Effect of Four Novel Bio-Based DES (Deep Eutectic Solvents) on Hardwood Fractionation.

Using the basic principle of construction between a hydrogen bond acceptor (HBA) and a hydrogen bond donor (HBD), four bio-based deep eutectic solvents (DESs) were prepared in a 1:2 molar ratio of HBA:HBD. 2,3-Dihydroxypropyl-1-triethylammonium chloride ([C9H22N+O2]Cl-) was synthesized from raw glycerol and used as an HBA. Lactic acid, urea, pure glycerol, and ethylene glycol were selected as HBD. Attempts to prepare DESs, using citric acid and benzoic acid as HBDs, were unsuccessful. All these DESs were characterized using FTIR and NMR techniques. Besides, physicochemical parameters such as pH, viscosity, density, and melting point were determined. The behavior of these DES to fractionate olive pomace was studied. Lignin recovery yields spanned between 27% and 39% (w/w) of the available lignin in olive pomace. The best DES, in terms of lignin yield ([C9H22N+O2]Cl- -lactic acid), was selected to perform a scale-up lignin extraction using 40 g of olive pomace. Lignin recovery on the multigram scale was similar to the mg scale (38% w/w). Similarly, for the holocellulose-rich fractions, recovery yields were 34% and 45% for mg and multi-gram scale, respectively. Finally, this DES was used to fractionate four fruit pruning samples. These results show that our novel DESs are alternative approaches to the ionic liquid:triethylammonium hydrogen sulfate and the widely used DES: choline chloride:lactic acid (1:10 molar ratio) for biomass processing.

Preparation and Uses of Chlorinated Glycerol Derivatives.

Crude glycerol (C3H8O3) is a major by-product of biodiesel production from vegetable oils and animal fats. The increased biodiesel production in the last two decades has forced glycerol production up and prices down. However, crude glycerol from biodiesel production is not of adequate purity for industrial uses, including food, cosmetics and pharmaceuticals. The purification process of crude glycerol to reach the quality standards required by industry is expensive and dificult. Novel uses for crude glycerol can reduce the price of biodiesel and make it an economical alternative to diesel. Moreover, novel uses may improve environmental impact, since crude glycerol disposal is expensive and dificult. Glycerol is a versatile molecule with many potential applications in fermentation processes and synthetic chemistry. It serves as a glucose substitute in microbial growth media and as a precursor in the synthesis of a number of commercial intermediates or fine chemicals. Chlorinated derivatives of glycerol are an important class of such chemicals. The main focus of this review is the conversion of glycerol to chlorinated derivatives, such as epichlorohydrin and chlorohydrins, and their further use in the synthesis of additional downstream products. Downstream products include non-cyclic compounds with allyl, nitrile, azide and other functional groups, as well as oxazolidinones and triazoles, which are cyclic compounds derived from ephichlorohydrin and chlorohydrins. The polymers and ionic liquids, which use glycerol as an initial building block, are highlighted, as well.

A simplified techno-economic model for the molecular pharming of antibodies.

By the end of 2017, the Food and Drug Administration had approved a total of 77 therapeutic monoclonal antibodies (mAbs), most of which are still manufactured today. Furthermore, global sales of mAbs topped $90 billion in 2017 and are projected to reach $125 billion by 2020. The mAbs approved for human therapy are mostly produced using Chinese hamster ovary (CHO) cells, which require expensive infrastructure for production and purification. Molecular pharming in plants is an alternative approach with the benefits of lower costs, greater scalability, and intrinsic safety. For some platforms, the production cycle is also much quicker. But do these advantages really stack up in economic terms? Earlier techno-economic evaluations have focused on specific platforms or processes and have used different methods, making direct comparisons challenging and the overall benefits of molecular pharming difficult to gauge. Here, we present a simplified techno-economic model for the manufacturing of mAbs, which can be applied to any production platform by focusing on the most important factors that determine the efficiency and cost of bulk drug manufacturing. This model develops economic concepts to identify variables that can be used to achieve cost savings by simultaneously modeling the dynamic costs of upstream production at different scales and the corresponding downstream processing costs for different manufacturing modes (sequential, serial, and continuous). The use of simplified models will help to achieve meaningful comparisons between diverse manufacturing technologies.

Combined Analysis of Primary Metabolites and Phenolic Compounds to Authenticate Commercial Monovarietal Peach Purees and Pear Juices.

Here we authenticated single-varietal peach purees and pear juices on the basis of primary metabolite and phenolic compound analysis by Proton Nuclear Magnetic Resonance (1H-NMR) and Ultra Performance Liquid Chromatography coupled to Photodiode Array and Tandem Mass Spectrometry (UPLC-PDA-MS/MS), respectively. After suitable preprocessing, the 1H-NMR and chromatographic data were evaluated by principal component analysis (PCA). The PCA combining data from primary metabolites and phenolic compounds allowed the separation of the clusters in all cases, allowing discrimination of processed and unprocessed peach purees, both separately and pooled. The PCA of primary metabolites allowed the cluster separation of purees of distinct peach varieties but not between processed and non-processed purees. The PCA of phenolic compounds allowed better cluster separation than of primary metabolites. For pear juices, both PCA approaches allowed satisfactory discrimination of Alejandrina, Conference, and Blanquilla cultivars. These approaches may help to better control cultivar authenticity in fruit products. It could therefore contribute to the development of a process to achieve products characterized by a quality characteristic of a given cultivar.

Synthesis and Thermophysical Characterization of Fatty Amides for Thermal Energy Storage.

Nine monoamides were synthesized from carboxylic acids (C8-C18) and crude glycerol. The final monoamides were the result of a rearrangement of the acyl chain during the final hydrogenation process. The purity of the final compounds was determined by spectroscopic and mass spectrometry (MS) techniques. The thermophysical properties of solid monoamides were investigated to determine their capability to act as phase change materials (PCM) in thermal energy storage. Thermophysical properties were determined with a differential scanning calorimeter (DSC). The melting temperatures of the analyzed material ranged from 62.2 °C to 116.4 °C. The analyzed enthalpy of these monoamides ranged from 25.8 kJ/kg to 149.7 kJ/kg. Enthalpy values are analyzed considering the carbon chain and the formation of hydrogen bonds.

Autoimmune-Mediated Psychosis: A Case of Susac Syndrome in a Drug User.

OBJECTIVE: Susac syndrome, a rare disorder, is thought to be mediated by autoantibodies. One of the potential targets of these autoantibodies could be an antigen in the microvessels of the brain, the retina, and the inner ear leading to central nervous system (CNS) alterations, visual disturbances, and hearing deficits. Our aim is to expand clinicians' diagnostic options when facing psychosis due to medical conditions. METHODS: A case report was conducted for this study. RESULTS: This paper reports the case of a young male drug user who presented with psychosis, confusion and CNS vasculitis. First deemed to be drug-induced CNS vasculitis, it was finally diagnosed as Susac syndrome. CONCLUSIONS: Although an infrequent entity, Susac syndrome should remain an option in the differential diagnosis of several neurological and psychiatric presentations.

Vegetable Oils as Alternative Solvents for Green Oleo-Extraction, Purification and Formulation of Food and Natural Products.

Since solvents of petroleum origin are now strictly regulated worldwide, there is a growing demand for using greener, bio-based and renewable solvents for extraction, purification and formulation of natural and food products. The ideal alternative solvents are non-volatile organic compounds (VOCs) that have high dissolving power and flash point, together with low toxicity and less environmental impact. They should be obtained from renewable resources at a reasonable price and be easy to recycle. Based on the principles of Green Chemistry and Green Engineering, vegetable oils could become an ideal alternative solvent to extract compounds for purification, enrichment, or even pollution remediation. This review presents an overview of vegetable oils as solvents enriched with various bioactive compounds from natural resources, as well as the relationship between dissolving power of non-polar and polar bioactive components with the function of fatty acids and/or lipid classes in vegetable oils, and other minor components. A focus on simulation of solvent-solute interactions and a discussion of polar paradox theory propose a mechanism explaining the phenomena of dissolving polar and non-polar bioactive components in vegetable oils as green solvents with variable polarity.

Methadone for the treatment of Prescription Opioids Dependence. A retrospective chart review. / Metadona para el tratamiento de la dependencia de opioides de prescripción médica. Una revisión retrospectiva de historias clínicas.

Prescription opioids (PO) addiction is increasing to an epidemic level. Few studies exist regarding its treatment. Although buprenorphine has been the mainstay so far, other treatment options might be considered, such as methadone. We conducted a retrospective assessment of all patients admitted to a psychiatry ward for PO detoxification using methadone between 2010 and 2013. The assessment and description was carried out during a 3-month follow-up period after their discharge. Although this is a retrospective chart review, our exploration included sociodemographic and treatment variables in addition to the abstinence rates for the whole sample. Eleven patients were included, mostly women (81.8%), with a median age of 50 years. The median duration of dependence was 8 years. Dependence on other substances and psychiatric comorbidities were high. Eight patients were monitored during three months. Of these, 7 (87.5%) were abstinent after that period. The results suggest that methadone deserves further exploration as a potentially efficacious treatment option for PO dependence.

La adicción a opioides de prescripción médica (OPM) está ahasta la fecha sobre su tratamiento se basan principalmente en el uso de buprenorfina. Sin embargo, la metadona puede considerarse como otra opción. El objetivo de nuestro estudio fue revisar las historias clínicas de todos los pacientes ingresados en una unidad de psiquiatría para la desintoxicación de OPM usando metadona entre el 2010 y el 2013. El periodo de evaluación finaliza a los 3 meses desde el alta médico. Pese a ser una revisión de historia clínicas, se evaluaron las características sociodemográficas de la muestra, así como las variables relacionadas con el tratamiento y la tasa de abstinencia durante el estudio. Se incluyeron 11 pacientes, mayoritariamente mujeres (81,8%), con una mediana de edad de 50 años. La mediana de duración de la dependencia fue de 8 años. Hubo una alta prevalencia de adicción a otras sustancias así como de comorbilidades psiquiátricas. Ocho pacientes fueron seguidos durante al menos 3 meses. De estos, 7 (87,5%) estuvieron abstinentes hasta el final del periodo evaluado por el estudio. Los resultados sugieren la necesidad de estudios de mayor rigor metodológico para la correcta evaluación de la metadona como un tratamiento potencialmente eficaz para la dependencia de los OPM.

Comprehensive Two-dimensional Gas Chromatography Time-of-flight Mass Spectrometry to Assess the Presence of α,α-Trehalose and Other Disaccharides in Apple and Peach.

INTRODUCTION: Carbohydrates are important constituents in fruits. Among the carbohydrates, disaccharides have rarely been studied in apple and peach. Indeed, the abiotic stress biomarker and preservation agent α,α-trehalose is a disaccharide. OBJECTIVES: To establish a comprehensive method based on two-dimensional gas chromatography combined with time-of-flight MS detection (GC × GC-ToF/MS) to analyse the disaccharide composition of apple and peach. METHODS: The sample preparation was based on aqueous-methanolic extraction of the analytes, followed by oxime formation and trimethylsilylation of the disaccharides. First, three columns were tested with standards on the one-dimensional system. Next, to perform the sample analysis using GC × GC-MS (which offers significant advantages over conventional GC because it allows higher separation efficiencies), various column configurations were assessed on the two-dimensional system to obtain enhanced separation and low detection limits. The column sets tested included non-polar/semi-polar, semi-polar/polar and polar/non-polar. RESULTS: Using the method that proved to be more efficient, namely the method developed with the semi-polar/non-polar configuration, ten disaccharides were identified, based on analytical standards, retention index and mass spectra. These compounds were quantified in several varieties of apple and peach fruit using the developed GC × GC method and linear curve calibration, resulting in substantial differences among the fruits. However, cultivars within the fruits exhibited no significant differences. CONCLUSION: The proposed method allowed for the identification and quantification of several disaccharides in apple and peach, including the biomarker α,α-trehalose.

Motivational interviewing for smoking cessation in a psychiatric day hospital: a feasibility study.

OBJECTIVE: Our main objective was to test the feasibility of adding motivational interviewing to the usual smoking cessation treatment for patients with psychiatric disorders attending a day hospital. METHODS: A total of 44 patients participated in the study: a comparison group of 25 patients, all of whom received the usual smoking cessation treatment (nicotine replacement therapy, 1 hour of weekly group therapy, and daily individual advice), and an intervention group of 19 patients who received the usual smoking cessation treatment plus up to four motivational interviewing sessions. Data included sociodemographics, psychiatric diagnosis, cigarette use, and engagement in treatment. Descriptive analyses were conducted, along with logistic regression to test for differences on abstinence and daily smoking rates. RESULTS: All 19 patients offered the motivational interviewing accepted it, and all of them completed at least one session (M = 2.53, SD = 0.234, Range = 1 to 4). At the end of treatment, four patients in the intervention group were abstinent (versus none in the comparison group), but this was not statistically significant. Both groups showed a mean daily reduction of eight cigarettes. After introducing all variables into the regression models, none reached significance. CONCLUSIONS: Adding motivational interviewing to usual smoking cessation treatment in a psychiatric day hospital seems feasible and acceptable. Further, more rigorous research is needed.

Environmental and Yield Comparison of Quick Extraction Methods for Caffeine and Chlorogenic Acid from Spent Coffee Grounds.

This study aims to provide an overview of different extraction methods to obtain chlorogenic acid (CA) and caffeine (Caf) from spent coffee grounds (SCG). This overview shows that the quantity extracted is highly dependent on the type of SCG, so experiments using the same SCG are needed to compare different methods. Three easy and simple extraction methods will be tested at a laboratory scale and environmentally compared. All three experiments were of 1 min duration: first, using supramolecular solvent; second, with water and vortex; and third, with water assisted by ultrasound. Water extraction assisted by ultrasound at room temperature yielded the greatest quantity of chlorogenic acid and caffeine, with 1.15 mg CA/g and 0.972 mg Caf/g, respectively. Extraction using supra-solvent leads to a lower content of CA in the supra-phase since it has more affinity for the water-based inferior phase. An environmental assessment using life cycle assessment has been carried out to compare water and supra extraction methods for the manufacture of two different commercial products: a face cream and an eye contour serum. Results show that the type of solvent and the amount of active substance extracted have a great influence on the environmental results. The results presented here are important for companies willing to obtain these active substances at an industrial scale.

Toxicity of allyl esters in insect cell lines and in Spodoptera littoralis larvae.

We investigated the effects of five allyl esters, two aromatic (allyl cinnamate and allyl 2-furoate) and three aliphatic (allyl hexanoate, allyl heptanoate, and allyl octanoate) in established insect cell lines derived from different species and tissues. We studied embryonic cells of the fruit fly Drosophila melanogaster (S2) (Diptera) and the beet armyworm Spodoptera exigua (Se4) (Lepidoptera), fat body cells of the Colorado potato beetle Leptinotarsa decemlineata (CPB) (Coleoptera), ovarian cells of the silkmoth Bombyx mori (Bm5), and midgut cells of the spruce budworm Choristoneura fumiferana (CF203) (Lepidoptera). Cytotoxicity was determined with use of MTT [3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide] and trypan blue. In addition, we tested the entomotoxic action of allyl cinnamate against the cotton leafworm Spodoptera littoralis .The median (50%) cytotoxic concentrations (EC50s) of the five allyl esters in the MTT bioassays ranged between 0.25 and 27 mM with significant differences among allyl esters (P = 0.0012), cell lines (P < 0.0001), and the allyl ester-cell line interaction (P < 0.0001). Allyl cinnamate was the most active product, and CF203 the most sensitive cell line. In the trypan blue bioassays, cytotoxicity was produced rapidly and followed the same trend observed in the MTT bioassay. In first instars of S. littoralis, allyl cinnamate killed all larvae at 0.25% in the diet after 1 day, while this happened in third instars after 5 days. The LC50 in first instars was 0.08%. In addition, larval weight gain was reduced (P < 0.05) after 1 day of feeding on diet with 0.05%. In conclusion, the data provide evidence of the significant but differential cytotoxicity among allyl esters in insect cells of different species and tissues. Midgut cells show high sensitivity, indicating the insect midgut as a primary target tissue. Allyl cinnamate caused rapid toxic effects in S. littoralis larvae at low concentrations, suggesting further potential for use in pest control.

Carbon Footprint: The Case of Four Chicken Meat Products Sold on the Spanish Market.

Despite its relatively low environmental impact within the livestock sector, the poultry sector still faces its own environmental challenges that need to be addressed. The present paper uses life cycle assessment to quantify greenhouse gas emissions, from cradle to slaughterhouse gate, of four chicken meat products: whole carcass, wings, breast fillets, and leg quarters. The main contribution of the present study is that it provides a detailed analysis of different chicken meat cuts, testing mass and economic allocation choices and showing that economic allocation better reflects the causality of the cutting process. We recommend that a distinction should be made between whole carcass and meat cuts, as there are significant differences in meat content and climate change results between these two categories. This is not so clear in the literature, nor in the LEAP guideline for the poultry sector. The study was performed by using disaggregated inventory data from Spain, for the first time. Results show that the major contributors to environmental impact are feed production (>70%), electricity use (10.2%), and fossil fuel combustion (8.1%). Packaging did not significantly contribute to the climate change impact of the chicken products evaluated (0.4−3.4% contribution, depending on the type of packaging and product considered).

Water-Energy-Food Nexus and Life Cycle Thinking: A New Approach to Environmental and Nutritional Assessment of Potato Chips.

The water-energy-food (WEF) nexus has become a key concept to promote the cross-sectoral coordination toward sustainable development. In particular, understanding the interdependences of these pillars, as well as addressing a life cycle perspective, is essential when evaluating food production systems. This study explores the environmental impacts and nutritional quality of potato chips, addressing life cycle thinking and a WEF nexus approach. For this purpose, the combined application of life cycle assessment (LCA) and the Nutrient-Rich Food 9.3 (NRF9.3) index was considered to identify the main environmental hotspots and advanced opportunities. The results indicated a major contribution of the cultivation stage on water use, whereas the processing accounted for most of the impacts in energy-related indicators and eutrophication potentials. Improvement opportunities reside in the joint application of drip irrigation, allowing to achieve important water savings, as well as the use of natural gas or pellets instead of diesel, which constitute cleaner energy sources. On the other hand, a poor nutritional density of potato chips became evident from the quantification of the NRF9.3, which can be significantly improved if potatoes undergo a roasted process instead of frying.

From symmetric glycerol derivatives to dissymmetric chlorohydrins.

The anticipated worldwide increase in biodiesel production will result in an accumulation of glycerol for which there are insufficient conventional uses. The surplus of this by-product has increased rapidly during the last decade, prompting a search for new glycerol applications. We describe here the synthesis of dissymmetric chlorohydrin esters from symmetric 1,3-dichloro-2-propyl esters obtained from glycerol. We studied the influence of two solvents: 1,4-dioxane and 1-butanol and two bases: sodium carbonate and 1-butylimidazole, on the synthesis of dissymmetric chlorohydrin esters. In addition, we studied the influence of other bases (potassium and lithium carbonates) in the reaction using 1,4-dioxane as the solvent. The highest yield was obtained using 1,4-dioxane and sodium carbonate.

Effect of Novel Deep Eutectic Solvents on the Endo/Exo Ratio of Diels-Alder Reactions at Room Temperature.

The Diels-Alder reaction is a prototypical example of a thermally allowed [4 + 2] cycloaddition with good control over the regio- and stereochemical outcomes. Therefore, Diels-Alder reactions in which adjacent stereocenters are generated at the two ends of the newly formed single bonds imply two different possible stereochemical outcomes. In cases where the dienophile has a single electron-withdrawing substituent, the outcome can often be predicted by applying the known "endo rule". Furthermore, the use of chiral eutectic solvents in asymmetric synthesis has become a novel tool to maintain sustainability in organic synthesis. In the present work, a set of recyclable and sustainable bio-based deep eutectic solvents (DESs) was designed using hydrogen bond acceptors (HBAs) with a chiral center. These compounds were used in their racemic and enantiomerically enriched forms to prepare DESs with lactic acid (LA), glycerol (Gly), and ethylene glycol, which act as hydrogen bond donors (HBDs) in the corresponding eutectic mixture. These DESs were used as solvents to study the reaction between cyclopentadiene and ethyl acrylate or butyl acrylate in typical [4 + 2] cycloadditions. The best yields and endo-selectivity were achieved using LA as the HBD in the eutectic mixtures. The results and adduct ratios obtained show that these DESs were able to improve both reaction yields and selectivity when compared to those observed in organic solvents or ionic liquids. Moreover, the reaction products (adducts) were easily recovered with diethyl ether from the reaction mixture, where they appeared as an upper layer.

Development of a SBSE-TD method coupled to GC-MS and chemometrics for the differentiation of variety and processing conditions in peach juices.

Peach juices of distinct varieties, namely yellow- and red-fleshed, and commercial and freshly blended were analyzed. The method used was based on Stir Bar Sorptive Extraction (SBSE) involving a polydimethylsiloxane-coated stir bar with thermal desorption (TD), followed by gas chromatography coupled to mass spectrometry (GC-MS) analysis. The resulting analytical data included 41 compounds belonging to several chemical classes, such as aldehydes, alcohols, lactones, terpenoids, fatty aldehydes, fatty acids and hydrocarbons. Furthermore, chemometric data treatment using unsupervised analysis (PCA) proved useful to classify peach juices on the basis of variety. Stepwise Linear Discriminant Analysis (SLDA) showed that a reduced number of variables (14 compounds), including lactones (6-pentyl-α-pyrone, γ-decalactone, γ-dodecalactone, and δ-dodecalactone), fatty acids (hexadecanoic acid), fatty aldehydes (tetracosanal and octacosanal), hydrocarbons (C23, C26, C27, C29, and C33), and alcohols (phytol and α-tocopherol), were necessary to classify the juice samples according to variety and processing conditions.

Bulk industrial fruit fibres. Characterization and prevalence of the original fruit metabolites.

Here we analysed the content of primary and secondary metabolites in nine types of industrially processed fibres derived from the juice industry. Specifically, we examined fibre from: apple, peach, and pear, as non-citrus fruits; the peel and flesh of orange and tangerine, and lemon flesh, as citrus fruits; and carrot, as vegetable. Regarding primary metabolites, the sugar content ranged from 21.6 mg/g in lemon to 290 mg/g in orange peel and lower mass organic acid content ranged from 25.0 mg/g in pear to 250 mg/g in lemon. The content of fatty acids were constant during fibre processing, ranging from 0.5 to 1.46%. Furthermore, the fatty acid profile was not affect for the processing. Concerning secondary metabolites, industrial processing did not decrease the sterols content, which ranged from 0.51 to 1.66 µg/g. Regarding carotenoids, of note was the presence of epoxycarotenoids, which may reflect the quality of the industrial process, thus giving added value to the by-product.

A fast and reliable ultrahigh-performance liquid chromatography method to assess the fate of chlorophylls in teas and processed vegetable foodstuff.

A total of 48 chlorophylls and derivatives were identified and successfully determined in tea and processed vegetable and fruit foodstuff by UHPLC with photodiode-array and mass spectrometry detection. The method allowed the proper separation of chlorophyll derivatives resulting from demetallation, dephytilation, decarbomethoxylation, epimerisation and copperisation. The method was performed in less than 12 min, using an optimised ternary gradient (MeOH, iPrOH, MeCN and H2O with 10 mM of ammonium acetate) on an ACQUITY HSS T3 column. Mass spectrometry, applying both ESI and APCI ionization sources, was used for identification purposes. The method was applied to evaluate the degree of processing in teas of different origin and quality. It allowed differentiation between supermarket own-brand tea bags and teas sold by specialised shops. Pheophytins, pheophorbides and pyro derivatives were found mainly in processed green vegetable and fruit products thereof. However, chlorophyll-derived food colorants, such as Cu-chlorophyllins, Cu-pheophytins, Cu-pyropheophytins, Cu-pheophorbides and Cu-pyropheophorbides, were also detected in several products.