Bimetallic Zinc Catalysts for Ring-Opening Copolymerization Processes.

Novel bimetallic zinc acetate complexes supported by heteroscorpionate ligands have been developed for the ring-opening copolymerization of cyclohexene oxide and CO2 and the terpolymerization of cyclohexene oxide, phthalic anhydride, and CO2. Heteroscorpionate ligands precursors L1-L3 were reacted with two equivalents of zinc acetate to afford the dinuclear zinc complexes [{Zn(κ3-bpzappe)}(µ-O2CCH3)3-{Zn(HO2CCH3)}] (1), [{Zn(κ3-bpzbdmape)}(µ-O2CCH3)3-{Zn(HO2CCH3)}] (2), and [{Zn(κ3-bpzbdeape)}(µ-O2CCH3)3{Zn(HO2CCH3)}] (3) in excellent yields. The molecular structure of these compounds was determined spectroscopically and confirmed by X-ray diffraction analysis. Zinc acetate complexes 1-3 were screened as catalysts for the copolymerization of cyclohexene oxide and CO2 to produce poly(cyclohexene)carbonate, and complex 3 was found to be the most active catalyst for this process in the absence of a cocatalyst. Furthermore, the terpolymerization of cyclohexene oxide, phthalic anhydride, and CO2 was studied using the combination of complex 3 and 4-dimethylaminopyridine as catalyst system yielding the corresponding polyester-polycarbonate materials.

Study of the Coordination Modes of Hybrid NNCp Cyclopentadienyl/Scorpionate Ligands in Ir Compounds.

A new coordination mode for the hybrid scorpionate/cyclopentadienyl ligand bpzcp, [bpzcp = 2,2-bis(3,5-dimethylpyrazol-1-yl)-1,1-diphenylethylcyclopentadienyl] is observed in iridium complexes. The reaction of the lithium precursor, [Li(bpzcp)(THF)], with a range of [IrCl(diene)]2 compounds leads to an unprecedented binding mode of the hybrid scorpionate/cyclopentadienyl ligand as η5-Cp-coordinated and the formation of Ir(I) derivatives [Ir(η5-Cp-bpzcp)(η4-cod)] (1), [Ir(η5-Cp-bpzcp){η4-CH2═C(Me)C(Me)═CH2}] (2), [Ir(η5-Cp-bpzcp)(η2-coe)2] (3), and [Ir(η5-Cp-bpzcp)(η2-CH2═CH2)2] (4). The Ir(I) complex 4 reacts with CO or bromine to afford the compound [Ir(η5-Cp-bpzcp)(CO)2] (5) and the 18e- Ir(III) complex [Ir(κ-N-η5-Cp-bpzcpBr2)Br2] (6), respectively. Reaction of the iridium compounds (2-4) with CuI or [PdCl2(CH3CN)2] yields the heterobimetallic iridium-copper or iridium-palladium complexes [Ir(η5-Cp-bpzcp){η4-CH2═C(Me)C(Me)═CH2}(µ-bpzcp){CuI(κ2-NN-bpzcp)}] (7), [Ir(η5-Cp-bpzcp)(η2-coe)2}(µ-bpzcp){CuI(κ2-NN-bpzcp)}] (8), [Ir(η5-Cp-bpzcp)(η2-CH2═CH2)2}(µ-bpzcp){CuI(κ2-NN-bpzcp)}] (9), [Ir(η5-Cp-bpzcp)(coe)2}(µ-bpzcp){PdCl2(κ2-NN-bpzcp)}] (10), and [Ir(η5-Cp-bpzcp)(η2-CH2═CH2)2(µ-bpzcp){PdCl2(κ2-NN-bpzcp)}] (11). All products were characterized by spectroscopic methods and the X-ray crystal structures of 1, 2, 3, 4, and 6 were also established.

Synthesis, In Silico, and In Vitro Evaluation of Long Chain Alkyl Amides from 2-Amino-4-Quinolone Derivatives as Biofilm Inhibitors.

Infection from multidrug resistant bacteria has become a growing health concern worldwide, increasing the need for developing new antibacterial agents. Among the strategies that have been studied, biofilm inhibitors have acquired relevance as a potential source of drugs that could act as a complement for current and new antibacterial therapies. Based on the structure of 2-alkyl-3-hydroxy-4-quinolone and N-acylhomoserine lactone, molecules that act as mediators of quorum sensing and biofilm formation in Pseudomonas aeruginosa, we designed, prepared, and evaluated the biofilm inhibition properties of long chain amide derivatives of 2-amino-4-quinolone in Staphylococcus aureus and P. aeruginosa. All compounds had higher biofilm inhibition activity in P. aeruginosa than in S. aureus. Particularly, compounds with an alkyl chain of 12 carbons exhibited the highest inhibition of biofilm formation. Docking scores and molecular dynamics simulations of the complexes of the tested compounds within the active sites of proteins related to quorum sensing had good correlation with the experimental results, suggesting the diminution of biofilm formation induced by these compounds could be related to the inhibition of these proteins.

Validation of rubric-based evaluation for bachelor's theses in a food science and technology degree.

An effective evaluation of a bachelor's thesis (BT) needs the use of valid tools such as rubrics. There are few studies providing a validation of rubrics for these theses and even fewer in the academic field of food science and technology; hence the aim of this study was to validate a rubric for the assessment of relevant competencies in the BT. Ninety-seven students presented their thesis and 56 teachers participated as members of the committees. The degree of relevance, suitability, and clarity of the rubrics were assessed as well as the relationship between student perception and academic performance and the congruence between the teacher's and students' evaluations. The content validity index and intraclass correlation coefficient (ICC) were calculated. Students had a moderate level of knowledge about rubrics, but they mostly agreed with the premise that the rubrics are an accurate tool to assess the quality of BTs. Teacher's and student's marks mostly aligned. No significant relationship was found between the positive perception of rubric's validity and the final grades. Regarding clarity, suitability, and relevance as perceived by teachers, the used rubrics were highly valued. The ICC of criteria indicated that the rubrics were valid in the studied terms. Hence, the validation of a food science and technology degree BT assessment system based on a rubric has been achieved. Supporting Information PRACTICAL APPLICATION: The conclusions drawn from this research could enable teachers at other universities to use this methodology for validating their rubrics for bachelor's theses. Furthermore, they could use this validated rubric to evaluate projects presented at their respective institutions.

Effect of Solar Pre-Drying and Yeast Starter Inoculation Treatments on the Chemical Composition of Cocoa (Theobroma cacao L.) Beans from Southwestern Colombia.

In Southwestern Colombia, cocoa clones are cultivated in which productivity characteristics predominate over bean quality. In this study, cocoa beans of the CCN-51 clone harvested in the Tumaco region (Nariño, Colombia) were fermented following four different treatments: (1) spontaneously (at room temperature for 120 h) in traditional conditions (Control); (2) traditional processing with a pre-drying (sun-dried for 24 h) treatment (PD); (3) with fermentation (for 120 h) after inoculation of a yeast starter culture (YS); and (4) including both treatments, pre-drying and yeast inoculation (PD + YS). Chemical composition, fatty acids, total polyphenol, methylxanthines (theobromine and caffeine) and lactic acid content of cocoa beans were determined. Chemical and fatty acid composition and theobromine content were not affected by the different fermentation treatments applied (p > 0.05). When analyzing total polyphenol content, YS (16.62 mg/g) and PD + YS (17.74) treatments significantly decreased (p < 0.05) the content of these compounds at the end of the fermentation process, affecting cocoa flavour, while PD treatment decreased (p < 0.05) the caffeine content (0.68 mg/g) of cocoa beans. Finally, lactic acid content decreased because of both inoculation of yeast starter (1.11 mg/g) and mainly the pre-drying treatment (0.60). In conclusion, solar pre-drying in the open air and the inoculation of yeast starter treatments could improve the final quality of cocoa beans.

Oxidation of Aldehydes Used as Food Additives by Peroxynitrite.

Benzaldehyde and its derivatives are used as food supplements. These substances can be used mainly as flavorings or as antioxidants. Besides, peroxynitrite, an oxidizing agent, could be formed in canned food. Both species could react between them. The present article has focused on the kinetic study of the oxidation of aldehydes by peroxynitrite. A reaction mechanism that justifies all the experimental results is proposed. This mechanism, in acidic media, passes through three competitive pathways: (a) a radical attack that produces benzoic acid. (b) peracid oxidation, and (c) a nucleophilic attack of peroxynitrous acid over aldehyde to form an intermediate, X, that produces benzoic acid, or, through a Cannizzaro-type reaction, benzoic acid and benzyl alcohol. All rate constants involved in the third pathway (c) have been calculated. These results have never been described in the literature in acid media. A pH effect was analyzed.

The effect of immunocastration of male and female Duroc pigs on the morphological, mechanical and compositional characteristics of pork belly.

Pork belly is an important and heterogeneous cut, characterized by its fat content. Immunocastration is an alternative to surgical castration that can modify the composition of carcasses and cuts and it can affect at its processing. This work compares the morphological, mechanical and compositional characteristics of pork belly of (1) pure Duroc pigs from surgically castrated males (CM), entire females (EF) and immunocastrated females (IF), and (2) Duroc crossbreed pigs from immunocastrated males (IM) and entire males (EM). Two trials were carried out: Trial 1, in which 36 bellies were evaluated, 12 from each sexual type, CM, EF and IF; and Trial 2, where 30 bellies were used, 15 from each sexual type, IM and EM. Results show few differences in bellies from EF and IF, while those from CM were fatter and firmer and with lower polyunsaturated fat. Bellies from IM were longer and firmer than those from EM, and their skin was thinner. IM bellies had higher saturated and lower polyunsaturated fat than those from EM. To conclude, the sex of the pigs affects belly characteristics and this could be a criterion for determining the destination of the bellies in the cutting plant. Immunocastration of pure Duroc females had a lower effect on the belly characteristics when compared to those from entire females, but some differences could be found in the fat distribution. Immunocastration of Duroc crossbred males produces firmer and thicker bellies, with a thinner skin, that could be advantageous for slicing and further processing.

One-pot terpolymerization of CHO, CO2 and L-lactide using chloride indium catalysts.

Ring-opening copolymerization reactions of epoxides, carbon dioxide and cyclic esters to produce copolymers is a promising strategy to prepare CO2-based polymeric materials. In this contribution, bimetallic chloride indium complexes have been developed as catalysts for the copolymerization processes of cyclohexene oxide, carbon dioxide and L-lactide under mild reaction conditions. The catalysts displayed good catalytic activity and excellent selectivity towards the preparation of poly(cyclohexene carbonate) (PCHC) at one bar CO2 pressure in the absence of a co-catalyst. Additionally, polyester-polycarbonate copolymers poly(lactide-co-cyclohexene carbonate) (PLA-co-PCHC) were obtained via an one-pot one-step route without the use of a co-catalyst. The degree of incorporation of carbon dioxide can be easily modulated by changing the CO2 pressure and the monomer feed, resulting in copolymers with different thermal properties.

Two by-products of the olive oil extraction industry as oleic acid supplement source for Iberian pigs: effect on the meat's chemical composition and induced lipoperoxidation.

BACKGROUND: The objective of the present study was to evaluate the effect of two by-products of the olive oil extraction industry-olive soapstocks and olive-pomace oil-as added fat sources into feed concentrates, in two different rearing systems (free-range complemented with concentrates and intensive rearing with concentrates) on the chemical composition and oxidative stability of Iberian pig meat. RESULTS: No differences in the chemical composition, colour and fatty acid composition of gluteobiceps m. were found due to added fat source. However, the feeding system had a significant effect on protein (P < 0.05), γ-tocopherol (P < 0.05), colour (P < 0.01) and fatty acid composition of gluteobiceps m. Neither added fat source nor the feeding system had an effect on the malondialdehyde content. CONCLUSION: The addition of olive soapstock or olive-pomace oil as fat sources into concentrates did not influence meat composition or fatty acid profile. However, there are differences in the fatty acid composition of meat from Iberian pigs as a result of the production system used.

Direct synthesis of NNN-donor enantiopure scorpionate ligands by an efficient diastereoselective nucleophilic addition to imines.

New enantiopure imines (1-9) with a chiral substrate to control the stereochemistry of a newly created stereogenic center have been synthesized by reaction of the commercially available (1R)-(-)-myrtenal and different primary amines. The diastereomerically enriched lithium-scorpionate compounds [Li(κ(3)-mobpza)(THF)] (10) (mobpza = N-p-methylphenyl-(1R and 1S)-1-[(1R)-6,6-dimethylbicyclo[3.1.1]-2-hepten-2-yl]-2,2-bis(3,5-dimethylpyrazol-1-yl)ethylamide), [Li(κ(3)-mobpza)(THF)] (11) (mobpza = N-p-methoxyphenyl-(1R and 1S)-1-[(1R)-6,6-dimethylbicyclo[3.1.1]-2-hepten-2-yl]-2,2-bis(3,5-dimethylpyrazol-1-yl)ethylamide), [Li(κ(3)-fbpza)(THF)] (12) (fbpza = N-p-fluorophenyl-(1R and 1S)-1-[(1R)-6,6-dimethylbicyclo[3.1.1]-2-hepten-2-yl]-2,2-bis(3,5-dimethylpyrazol-1-yl)ethylamide), and [Li(κ(3)-clbpza)(THF)] (13) (clbpza = N-p-chlorophenyl-(1R and 1S)-1-[(1R)-6,6-dimethylbicyclo[3.1.1]-2-hepten-2-yl]-2,2-bis(3,5-dimethylpyrazol-1-yl)ethylamide) were obtained by a diastereoselective 1,2-addition of an organolithium reagent to imines in good yield and with good diastereomeric excess (ca. 80%). The complexes [LiCl(κ(2)-R,R-fbpzaH)(THF)] (14) and [LiCl(κ(2)-R,R-clbpzaH)(THF)] (15) were obtained in enantiomerically pure form by the treatment of THF solutions of 12 or 13 with NH(4)Cl. The enantiomerically pure amines (R,R-mbpzaH) (16), (R,R-mobpzaH) (17), (R,R-fbpzaH) (18), and (R,R-clbpzaH) (19) were obtained by hydrolysis of the lithium-scorpionate compounds 10-13 with H(2)O. The lithium compound 12 was reacted with [TiCl(4)(THF)(2)] or [ZrCl(4)] to give the enantiopure complexes [MCl(3)(κ(3)-R,R-fbpza)] [M = Ti (20), Zr (21)]. The amine compound 18 reacted with [MX(4)] (M = Ti, X = O(i)Pr, OEt; M = Zr; X = NMe(2)) to give the complexes [MX(3)(κ(3)-R,R-fbpza)] (22-24). The reaction of Me(3)SiCl with [Zr(NMe(2))(3)(κ(3)-R,R-fbpza)] (24) in different molar ratios led to the halide-amide-containing complexes [ZrCl(NMe(2))(2)(κ(3)-R,R-fbpza)] (25) and [ZrCl(2)(NMe(2))(κ(3)-R,R-fbpza)] (26) and the halide complex 21. The isolation of only one of the three possible diastereoisomers of complexes 25 and 26 revealed that chiral induction from the ligand to the zirconium center took place. The structures of these compounds were elucidated by (1)H and (13)C{(1)H} NMR spectroscopy, and the X-ray crystal structures of 5, 12, 14, 15, and 24 were also established.

Contents and composition of individual phospholipid classes from biceps femoris related to the rearing system in Iberian pig.

During dry-cured ham processing, phospholipids (PL) are the main substrates of lipolysis and oxidation. However, the published data on individual PL classes in the pig muscle are inconsistent. This study determined the PL class contents and composition in biceps femoris of Iberian pigs according to the rearing system (Montanera vs Pienso). Phosphatidylcholine (PC), phosphatidylethanolamine (PE), cardiolipin (CL) and sphingomyelin contents were higher in the Montanera pigs than in the Pienso pigs. Total PL and PC, PE, phosphatidylinositol + phosphatidylserine and CL contained higher levels of oleic acid and slightly higher levels of n-3 polyunsaturated fatty acids (PUFA) but lower levels of n-6 PUFA in the Montanera pigs than in the Pienso pigs. The rearing system had no effect on the plasmalogen content but influenced aldehyde composition, mainly in PE and in total PL. These results can partially explain the differences in sensory properties of dry-cured ham between the Montanera and Pienso systems.

Comparative Transcriptome Profile between Iberian Pig Varieties Provides New Insights into Their Distinct Fat Deposition and Fatty Acids Content.

The high deposition of intramuscular fat and the content of oleic fatty acid are characteristic of the Iberian pig. These two parameters present great variability and are differentiated amongst the varieties that make up the Iberian pig population. Although previous studies generated evidence for causal genes and polymorphisms associated to the adipogenic potential of the Iberian pig, there is little information about how genetic expression influences this trait's variability. The aim of this study was to analyses the expression profile between two varieties of Iberian pig (Torbiscal and Retinto) and their reciprocal crosses differentiated in their intramuscular fat (IMF) content and fatty acid (FA) composition in the Longissimus thoracis muscle using an RNA-seq approach. Our results corroborate that the Retinto variety is the fattiest amongst all studied varieties as its upregulated genes, such as FABP3 and FABP5, SLC27A1 and VEGFA among others, contribute to increasing adiposity. In its turn, Torbiscal pigs showed an upregulation of genes associated with the inhibition of fat deposition such as ADIPOQ and CPT1A. Further genetic variation analysis in these Iberian varieties showed relevant associations for SNP located within the differentially expressed genes with IMF and FA content. Thus, the differences found in the genetic architecture and the muscle transcriptome of these Iberian varieties might explain the variability in their fat content and composition and hence, their meat quality.

Free-Range and Low-Protein Concentrated Diets in Iberian Pigs: Effect on Plasma Insulin and Leptin Concentration, Lipogenic Enzyme Activity, and Fatty Acid Composition of Adipose Tissue.

The purpose of this study was to investigate the effect of diets with different protein contents on carcass traits, plasma hormone concentration, lipogenic enzyme activities, and fatty acid (FA) composition in the adipose tissue of Iberian pigs. Twenty-four castrated male Iberian pigs (eight per feeding diet) were fed under free-range conditions with acorns and grass (FR), and in confinement with concentrated diets with standard (SP) and low-protein contents (LP) from 116.0 to 174.2 kg live weight. Backfat thickness was not affected by diet. The plasma leptin concentration was higher (p < 0.001) in the FR group than in the LP and SP groups, while insulin concentration was higher in the SP group than in the LP and FR groups. The lipogenic enzyme activities of glucose-6-phosphate dehydrogenase, malic enzyme, and glycerol-3-phosphate dehydrogenase were lower in the FR group compared to the LP and SP pigs. The activities of these enzymes were adipose-tissue-specific. No differences were found in FA composition of adipose tissue between the SP and LP groups, while the FR pigs had lower proportions of saturated FA and higher proportions of monounsaturated and polyunsaturated FA than the SP and LP pigs. In conclusion, feeding low-protein diets in Iberian pigs does not seem to affect adipose carcass traits, strengthening previous findings that indicate that this is a good strategy to improve meat and dry-cured product quality.

Effect of Free-Range and Low-Protein Concentrated Diets on Growth Performance, Carcass Traits, and Meat Composition of Iberian Pig.

The feeding system is one of the main factors influencing the Iberian pig meat quality. This experiment was undertaken to evaluate the influence of feeding diets containing different levels of protein on performance, carcass, and meat quality of Iberian pigs. To that aim, 24 castrated male Retinto Iberian pigs with an average weight of 116 kg were fed under free-range conditions with acorns and grass (FR), and on concentrated diets in confinement with standard (SP) and low protein content (LP). The crude protein content in acorns was lower than that in the grass and SP diet, but similar to that in the LP diet. FR pigs needed more time to achieve slaughter weight than LP and SP pigs. Iberian pigs fed on low-protein diet (FR and LP) had a higher intramuscular fat content in the musculus serratus ventralis than SP pigs. The influence of diet on the fatty-acid composition was reflected more markedly in subcutaneous fat than in muscles. FR pigs showed a higher level of C18:1 n-9 and total polyunsaturated fatty acids and lower total saturated fatty acids in subcutaneous fat than LP and SP. It is concluded that diets with low protein levels do not affect Iberian pig productive traits but change the meat composition, rendering them an interesting strategy to improve the quality of Iberian pig meat and dry-cured products.

Effect of the genetic line and oleic acid-enriched mixed diets on the subcutaneous fatty acid composition and sensory characteristics of dry-cured shoulders from Iberian pig.

The aim of this study was to research the effect of the genetic background (Retinto, Torbiscal, and their reciprocal crosses) on the subcutaneous fatty acids and the sensory characteristics of dry-cured shoulders from Iberian pig, and also to investigate whether there is some interaction between genotype and diet composition when pigs are reared indoors, to obtain information to improve the selection strategies for purebred Iberian pig. The genetic background affected both the fatty acid composition (C17:0, C17:1 n-7, C18:3 n-3 and C20:0 were significantly different) and the sensory characteristics (marbling, lean fibrousness, and flavour intensity and persistence were significantly influenced), which indicates that they should be taken into account in the selection strategies for purebred Iberian pig. In a similar way, the genotype × diet composition interaction also should be taken into account when selecting a genetic line or cross to be fed indoors on a particular diet because of its repercussion on the sensory characteristics.

A Definition of "Multitargeticity": Identifying Potential Multitarget and Selective Ligands Through a Vector Analysis.

The design of multitarget drugs is an essential area of research in Medicinal Chemistry since they have been proposed as potential therapeutics for the management of complex diseases. However, defining a multitarget drug is not an easy task. In this work, we propose a vector analysis for measuring and defining "multitargeticity." We developed terms, such as order and force of a ligand, to finally reach two parameters: multitarget indexes 1 and 2. The combination of these two indexes allows discrimination of multitarget drugs. Several training sets were constructed to test the usefulness of the indexes: an experimental training set, with real affinities, a docking training set, within theoretical values, and an extensive database training set. The indexes proved to be useful, as they were used independently in silico and experimental data, identifying actual multitarget compounds and even selective ligands in most of the training sets. We then applied these indexes to evaluate a virtual library of potential ligands for targets related to multiple sclerosis, identifying 10 compounds that are likely leads for the development of multitarget drugs based on their in silico behavior. With this work, a new milestone is made in the way of defining multitargeticity and in drug design.

On the search for NNO-donor enantiopure scorpionate ligands and their coordination to group 4 metals.

The preparation of new chiral bis(pyrazol-1-yl)methane-based NNO-donor scorpionate ligands in the form of the lithium derivatives [Li(bpzb)(THF)] [1; bpzb = 1,1-bis(3,5-dimethylpyrazol-1-yl)-3,3-dimethyl-2-butoxide] and [Li(bpzte)(THF)] [2; bpzte = 2,2-bis(3,5-dimethylpyrazol-1-yl)-1-p-tolylethoxide] or the alcohol ligands (bpzbH) (3) and (bpzteH) (4) has been carried out by 1,2-addition reactions with trimethylacetaldehyde or p-tolualdehyde. The separation of a racemic mixture of the alcohol ligand 3 has been achieved and gave an enantiopure NNO alcohol-scorpionate ligand in three synthetic steps: (i) 1,2-addition of the appropriate lithium derivative to trimethylacetaldehyde, (ii) esterification and separation of diastereoisomers 5, (iii) saponification. Subsequently, the enantiopure scorpionate ligand (R,R)-bpzmmH {6; R,R-bpzmmH = (1R)-1-[(1R)-6,6-dimethylbicyclo[3.1.1]2-hepten-2-yl]-2,2-bis(3,5-dimethylpyrazol-1-yl)ethanol} was obtained with an excellent diastereomeric excess (>99% de) in a one-pot process utilizing the aldehyde (1R)-(-)-myrtenal as a chiral substrate to control the stereochemistry of the newly created asymmetric center. These new chiral heteroscorpionate ligands reacted with [MX(4)] (M = Ti, Zr; X = NMe(2), O(i)Pr, OEt, O(t)Bu) in a 1:1 molar ratio in toluene to give, after the appropriate workup, the complexes [MX(3)(kappa(3)-NNO)] (7-18). The reaction of Me(3)SiCl with [Ti(NMe(2))(3)(bpzb)] (7) or [Ti(NMe(2))(3)(R,R-bpzmm)] (11) in different molar ratios gave the halide-amide-containing complexes [TiCl(NMe(2))(2)(kappa(3)-NNO)] (19 and 20) and [TiCl(2)(NMe(2))(kappa(3)-NNO)] (21 and 22) and the halide complex [TiCl(3)(kappa(3)-NNO)] (23 and 24). The latter complexes can also be obtained by reaction of the lithium compound 1 with TiCl(4)(THF)(2) and deprotonation of the alcohol group of 6 with NaH, followed by reaction with TiCl(4)(THF)(2) in a 1:1 molar ratio, respectively. Isolation of only one of the three possible diastereoisomers of the complexes 19 and 22 revealed that chiral induction from the ligand to the titanium center took place. The structures of these complexes were elucidated by (1)H and (13)C{(1)H} NMR spectroscopy, and the X-ray crystal structures of 3-7, 12, and 24 were also established. Finally, we evaluated the influence that the chiral center of the new heteroscorpionate complexes has on the enantioselectivity of the asymmetric epoxidation of allylic alcohols.

Effect of live weight and sex on physico-chemical and sensorial characteristics of Merino lamb meat.

Forty-eight lamb carcasses were divided into four groups (n=12) according to slaughter weight (24 and 29kg) and sex (male and female). Colour, pH, moisture, and intramuscular fat were not affected (p>0.05) by slaughter weight or sex. With respect to fatty acid composition, slaughter weight had significant effects on C12:0 (p<0.01), C14:0, C16:0, and C18:1 n-9 (p<0.05) in Longissimus lumborum (LL) muscle. The percentage of C12:0 and C14:0 decreased as slaughter weight increased, while C16:0 increased. In Semimembranosus (SM) m., only C18:3 n-3 and C20:2 n-6 were affected (p<0.001) by slaughter weight. Total PUFA in LL m. was greater (p<0.01) in females than in males. Although in general, sensorial quality was not significantly affected by slaughter weight or sex, meat from lighter lambs (24kg) had greater general acceptability than meat from heavier lambs (29kg).

In Silico Studies on Compounds Derived from Calceolaria: Phenylethanoid Glycosides as Potential Multitarget Inhibitors for the Development of Pesticides.

An increasing occurrence of resistance in insect pests and high mammal toxicity exhibited by common pesticides increase the need for new alternative molecules. Among these alternatives, bioinsecticides are considered to be environmentally friendly and safer than synthetic insecticides. Particularly, plant extracts have shown great potential in laboratory conditions. However, the lack of studies that confirm their mechanisms of action diminishes their potential applications on a large scale. Previously, we have reported the insect growth regulator and insecticidal activities of secondary metabolites isolated from plants of the Calceolaria genus. Herein, we report an in silico study of compounds isolated from Calceolaria against acetylcholinesterase, prophenoloxidase, and ecdysone receptor. The molecular docking results are consistent with the previously reported experimental results, which were obtained during the bioevaluation of Calceolaria extracts. Among the compounds, phenylethanoid glycosides, such as verbascoside, exhibited good theoretical affinity to all the analyzed targets. In light of these results, we developed an index to evaluate potential multitarget insecticides based on docking scores.

Alternating Copolymerization of Epoxides and Anhydrides Catalyzed by Aluminum Complexes.

The optimization of an organoaluminum catalytic system for the copolymerization of epoxides and anhydrides is presented. For this purpose, the influence of different variables in the process, such as catalysts, cocatalyst, solvent, or substrates, has been analyzed. Kinetic studies, a proposal for the catalytic mechanism, and full characterization of the copolymers obtained are also discussed. Finally, a new copolymer, poly(limonene succinate), obtained by the optimized catalytic system is reported.