Intrinsic energy landscapes of amino acid side-chains

Amino acid side-chain conformational properties influence the overall structural and dynamic properties of proteins and, therefore, their biological functions. In this study, quantum mechanical (QM) potential energy surfaces for the rotation of side-chain χ(1) and χ(2) torsions in dipeptides in the alphaR, beta, and alphaL backbone conformations were calculated. The QM energy surfaces provide a broad view of the intrinsic conformational properties of each amino acid side-chain. The extent to which intrinsic energetics dictates side-chain orientation was studied through comparisons of the QM energy surfaces with χ(1) and χ(2) free energy surfaces from probability distributions obtained from a survey of high resolution crystal structures. In general, the survey probability maxima are centered in minima of the QM surfaces as expected for sp(3) (or sp(2) for χ(2) of Asn, Phe, Trp, and Tyr) atom centers with strong variations between amino acids occurring in the energies of the minima indicating intrinsic differences in rotamer preferences. High correlations between the QM and survey data were found for hydrophobic side-chains except Met, suggesting minimal influence of the protein and solution environments on their conformational distributions. Conversely, low correlations for polar or charged side-chains indicate a dominant role of the environment in stabilizing conformations that are not intrinsically favored. Data also link the presence of off-rotamers in His and Trp to favorable interactions with the backbone. Results also suggest that the intrinsic energetics of the side-chains of Phe and Tyr may play important roles in protein folding and stability. Analyses on whether intrinsic side-chain energetics can influence backbone preference identified a strong correlation for residues in the alphaL backbone conformation. It is suggested that this correlation reflects the intrinsic instability of the alphaL backbone such that assumption of this backbone conformation is facilitated by intrinsically favorable side-chain conformations. Together our results offer a broad overview of the conformational properties of amino acid side-chains and the QM data may be used as target data for force field optimization.     

Characterization of natural cellulosic fibers from Yucca aloifolia L. leaf as potential reinforcement of polymer composites

Cellulose - In this work lignocellulosic fibers were obtained from Yucca aloifolia L. leaves and their chemical, morphological, thermal and mechanical properties were studied. The fibers were...     

Asymmetric Diels–Alder cycloadditions of d-erythrose 1,3-butadienes to achiral t-butyl 2H-azirine 3-carboxylate

Two d-erythrose 1,3-butadienes were reacted with electrophilic achiral t-butyl 2H-azirine 3-carboxylate giving cycloadducts with good yields and moderate selectivity. The isomers could be separated to give the major (R)-isomers at C-2 in approximately 50% yield in both cases. Alternatively LACASA-DA methodology was applied to one of the reactions leading to homochiral (R)- and (S)-products by changing the chiral nature of an extra chiral BINOL inductor used.     

Pigment Production by Filamentous Fungi on Agro-Industrial Byproducts: an Eco-Friendly Alternative

The search for new sources of natural pigments has increased, mainly because of the toxic effects caused by synthetic dyes used in food, pharmaceutical, textile, and cosmetic industries. Fungi provide a readily available alternative source of natural pigments. In this context, the fungi Penicillium chrysogenum IFL1 and IFL2, Fusarium graminearum IFL3, Monascus purpureus NRRL 1992, and Penicillium vasconiae IFL4 were selected as pigments producers. The fungal identification was performed using ITS and part of the β-tubulin gene sequencing. Almost all fungi were able to grow and produce water-soluble pigments on agro-industrial residues, with the exception of P. vasconiae that produced pigments only on potato dextrose broth. The production of yellow pigments was predominant and the two strains of P. chrysogenum were the largest producers. In addition, the production of pigments and mycotoxins were evaluated in potato dextrose agar using TOF-MS and TOF-MS/MS. Metabolites as roquefortine C, chrysogine were found in both extracts of P. chrysogenum, as well fusarenone X, diacetoxyscirpenol, and neosolaniol in F. graminearum extract. In the M. purpureus extract, the pigments monascorubrin, rubropunctatin, and the mycotoxin citrinin were found. The crude filtrates have potential to be used in the textile industry; nevertheless, additional pigment purification is required for food and pharmaceutical applications.     

Catalytic Asymmetric Synthesis of Cyclohexanes by Hydrogen Borrowing Annulations

Hydrogen borrowing catalysis serves as a powerful alternative to enolate alkylation, enabling the direct coupling of ketones with unactivated alcohols. However, to date, methods that enable control over the absolute stereochemical outcome of such a process have remained elusive. Here we report a catalytic asymmetric method for the synthesis of enantioenriched cyclohexanes from 1,5‐diols via hydrogen borrowing catalysis. This reaction is mediated by the addition of a chiral iridium(I) complex, which is able to impart high levels of enantioselectivity upon the process. A series of enantioenriched cyclohexanes have been prepared and the mode of enantioinduction has been probed by a combination of experimental and DFT studies.     

Development and validation studies for determination of phenylpropanoid‐substituted flavan‐3‐ols in semipurified extract of Trichilia catigua by high‐performance liquid chromatography with photodiode array detection

The phenolic compounds are the main phytochemical constituents of the bark of Trichilia catigua and are commonly used for medicinal purposes. An HPLC method for the simultaneous quantification of phenolic compounds (procyanidin B2 (PB2), epicatechin (EPC), chinchonains Ia, Ib, IIa, IIb, catechin, and chrologenic acid) in T. catigua extract was developed and validated. A suitable chromatographic system was selected, which uses a gradient elution with methanol/ACN (75:25), and water both with 0.05% TFA, as mobile phase, column Luna, 280 nm, and flow 0.4 mL/min. Validation of the analytical method was based on the parameters: linearity, precision, LODs and LOQs, accuracy, robustness, and stability. The method showed linearity for PB2 and EPC, in the range 10–120 μg/mL with good correlation coefficients (>0.996). For precision, the repeatability ranged from 1.89 to 3.23%, and the values for accuracy for PB2 and EPC were 95 and 89%, respectively. The LODs and LOQs for PB2 were 1.36 and 4.12 μg/mL, and for EPC were 2.18 and 6.61 μg/mL, respectively. The method was robust under the conditions employed. The proposed method could be employed for quality assessment of T. catigua, as well as pharmaceutical products.     

Viscosity Mixing Rules for Binary Systems Containing One Ionic Liquid

In this work the applicability of four of the most commonly used viscosity mixing rules to [ionic liquid (IL)+molecular solvent (MS)] systems is assessed. More than one hundred (IL+MS) binary mixtures were selected from the literature to test the viscosity mixing rules proposed by 1) Hind (Hi), 2) Grunberg and Nissan (G–N), 3) Herric (He) and 4) Katti and Chaudhri (K–C). The analyses were performed by estimating the average (absolute or relative) deviations, AADs and ARDs, between the available experimental data and the predicted ideal mixture viscosity values obtained by means of each rule. The interaction terms corresponding to the adjustable parameters inherent to each rule were also calculated and their trends discussed.     

Cleansing contaminated seawaters using marine cyanobacteria: evaluation of trace metal removal from the medium

The use of microbial biomass in biosorption is already being studied as a potential alternative to (or combined with) conventional processes, where several algae and microorganisms have already shown promising ability to uptake metals. Cyanobacteria (blue-green algae) are widespread organisms, with specific properties, such as high nutrient removal capacity and tolerance to highly variable conditions which make them well-suited for wastewater and remediation purposes. The main aim of this work was to evaluate the use of a marine cyanobacterium LEANCYA 21 (Synechocystis sp.), collected from the Portuguese southern border, for the removal of selected trace metals when in natural seawater culture medium. It was observed, for the first time, that this particular strain is capable of uptaking Pb, Ni and Zn (at nM levels) from seawater solutions using small amounts of biomass. Uptake values for Pb were up to 90% (0.75 mg g^?1 biomass) in 6 h. The specific biosorption curves of Ni and Zn showed that these metals follow a first order kinetics biosorption in batch conditions. Solutions containing multimetals have revealed that Ni uptake is affected by the presence of Pb and Zn. The calculated specific absorption values were high enough to predict a possible application in aquaculture where such low levels of metals may inhibit microalgae growth.     

3β‐(Stearyloxy)olean‐12‐ene from Austroplenckia populnea: Structure Elucidation by 2D‐NMR and Quantitative 13C‐NMR Spectroscopy

3β‐(Stearyloxy)olean‐12‐ene was isolated from a hexane extract of Austroplenckia populnea Reiss (Celastraceae) leaves. The structure was solved by means of quantitative ¹³C‐NMR, HMBC, HMQC, COSY, NOESY, and NOE difference spectra. The mass spectrum showed an [M+1]⁺ ion peak at m/z 693, and the molecular formula C₄₈H₈₄O₂ was confirmed by combustion analysis.