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The interests in biobased wood adhesives have been steadily increasing in recent years. Cottonseed protein isolate has shown potential as a renewable biobased adhesives. For a better understanding ...

In order to decrease the usage of formaldehyde and petroleum-derived raw materials, there has been a lot of interest in using protein-based wood adhesives as more eco-friendly and less hazardous al...

There has been increasing interest in recent years in the use of agro-based raw materials for the production of bio-friendly and sustainable products. Plant-based proteins are among the popular materials being studied. In particular, cottonseed protein (a byproduct of cotton fiber production) is widely available and has useful properties. Although not as well-known as soy protein, cottonseed protein has been shown to be a potentially valuable raw material for numerous applications. In this review, the latest developments in isolation, composition and molecular weight, chemical and enzymatic modifications, and non-food applications are delineated. Among these applications, films and coatings, interfacial and emulsifying applications, adhesives, and bioplastics seem to attract the most attention. A particular effort has been made to cover the literature on these topics in the past 10 years.

The purpose of this work was to explore the possibility of using cotton gin trash (CGT) as an inexpensive and biodegradable filler for poly(vinyl alcohol) (PVOH). CGT was milled and screened to give fine particles, and the particles less than 150 um in size were used together with three PVOH polymers (with 1–20% vinyl acetate levels) to form composites. Up to 60% by weight of CGT could be incorporated into PVOH to form composite films. Relative to PVOH, these PVOH/CGT films showed reduced tensile strength and elongation at break but enhanced Young’s modulus. CGT was chemically modified through acetylation and succinylation; however, no significant improvement in mechanical properties was observed with these modifications, although acetylated CGT did exhibit somewhat improved elongation at break relative to unmodified CGT for the two PVOH polymers with higher vinyl acetate contents. Thus, for PVOH applications that need reduced cost but can tolerate decreased tensile strength and elongation, cotton gin trash can be used as a cost-effective filler.

Currently, there is an increasing interest in the use of biopolymers in industrial applications to replace petroleum-based additives, since they are abundantly available, renewable and sustainable. Cottonseed protein is a biopolymer that, when used as a modifier, has shown improved performance for wood adhesives and paper products. Thus, it would be useful to explore the feasibility of using cellulose nanomaterials to further improve the performance of cottonseed protein as a paper strength agent. This research characterized the performance of cottonseed protein isolate with/without cellulose nanofibers (CNFs) and cellulose nanocrystals (CNCs) to increase the dry strength of filter paper. An application of 10% protein solution with CNCs (10:1) or CNFs (50:1) improved the elongation at break, tensile strength and modulus of treated paper products compared to the improved performance of cottonseed protein alone. Further analysis using scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) indicated that the cottonseed protein/nanocellulose composites interacted with the filter paper fibers, imparting an increased dry strength.

There is current interest in active packaging, where the packaging material exhibits desirable functions in addition to containment of product. One of these functions is to reduce the oxygen content in the package in order to minimize product oxidation and spoilage, and prolong product shelf-life. In this work, we have developed novel nanocomposites, comprising cellulose nanocrystals and Pd nanoparticles embedded in an ethylene–vinyl alcohol copolymer (EVOH). The nanocellulose is a critical component in the nanocomposite because it acts not only as reducing agent for PdCl2 but also as support for the dispersion of Pd nanoparticles on EVOH film and enhances the physical properties of the EVOH. Pd nanoparticles react with oxygen to serve as oxygen scavenger. The cellulose nanocrystals have also been optionally oxidized, and the increased presence of carboxyl groups favored a better distribution of the Pd nanoparticles, thereby enabling improved oxygen absorption. These features make the nanocomposites promising candidates as active packaging materials. Included in this work are the preparation and the characterization of these materials.

Recently, there has been an increasing trend toward replacing conventional fossil-based plastics with bioplastics that are eco-friendly and biodegradable. In this work, blends of polycaprolactone (...

High performance nanocomposites with good interfacial miscibility and phase separated morphology have received a lot of attention. In this work, cellulose nanocrystals (CNCs) were first grafted with hydrophobic poly(methyl methacrylate) (PMMA) chains to produce modified CNCs (PMCNCs) with increased thermal stability. Such surface-tailored CNCs effectively influenced the phase morphology and improved the mechanical properties of poly(butyl acrylate-co-MMA) (PBA-co-PMMA) nanocomposites. Morphological analysis indicated the presence of microphase separation in PMCNCs/PBA-co-PMMA nanocomposites with PBA as the soft domain and PMMA as well as CNCs as the hard domain. The nanocomposites with 10 wt% PMCNCs/PBA-co-PMMA showed increases in Young’s modulus of more than 20-fold and in tensile strength of about 3-fold compared to those of the unmodified PBA-co-PMMA copolymer. Therefore, the PMCNCs played a crucial role in controlling the interfacial miscibility and tuning the phase morphology of the nanocomposites. It is also essential to understand the role played by microphase separation in achieving nano-scaled morphological control and in fine-tuning the resultant composite properties.

Cellulose is often described as a mixture of crystalline and amorphous material. A large part of the general understanding of the chemical, biochemical and physical properties of cellulosic materials is thought to depend on the consequences of the ratio of these components. For example, amorphous materials are said to be more reactive and have less tensile strength but comprehensive understanding and definitive analysis remain elusive. Ball milling has been used for decades to increase the ratio of amorphous material. The present work used 13 techniques to follow the changes in cotton fibers (nearly pure cellulose) after ball milling for 15, 45 and 120 min. X-ray diffraction results were analyzed with the Rietveld method; DNP (dynamic nuclear polarization) natural abundance 2D NMR studies in the next paper in this issue assisted with the interpretation of the 1D analyses in the present work. A conventional NMR model’s paracrystalline and inaccessible crystallite surfaces were not needed in the model used for the DNP studies. Sum frequency generation (SFG) spectroscopy also showed profound changes as the cellulose was decrystallized. Optical microscopy and field emission-scanning electron microscopy results showed the changes in particle size; molecular weight and carbonyl group analyses by gel permeation chromatography confirmed chemical changes. Specific surface areas and pore sizes increased. Fourier transform infrared (FTIR) and Raman spectroscopy also indicated progressive changes; some proposed indicators of crystallinity for FTIR were not in good agreement with our results. Thermogravimetric analysis results indicated progressive increase in initial moisture content and some loss in stability. Although understanding of structural changes as cellulose is amorphized by ball milling is increased by this work, continued effort is needed to improve agreement between the synchrotron and laboratory X-ray methods used herein and to provide physical interpretation of the SFG results.

Water washed cottonseed meal (WCSM) is an excellent bio-adhesive resource because of its cost-effective extraction process and environmentally friendly performance. To evaluate the effects of protein content on the adhesive performance of cottonseed meal-based adhesives, we reconstituted cottonseed meal products with protein contents ranged from 34.9% to 94.8% by blending different amounts of WCSM, cottonseed protein isolate (CSPI), and residues after protein extraction (CSIR). Their physicochemical properties and three types of adhesive strengths (dry, wet, and soaked) were measured with press temperatures at 100, 150 and 170 °C. The morphological and rheological data showed that the low-protein-content adhesives with a high amount of residual cotton hull and fiber possessed poor spreadability and adhesive strength. Molecular and thermal analysis suggested that protein ratio had a stronger influence than press temperature to thermal property and adhesive strength. With these data, multiple linear regression models were established, providing analytical tools to predict the bonding strength affected by protein content and press temperature in cottonseed meal-based adhesives. On the other hand, the blends with 65–70% of protein content demonstrated the bonding performance and flowability comparable to highest protein product CSPI (94.8% protein) within the acceptable standard deviations. Thus, these observations and data could be helpful in set-up of industrial standard requirements and quality control for protein content in cost-effective adhesive-grade WCSM products.

This study focuses on the production and characterization of electrosprayed cashew gum (CG) microparticles that encapsulate β-carotene. CG is an inexpensive, non-toxic polysaccharide obtained from Anacardium occidentale trees. Encapsulation of β-carotene in CG was performed by electrospraying from two emulsion formulations (water : oil ratios 80:20 and 90:10 (v/v)) in which the dispersed phase consisted of β-carotene dissolved in castor oil, and the continuous phase was a CG aqueous solution. Spherical particles with smooth surface and medium size between 3 and 6 μm were obtained. The particles produced from the 90:10 (v/v) emulsion showed a loading capacity of 0.075 ± 0.006 % and a minor amount of extractable β-carotene, 10.75 ± 2.42 %. ATR-FTIR confirmed the absence of interaction between the particles’ components. CG demonstrated to offer thermoprotection, and photoprotection for short periods of time. These results make CG a viable candidate to encapsulate bioactive compounds via electrospraying for agricultural, food and pharmaceutical applications., This work was supported in part by the U.S. Department of Agriculture, Agricultural Research Service.

Cotton is one of the most important and widely grown crops in the world. Understanding the synthesis mechanism of cotton fiber elongation can provide valuable tools to the cotton industry for improving cotton fiber yield and quality at the molecular level. In this work, the surface and thermal characteristics of cotton fiber samples collected from a wild type (WT) and three mutant lines (Li1, Li2-short, Li2-long, Li2-mix, and liy) were comparatively investigated. Microimaging revealed a general similarity trend of WT ≥ Li2-long ≈ Li2-mix &gt, Li1 &gt, Li2 short ≈ liy with Ca detected on the surface of the last two. Attenuated total reflectance Fourier transform infrared (ATR FT-IR) spectroscopy and thermogravimetric measurements also showed that Li2-short and liy were more similar to each other, and Li2-long and Li2-mix closer to WT while Li1 was quite independent. FT-IR results further demonstrated that wax and amorphous cellulose were co-present in fiber structures during the fiber formation processes. The correlation analysis found that the FT-IR-based maturity parameter was well correlated (p ≤ 0.05) to the onset decomposition temperature and all three weight-loss parameters at onset, peak, and end decomposition stages, suggesting that the maturity degree is a better parameter than crystallinity index (CI) and other FT-IR parameters that reflect the thermal stability of the cotton fiber. In summary, this work demonstrated that genetic mutation altered the surface and thermal characteristics in the same way for Li2-short and liy, but with different mechanisms for the other three mutant cotton fiber samples.

Novel nanocomposite hydrogels were successfully prepared by blending and crosslinking sodium alginate (SA), poly(vinyl alcohol) (PVA) and cellulose nanofibers (CNFs) in the presence of a fertilizer formulation containing nitrogen (N), phosphorus (P) and potassium (K). The hydrogels had a macroporous flexible core and a microporous semi- interpenetrating polymer network (IPN) shell. The crystalline nature of the NPK chemicals was retained in the hydrogel nanocomposite network. Furthermore, the SA/CNF/PVA-based hydrogels showed a higher water-retention capacity in both deionized water and mixed soil. The swelling behavior in various physiological pH, salt and alkali solutions exhibited good sensitivity. The NPK release from SA/CNF/NPK and SA/CNF/PVA/NPK hydrogels was controlled by Fickian diffusion in both water and soil based on the Korsmeyer-Peppas release kinetics model (n

Cashew gum (CG) shows promise of being useful as an agro-based raw material for the production of eco-friendly and biodegradable polymers. In this work, we modified this water-soluble polymer with alkenyl succinic anhydride in order to attach a hydrophobic group to it. The modification used two reagents: octenyl succinic anhydride and tetrapropenyl succinic anhydride. Reactions were conducted at 120 &deg, C using dimethyl sulfoxide as a solvent, with conversions better than 88%. Samples with degrees of substitution (DS) between 0.02 and 0.20 were made. The resulting polymers were characterized using 1H NMR, 13C NMR, FTIR, TGA, and GPC. The addition of the hydrophobe decreased the affinity of cashew gum for water absorption. Hydrophobically modified polysaccharides are often used as polymeric emulsifiers, thickeners, and compatibilizers, we anticipate that these new hydrophobically modified CGs may be used for the same applications.

Polyhydroxyalkanoates (PHAs) are considered promising “green” alternatives to synthetic polymers because they are bio-derived, biodegradable and biocompatible. The properties of bacterial PHA copolymers depend on their microstructures, which can be modified with the use of different fermentation processes and feed materials. Thus, it is desirable to have an improved testing method for the determination of PHA microstructures. In this work, a detailed NMR analysis of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) microstructure was made. Previously only two of the hydroxyvalerate 13C NMR peaks have been assigned at the triad level. In this work, three of the 13C hydroxyvalerate peaks and two of the hydroxybutyrate peaks were found to be split into four peaks each due to comonomer sequence effects. Using eight copolymer samples with a wide compositional range, we were able to assign all these peaks to B-centered and V-centered triad sequences. Through curve deconvolution, the triad intensities were determined. These triad sequence intensities can then be analyzed via both the first-order Markovian and two-component Bernoullian models to obtain more in-depth information on copolymer composition and comonomer reactivities., The authors would like to thank the Spanish Ministry of Science and Innovation (MICI) through the RTI2018-097249-B-C21 program number and the EU H2020 YPACK (reference number 773872) for funding.

There is increasing interest in agro-based, biodegradable and eco-friendly wood adhesives as partial replacements for petroleum-based adhesives. In this work, we studied the adhesion of cottonseed ...

In this study, a polysaccharide and a protein were combined to form a polyblend that can be used for food packaging. Cashew gum (CG) and gelatin (G) films were generated by the casting method with the help of the central composite rotational design. When filmogenic solutions of 2.5–7.5 g of G and CG were dissolved in 100 mL water with 10% glycerol, the resulting films were compact and homogeneous with no pores present. Different CG/G ratios were examined for water vapor permeability (WVP), thickness, solubility, mechanical and thermal properties, surface morphology, and biodegradability. The results showed that at around 1:1 CG/G weight ratio the solubility decreased, reaching the minimum value at the CG composition of 45%. The blend of 50/50 CG:G showed the best WVP (1.16 g mm k Pa−1 h−1 m−2). For elongation at break, the combination of 5 g CG and 2.5 g G provided the best results with over 100% elongation. The films were shown to be easily biodegradable, producing as much CO2 as starch during the 22 days of an aerobic biodegradability test.

Acylation of polysaccharides is a commercially important reaction and is usually performed in a process involving the polysaccharide, an acid anhydride, and an inorganic acid. As an alternative to inorganic acid, many catalysts, including some metal chlorides, have been previously reported as catalysts. In this work, we took a more comprehensive look at several metal chlorides to observe trends and reactivities among them, particularly relating to reaction temperature, time, and amount of acetic anhydride used. Iodine was also included for comparison. Almost all the metal chlorides studied were found to be active as catalysts for the acetylation of starch under suitable reaction conditions. However, each metal chloride had a somewhat different reactivity with a different optimal temperature needed for satisfactory reactions to take place. The molecular weight of the starch acetate products decreased in all cases observed. The reactivity trends among the metal halides seemed to correlate both with ...

Although hemicellulose is found widely in nature, it is currently under-utilized as a raw material for commercial applications. It would be desirable to find new uses for hemicellulose in order to add value to this agro-based material. A common type of hemicellulose is xylan, which is found in a number of wood species and in cotton. In this work we prepared cationic and anionic xylan derivatives and characterized them by 13C NMR, FT-IR, size exclusion chromatography (SEC), thermal analysis, and rheology. In particular, the 13C NMR spectra of carboxymethyl xylan (CMX) and quaternary ammonium-adducted xylan (QAX) were fully assigned with the help of samples with different degrees of substitution. SEC indicated that the beechwood xylan showed a bimodal molecular weight distribution, but with derivatization the distribution tended to become unimodal. Thermal analysis and rheology studies did not uncover any surprises; the solution of xylan and its derivatives exhibited mostly Newtonian behavior. The blends of CMX and QAX produced a precipitate at almost all ratios, indicating the formation of a polyelectrolyte complex. When cationic and anionic xylan samples were added together to paper, the paper dry strength increased. Thus, the combination of cationic/anionic xylan may be of interest in selected applications.

Nonwoven fabrics have grown in popularity in recent years due to their overwhelming usage in a wide range of consumer products. Cotton-based nonwovens are of particular interest because of their ability to be recycled and reused, resulting in a more environmentally friendly product compared to their petroleum-based counterparts. The current research characterized the use of cottonseed protein as an additive to increase the dry strength of cotton-based nonwovens. The tensile strength of nonwovens was found to increase as the concentration of protein applied was increased. At 11% protein concentration, the tear strength and burst strength increased significantly (relative to the nonwoven by itself) by 288% (machine direction) and 295%, respectively. Further characterization by thermogravimetric analysis, Fourier transform infrared spectroscopy, and scanning electron microscopy suggested that cottonseed protein interacted with the cotton fiber in the nonwoven fabric to produce the increased dry strength.

Because of the current interest in sustainability, environmental stewardship, and green chemistry, there has been a lot of interest in using agro-based raw materials for the design of polymeric materials. One of the promising biorenewable materials is sucrose, which is inexpensive and widely available. In this work we have carried out the synthesis of sucrose–toluene diisocyanate-based polyurethane through microwave-assisted reactions. Comparisons of conventional heat versus microwave reactions have been made. Microwave-assisted synthesis has been found to significantly decrease the reaction time and save energy relative to conventional heat. The sucrose polyurethane has turned out to be a suitable matrix to prepare semi-interpenetrating polymer networks (semi-IPNs) involving a second material. Two examples shown in this work are the semi-IPNs of sucrose polyurethane with polycaprolactone and soybean oil. Characterization of the polymers has been conducted with 13C NMR, FT-IR, size-exclusion chromatograph...

This paper reports the application of an amperometric biosensor for rapid and specific Salmonella Typhimurium detection in milk. This device was developed from self-assembled monolayer technique on a gold screen-printed electrode, using cysteamine thiol. Polyclonal antibodies were oriented by protein A immobilization. The biosensor structure was characterized by cyclic voltammetry, Fourier transform infrared spectroscopy, and scanning electron microscopy. The analytical response was obtained by a chronoamperometry technique, using a direct-sandwich peroxidase-labeled system. The biosensor device showed a qualitative behavior with a very low limit of detection of 10 CFU mL−1 and a detection time of 125 min. The biosensor specificity was demonstrated in pure and mixed samples with strains of Escherichia coli and Citrobacter freundii. The performance of the biosensor was found satisfactory, and the device was tested in skimmed and whole milk samples, being able to detect S. Typhimurium quickly, without an enrichment step. This structure of immunosensor assembly can be expended in future studies for other food matrices and bacterial species, making it a useful tool to ensure food safety.

Carboxymethylated cashew gum (CMCG) film was electrodeposited on a gold surface for immobilization of polyclonal anti-Salmonella antibodies. The immunosensor response was obtained by chronoamperometry in milk contaminated with Salmonella enterica serovar Typhimurium. The CMCG film was a suitable platform for the immunosensor assembly and showed a stable structure with a 12% coefficient of variation after 30 sweeps in phosphate saline buffer (pH 7.4). The current (i) measured during the S. Typhimurium detection presented a linear calibration curve up to 105 CFU mL−1. The limit of detection was 10 CFU mL−1 with a detection time of 125 min. The immunosensor had a good performance in raw, whole and skimmed ultra-high temperature (UHT) milk without pre-enrichment step thus proving its efficacy in detecting bacteria in a complex food matrix. In addition, a high specificity was observed in the cross-reactivity tests with other bacteria. The CMGC-based immunosensor has a good potential for use as a screening test for Salmonella in the food control and prevention of foodborne diseases.

Cottonseed protein has great potential to replace formaldehyde-based adhesives due to the nature of non-toxicity, harmlessness, and non-pollution. Like soy protein-based adhesives, cottonseed protein-based adhesives also face a huge challenge in water resistance. In this work, the adhesion performance of cottonseed protein isolate (CSPI) modified by combination of H3PO4 and CaCl2 with different mole ratios was investigated and compared with those modified by 40 mM H3PO4, CaCO3, CaO, or CaHPO4. Results showed that CSPI with 40 mM CaHPO4 did not show better adhesion performance when compared with 40 mM H3PO4, CaCO3, or CaO, indicating the little/no synergy between Ca and P due to the spatial structure restriction of water insoluble CaHPO4. However, the combination of H3PO4 and CaCl2 enhanced the adhesion performance of CSPI in comparison with other modifiers, due to free Ca2+ released from water soluble CaCl2 presenting a better synergy with PO43-. At the optimal loadings of 40 mM H3PO4 and 20 mM CaCl2, 71, 86, and 56% increase in dry, wet, and soaked strengths was achieved. In addition, comparison of CSPIs with H3PO4/CaCl2 and H3PO4/Ca(NO3)2 indicates that the anions of water soluble calcium salts (CaCl2 and Ca(NO3)2) had insignificant effects on adhesion performance of CSPI. Those findings indicated that mixing of phosphoric acid and some water soluble calcium salts could synergistically enhance the adhesion performance of CSPI, thus improving the industrial acceptability of CSPI-based adhesives.

The performance of biosensors depends directly on the strategies adopted during their development. In this paper, a fast and sensitive biosensor for Salmonella Typhimurium detection was assembled by using optimization studies in separate stages. The pre-treatment assays, biomolecular immobilization (primary antibody and protein A concentrations), and analytical response (hydroquinone and hydrogen peroxide concentrations) were optimized via voltammetric methods. In the biosensor assembly, a gold surface was modified via the self-assembled monolayer technique (SAM) using cysteamine thiol and protein A for immobilization of anti-Salmonella antibody. The analytical response of the biosensor was obtained through the use of a secondary antibody labeled with a peroxidase enzyme, and the signal was evaluated by applying the chronoamperometry technique. The biosensor was characterized by infrared spectroscopy and cyclic voltammetry. Optimization of protein A and primary antibody concentrations enabled higher analytical signals of 7.5 and 75 mg mL−1, respectively, to be achieved. The hydroquinone and H2O2 concentrations selected were 3 and 300 mM, respectively. The biosensor developed attained a very low detection limit of 10 CFU mL−1 and a fast response with a final detection time of 125 min. These results indicate that this biosensor is very promising for the food safety and emergency response applications.

Soy and cottonseed proteins appear promising as sustainable and environment-friendly wood adhesives. Because of their higher cost relative to formaldehyde-based adhesives, improvement in the adhesive performance of proteins is needed. In this work, we evaluated the adhesive properties of soy and cottonseed protein formulations that included phosphorus-containing acids and esters. For cottonseed protein isolate, most of these additives improved dry adhesive strength, with methylphosphonic acid, phosphorous acid, and phosphoric acid increasing the dry strength by 47, 44, and 42%, respectively, at their optimal concentrations. For soy protein isolate, these additives did not show significant benefits. The phosphorus-containing additives also improved the hot water resistance of the cottonseed protein formulations but showed either no effect or a negative effect for the of soy protein formulations. Thus, the combination of cottonseed protein with phosphorus additives appears to be attractive as wood adhesives.

Most commercial wood adhesive use either formaldehyde-based resins or polyurethanes, both of which include potentially toxic chemicals in their formulations. As a result, proteins are being considered as greener and more sustainable wood adhesives. While most of the protein adhesive studies focus on soy proteins, there is also interest in exploring alternatives. In this work, testing of the adhesive performance of cottonseed protein isolate was undertaken in the presence of protein denaturants, i.e. guanidine hydrochloride (GuHCl), sodium dodecyl sulfonate (SDS), urea, and alkali. For comparison, soy protein isolate was also included in the study. At optimal dosage levels, the dry adhesive strength of cottonseed protein isolate could be enhanced by 38, 25, or 47% with SDS, GuHCl, or urea, respectively. The dry adhesive strength and hot water resistance of cottonseed protein isolate was generally superior to that of soy protein isolate, with or without the denaturants. Thus, the combination of cott...

Water-washed cottonseed meal (WCSM) has been shown as a promising bio-based wood adhesive. In this work, we tested the bonding strength of WCSM slurries with high solid contents and low press temperatures per industrial input for non-structural applications as European Standard Class D1 wood adhesives. Increasing the WCSM content from 11 to 20% and 30% did not substantially change the adhesive strength but increased the viscosity of WCSM slurries dramatically. The shear strength at break of the maple wood pairs bonded at 40 and 60 °C was lower than that of maple pairs bonded at 100 °C. However, the shear strength of the pairs bonded at lower temperatures (40 and 60 °C) could be improved by extending the press time from 20 to 120 min. Addition of citric acid (CA) improved the viscosity of the WCSM adhesive at 20% solid content, but lowered the adhesive strength. The addition of denaturing reagent sodium dodecyl sulfate (SDS) showed reverse impacts on the adhesive strength and viscosity, compared to...

The focus of this work was on the significant changes in the water dynamics of aqueous poly (N-isopropylacrylamide) (PNIPAM) solution during sol-to-gel transition. Through the use of NMR (particularly two-dimensional 2H NMR T1-T2 relaxation) and rheology, we were able to show that below 34° C fast exchange occurs among free water and water molecules adsorbed on the surface of PNIPAM molecules. At 34° C, PNIPAM becomes aggregated; most of the water molecules are trapped in the PNIPAM aggregates, where water molecules with different dynamics are found. Above 34° C, PNIPAM molecules aggregate further to form a gel network; the free bulk water then becomes dominant at this stage. On the basis of these observations, a model where water molecules interact with PNIPAM in different ways during the transition was proposed. We believe that our experimental approach provides new information and fresh perspectives on the sol-to-gel transition of PNIPAM.

This report details the design of carboxymethylated cashew gum (CG) as a platform for antibody (Ab) immobilization, which can then be used as a biosensor for bacteria detection. The CG was isolated and characterized, followed by conversion to carboxymethyl cashew gum (CMCG). The CMCG film was a viable support for antibody immobilization; it was electrodeposited on gold surface using the cyclic voltammetry technique, applying a potential sweep from −1.0 V to 1.3 V with a scan rate of 50 mV s−1 and 10 scans. The COOH groups on the surface of the film were critical in promoting Ab bonding. The immobilization of the Ab was mediated by protein A (PrA) for recognition of the antigen. Voltammetry studies were used to monitor the antibody immobilization. Finally, the analytical response of the CMCG-PrA-Ab system was evaluated with the chronoamperometry technique and was found to detect Salmonella Typhimurium bacteria rapidly and efficiently.

The physical properties of poly(lactic acid) (PLA) are influenced by its stereoregularity and stereosequence distribution, and its polymer stereochemistry can be effectively studied by NMR spectroscopy. In previously published NMR studies of PLA tacticity, the NMR data were fitted to pair-addition Bernoullian models. In this work, we prepared several PLA samples with a tin catalyst at different L,L-lactide and D,D-lactide ratios. Upon analysis of the tetrad intensities with the pair-addition Bernoullian model, we found substantial deviations between observed and calculated intensities due to the presence of transesterification and racemization during the polymerization processes. We formulated a two-state (pair-addition Bernoullian and single-addition Bernoullian) model, and it gave a better fit to the observed data. The use of the two-state model provides a quantitative measure of the extent of transesterification and racemization, and potentially yields useful information on the polymerization mechanism.

One of the desirable research goals today is to convert agro-based raw materials into low-cost functional polymers. Among the readily available natural raw materials are the fatty acids that can be obtained from the hydrolysis of plant oils or from the paper industry as byproducts. In this work, a novel iron-containing ionomer has been prepared through the reaction of fatty acids with steel dust or iron powder in the presence of carbon dioxide and water. Characterization has been achieved via 1H and 13C NMR, FT-IR, and size exclusion chromatography. The product has been shown to have an ionomeric structure, consisting of oligomers of fatty acid carboxylates (derived from Diels-Alder reaction) coupled with iron(II) and iron(III) ions (from the oxidation of iron). Because the fatty acid oligomers have low molecular weights, the ionomer easily dissolves in a solvent and can be made into different physical forms, such as liquid, solid, film, or foam.

Cardanol is a biobased raw material derived from cashew nut shell liquid. In order to extend its utility, new derivatives and additional applications are useful. In this work cardanol was first epoxidized, and a novel aniline derivative prepared from it under mild reaction conditions with the help of an ionic liquid catalyst. The reaction chemistry was studied by using nuclear magnetic resonance. The resulting aminohydrin adduct showed antioxidant property and should also be a useful synthon for further reactions. As an example, the aminohydrin was shown to undergo a condensation reaction with formaldehyde to form a prepolymer, which could be further reacted to form thermosetting resins.

Xylan is a hemicellulose, which is found abundantly in nature. In this work, a novel polyurethane was developed involving xylan and tolylene-2,4-diisocyanate (TDI). Polymer synthesis was achieved through conventional heat or microwave-assisted reaction in dimethyl sulfoxide. Because xylan has multiple OH groups on each polymer chain, the TDI/xylan molar ratio had to be adjusted to produce a soluble polymeric product. The reaction products were characterized by 13C NMR, FTIR, thermogravimetric analysis, and differential scanning calorimetry. The xylan polyurethane was shown to exhibit improved thermal stability over xylan.

The development of edible, environmentally friendly, mechanically strong and antimicrobial biopolymer films for active food packaging has gained considerable interest in recent years. The present work deals with the extraction and deacetylation of chitin nanofibers (ChNFs) from crab shells and their utilization as reinforcing and antimicrobial agents in carboxymethyl cellulose (CMC) films. ChNFs were successfully isolated from the speckled swimming crab shells for the first time through the multistep procedures involving deproteinization, demineralization, depigmentation and mechanical disintegration. Afterward, the partially deacetylated ChNFs (dChNFs) were obtained through alkali treatment. It was found that the partial deacetylation led to the exposure of more amino groups on the surface of dChNFs and thus remarkably improved their dispersion state in an aqueous solution. The ChNF/CMC and dChNF/CMC films comprising up to 10 wt % nanofibers were prepared through the solution casting method, and their pe...

As an environmentally friendlier alternative to adhesives from petroleum feedstock, soy proteins are currently being formulated as wood adhesives. Cottonseed proteins have also been found to provide good adhesive properties. In at least some cases, cottonseed proteins appear to form greater shear strength and improved hot water resistance compared with soy proteins. In the present study, blends of soy and cottonseed proteins were prepared, and their adhesive properties were found to decrease steadily with increased levels of soy protein in the formulations. In addition, cottonseed- and soy-protein based adhesives were also formulated with xylan, starch, or celluloses to determine the influence of polysaccharide fillers on protein-based adhesive properties. In some cases, adhesive shear strength was retained even when the cottonseed or soy protein was mixed with up to 75% polysaccharide. For cottonseed protein/polysaccharide formulations, hot water adhesive resistance was retained when the blend contains about 50% polysaccharides. Soy protein formulations and its polysaccharide blends generally exhibited somewhat lower hot water resistance. In view of the ability of cottonseed protein/polysaccharide blends to retain shear strength and hot water resistance properties, these blends may provide an opportunity to decrease the amount of protein used in adhesive formulations, thereby decreasing cost.

Soy protein is currently being used commercially as a “green” wood adhesive. Previous work in this laboratory has shown that cottonseed protein isolate, tested on maple wood veneer, produced higher adhesive strength and hot water resistance relative to soy protein. In the present study, cottonseed protein and soy protein isolates were tested on different wood types, and cottonseed protein again showed better performance relative to soy protein. Furthermore, the effects of several protein modifiers were evaluated, including amino acids, fatty acids, and other organic molecules with cationic or anionic charges. Aspartic acid, glutamic acid, acetic acid, butyric acid, and adipic acid gave improved performance when included with cottonseed protein isolate whereas no significant effect was observed on soy protein isolate. Both dry adhesive strength and hot water resistance were tested. The enhanced performance observed with these additives provides an additional incentive for the use of cottonseed protein in this application.

Pathogen detection is a critical point for the identification and the prevention of problems related to food safety. Failures at detecting contaminations in food may cause outbreaks with drastic consequences to public health. In spite of the real need for obtaining analytical results in the shortest time possible, conventional methods may take several days to produce a diagnosis. Salmonella spp. is the major cause of foodborne diseases worldwide and its absence is a requirement of the health authorities. Biosensors are bioelectronic devices, comprising bioreceptor molecules and transducer elements, able to detect analytes (chemical and/or biological species) rapidly and quantitatively. Electrochemical immunosensors use antibody molecules as bioreceptors and an electrochemical transducer. These devices have been widely used for pathogen detection at low cost. There are four main techniques for electrochemical immunosensors: amperometric, impedimetric, conductometric, and potentiometric. Almost all types of immunosensors are applicable to Salmonella detection. This article reviews the developments and the applications of electrochemical immunosensors for Salmonella detection, particularly the advantages of each specific technique. Immunosensors serve as exciting alternatives to conventional methods, allowing "real-time" and multiple analyses that are essential characteristics for pathogen detection and much desired in health and safety control in the food industry.

The interest in natural product-based wood adhesives has been steadily increasing due to the environmental and sustainable concerns of petroleum-based adhesives. In this work, we reported our research on the utilization of water-washed cottonseed meal (WCM) as wood adhesives. The adhesive strength and water resistance of WCM adhesive preparations on poplar, Douglas fir, walnut, and white oak wood veneers were tested with press temperatures of 80, 100, and 130 °C. Our data indicated that raising the hot press temperature from 80 to 100–130 °C greatly increased the bonding strength and water resistance of the WCM adhesives. The general trend of the adhesive strength of WCM on the four wood species was Douglas fir > poplar ≈ white oak > walnut. The rough surface of Douglas fir with tipping features could enhance the mechanical interlocking between the wood fibers and adhesive slurry, contributing to the high adhesive strength. The dimensional swelling of the bonded wood pairs due to water soaking was...

Polymer films made from cellulose esters are useful for embedding plant essential oils, either for food packaging or air freshener applications. Studies and testing were done on the physical and mechanical properties of cellulose ester-based films incorporating essential oils (EO) from lemongrass (Cybopogon citratus), rosemary pepper (Lippia sidoides) and basil (Ocimum gratissimum) at concentrations of 10 and 20% (v/w). Results obtained showed that, in all films, the addition of the essential oil caused a decrease in the water vapor permeability due to the hydrophobic nature of the oil. The use of 20% of EO caused lower transparency of the films, although the change was not observed visually. Mechanical testing was done on cellulose acetate, cellulose acetate propionate and cellulose acetate butyrate. It was found that incorporation of lemongrass, basil and rosemary pepper EO significantly affected the Young's modulus, tensile strength and elongation at break of the cellulose ester films. The results suggested that the essential oils interacted with the polymers like plasticizers. The results were confirmed with thermal and microscopic studies.

Micro and mesoporous materials are often used in catalysis, purification, composite filler, and other applications. Almond shell is an important agricultural byproduct that can be transformed to microporous and mesoporous carbon. In this work, we produced biochar from almond shell using a thermal treatment procedure in an inert atmosphere and characterized the pores with nitrogen adsorption, environmental SEM, and 129Xe NMR. The latter technique differentiates adsorbed and nonadsorbed xenon and permits the correlation of different processing conditions with xenon adsorption and diffusivity. The relevance of removing the ash produced during the charring process has been included in the study. Moreover, the xenon exchange between meso- and micro-pores has been directly observed by 129Xe NMR, demonstrating that after ash removal by water the materials have high accessibility of the pores by external fluids, thus increasing the usefulness as filtration or adsorption material.

The interest in biobased wood adhesives has steadily increased in recent years. Our previous studies have shown that water-washed cottonseed meal (WCSM) could be used as low-temperature and high-solid content biobased wood adhesives for non-structural bonding as European Standard Class D1 adhesives. In this work, we optimized WCSM-based adhesive formulations with high solid contents up to 49% for bonding of small wood items at low temperatures (40 °C). Chemical denaturing reagents guanidine hydrochloride (GdmCl) and sodium dodecyl sulfate (SDS) were added to improve the bonding capability and viscosity of WCSM. Reviewing industry preferences, four formulations with 20% and 30% of WCSM as well as 9.6% and 19.1% of SDS were used to glue “real world” pencil slat sandwiches for pencil making. All the pencils made from these sandwiches bonded at 40 °C and 1 MPa for 120 min passed the Industrial Temperature Cycle test. The results indicated that WCSM could be used as a low temperature wood adhesive, possibly for the domestic furniture and small utensils niche markets. The pencil sandwich bonding represents a specific application that could benefit from the non-toxic glue and also be an example of an interior application.

Water washing of cottonseed meal is more cost-efficient and environmentally friendly than protein isolation by means of alkaline extraction and acidic precipitation. Thus, water-washed cottonseed meal (WCSM) is more promising as biobased wood adhesives. In this work, we examined the effects of the particle size on the morphology and adhesive performance of WCSM. Pilot-scale produced and dried WCSM was treated by three grinding methods: (1) ground by a hammer mill and passed through a 0.5-mm screen, (2) further ground by a cyclone mill and passed through a 0.5-mm screen, or (3) further ground by a ball mill and passed through a 0.18-mm screen. Micro-morphological examination revealed two types of particles. The filament-like particles were mainly fibrous materials from residual linters. Chunk-like particles were more like aggregates or accumulations of small particles, with proteins as the major component. Further grinding of the 0.5-mm Hammer product with the Cyclone and Ball mill led to more fine (smaller) particles in the WCSM products. The impact of further grinding on the dry and soaked adhesive strengths was minimal. However, the decrease of the hot and wet strengths of WCSM products by the additional grinding was significant (p ≤ 0.05). Data presented in this work is useful in developing the industrial standards of WCSM products used in wood bonding.

The present work describes the isolation of cellulose nanoparticles (CNs) with different morphologies and their influence on rheological properties of CN and CN-poly (vinyl alcohol) (PVA) suspensions. Cottonseed hulls were used for the first time to extract three types of CNs, including fibrous cellulose nanofibers, rod-like cellulose nanocrystals and spherical cellulose nanoparticles through mechanical and chemical methods. Rheology results showed that the rheological behavior of the CN suspensions was strongly dependent on CN concentration and particle morphology. For PVA/CN systems, concentration of PVA/CN suspension, morphology of CNs, and weight ratio of CN to PVA were three main factors that influenced their rheology behaviors. This research reveals the importance of CN morphology and composition concentration on the rheological properties of PVA/CN, providing new insight in preparing high performance hydrogels, fibers and films base on PVA/CN suspension systems.

The utilization of cottonseed meal products as valuable industrial materials needs to be exploited. We have recently produced water-washed cottonseed meal, total cottonseed protein, sequentially extracted water- and alkali-soluble proteins, and two residues after the total and sequential protein extractions at a pilot scale. In this work, the surface characteristics of the six cottonseed meal products were examined by scanning electron microscopy (SEM), scanning electron microscopy- energy dispersive spectrometer (SEM-EDS), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The results showed that the surface properties of the six products differed from those of a commercial soy protein flour examined comparatively in this work. The compact morphology and relative-high N composition were observed in all three protein products, with greater similarity between the total protein and alkali-soluble protein. The surfaces of the two residue products were more porous with polysaccharide features. Washed cottonseed meal possessed the surface features similar to those of the residues. In the meantime, the N-associated functional groups were under-represented in the surfaces of all samples, compared to their bulk composition. Information derived from this work increased the understanding of the surface functional properties of cottonseed meal products, which would benefit their practical utilization.

Homogeneous modification of cellulose with succinic anhydride was performed using tetrabutylammonium acetate (TBAA)/dimethyl sulfoxide (DMSO) mixed solvent. The molar ratio of succinic anhydride (SA) to free hydroxyl groups in the anhydroglucose units (AGU), TBAA dosage, reaction temperature, and reaction time were investigated. The highest degree of substitution (DS) value of 1.191 was obtained in a 10 wt% TBAA/DMSO mixed solvent at 60 °C for 60 min, and the molar ratio of SA/AGU was 6/1. The molar ratio of SA/AGU and the TBAA dosage showed a significant influence on the reaction. The succinoylated cellulose was characterized by ATR-FTIR, TGA, XRD, solid state CP/MAS 13C NMR spectroscopy (CP/MAS 13C NMR), and SEM. Moreover, the modified cellulose was applied for the adsorption of Cu2+ and Cd2+, and both the DS values of modified cellulose and pH of the heavy metal ion solutions affected the adsorption capacity of succinylated cellulose. The highest capacity for Cu2+ and Cd2+ adsorption was 42.05 mg/g and 49.0 mg/g, respectively.

Adhesive bonding of wood plays an increasing role in the forest products industry and is a key factor for efficiently utilizing timber and other lignocellulosic resources. In this work, we obtained five soy meal products through commercial sources or in-house preparations. The protein content was 49.6%, 56.9%, 66.2%, 86.3%, and 91.9% for untreated defatted soy meal, pH 8.5 water washed meal, neutral water washed meal, commercial protein isolate, and in-house prepared protein isolate. The adhesive performances measured by the maximal dry and soaked shear strength of the bonded maple veneers at break were not exactly in the same order of the protein content, indicating that other components (e.g. carbohydrates, metals) might also have played certain roles in the adhesive ability of these products. Data at two press temperatures (i. e. 100, and 130 oC) with or without the addition of tung oil revealed that water washed soy meals behaved more like untreated meal than soy protein isolates. This observation is different from a recent report on the effect of water washing on cottonseed meal products. Thus, further elucidation of the mechanisms or causes of the differing effects of water washing would shed light on the adhesive mechanisms of the two types of oilseed meal materials, thus optimizing use of these materials and their fractions for wood bonding.