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11.
Yang Shen Ioanna Kalograiaki Alessio Prunotto Matthew Dunne Samy Boulos Nicholas M. I. Taylor Eric T. Sumrall Marcel R. Eugster Rebecca Martin Alicia Julian-Rodero Benjamin Gerber Petr G. Leiman Margarita Menndez Matteo Dal Peraro Francisco Javier Caada Martin J. Loessner 《Chemical science》2021,12(2):576
Endolysins are bacteriophage-encoded peptidoglycan hydrolases targeting the cell wall of host bacteria via their cell wall-binding domains (CBDs). The molecular basis for selective recognition of surface carbohydrate ligands by CBDs remains elusive. Here, we describe, in atomic detail, the interaction between the Listeria phage endolysin domain CBD500 and its cell wall teichoic acid (WTA) ligands. We show that 3′O-acetylated GlcNAc residues integrated into the WTA polymer chain are the key epitope recognized by a CBD binding cavity located at the interface of tandem copies of beta-barrel, pseudo-symmetric SH3b-like repeats. This cavity consists of multiple aromatic residues making extensive interactions with two GlcNAc acetyl groups via hydrogen bonds and van der Waals contacts, while permitting the docking of the diastereomorphic ligands. Our multidisciplinary approach tackled an extremely challenging protein–glycopolymer complex and delineated a previously unknown recognition mechanism by which a phage endolysin specifically recognizes and targets WTA, suggesting an adaptable model for regulation of endolysin specificity.Combining genetic, biochemical and computational approaches, we elucidated the molecular mechanisms underlying the recognition of Listeria wall teichoic acid by bacteriophage-encoded SH3b repeats. 相似文献
12.
Roman E. Enrique Castro W. Veronica Camus O. Margarita 《Journal of organometallic chemistry》1985,293(1):93-101
The reactions between the phosphine-organoiron [CpFeII-η6-C6Me5CH2PPh2]+ PF6? (1) and [RhCl(η4-diolefin)(μ-Cl)]2 in CH2Cl2 at reflux give the new heterobinuclear air-stable crystalline complexes [CpFeII-η6-C6Me5CH2)P(Ph)2Rh(η4-diene)Cl]PF6,(D'*-diene=cyclooctadiene (COD): 65%, 2; trimethylfluorobenzobicyclo[2.2.2]octadiene (Me3TFB): 48%, 3). Complexes 2 and 3 have been studied by 1H, 13C and 31P NMR spectroscopy and they are carbonylated (CO, 1 atm). Cyclic voltammetry experiments with addition of MeOH show electron transfer FeIRhI → FeIIRh0, the presence of a catalytic wave FeI/FeII and the possible formation of Rh hydrides. Under normal conditions 2 is a catalyst for hydrogenation of cyclohexene, but it is less efficient than the known mononuclear Rh1 analogues. 相似文献
13.
Junquera E Laynez J Menéndez M Sharma S Penadés S 《The Journal of organic chemistry》1996,61(20):6790-6798
Thermodynamic studies of the binding of a series of p-nitrophenyl glycosides (PNPGly) of varying stereochemistry to alpha-cyclodextrin (alpha-CD) were performed at three different temperatures (25, 35, and 42 degrees C) using a microcalorimetric technique. The system p-nitrophenol (PNP) at pH = 3 and alpha-CD was also studied for the sake of comparison. All these complexes were found to be enthalpy driven with a favorable enthalpic term clearly dominant over an unfavorable entropic term. A clear enthalpy-entropy compensation effect was observed at all the temperatures, with a slope close to unity (alpha = 1.02) and an intercept TDeltaS degrees (o) = 2.91 kcal mol(-)(1). This thermodynamic pattern is in agreement with those usually found for lectin-carbohydrate associations and for the binding processes of several host-guest systems. This pattern is explained in terms of the contribution of primarily two driving forces: the van der Waals interactions between the host and the guest, and the solvation/desolvation processes which accompany the association reaction. The presence of the carbohydrate molecule in the PNP ring causes a slight destabilization of the complex at 25 degrees C with respect to the alpha-CD-PNP (pH = 3) complex, although a different behavior has been observed depending on the axial/equatorial configuration of the glycoside and the temperature. This behavior is modulated by the stereochemistry of the glycoside. Differences were observed between the deoxy-derivatives (LAra and LFuc) and those derivatives with a hydroxymethyl group (Glc, Gal, Man). DeltaC(p) degrees values were obtained from the dependency of DeltaH degrees on temperature (=( partial differentialDeltaH degrees / partial differentialT)(p)). These values are small and negative except for alphaMan complex. For the latter complex, discrepancy between the calorimetric and the calculated van't Hoff enthalpies was observed. Parallels are drawn between the thermodynamics of our model and those proposed for carbohydrate-protein associations. 相似文献
14.
de la Fuente JM Eaton P Barrientos AG Menéndez M Penadés S 《Journal of the American Chemical Society》2005,127(17):6192-6197
Thermodynamic evidence for the selective Ca(2+)-mediated self-aggregation via carbohydrate-carbohydrate interactions of gold glyconanoparticles functionalized with the disaccharides lactose (lacto-Au) and maltose (malto-Au), or the biologically relevant trisaccharide Lewis X (Le(X)-Au), was obtained by isothermal titration calorimetry. The aggregation process was also directly visualized by atomic force microscopy. It was shown in the case of the trisaccharide Lewis X that the Ca(2+)-mediated aggregation is a slow process that takes place with a decrease in enthalpy of 160 +/- 30 kcal mol(-)(1), while the heat evolved in the case of lactose and maltose glyconanoparticles was very low and thermal equilibrium was quickly achieved. Measurements in the presence of Mg(2+) and Na(+) cations confirm the selectivity for Ca(2+) of Le(X)-Au glyconanoparticles. The relevance of this result to cell-cell adhesion process mediated by carbohydrate-carbohydrate interactions is discussed. 相似文献
15.
Carlos Seoane Jos L. Soto Pilar Zamorano Margarita Quinteiro 《Journal of heterocyclic chemistry》1981,18(2):309-314
Ring transformations of 4H-pyrans into pyridines are reported. Treatment of 2-amino-4,6-diaryl-3,5-dicyano-4H-pyrans (I) with nitrosylsulfuric acid brings about their transformation into 3,5-dicyano-4,6-diaryl-2-pyridones (VI) which can also be obtained from α-benzoylcinnamonitriles (IX) and cyanoacetamide. Similarly, 2-amino-4,6-diaryl-5-carbethoxy-3-cyano-4H-pyrans (II) lead to 4,6-diaryl-5-carbethoxy-3-cyano-2-pyridones (VII). Treatment of both series of pyrans with sulfuric acid results in the formation of the corresponding 3,4-dihydro-2-pyridones (IV and V). Reaction of pyrans II with ammonium acetate in acetic acid yields 2-amino-4,6-diaryl-5-carbethoxy-3-cyanopyridines (XII). Pyrans I undergo an entirely different type of reaction upon treatment with this reagent leading to 2,4,6-triaryl-3,5-dicyano-1,4-dihydropyridines (XV). 相似文献
16.
[reaction: see text] The reactions of secondary alicyclic (SA) amines and quinuclidines (QUI) with 4-nitrophenyl and 2,4-dinitrophenyl S-methyl thiocarbonates (1 and 2, respectively) and those of SA amines with 2,3,4,5,6-pentafluorophenyl S-methyl thiocarbonate (3) are subjected to a kinetic study in aqueous solution, at 25.0 degrees C, and an ionic strength of 0.2 M (KCl). The reactions of thiocarbonates 1, 2, and 3 were followed spectrophotometrically at 400, 360, and 220 nm, respectively. Under amine excess, pseudo-first-order rate coefficients (k(obsd)) are found. Plots of k(obsd) vs amine concentration at constant pH are linear, with the slope (kN) independent of pH. The Br?nsted-type plots (log kN vs pKa of aminium ions) are linear for all the reactions, with slopes beta = 0.9 for those of 1 with SA amines and QUI, beta = 0.36 and 0.57 for the reactions of 2 with SA amines and QUI, respectively, and beta = 0.39 for the reactions of SA amines with 3. The magnitude of the slopes indicates that both aminolyses of 1 are governed by stepwise mechanisms, through a zwitterionic tetrahedral intermediate (T+/-), where expulsion of the nucleofuge from T+/- is the rate-determining step. The values of the Br?nsted slopes found for the aminolyses of thiocarbonates 2 and 3 suggest that these reactions are concerted. By comparison of the reactions under investigation between them and with similar aminolyses, the following conclusions arise: (i) Thiocarbonate 2 is more reactive than 1 toward the two amine series. (ii) The change of the nonleaving group from MeO in 4-nitrophenyl methyl carbonate to MeS in thiocarbonate 1 results in lower kN values. (iii) The greater reactivity of this carbonate than thiocarbonate 1 is attributed to steric hindrance of the MeS group, compared to MeO toward amine attack. (iv) The change of a pyridine to an isobasic SA amine or QUI destabilizes the T+/- intermediate formed in the aminolyses of 2. (v) The change of 4-nitrophenoxy to 2,3,4,5,6-pentafluorphenoxy or 2,4-dinitrophenoxy as the leaving group destabilizes the tetrahedral intermediate formed in the reactions with SA amines, changing the mechanism from a stepwise process to a concerted reaction. 相似文献
17.
Emmanuel Blas Patricio-Rangel Margarita Tlahuextl Hugo Tlahuext Antonio Rafael Tapia-Benavides 《Acta Crystallographica. Section C, Structural Chemistry》2020,76(4):322-327
The synthesis and characterization of two new 1,3,5‐triazines containing 2‐(aminomethyl)‐1H‐benzimidazole hydrochloride as a substituent are reported, namely, 2‐{[(4,6‐dichloro‐1,3,5‐triazin‐2‐yl)amino]methyl}‐1H‐benzimidazol‐3‐ium chloride, C11H9Cl2N6+·Cl? ( 1 ), and bis(2,2′‐{[(6‐chloro‐1,3,5‐triazine‐2,4‐diyl)bis(azanediyl)]bis(methylene)}bis(1H‐benzimidazol‐3‐ium)) tetrachloride heptahydrate, 2C19H18ClN92+·4Cl?·7H2O ( 2 ). Both salts were characterized using single‐crystal X‐ray diffraction analysis and IR spectroscopy. Moreover, the NMR (1H and 13C) spectra of 1 were obtained. Salts 1 and 2 have triclinic symmetry (space group P) and their supramolecular structures are stabilized by hydrogen bonding and offset π–π interactions. In hydrated salt 2 , the noncovalent interactions yield pseudo‐nanotubes filled with chloride anions and water molecules, which were modelled in the refinement with substitutional and positional disorder. 相似文献
18.
Alberto Fernández Jesús J. Fernández Margarita López-Torres José M. Vila 《Journal of organometallic chemistry》2005,690(16):3669-3679
Reaction of the ligand C6H5N(H)NCMe(C5H4N) (a) with palladium(II) acetate in toluene gave the mononuclear cyclometallated complex [Pd{C6H4N(H)NCMe(C5H4N)}(AcO)] (1a). Reaction of 1a with sodium chloride gave the analogous chlorine compound [Pd{C6H4N(H)NCMe(C5H4N)}(Cl)] (3a) which could also be prepared by reaction of a with lithium tetrachloropalladate and sodium acetate in methanol for 48 h; whereas shorter reaction times afforded the non-cyclometallated complex [Pd{C6H5N(H)NCMe(C5H4N)}(Cl)2] (2a). Reaction of the ligand 2-ClC6H4N(H)NCMe(C5H4N) · HCl (b), with palladium(II) acetate, or with lithium tetrachloropalladate and sodium acetate, yielded the cyclometallated complex [Pd2-ClC6H3N(H)NCMe(C5H4N)(Cl)] (1b). Treatment of 3a and 1b with silver trifluoromethanesulphonate (triflate) and triphenylphosphine in acetone gave the mononuclear complexes [Pd{2-RC6HnN(H)NCMe(C5H4N)}(PPh3)][CF3SO3], (R = H, n = 4, 4a; R = Cl, n = 3, 2b) with the ligand as C,N,N′ terdentate and substitution of chlorine by triphenylphosphine. Reaction of 3a and 1b with silver triflate and the tertiary diphosphine Ph2P(CH2)4PPh2 (dppb) in a 2:1 molar ratio gave the dinuclear cyclometallated complexes [{Pd[2-RC6H3N(H)NCMe(C5H4N)]}2(μ-Ph2P(CH2)4PPh2)][CF3SO3]2 (R = H, 5a; R = Cl, 3b) with a μ2-diphosphine bridging ligand. Similarly, treatment of 3a and 1b with silver triflate and the tertiary triphosphines MeC(CH2PPh2)3 (tripod) and (Ph2PCH2CH2)2PPh (triphos), in 3:1 molar ratio, gave the novel trinuclear complexes [{Pd[C6H4N(H)NCMe(C5H4N)]}3{μ3-MeC(CH2Ph2)3}][CF3SO3]3 (6a) and [{Pd[2-ClC6H3N(H)NCMe(C5H4N)]}3{μ3-(PPh2CH2CH2)2PPh}][CF3SO3] 3 (4b) regioselectively, with the phosphine as a μ3-bridging ligand. When the reaction between 3a and triphos was carried out in 1:1 molar ratio the mononuclear complex [Pd{C6H4N(H)NCMe(C5H4N)}{(PPh2CH2CH2)2PPh-P,P,P}][ClO4] (7a) was obtained. The crystal structures of 2b, 3a and 4a have been determined by X-ray crystallography. 相似文献
19.
Margarita Acevedo Alain Fradet 《Journal of polymer science. Part A, Polymer chemistry》1993,31(3):817-830
2,2′-Bis(4,4-dimethyl-5(4H)-oxazolone) ( B3 ) and 2,2′-(1,2-ethylene)-bis(4,4-dimethyl-5(4H)oxazolone) ( B4 ) have been reacted in the bulk with α, ω-diamino polyamide-12 ( PA12 ) of M?n = 1000. The reactions have been studied by SEC, and 1H- and 13C-NMR and resulting polymers characterized by DSC and TGA. The chain coupling reaction is fast and gives high molar mass polymers within 10 min at 200°C with B4 while some side reactions occur with B3 leading to polymers of lower molar mass. The crystallinity of resulting polymers is lower than that of starting oligomer. However, the thermal stability is higher. Model reactions using B3 or B4 and hexamethylene diamine or 1-dodecanamine have been carried out and studied. An intramolecular cyclodehydration giving 2-imidazolin-5-ones takes place during the reactions. Higher cyclization extent is found in the presence of amino group excess. 2-Imidazolin-5-one heterocyclic structures are also observed in the chains of the polymers obtained from PA12 and B3 or B4 . © 1993 John Wiley & Sons, Inc. 相似文献
20.
Josep Castells Elisabet Duñach Fernando Geijo Francisco López-Calahorra Margarita Prats Olga Sanahuja Laura Villanova 《Tetrahedron letters》1980,21(23):2291-2294
Triethylamine catalyzed Michael additions of benzoins to chalcone can prevail over the expected Michael-Stetter additions when certain thiazolium ion conjugate bases - prepared from the pertinent thiazolium salts and triethylamine- are used as catalysts. 相似文献