including LiF, LiNxOy, and Li2O) that promotes a uniform Li electro-plating/stripping process but also results in a low charge overpotential, a stable discharge terminal plateau, and reversible O2 generation of the Li-O2 battery conducted in an open O2 environment.

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Sulfolane is explored as a novel stationary phase for use in analytical separations by capillary column gas chromatography with flame ionization detection (GC-FID). Stainless steel capillaries were found to provide a good substrate for coating and retaining a sulfolane phase, whereas fused silica tubing did not perform well for this. In general, the phase was found to be stable for several hours of use when using elevated carrier gas pressures (90 psi) and a small restriction (25 µm I.D. tubing) at the outlet. This normally provided good performance at temperatures up to about 200 °C with very little background interference in the FID. Given its separation properties, a short 2 m × 100 µm I.D. column was found to be preferable for most separations in this study. Measurements indicated the coating procedure yielded a sulfolane film near 4 µm thick on this column, which produced 4400 plates for benzene with a sample capacity near 30 µg. The sulfolane phase yielded good retention and peak shape for many analytes including alkanes, aromatics, alcohols, bases, sulfides, phosphites, thiols, and others. Compared to longer conventional GC columns, the relatively short sulfolane column was found to offer improved selectivity in the separation of unsaturated, aromatic, and alkane test analytes. As such the method was successfully applied to the analysis of aromatics in gasoline headspace. Results suggest that sulfolane could be a potentially useful stationary phase to further explore in GC separations.

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Sulfolane is a solvent used in the petrochemical industry and a groundwater contaminant in areas near refineries. The current studies were conducted to assess the impact of oral exposure to sulfolane on the immune system using two models: (1) a perinatal drinking water exposure to 0, 30, 100, 300, or 1000 mg/L from gestation day (GD) 6 until ∼13 weeks-of-age in Harlan Sprague Dawley rats; and, (2) a 90-day gavage exposure of adult female B6C3F1/N mice to 0, 1, 10, 30, 100, or 300 mg/kg/day. Immune parameters evaluated included measurement of antibody production against sheep red blood cells (SRBC) and keyhole limpet hemocyanin (KLH), ex vivo measurements of natural killer (NK) cell activity, cytotoxic T-cell (CTL) activity, and T-cell proliferation, as well as measures of splenic immune cell populations, hematological parameters, and histopathology of immune tissues. A decrease in ex vivo NK cell activity was observed in cells from female - but not male - F1 rats following developmental exposure. In adult female mice, splenic NK cell number was lower than the vehicle controls at doses ≥ 100 mg/kg; however, ex vivo NK cell activity was not affected by sulfolane treatment. In female mice, a decrease in the number of large unstained cells at doses ≥ 30 mg/kg was observed. In F1 rats, effects on white blood cells (WBC) were limited to a decreasing trend in leukocytes in females; no effects were observed in males. Under the conditions of this study, a no-observed-effect level (NOEL) of 3 mg/kg/day was identified based on reduced NK cell activity in female F1 rats. Overall, these findings suggest that oral exposure to sulfolane in rodents had minimal effects on the immune system.

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The use of dipolar aprotic solvents to swell lithiated Nafion ionomer membranes simultaneously serving as electrolyte and separator is of great interest for lithium battery applications. This work attempts to gain an insight into the physicochemical nature of a Li-Nafion ionomer material whose phase-separated nanostructure has been enhanced with a binary plasticiser comprising non-volatile high-boiling ethylene carbonate (EC) and sulfolane (SL). Gravimetric studies evaluating the influence both of mixing temperature (25 to 80 °C) and plasticiser composition (EC/SL ratio) on the solvent uptake of Li-Nafion revealed a hysteresis between heating and cooling modes. Differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) revealed that the saturation of a Nafion membrane with such a plasticiser led to a re-organisation of its amorphous structure, with crystalline regions remaining practically unchanged. Regardless of mixing temperature, the preservation of crystallites upon swelling is critical due to ionomer crosslinking provided by crystalline regions, which ensures membrane integrity even at very high solvent uptake (≈200% at a mixing temperature of 80 °C). The physicochemical properties of a swollen membrane have much in common with those of a chemically crosslinked polymer gel. The conductivity of ≈10-4 S cm-1 demonstrated by Li-Nafion membranes saturated with EC/SL at room temperature is promising for various practical applications.

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Sulfolane is a solvent used in industrial refining with identified environmental exposure in drinking water. Due to potential large species differences, the National Toxicology Program (NTP) conducted 28-day toxicity studies in male and female Hsd:Sprague Dawley® SD® rats, B6C3F1/N mice, and Hartley guinea pigs. A wide dose range of 0, 1, 10, 30, 100, 300, and 800 mg/kg was administered via gavage. Histopathology, clinical pathology, and organ weights were evaluated after 28 days of exposure. In addition, plasma concentrations of sulfolane were evaluated 2 and 24 h after the last dose. Increased mortality was observed in the highest dose group of guinea pigs and mice while decreased body weight was observed in rats compared to controls. Histopathological lesions were observed in the kidney (male rat), stomach (male mice), esophagus (male and female guinea pigs), and nose (male guinea pigs). Plasma concentrations were generally higher in rats and guinea pigs compared to mice with evidence of saturated clearance at higher doses. Male rats appear to be the most sensitive with hyaline droplet accumulation occurring at all doses, although the human relevance of this finding is questionable.

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Column systems were used to evaluate the effectiveness of different bioremediation methods (biostimulation (BS) and bioaugmentation (BA)) in treating sulfolane-contaminated groundwater. Batch test results confirmed that Cupriavidus sp. Y9 (Y9) was the most effective strain for BA. The optimal ratio of added native bacteria to Y9 was 10:3. The BA column adapted to a high sulfolane concentration (150 mg L-1) more rapidly and had higher sulfolane removal efficiency (90%) than did the BS column. The change in the biotoxicity of sulfolane-contaminated groundwater upon bioremediation, according to a Microtox test, revealed decreases in the inhibition of the passing of light by the BS column and BS + BA column of 38% and 63%, respectively. These results reveal that combining BS with BA can reduce the biotoxicity of sulfolane. The column tests confirmed the most effective added bacterium in BA, the operating conditions for high-efficiency bioremediation, and possible problems in its future application. The results provide an important reference for the design of methods for the remediation of contaminated sites.

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Groundwater near refinery and natural gas plants often contain elevated concentrations of toxic sulfolane. Studies on any concentration of sulfolane are limited. Column experiment was conducted to investigate the effects of adding a low dose of H2O2 and nutrient on bioremediation. Vibrio fischeri light inhibition test was used evaluate the toxicity of effluents. The continuous column experiment conditions were sulfolane at 100 mg L-1, dissolved oxygen at 7 mg L-1, absence of phosphorus, and very short hydraulic retention time (7.9 h). A low dose of H2O2 (5.88 mM) enhanced the sulfolane (27.1%) and COD removal (11.8%) in comparison with the control set. Adding nutrient increased bicinchoninic acid protein assay levels, sulfolane removal (99.6%) and COD removal (80.3%). Addition of both H2O2 and nutrient further improved COD removal (90.3%) and COD/sulfolane ratio (0.90) and toxicity removal (Vibrio fischeri light inhibition ratio < 1%). Batch experiment indicated the degraders tolerated sulfolane up to 400 mg L-1. The DGGE method and dendrogram analysis were utilized to investigate the changes of degrader community structure.

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In this study, oxidants and nanomaterials were used to improve titanium dioxide based photocatalytic degradation of sulfolane. Hydrogen peroxide (H2O2), sodium persulfate (SPS) and ozone (O3) were the oxidants studied and carbon nanotubes (CNT) and nanosized zero valent iron (nZVI) were used as the nanomaterials. The impact of these oxidants and nanomaterials was evaluated at various dosages in both Milli-Q water and groundwater. The results indicate that with a suitable dose of oxidants or nanomaterials, photocatalytic degradation of sulfolane in Milli-Q water can be enhanced. The addition of ozone contributed to a significant increase in sulfolane degradation rate in Milli-Q water. The experiments conducted in groundwater showed that oxidants (H2O2, SPS and O3) increased the degradation of sulfolane while the nanomaterials (CNT and nZVI) impeded sulfolane degradation in groundwater.

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Potentiostatic deposition of silicon is performed in sulfolane (SL) and ionic liquid (IL) electrolytes. Electrochemical quartz crystal microbalance with damping monitoring (EQCM-D) is used as main analytical tool for the characterization of the reduction process. The apparent molar mass (Mapp) is applied for in situ estimation of the layer contamination. By means of this approach, appropriate electrolyte composition and substrate type are selected to optimize the structural properties of the layers. The application of SL electrolyte results in silicon deposition with higher efficiency compared to the IL 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, [BMP][TFSI]. This has been associated with the instability of the IL in the presence of silicon tetrachloride and the enhanced incorporation of IL decomposition products into the growing silicon deposit. X-ray photoelectron spectroscopy (XPS) analysis supports the results about the layer composition, as suggested from the microgravimetric experiments. Attention has been given to the impact of practically relevant substrates (i.e., Cu, Ni, and vitreous carbon) on the reduction process. An effective deposition can be carried out on the metal electrodes in both electrolytes due to accelerated reaction kinetics for these types of substrates. However, on vitreous carbon (VC), a successful reduction of SiCl4 can only be accomplished in the IL, while the electroreduction process in SL is dominated by the decomposition of the electrolyte. For short deposition times, the scanning electron microscopy (SEM) images display rough morphologies in the nanometer range, which evolve further to structures with increased length scale of the surface roughness. The development of a rough interface during deposition, resulting in QCM damping at advanced stages of the process, is interpreted by a model accounting for the resistive force caused by the interaction of the liquid with a nonuniform layer interface. By using this approach, the individual contributions of the surface roughness and viscoelastic effects to the measured damping values are estimated.

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Sulfolane-induced corrosion can lead to severe impairment in industrial systems. Therefore, determination of solvent corrosivity is valid. Under standard conditions, pure sulfolane is considered to be thermally stable and chemically inert, hence non-aggressive towards carbon/stainless steel. Unfortunately, the sulfolane-evoked corrosion of the industrial installations is observed for sulfolane-based systems polluted by small quantities of oxygen, water and some oxidizing agents. Moreover, sulfolane decomposition with formation of corrosive (by-)products can be escalated by some process parameters, e.g., temperature. The main objective of this study was to determine the corrosion resistance of AISI 1010 steel immersed in sulfolane at temperatures ranging from 25 to 230 °C. Evaluation of the corrosion damage was carried out using electrochemical techniques and scanning probe/electron microscopy, respectively. The general corrosion tendency, corrosion rate and surface corrosion degree were taken into account as well. It was noticed that the corrosion rate linearly increases with the enhancement of sulfolane temperature. Moreover, the interfacial reaction of steel with sulfolane resulted in the formation of corrosion product layer, which is a physical barrier between the corrosive environment and steel improving corrosion resistance of the latter. In fact, the increment of the sulfolane temperature caused a gradual breakdown of the protective layer and the increase in the corrosion degree of the investigated steel. Finally, it was found that the corrosion degree doubles approximately every 42 °C.

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In this study, an alkaline-catalyzed sulfolane/water solvent system was developed for isolating high-purity and antioxidative lignin from willow (Salix matsudana cv. Zhuliu). Optimization of the pretreatment conditions such as temperature, sulfolane/water ratio, and alkaline catalyst (NaOH) dosage were comprehensively investigated for effective lignin extraction from willow. The 44.4% of lignin was recovered from the biomass with 54% of delignification in 50/50 (w/w) sulfolane/water system at 170 °C. As the addition of the alkaline catalyst (NaOH) increased to 4%, the delignification yield was increased up to 94% with about 70% of lignin recovery yield. The recovered lignin was comparatively investigated with its control, milled wood lignin (MWL). The ß-O-4 linkages and phenolic hydroxyl were well preserved in the extracted lignin fractions with the sulfolane/water system. Furthermore, excellent radical scavenging ability was observed with the extracted lignins by sulfolane/water pretreatments owing to rich phenolic hydroxyl groups in the lignins. Hence, systematical investigation on the lignin properties and potential applications under sulfolane organosolv pretreatment would promote the utilization of lignin in biorefinery processes.

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The microwave-assisted heating reaction of N-acetyl glucosamine (GlcNAc) in sulfolane is described. The reaction produces two major products that are assignable to 1,6-anhydro-2-acetamido-2-deoxy-ß-d-glucopyranose (AGPNAc) and 1,6-anhydro-2-acetamido-2-deoxy-ß-d-glucofuranose (AGFNAc). In order to reveal a general feature of the system, the 3, 5, and 10 min reactions were performed at 140, 160, 180, 200, and 220 °C to clarify the time course changes in the conversion of GlcNAc and the yields of the two produced 1,6-anhydrosugars. Temperature is a crucial factor that significantly affects the conversion of GlcNAc. The yields of AGPNAc and AGFNAc are also drastically changed depending on the reaction conditions. The 5-min reaction at 200 °C is shown to be the optimal condition to generate the 1,6-anhydrosugars with a high efficiency in which AGPNAc and AGFNAc are produced in the yields of 21% and 44%, respectively. Consequently, the microwave-assisted heating reaction of GlcNAc in sulfolane is shown to be a simple and promising pathway to generate 1,6-anhydrosugars consisting of amino monosaccharide backbones, which have high potentials as raw materials leading to biological oligosaccharides and biomimetic polysaccharides.

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