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At least 91 records · Page 5

Temporary arterial shunts to maintain limb perfusion after arterial injury: an animal study

BACKGROUND: Temporary shunt placement can quickly restore perfusion after extremity arterial injury. This study examined the adequacy of limb blood flow with shunt use, non-heparin-bonded shunt patency over prolonged periods, and the safety of this technique. METHODS: Common iliac arteries were divided and 4.0-mm Silastic Sundt shunts placed in 16 anesthetized pigs. Eight (group I) had shunts placed immediately; eight others (group II) were shunted after an hour of limb ischemia and hemorrhagic shock. Physiologic parameters and femoral artery blood flow in both hindlimbs were continuously monitored. Limb lactic acid generation, oxygen utilization, and hematologic and metabolic effects were serially evaluated for 24 hours. RESULTS: Shunts remained patent in 13 of 16 pigs. Shunts thrombosed in two group I animals because of technical errors, but functioned well after thrombectomy and repositioning. Patency could not be maintained in one animal that died from shock. Flow in group I shunted limbs was 57 (+/-11 SD) % of control. For group II animals in shock, shunted limb flow initially averaged 46 +/- 15% of control, but 4 hours after shunt placement, the mean limb blood flow was the same as in group I. Increased oxygen extraction compensated for the lower flow. Lactic acid production was not increased in comparison to control limbs. CONCLUSION: Shunts provided adequate flow in this model of extremity trauma. Correctly placed shunts stayed patent for 24 hours, without anticoagulation, if shunt placement followed resuscitation.

Hindlimb/blood supply/injuries↗

Manufacture of porous biodegradable polymer conduits by an extrusion process for guided tissue regeneration

We have fabricated porous, biodegradable tubular conduits for guided tissue regeneration using a combined solvent casting and extrusion technique. The biodegradable polymers used in this study were poly(DL-lactic-co-glycolic acid) (PLGA) and poly(L-lactic acid) (PLLA). A polymer/salt composite was first prepared by a solvent casting process. After drying, the composite was extruded to form a tubular construct. The salt particles in the construct were then leached out leaving a conduit with an open-pore structure. PLGA was studied as a model polymer to analyze the effects of salt weight fraction, salt particle size, and processing temperature on porosity and pore size of the extruded conduits. The porosity and pore size were found to increase with increasing salt weight fraction. Increasing the salt particle size increased the pore diameter but did not affect the porosity. High extrusion temperatures decreased the pore diameter without altering the porosity. Greater decrease in molecular weight was observed for conduits manufactured at higher temperatures. The mechanical properties of both PLGA and PLLA conduits were tested after degradation in vitro for up to 8 weeks. The modulus and failure strength of PLLA conduits were approximately 10 times higher than those of PLGA conduits. Failure strain was similar for both conduits. After degradation for 8 weeks, the molecular weights of the PLGA and PLLA conduits decreased to 38% and 43% of the initial values, respectively. However, both conduits maintained their shape and did not collapse. The PLGA also remained amorphous throughout the time course, while the crystallinity of PLLA increased from 5.2% to 11.5%. The potential of seeding the conduits with cells for transplantation or with biodegradable polymer microparticles for drug delivery was also tested with dyed microspheres. These porous tubular structures hold great promise for the regeneration of tissues which require tubular scaffolds such as peripheral nerve, long bone, intestine, or blood vessel.

NASA Discipline Cell Biology↗

Biological toxicity and environmental hazards associated with PLGA nanoparticles

There have been tremendous advances in nanotechnology. More recently, the use of nanoparticles has expanded to applications including materials, packaging, energy, and medical uses such as drug delivery, diagnostics, and therapeutics. The American Society for Testing and Materials (ASTM) and the International Organization for Standardization (ISO) define nanoparticles as particles with at least one dimension measuring between 1 and 100 nm (2), but this view is generally too limited, and recommendations have been made to consider all materials with a dimension measuring under 1,000 nm as nanoparticles. The biomedical uses of nanoparticles are particularly promising because of their ability to reach and target various sites and organs. However, some nanoparticles can be composed of toxic materials or are limited by issues of biodistribution and bioaccumulation, which have hampered their use in biomedicine. The copolymer poly lactic-co-glycolic acid (PLGA) has gained use in biomedical applications as a delivery system because it is considered biocompatible and can be formulated with controlled degradation in physiological environments. PLGA has a history in biomedicine that dates to the 1970s when biodegradable sutures were developed using PLGA. In addition, the United States (US) Food and Drug Administration (FDA) and the European Medicine Agency (EMA) have approved various PLGA particle formulations as therapeutic delivery vehicles. Interest in biocompatible materials to deliver a range of therapeutic drugs, proteins, nucleic acids, and other molecules has risen recently. In addition to drug delivery, sustained drug release can be achieved by tuning the physical properties of PLGA, such as the molecular weight, ratio of lactic to glycolic acid, drug concentration, stabilizing molecules, and particle size. Given the rise of nanoparticles, human and environmental exposure to them is inevitable as more applications use free, unbound, and highly mobile particles. Although PLGA is generally considered safe, a detailed understanding of how PLGA and the other components used to help formulate this copolymer into a nanoparticle delivery vehicle is useful for assessing potential harmful effects. Despite recent advances in PLGA nanoparticle formulations, residual stabilizing molecules, inconsistent preparations, and batch-to-batch variations can lead to toxicity. Poor preparations of PLGA can lead to common mechanisms of toxicity observed with nanoparticles, such as inflammation and oxidative stress. Consistency in PLGA formulations and accurate methods to evaluate nanoparticle toxicity are needed to ensure safety. In order to better assess PLGA nanoparticles as non-toxic delivery systems, it is critical to understand their physical and chemical properties and the formulation protocols that may introduce toxic components into particles.

Biology, nanoparticle, toxicity↗

Process strategies for recovery of sugars, lipids, and lignin from oilcane bagasse using natural deep eutectic solvents (NADES)

Sugarcane is being enhanced as a bioenergy crop by engineering it to accumulate and store lipids along with polymeric sugars in vegetative tissues. However, there is no existing process that allows for processing this new crop to recover both lipid and cellulosic sugars from the oilcane bagasse. Therefore, a comprehensive investi- gation of two pretreatment methods—natural deep eutectic solvents (NADES) and chemical-free hydrothermal pretreatment (HT) was conducted to judge their suitability for recovering fermentable sugars, lipids, and lignin from bagasse. Two NADES, i.e., choline chloride: lactic acid (ChCl:LA) and betaine: lactic acid (BT:LA) were prepared using a 1:2 M ratio and were evaluated for pretreatment of oilcane bagasse at 10, 20, and 50 % (w/w) solids, followed by enzymatic hydrolysis at 10 % (w/w) solids. Notably, ChCl:LA NADES treatment at 10 % (w/ w) solids at 140 °C for 2 h, solubilized 78.8 % of lignin and 80.4 % of hemicellulose and allowed 82.7 % enzymatic conversion of glucans to glucose. In contrast, HT pretreatment removed approximately 87.6 % of the hemicellulose and provided an enzymatic glucose yield of 69.7 %. Furthermore, ChCl:LA operated at 50 % solids loading the enriched lipids 2.6-fold (9.2 wt%) in recovered solids compared to HT (6.4 %) and BT:LA (5.1 %) pretreatment processes. NMR-HSQC and GPC analysis showed that ChCl:LA also cleaved the most lignin β–O–4 linkages and demonstrated lower molecular weight compared to HT. As a result, this study demonstrates that NADES pretreatment is an effective green processing method for recovering lipids, sugars, and lignin from bioenergy crops at high solid loading (50 % w/w) within the context of an integrated biorefinery.

09 BIOMASS FUELS↗

Greenhouse Gas Emissions Associated with Pretreatment Techniques Utilized for Biosugar Production

Less carbon-intensive production of biosugars from lignocellulosic materials can lead to improved manufacturing of biofuels and bioproducts. In this study, the production of biosugars is analyzed to understand the potential of producing bioproducts from biosugars with a low carbon intensity. Life-cycle assessment is conducted on five lignocellulosic feedstocks along with seven pretreatment techniques to produce biosugars as an important platform intermediate for producing bioproducts. The production of electricity using lignin with and without heat integration was also incorporated. In addition, seven bioproducts are analyzed for the estimation of the GHG emissions budget, which represents the emissions available to convert, separate, and upgrade biosugars into bioproducts within the 70% emissions reduction target. Corn stover-deacetylation and dilute acid pretreatment (CS-DDA) provide the lowest GHG emissions for biosugar (0.03 kg CO 2 eq/kg biosugar) and thereby the highest GHG emissions budget for the case of lactic acid production (3.76 kg CO 2 eq/kg lactic acid). Natural gas and chemicals are the major contributors to all of the pretreatment techniques under study. The outcomes from this study can benefit the advancement of upcoming biobased processes that meet decarbonization targets.

Biopolymers↗

Heterogenization of polyoxometalates as solid catalysts in aerobic oxidation of glycerol

A series of heterogeneous catalysts based on phosphomolybdic salts with different metals in counter or substituent positions, L n PMo 12 O 40 (L = Al 3+ , Fe 3+ , Cr 3+ , Ti 4+ , Zr 4+ and Zn 2+ , abbreviated as LPMo 12 ) and H x PMo 11 LO 39 (L = Zn 2+ , Cr 3+ , Fe 3+ , Al 3+ , Ti 4+ , for Ti 4+ ; the amount of O is 40, abbreviated as HPMo 11 L), were prepared using a simple calcination treatment and were evaluated in aerobic oxidation of glycerol. After calcination at about 250 °C for 4 h, homogeneous Ln P Mo 12 O 40 ·nH 2 O and H x PMo 11 LO 39 ·mH 2 O became heterogeneous. Their specific surface areas were also enhanced as well as their activity and reusability. Similar to the homogeneous catalysts, AlPMo 12 treated at 400 °C (AlPMo 12 -400) was found to be the most active catalyst in glycerol oxidation to lactic acid, with 96.1% yield and 98.6% conversion at 60 °C for 5 h with 1 MPa of O 2 ; it gave a turnover number (TON; TON = [LA]/[catalyst]) of 2.4 × 10 2 , higher than that of AlPMo 12 -250 treated at 250 °C (TON = 2.0 × 10 2 ). AlPMo 12 behaved as a heterogeneous catalyst in glycerol oxidation and could be reused at least 12 times. AlPMo 12 -400 also performed well in crude glycerol oxidation, affording lactic acid yields as high as 86.8%.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Lignin with controlled structural properties by N-heterocycle-based deep eutectic solvent extraction

The complex and heterogeneous nature of the lignin macromolecule has presented a lasting barrier to its utilization. To achieve high lignin yield, the technical lignin extraction process usually severely modifies and condenses the native structure of lignin, which is a critical drawback for its utilization in conversion processes. In addition, there is no method capable of separating lignin from plant biomass with controlled structural properties. Here, we developed an N-heterocycle-based deep eutectic solvent formed between lactic acid and pyrazole (La–Py DES) with a binary hydrogen bonding functionality resulting in a high affinity toward lignin. In this study, up to 93.7% of lignin was extracted from wheat straw biomass at varying conditions from 90 °C to 145 °C. Through careful selection of treatment conditions as well as lactic acid to pyrazole ratios, lignin with controlled levels of ether linkage content, hydroxyl group content, and average molecular weight can be generated. Under mild extraction conditions (90 °C to 120 °C), light-colored native-like lignin can be produced with up to 80% yield, whereas ether linkage–free lignin with low polydispersity can be obtained at 145 °C. Overall, this study offers a new strategy for native lignin extraction and generating lignin with controlled structural properties.

59 BASIC BIOLOGICAL SCIENCES↗

Data for Process Strategies for Recovery of Sugars, Lipids, and Lignin from Oilcane Bagasse Using Natural Deep Eutectic Solvents (NADES)

Sugarcane is being enhanced as a bioenergy crop by engineering it to accumulate and store lipids along with polymeric sugars in vegetative tissues. However, there is no existing process that allows for processing this new crop to recover both lipid and cellulosic sugars from the oilcane bagasse. Therefore, a comprehensive investigation of two pretreatment methods—natural deep eutectic solvents (NADES) and chemical-free hydrothermal pretreatment (HT) was conducted to judge their suitability for recovering fermentable sugars, lipids, and lignin from bagasse. Two NADES, i.e., choline chloride: lactic acid (ChCl:LA) and betaine: lactic acid (BT:LA) were prepared using a 1:2 M ratio and were evaluated for pretreatment of oilcane bagasse at 10, 20, and 50 % (w/w) solids, followed by enzymatic hydrolysis at 10 % (w/w) solids. Notably, ChCl:LA NADES treatment at 10 % (w/w) solids at 140 °C for 2 h, solubilized 78.8 % of lignin and 80.4 % of hemicellulose and allowed 82.7 % enzymatic conversion of glucans to glucose. In contrast, HT pretreatment removed approximately 87.6 % of the hemicellulose and provided an enzymatic glucose yield of 69.7 %. Furthermore, ChCl:LA operated at 50 % solids loading the enriched lipids 2.6-fold (9.2 wt%) in recovered solids compared to HT (6.4 %) and BT:LA (5.1 %) pretreatment processes. NMR-HSQC and GPC analysis showed that ChCl:LA also cleaved the most lignin β–O–4 linkages and demonstrated lower molecular weight compared to HT. This study demonstrates that NADES pretreatment is an effective green processing method for recovering lipids, sugars, and lignin from bioenergy crops at high solid loading (50 % w/w) within the context of an integrated biorefinery.

Conversion↗

Dissecting the Division of Labor in Microbial Consortia for the Production of Biofuels and Chemicals (Final Technical Report)

The overarching objective of this project is to elucidate the fundamental design rules for microbial division of labor (DOL), the core of ecosystem organization, in the context of artificial yeast—lactic acid bacteria consortia that produce advanced biofuel and chemical from cellulosic biomass. Over the course of four years, we have successfully achieved the objective through three lines of research that combines experiment with mathematical modeling. Specifically, we have shown that compositional and temporal DOL is effective in modulating mixed sugar fermentation by an engineered consortium and uncovered general quantitative criteria for conditions under which microbial DOL outperforms single superbugs for simultaneous utilization of mixed substrates. We also demonstrated, in synthetic consortia of yeast and lactic acid bacteria, that partitioning the labor for substrate breakdown and end-product synthesis can allow an efficient production of 2-butanol that is difficult otherwise for a single yeast strain. Additionally, by systematically probing the stability of an engineered cooperative consortium, we found that the stability of microbial symbiosis is governed by the topological structure of the underlying cellular interactions rather than specific microbial species and that rational modulation of the interactions may facilitate the restoration of collapsed consortia as well as the intervention of target communities. Together, this project has advanced the fundamental knowledge of microbial DOL in terms of its strength in mixed substrate fermentation, production of complex chemicals, and ecological system stability in the context of microbial consortia. It also provides valuable insights into the design, construction and optimization of artificial consortia for the utilization of cellulosic biomass and economic production of biofuel and chemicals.

59 BASIC BIOLOGICAL SCIENCES↗

Enhancing organic matter removal, product recovery, and hydrogen generation from fermentation wastewater

Existing ethanol biorefineries produce billions of gallons of wastewater (stillage) that must be treated extensively prior to discharge or concentrated in an energy intense evaporation step to produce animal feed as a value-added bioproduct. Yeasts and filamentous fungi were screened for growth and reduction of soluble organic compounds, carbohydrates, and protein from stillage to identify species capable of rapidly concentrating organic compounds into readily separable biomass in an attempt to concentrate the product using a much more efficient centrifugation step. Yeasts amenable to production of biomass derived products including bio-oils (Yarrowia lipolytica and Rhodotorula pallida), chitosan (Aspergillus niger) and animal feed (Cyberlindnera jadinii) were identified as well as microbes capable of efficient production of small organic acids with applications as bioderived polymers including 3-hydroxypropionic acid (engineered A. niger) and lactic acid using a co-culture of Debaryomyces udenii and Lactobacillus pentosus. The filamentous fungus A. niger eliminated all specifically measured soluble organics (glycerol, acetate, lactate, ethanol, and citrate) in under 48 hours and reduced total soluble protein content by 46% and total carbohydrate content by 83% within 96 hours, the greatest reduction in organic content observed. During this process an A. niger strain engineered to produce 3-hydroxypropionic acid achieved a yield of 0.35 C-mol 3HP / C-mol non-protein organics consumed at an overall rate of 0.09 g/Lh in unmodified stillage without pH control. Stillage treated by the fodder yeast C. jadinii as well as stillage containing acetic or lactic acid was found to be most suitable for growth by electrogenic bacteria with applications in production of electricity or hydrogen from wastewater. This work establishes fungal and bacterial strains appropriate for biological treatment of stillage to produce biomass derived products, soluble commodity chemicals, energy, and treated water to reduce the energy intensity and improve the economics of ethanol biorefineries.

09 BIOMASS FUELS↗

Diverse Profile of Fermentation Byproducts From Thin Stillage

The economy of biorefineries is influenced not only by biofuel production from carbohydrates but also by the production of valuable compounds from largely underutilized industrial residues. Currently, the demand for many chemicals that could be made in a biorefinery, such as succinic acid (SA), medium-chain fatty acids (MCFAs), and lactic acid (LA), is fulfilled using petroleum, palm oil, or pure carbohydrates as raw materials, respectively. Thin stillage (TS), the residual liquid material following distillation of ethanol, is an underutilized coproduct from the starch biofuel industry. This carbon-rich material has the potential for chemical upgrading by microorganisms. Here, we explored the formation of different fermentation products by microbial communities grown on TS using different bioreactor conditions. At the baseline operational condition (6-day retention time, pH 5.5, 35°C), we observed a mixture of MCFAs as the principal fermentation products. Operation of a bioreactor with a 1-day retention time induced an increase in SA production, and a temperature increase to 55°C resulted in the accumulation of lactic and propionic acids. In addition, a reactor operated with a 1-day retention time at 55°C conditions resulted in LA accumulation as the main fermentation product. The prominent members of the microbial community in each reactor were assessed by 16S rRNA gene amplicon sequencing and phylogenetic analysis. Under all operating conditions, members of the Lactobacillaceae family within Firmicutes and the Acetobacteraceae family within Proteobacteria were ubiquitous. Members of the Prevotellaceae family within Bacteroidetes and Lachnospiraceae family within the Clostridiales order of Firmicutes were mostly abundant at 35°C and not abundant in the microbial communities of the TS reactors incubated at 55°C. The ability to adjust bioreactor operating conditions to select for microbial communities with different fermentation product profiles offers new strategies to explore and compare potentially valuable fermentation products from TS and allows industries the flexibility to adapt and switch chemical production based on market prices and demands.

59 BASIC BIOLOGICAL SCIENCES↗

Effects of antibacterial peptide-producing Bacillus subtilis, gallic acid, and cellulase on fermentation quality and bacterial community of whole-plant corn silage

In the current study, we assessed the effects of antibacterial peptide-producing Bacillus subtilis (BS), gallic acid (GA) and cellulase (CL) on the fermentation quality and bacterial community of various varieties of whole-plant corn silage. Three different varieties of whole-plant corn (Yuqing386, Enxiai298, and Nonghe35) were treated with 0.02% BS (fresh material basis), 0.2% GA (fresh material basis) and 0.02% CL (fresh material basis), after which 45 days of anaerobic fermentation were conducted. With the exception of its low dry matter content, the results showed that Yuqing386’s crude protein, water-soluble carbohydrate, and lactic acid contents were significantly higher than those of the other two corn varieties. However, its acid detergent fiber and cellulose contents were significantly lower than those of the other two corn varieties. Among the three corn variety silages, Yuqing386 had the highest relative abundance of Lactobacillus at the genus level and the biggest relative abundance of Firmicutes at the phylum level. In addition, the three additives markedly enhanced the quantity of dry matter and crude protein as compared to the control group. The application of GA considerably decreased the level of neutral detergent fiber while significantly increasing the content of lactic acid and water-soluble carbohydrates. Even though all additives enhanced the structure of the bacterial community following silage, the GA group experienced the greatest enhancement. On a phylum and genus level, the GA group contains the highest relative abundance of Firmicutes and Lactobacillus , respectively. Overall, of the three corn varieties, Yuqing386 provides the best silage qualities. GA has the biggest impact among the additions employed in this experiment to enhance the nutritional preservation and fermentation quality of whole-plant corn silage.

Zhang, Zhiheng↗

Efficient Leaching of Metal Ions from Spent Li-Ion Battery Combined Electrode Coatings Using Hydroxy Acid Mixtures and Regeneration of Lithium Nickel Manganese Cobalt Oxide

Extensive use of Li-ion batteries in electric vehicles, electronics, and other energy storage applications has resulted in a need to recycle valuable metals Li, Mn, Ni, and Co in these devices. In this work, an aqueous mixture of glycolic and lactic acid is shown as an excellent leaching agent to recover these critical metals from spent Li-ion laptop batteries combined with cathode and anode coatings without adding hydrogen peroxide or other reducing agents. An aqueous acid mixture of 0.15 M in glycolic and 0.35 M in lactic acid showed the highest leaching efficiencies of 100, 100, 100, and 89% for Li, Ni, Mn, and Co, respectively, in an experiment at 120 °C for 6 h. Subsequently, the chelate solution was evaporated to give a mixed metal-hydroxy acid chelate gel. Pyrolysis of the dried chelate gel at 800 °C for 15 h could be used to burn off hydroxy acids, regenerating lithium nickel manganese cobalt oxide, and the novel method presented to avoid the precipitation of metals as hydroxide or carbonates. The Li, Ni, Mn, and Co ratio of regenerated lithium nickel manganese cobalt oxide is comparable to this metal ratio in pyrolyzed electrode coating and showed similar powder X-ray diffractograms, suggesting the suitability of α-hydroxy carboxylic acid mixtures as leaching agents and ligands in regeneration of mixed metal oxide via pyrolysis of the dried chelate gel.

Electrochemistry↗

Integrated Biorefinery of Brewer’s Spent Grain for Second-Generation Ethanol, Mycoprotein, and Bioactive Vinasse Production

Brewer’s spent grain (BSG), the main lignocellulosic by-product of the beer industry, represents an abundant yet underutilized resource with high potential for valorization. This study presents an integrated biorefinery approach to convert BSG into second-generation (2G) ethanol, bioactive vinasse for plant growth promotion, and fungal biomass as a potential mycoprotein source. The biomass was first subjected to biological delignification using the white-rot fungus Ganoderma lucidum, after which two valorization routes were explored: (i) evaluation of the fungal biomass as a mycoprotein candidate and (ii) alcoholic fermentation for ethanol production. For the latter, three pretreatment strategies were assessed (diluted sulfuric acid and two deep eutectic solvents (DESs) based on choline chloride combined with either glycerol or lactic acid) followed by a one-pot enzymatic saccharification and fermentation using Kluyveromyces marxianus SLP1. The highest ethanol yield on substrate (YP/S) was achieved with [Ch]Cl:lactic acid pretreatment (0.46 g/g, 89.32% of theoretical). Vinasse, recovered after distillation, was characterized for organic acid content and tested on Solanum lycopersicum seed germination, showing promising biostimulant activity. Overall, this work highlights the potential of BSG as a sustainable feedstock within circular economy models, enabling the production of multiple bio-based products from a single residue.

Ganoderma lucidum↗

Effect of hand-arm exercise on venous blood constituents during leg exercise

Contributions by ancillary hand and arm actions to the changes in blood constituents effected by leg exercises on cycle ergometer were assessed. Static or dynamic hand-arm exercises were added to the leg exercise (50 percent VO2 peak)-only control regimens for the subjects (19-27 yr old men) in the two experimental groups. Antecubital venous blood was analyzed at times 0, 15, and 30 min (T0, T15, and T30) for serum Na(+), K(+), osmolality, albumin, total CA(2+), and glucose; blood hemoglobin, hematocrit, and lactic acid; and change in plasma volume. Only glucose and lactate values were affected by additional arm exercise. Glucose decreased 4 percent at T15 and T30 after static exercise, and by 2 percent at T15 (with no change at T30) after dynamic arm exercise. Conversely, lactic acid increased by 20 percent at T30 after static exercise, and by 14 percent by T15 and 6 percent at T30 after dynamic arm exercise. It is concluded that additional arm movements, performed usually when gripping the handle-bar on the cycle ergometer, could introduce significant errors in measured venous concentrations of glucose and lactate in the leg-exercised subjects.

Wong, N.↗

Analysis of Chiral Carboxylic Acids in Meteorites

Homochirality of amino acids in proteins and sugars in DNA and RNA is a critical feature of life on Earth. In the absence of a chiral driving force, however, reactions leading to the synthesis of amino acids and sugars result in racemic mixtures. It is currently unknown whether homochirality was necessary for the origins of life or if it was a product of early life. The observation of enantiomeric excesses of certain amino acids of extraterrestrial origins in meteorites provides evidence to support the hypothesis that there was a mechanism for the preferential synthesis or destruction of a particular amino acid enantiomer [e.g., 1-3]. The cause of the observed chiral excesses is un-clear, although at least in the case of the amino acid isovaline, the degree of aqueous alteration that occurred on the meteorite parent body is correlated to the isovaline L-enantiomeric excess [3, 4]. This suggests that chiral symmetry is broken and/or amplified within the meteorite parent bodies. Besides amino acids, there have been only a few reports of other meteoritic compounds found in enantiomeric excess: sugars and sugar acids [5, 6] and the hydroxy acid lactic acid [7]. Determining whether or not additional types of molecules in meteorites are also present in enantiomeric excesses of extraterrestrial information will provide insights into mechanisms for breaking chiral symmetry. Though the previous measurements (e.g., enantiomeric composition of lactic acid [7], and chiral carboxylic acids [8]) were made by gas chromatography-mass spectrometry, the potential for increased sensitivity of liquid chromatography-mass spectrometry (LC-MS) analyses is important because for many meteorite samples, only small sample masses are available for study. Furthermore, at least in the case of amino acids, many of the largest amino acid enantiomeric excesses were observed in samples that contained lower abundances (tens of ppb) of a given amino acid enantiomer. In the present work, we describe our efforts to develop highly sensitive LC-MS methods for the analysis of chiral carboxylic acids including hydroxy acids.

Burton, A. S.↗

Exploiting chitosan to improve the interface of nanocellulose reinforced polymer composites

Cellulose nanofibrils (CNFs) have been widely used as a nanofiller for polymer composite reinforcement due to their excellent mechanical properties. However, CNF is produced in water and needs to be dried prior to use in composite materials. The presence of hydroxyl groups on the surface of CNF creates strong hydrogen bonding that makes it difficult and costly to dry. Additionally, the hydrophilicity at the fiber surface results in agglomeration of CNFs within many polymer matrices. In this study, chitosan (CS) was co-precipitated with CNF to produce a dual-bonding filler for use in poly (lactic acid) (PLA) composites. CS promotes improved interfacial interaction within the polymer matrix by forming strong hydrogen bonds with the CNF and potential covalent bonds with the PLA. Finally, the results confirmed that the addition of a small amount of CS significantly improved the mechanical properties compared to PLA + CNF composites and neat PLA. The detailed study of the PLA + CNF/CS composites reveals the synergetic effect of the hydrogen and covalent bonding mechanism for PLA reinforcement.

59 BASIC BIOLOGICAL SCIENCES↗

Improving the Recyclability of Polymer Composites With Cellulose Nanofibrils

Cellulose nanofibers (CNFs) have been widely studied for their reinforcing potential in high-performance composites. While there are numerous publications on CNF-reinforced composites in a variety of polymer matrices, few have considered the recyclability of such thermoplastic composites and whether the incorporation of CNFs deteriorates or improves their performance upon reprocessing. In this study, two thermoplastic resins, poly(lactic acid) (PLA), and glycol-modified polyethylene terephthalate (PETg), were prepared with CNF reinforcement and thermomechanically recycled to investigate the effect of CNF inclusion on the composite properties after reprocessing as well as their effect on the composites’ number of useful life cycles. Additionally, changes in mechanical, thermal, rheological, molecular, and microstructural properties of the composites and/or base resins were monitored as a function of cycle numbers. As is typical, the polymers’ molecular weight and mechanical performance deteriorated with continued processing. However, the addition of spray dried CNF was found to better maintain the mechanical performance of both polymers throughout multiple recycling steps as compared to neat samples. For example, the tensile strength of PETg with 20 wt% CNF after 6 processing cycles was found to exceed that of virgin neat PETg, and higher loadings of CNF were found to preserve a higher yield strength during multiple rounds of reprocessing compared to PETg composites with lower CNF loadings. Ultimately this study indicates that the addition of CNF to some thermoplastic materials can increase both their sustainability by offsetting the use of high-embodied energy resins and their circularity by enabling performance retention over more use cycles.

42 ENGINEERING↗