Electrosprayed cashew gum microparticles for the encapsulation of highly sensitive bioactive materials.

This study focuses on the production and characterization of electrosprayed cashew gum (CG) microparticles that encapsulate ß-carotene. CG is an inexpensive, non-toxic polysaccharide obtained from Anacardium occidentale trees. Encapsulation of ß-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 ß-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 ß-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.

Changing the Landscape: An Introduction to the Agricultural and Food Chemistry Technical Program at the 258th American Chemical Society National Meeting in San Diego.

This special issue of the Journal of Agricultural and Food Chemistry (JAFC) is a highlight of the Agricultural and Food Chemistry Division (AGFD) technical program at the 258th National Meeting of the American Chemical Society (ACS) in San Diego, CA, U.S.A., on August 25-29, 2019. At the conference, AGFD had 44 oral sessions at 19 symposia and 100 poster presentations with more than 400 abstract submissions. The technical program covered a broad range of current research and development topics in agricultural and food chemistry, including bioactive food components, diet and human nutrition, utilization of agricultural materials in food systems, food packaging, nanotechnology, and food safety, as well as several special award symposia. This is the first JAFC special issue that highlights an ACS national meeting program with joint efforts from AGFD.

Hydrophobic Modification of Cashew Gum with Alkenyl Succinic Anhydride.

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 °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.

NMR Analysis of Poly(Lactic Acid) via Statistical Models.

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.

Cellulose nanocrystal driven microphase separated nanocomposites: Enhanced mechanical performance and nanostructured morphology.

The interest in the modification of cellulose nanocrystals (CNCs) lies in the potential to homogenously disperse CNCs in hydrophobic polymer matrices and to promote interfacial adhesion. In this work, poly(methyl methacrylate) (PMMA) and poly(butyl acrylate) (PBA) were grafted onto CNCs, thereby imparting their hydrophobic traits. The successful grafting modification led to the increased thermal stability of modified CNCs (MCNCs), and the hydrophobic surface modification was integrated with crystalline structure and morphology of CNCs. The nanocomposites with 7 wt% MCNCs/PBA-co-PMMA had an increase in Young's modulus of >25-fold and in tensile strength at about 3 times compared to these of neat PBA-co-PMMA copolymer. In addition, a micro-phase separated morphology (PBA soft domains, and PMMA and CNC hard domains) of MCNCs/PBA-co-PMMA nanocomposites was observed. The large increase in the storage moduli (glass transition temperatures) and organized morphology of MCNCs/PBA-co-PMMA nanocomposites also elucidated the relationship between mechanical properties and micro-phase separated morphology. Therefore, the MCNCs are effective reinforcing agents for the PBA-co-PMMA thermoplastic elastomers, opening up opportunities for their wide-spread applications in polymer composites.

Slow Down and Enjoy: The Effects of Cycling Cadence on Pleasure.

Pleasure plays a key role in exercise behavior. However, the influence of cycling cadence needs to be elucidated. Here, we verified the effects of cycling cadence on affect, perceived exertion (ratings of perceived exertion), and physiological responses. In three sessions, 15 men performed a maximal cycling incremental test followed by two 30-min constant workload (50% of peak power) bouts at 60 and 100 r/min. The pleasure was higher when participants cycled at 60 r/min, whereas ratings of perceived exertion, heart rate, and oxygen uptake were lower ( p < .05). Additionally, the rate of decrease in pleasure and increase in ratings of perceived exertion was less steep at 60 r/min ( p < .01). Cycling at 60 r/min is more pleasant, and the perceived effort and physiological demand are lower than at 100 r/min.

Morphological influence of cellulose nanoparticles (CNs) from cottonseed hulls on rheological properties of polyvinyl alcohol/CN suspensions.

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.

Microwave-assisted synthesis of cyclodextrin polyurethanes.

Cyclodextrin (CD) has often been incorporated into polyurethanes in order to facilitate its use in encapsulation or removal of organic species for various applications. In this work a microwave-assisted method has been developed to produce polyurethanes consisting of α-, ß-, and γ-CD and three common diisocyanates. As compared to conventional heating, this new synthetic method saves energy, significantly reduces reaction time, and gets similar or improved yield. The reaction products have been fully characterized with (13)C, (1)H, and two-dimensional NMR spectroscopy. With suitable stoichiometry of starting CD and diisocyanate, the resulting CD polyurethane is organic-soluble and water-insoluble and is shown to remove Nile red dye and phenol from water. Possible applications include the removal of undesirable materials from process streams, toxic compounds from the environment, and encapsulation of color or fragrance molecules.

Rating of perceived exertion and affective responses during Tai Chi Chuan.

Ratings of perceived exertion (RPE) and affective responses were assessed during Tai Chi Chuan. A total of 16 women (M age = 61.2 yr., SD = 8.8) participated in this study. Individuals practiced Tai Chi Chuan three times/week during seven weeks, and were assessed session-by-session (21 Wu Tai Chi Chuan sessions) in three moments (15, 30, and 45 min.) using Borg's scale (CR 0-10) and the Feeling Scale (+5/-5). With regard to RPE, there was a difference between 15 and 30 min. and between 15 and 45 min. The same pattern of differences was observed for the affective response. The RPE during the seven weeks ranged from "fairly light" to "moderate" and the affective response from "good" to "very good." Thus, Tai Chi Chuan was perceived as a low-moderate intensity and pleasurable (positive affect) exercise by middle-aged and elderly women.

Microwave-assisted synthesis of alkyl cellulose in aqueous medium.

Alkyl celluloses are commercial products that are made typically in an alcohol medium over the course of several hours. In this work an alternative, simplified synthesis of alkyl cellulose is reported, using microwave irradiation and aqueous alkaline medium. No alcohol is needed during the reaction. Reaction time is less than 30 min. Conversion varies from 54 to 87%. The degree of substitution varied from 0.2 to 1.0. The production of methyl cellulose and ethyl cellulose was confirmed by (13)C NMR and FTIR analysis.

Preparation of acetonides from soybean oil, methyl soyate, and fatty esters.

This paper describes the preparation of a new type of branched vegetable oil and its methyl ester that involves the formation of acetonides. A facile and environmentally friendly synthesis has been found to produce acetonides that entails the use of ferric chloride as a catalyst and is conducted at room temperature. The products have been fully characterized with the help of model compounds, including elemental analysis, infrared (IR) spectroscopy, nuclear magnetic resonance (NMR), and gas chromatography-mass spectrometry (GC-MS).

A versatile approach for modeling and simulating the tacticity of polymers.

We are introducing a versatile computerized approach to model and simulate polymer tacticities using seven single-stage statistical models. The theory behind the models, e.g., Bovey's versus Price's, Bernoullian, 1st or 2nd order Markovian, enantiomeric types, and combinations thereof is explained. One of the models, "E-B gen", which can be used to produce four types of enantiomorphically controlled tacticities, and the pentad distribution for the model "E-M1" are reported here for the first time. The relations of chain-end controlled models to binary copolymerizations are discussed in detail, and equations for the conversion of tacticity based probabilities to reactivity ratios to obtain related n-ad distributions are presented. The models were applied to 20 polymers with exemplary tacticities found in the literature. A related software program ("Polytact") based on Microsoft's Excel has been designed to calculate all relevant characteristics of the polymer tacticity and to present them in graphical form in a user-friendly manner. The program can be used to produce graphs of the triad, pentad and sequence length distributions and a simulation of 50 monomer repeat units in the polymer for each of the seven models. One of the main intended uses of the program is to compare the computed n-ad distributions to those of experimental polymers obtained from NMR spectroscopy and to gain insight into the polymerization mechanisms.

Synthesis of an amine-oleate derivative using an ionic liquid catalyst.

A facile (and environmentally friendly) reaction between epoxidized methyl oleate and aniline to produce an oleate-aniline adduct, without the formation of fatty amide, was discovered. This reaction was carried out neat, with a catalytic amount of an ionic liquid. No solvent was used, no byproducts were produced, and the ionic liquid could be recovered and recycled. The reaction products were fully characterized by NMR and GC-MS.

Azide derivatives of soybean oil and fatty esters.

An environmentally friendly water-based pathway to form the azide derivatives of soybean oil and fatty esters is reported. This entails first the formation of epoxides and then the azidization of the epoxides. The azidization reaction is carried out at high yields in water with only a small amount of an ionic liquid as a catalyst. The distribution of azide and alcohol functionalities on the fatty acid moiety is approximately random. This reaction has been applied to methyl oleate, methyl linoleate, soybean oil, and methyl soyate. The resulting structures have been studied by NMR.

Enzymatic modification of hydroxyethylcellulose by transgalactosylation with beta-galactosidases.

beta-galactosidases from A. oryzae and a thermophilic CLONEZYME glycosidase library were used to catalyze the transfer of the beta-D-galactopyranosyl moiety from lactose to the hydroxyl groups of hydroxyethylcellulose (HEC) in sodium acetate buffer. The degree of substitution was quantified by using galactose oxidase enzymatic assays. Depolymerization was also observed in the course of the transglycosylation reactions.