Reliable folding of hybrid tetrapeptides into short β-hairpins

Five hybrid tetrapeptides, each consisting a central dipeptide segment of α-amino acid residues flanked by two aromatic γ-amino acid residues, are found to fold into well-defined β-hairpin conformations as shown by NMR, computational study, and X-ray structures. The turn loop of this β-hairpin motif accommodates different two-residue α-amino acid sequences from the highly flexible Gly-Gly, to the more restricted D-Pro-Gly. The presence of α-amino acid side chains enhances the stabilities of the ...     

A short and concise synthetic route to (−)-coniceine

(−)-Coniceine, the simplest framework of indolizidine alkaloids, has been successfully accessed using a route in which ruthenium-catalyzed ring-closing olefin metathesis (RCM) was the key reaction to establish the unsaturated bicyclic lactam system.     

Taylor dispersion analysis of metallic-based nanoparticles – A short review

Taylor dispersion analysis (TDA) is an interesting tool for nanoparticle (NP) size determination, feasible using simple capillary electrophoresis apparatus. Based upon the radial diffusion of analytes upon a laminar stream, the diffusion coefficient of species is easily estimable. Moreover, TDA is generally more adequate than conventional dynamic light scattering methodologies as it is less dependent on the polydispersity of the sample, leading to accurate measurement and reliable results. This review provides every paper mentioning the use of TDA for metallic-based NPs size determination. Diverse strategies for the detection of metallic NPs (like UV–visible and inductively coupled plasma–mass spectrometry – ICP–MS – for instance) and interpretation of the Taylorgrams are discussed. Based upon the literature, advices on future prospects are also indicated, especially for the comparison of TDA results with other classical techniques.     

Why is the linking C-C bond in tetrahedranyltetrahedrane so short?

[structure: see text]. The block-localized wave function (BLW) method has been employed to probe the origin of the very short linking C-C bond (1.436 A) in tetrahedranyltetrahedrane. Computations show that the vicinal hyperconjugative interactions between the two tetrahedranyl groups is stronger than the conjugation in butadiene, and if there were no hyperconjugation effect, the bond distance would be 1.491 A. Thus, both the hybridization mode and hyperconjugative interactions contribute to the shortening of the central C-C bond in tetrahedranyltetrahedrane.     

Design of phosphonate analogs of short peptides by “click” chemistry

Methods were developed for the first time for the modification of the natural neuropeptides Ile–Gly–Leu and Leu–Gly–Leu simultaneously with the phosphonate moiety and the triazole ring or solely with the triazole ring by means of click chemistry. All of the peptidomimetics synthesized were isolated as a mixture of diastereomers and were characterized by spectroscopic methods.

     

Redox chemistry of coenzyme Q—a short overview of the voltammetric features

Quinones constitute a big family of organic redox active compounds that are overwhelmingly involved in important physiological processes. The most important members in the class of quinones are, indeed, the plastoquinones and the coenzyme Q (CoQ) derivatives. Voltammetry of coenzyme Q family members attracts significant attention since 50 years ago. In this work, we refer to some of the most important voltammetric features of coenzyme Qs studied in aprotic and in aqueous media. While the redox chemistry of coenzyme Q members in non-aqueous aprotic organic solvents can be described by two consecutive one-electron transfer steps, more complex situation exists in the voltammetry of coenzyme Qs performed in aqueous media. Although it has been claimed for a while that the voltammetric processes of coenzyme Qs in aqueous solutions proceed via formation of semiquinone radical intermediate species, it has been recently proven that this can be not completely true. Intensive voltammetric and spectroscopic studies of coenzyme Q systems in buffered and non-buffered aqueous media revealed that hydrogen bonding between electrochemically created CoQ species and the water molecules plays an important role in stabilizing electrochemically generated species of these systems. We also pay attention to the amazing redox chemistry of coenzyme Qs in strong alkaline media, while we refer to the chemical features of novel coenzyme Q derivatives obtained under such conditions. Hints are presented about the antioxidant capacity of some of the novel hydroxylated coenzyme Q systems. Also, the possibility of these systems to bind and transfer earth-alkaline cations across biomimetic membranes is shortly elaborated. In the end, we refer to some relevant theoretical works that describe closely the voltammetric behavior of various coenzyme Q systems. We believe that this short review will contribute towards better understanding of the amazing chemistry of coenzyme Q derivatives.     

A new short route for the production of Δ2-cyclopentenone from cyclopentadiene

Summary A new 3-stage method for the production of ²-cyclopentenone from cyclopentadlene with an over-all yield of 15% has been described.     

A facile synthesis and crystallographic analysis of N-protected β-amino alcohols and short peptaibols

A facile, efficient and racemization-free method for the synthesis of N-protected β-amino alcohols and peptaibols using N-hydroxysuccinimide active esters is described. Using this method, dipeptide, tripeptide and pentapeptide alcohols were isolated in high yields. The conformations in crystals of β-amino alcohol, dipeptide and tripeptide alcohols were analysed, with a well-defined type III β-turn being observed in the tripeptide alcohol crystals. This method is found to be compatible with Fmoc-, Boc- and other side-chain protecting groups.     

Structure and stability of short beta-peptide nanotubes: a non-natural representative of collagen?

Since secondary structure elements are known to play a key role in stabilizing the 3D-fold of proteins for the design of non-natural proteins composed of beta-amino acid residues, the construction of suitable secondary structural elements is mandatory. Folding analogues of alpha-helices and beta-strands of beta-polypeptides were already described (Chem. Biodiversity 2004, 1, 1111 (1)). Here, we present several collagen-like folds composed exclusively of beta-Ala(s). Unlike their natural counterpart, these tubular nanostructures can be composed of more than three polypeptide chains aligned parallel and/or antiparallel. By using ab initio and DFT calculations we have optimized a large number of versatile collagen-like antiparallel nanostructures. In these tubular systems, oligopeptide strands are interconnected by i --> (i) type H-bonds, except for the "closing" set. This latter is called "the H-bond zipper" and is either (i) --> i, ( i + 1) --> i, or ( i + 2) --> i type. Antiparallel, tubular foldamers composed of l number of strands, each of k number of beta-amino acid residues (e.g., apbeta-T(l) i+l ) k , ap(beta-T(l) i+1 ) k , or ap(beta-T(l) i+2 ) k ), are unexpectedly stable supramolecular complexes. Independent of k and l, the local backbone fold of the amino acid residues is usually spiral, abbreviated as "S(P)" or "S*(P)". Nevertheless, in contrast to parallel, in antiparallel nanotubes the backbone fold can occasionally twist out from S(P) or S*(P) type into an alternative local structure. However, the more the local geometry of the strands resembles to S(P) or S*(P), the higher the stability is. Besides the backbone twisting, the overall stability is determined by the type and the geometrical properties of the constituent H-bonds. Interestingly, higher number of total H-bonds can provide a lower overall stability, when H-bond parameters are inferior. In general, the increase of both the number of strands and their length stabilize the supramolecular complex. Now that, for beta-peptides, collagen-like overall folds with their stability were determined, their POG- or PPG-like sequence specificity has to be revealed.     

Anion-templated self-assembly of highly stable Fe(II) pentagonal metallacycles with short anion-π contacts

The crystal structures of the self-assembled metallapentacycles [{Fe(5)(bptz)(5)(CH(3)CN)(10)} ? 2SbF(6)][SbF(6)](8) (1) and [{Fe(5)(bmtz)(5)(CH(3)CN)(10)} ? SbF(6)][SbF(6)](9) (2) with the π-acidic ligands bptz (3,6-bis(2-pyridyl)-1,2,4,5-tetrazine) and bmtz (3,6-bis(2-pyrimidyl)-1,2,4,5-tetrazine), respectively, revealed cationic pentagons templated by [SbF(6)](-) ions. The short anion-π contacts established between the anions and the tetrazine rings play an important role in the stability of the pentagons.     

A short asymmetric synthesis of 4,4-disubstituted-γ-butyrolactones from racemic 2-methylcyclohexanone in multigram scale

A short and efficient asymmetric synthesis of both enantiomers (R)-1a–c and (S)-1a–c has been performed on a large scale and with high stereoselectivities from 2-methylcyclohexanone.     

Cationic–anionic fluorinated surfactant mixtures based on short fluorocarbon chains as potential aqueous film-forming foam

A strategy for aqueous film-forming foam (AFFF) using cationic-anionic surfactant mixtures with short fluorocarbon chains (≤C₄) in both cationic and anionic surfactants was proposed. The minimum surface tension (γ_min) of mixtures of C₄F₉SO₂NH(CH₂)₃N(CH₃)₃I (C₄FI) and C_nF_2n+1COONa (n?=?1, 2, 3, 4) with different molar ratios (5:1, 2:1, 1:1, 1:2, 1:5) was measured at 25?°C. The γ_min for all mixtures of C₄FI–C_nF_2n+1COONa were remarkably lower than that of pure C₄FI. Among these mixtures, the equimolar mixture of C₄FI–C₃F₇COONa was chosen because of the low γ_min, qualified solubility and relatively high fluorine efficiency. The spreading coefficients of its aqueous solution on n-heptane, toluene, benzene, cyclohexane and gasoline were all positive, indicative of its potential in AFFF. The film spreading, sealability and foaming were also tested. The influences of ‘green’ additives (alkyl glucose amide, xanthan gum and sodium carboxymethylcellulose) on foaming performance were studied, in which small dosage of xanthan gum could greatly retard the drainage of foam. It was confirmed that the mixing of oppositely charged surfactants both possessing short fluorocarbon chains was a valuable thought to design AFFF. In application, the quaternary ammonium surfactant likewise can be bromide or chloride rather than iodide for reasons of cost-reduction and stability.     

Parallel and antiparallel β-strands differ in amino acid composition and availability of short constituent sequences

One of the important secondary structures in proteins is the β-strand. However, due to its complexity, it is less characterized than helical structures. Using the 1641 representative three-dimensional protein structure data from the Protein Data Bank, we characterized β-strand structures based on strand length and amino acid composition, focusing on differences between parallel and antiparallel β-strands. Antiparallel strands were more frequent and slightly longer than parallel strands. Overall, the majority of β-sheets were antiparallel sheets; however, mixed sheets were reasonably abundant, and parallel sheets were relatively rare. Notably, the nonpolar, aliphatic hydrocarbon amino acids, valine, isoleucine, and leucine were observed at a high frequency in both strands but were more abundant in parallel than in antiparallel strands. The relative amino acid occurrence in β-sheets, especially in parallel strands, was highly correlated with amino acid hydrophobicity. This correlation was not observed in α-helices and 3(10)-helices. In addition, we examined the frequency of 400 amino acid doublets and 8000 amino acid triplets in β-strands based on availability, a measurement of the relative counts of the doublets and triplets. We identified some triplets that were specifically found in either parallel or antiparallel strands. We further identified "zero-count triplets" which did not occur in either parallel or antiparallel strands, despite the fact that they were probabilistically supposed to occur several times. Taken together, the present study revealed essential features of β-strand structures and the differences between parallel and antiparallel β-strands, which can potentially be applied to the secondary structure prediction and the functional design of protein sequences in the future.     

Identification of sildenafil,tadalafil and vardenafil by gas chromatography–mass spectrometry on short capillary column

Sildenafil and its analogues (tadalafil and vardenafil) are phosphodiesterase type 5 inhibitors used in the treatment of male erectile dysfunction. Some dietary supplements, herbal preparations and food products which claim to enhance male sexual function have been found to be adulterated with these drugs. In this study, a gas chromatograph–mass spectrometer (GC–MS) assay was developed for identification of the drugs. In addition to good and short chromatographic separation that can be achieved within 6 min by using a short 10 m capillary column, no prior sample clean-up before GC–MS analysis was required, thus making this assay a cost saving and rapid method. Furthermore, the assay is specific as the identification of sildenafil, tadalafil and vardenafil were done by detection of molecular ions; m/z 474, 389 and 448, respectively, and several other characteristic ions resulted from the mass fragmentation of individual molecules. Using our currently developed assay, sildenafil and its analogues were successfully identified in food and herbal matrices.     

The β-nucleated ternary composites of polypropylene/nano-CaCO3/short poly(ethylene-terephthalate) fiber

A serial of β-nucleated polypropylene (β-PP)/nano-calcium carbonate (nano-CaCO₃)/ short poly(ethylene-terephthalate) (PET) fiber composites were prepared using extrusion blending. Maleic anhydride grafted PP (PP-g-MA) was used to modify the compatibility. The relationships among components, structure, and properties of the PP composites were studied. The results show that adding nano-CaCO₃ improved the mechanical properties of the materials. Adding PET fiber increased the rigidity and toughness but the tensile strength decreased. PP-g-MA modified the compatibility of the components of the composites. Both PET fiber and nano-CaCO₃ had nucleation effect on the PP crystallization and slightly induced the formation of β crystals. Ternary β-PP/nano-CaCO₃/PET fiber composites contained high β-crystal content, and the compatibilizer exhibited synergy effect with β nucleating agent to further increase the β-crystal content in the blends. Mo’s method could satisfactorily describe the nonisothermal crystallization behavior of ternary composites, whereas Jeziorny and Ozawa methods failed to do the same ideally.     

A short synthesis of 3-enoyltetramic acids employing a new acyl ylide conjugate of Meldrum’s acid

2,2-Dimethyl-5-(triphenylphosphoranylidene)acetyl-1,3-dioxan-4,6-dione (3) is a new activated β-ketoacyl equivalent, readily prepared in quantitative yield by reaction of Meldrum’s acid with the stable ylide Ph₃PCCO. Its reaction with α-amino esters affords the corresponding N-(β-ketoacyl)amino ester ylides which, when treated with aldehydes and KOtBu, undergo a simultaneous Wittig olefination cum Dieckmann cyclisation to yield the respective 3-enoyltetramic acids.     

Ultraviolet nanosecond laser ablation behavior of silver nanoparticle and melamine–formaldehyde resin-coated short sisal fiber-modified PLA composites

Nd:YAG laser (355 nm) induced surface modifications in polylactic acid (PLA), and its composites with silver nanoparticles (AgNPs, size range between 120 and 150 nm) with and without additional melamine–formaldehyde-coated short sisal fibers were studied as a function of laser pulse numbers. The AgNP content was varied (100, 300 and 500 ppm), whereas the sisal content kept as constant (9 mass%). The PLA-based systems with a fully amorphous matrix were irradiated with 1–256 laser pulses at a constant fluence of 0.32 µJ µm^?2. Changes in the irradiated surfaces were assessed and quantified by light and scanning electron microscopic pictures. Protrusion with bubbling, bubbled protrusion with cratering and crater formation with more or less bubbled ridges were found as characteristic ablation features. Bubbling was traced to entrapped gaseous products of PLA degradation, while the onset of ridges was ascribed to the melt flow of the PLA matrix caused by laser shock waves. The laser irradiation caused damage and ablation highly depended on the actual composition, which influenced the UV absorption at 355 nm, which was measured as well.     

Brønsted acid-catalyzed allylboration: short and stereodivergent synthesis of all four eupomatilone diastereomers with crystallographic assignments

This study describes a novel Br?nsted acid-catalyzed allylboration method suitable for the most difficult, electronically deactivated allylboronate and aldehyde substrates. This method circumvents the use of metal ions, and rather employs a simple and cheap catalyst, triflic acid. Its usefulness as a complementary allylboration variant was demonstrated with a four-step, stereodivergent synthesis of all four diastereomers of eupomatilone-6 from a single allylboronate. A thorough proof of stereochemistry supported by as many as five X-ray crystallographic structures brings an end to the ambiguity of the original stereochemical assignments. Further to the TfOH-catalyzed allylboration, the synthetic route featured a number of remarkable observations: the surprising reactivity of 2-bromo-3,4,5-trimethoxybenzaldehyde, the subtle reagent control observed in the hydrogenation of an alpha-exo-methylene lactone intermediate, and the success of a difficult case of Suzuki biaryl coupling using Buchwald's conditions.