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111.
Vieira Joana Costa Morais Flvia de Oliveira Mendes Antnio Ribeiro Marcelo Leite Carta Ana Margarida Curto Joana Amaral Maria Emlia Fiadeiro Paulo Torro Costa Ana Paula 《Cellulose (London, England)》2022,29(10):5895-5912
Cellulose - An innovative approach of using a laboratory embossing prototype was carried out to develop and optimize tissue papers, to quantify the influence of “deco” and... 相似文献
112.
Effect of the Peptidic Scaffold in Copper(II) Coordination and the Redox Properties of Short Histidine‐Containing Peptides
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Ana Fragoso Tiago Carvalho Dr. Pierre Rousselot‐Pailley Prof. Margarida M. Correia dos Santos Prof. Rita Delgado Dr. Olga Iranzo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(37):13100-13111
A linear decapeptide containing three His and one Asp residues and a β‐turn‐inducing dProPro unit was synthesised. A detailed potentiometric, mass spectrometric and spectroscopic study showed that at a 1:1 ratio of CCu/Cpeptide this peptide formed a major [CuH(OdPro?Asp)]2+ species (pH range 5.5–7.0), in which the Cu2+ ion was bound to the His and Asp residues in square‐planar or square‐pyramidal geometries. The stability constant corrected for protonated species (log K*=9.33) is almost equal to the value obtained for the parent [CuH(O?Asp)]2+ species (log K*CuH(O‐Asp)=9.28), but lower than that obtained for the cyclic [CuH(C?Asp)]2+ complex (log K*CuH(C‐Asp)=10.79) previously published. Thus, the replacement of the ProGly unit by the stronger β‐turn‐inducing dProPro unit did not generate a more stable copper(II) species, although the OdPro?Asp peptide was structured in solution, as shown by circular dichroism (CD) spectroscopy. Interestingly, the calculated value of Keff showed that this peptide behaved similarly to the O?Asp or C?Asp counterparts, depending on the pH value. The cyclic voltammetry data indicated that the most easily reducible species were [CuH(O?Asp)]2+ (E′0=262 mV versus a normal hydrogen electrode (NHE)) and [CuH(OdPro?Asp)]2+ (E′0=294 mV versus NHE) complexes, the peptidic scaffolds of which are open. A lower value was obtained for [CuH(C?Asp)]2+ (E′0=24 mV versus NHE). A different degree of non‐reversibility was observed for the three copper(II) complexes; this could reflect a different degree of flexibility in their respective peptidic scaffolds. 相似文献
113.
Dr. Pedro N. Leão Hitomi Nakamura Margarida Costa Dr. Alban R. Pereira Prof. Rosário Martins Prof. Vitor Vasconcelos Prof. William H. Gerwick Prof. Emily P. Balskus 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(38):11215-11219
The isolation of the bartolosides, unprecedented cyanobacterial glycolipids featuring aliphatic chains with chlorine substituents and C‐glycosyl moieties, is reported. Their chlorinated dialkylresorcinol (DAR) core presented a major structural‐elucidation challenge. To overcome this, we discovered the bartoloside (brt) biosynthetic gene cluster and linked it to the natural products through in vitro characterization of the DAR‐forming ketosynthase and aromatase. Bioinformatic analysis also revealed a novel potential halogenase. Knowledge of the bartoloside biosynthesis constrained the DAR core structure by defining key pathway intermediates, ultimately allowing us to determine the full structures of the bartolosides. This work illustrates the power of genomics to enable the use of biosynthetic information for structure elucidation. 相似文献
114.
Alberto Calabri Ciro Ciliberto Margarida Mendes Lopes 《Transactions of the American Mathematical Society》2007,359(4):1605-1632
Minimal algebraic surfaces of general type with the smallest possible invariants have geometric genus zero and and are usually called numerical Godeaux surfaces. Although they have been studied by several authors, their complete classification is not known.
In this paper we classify numerical Godeaux surfaces with an involution, i.e. an automorphism of order 2. We prove that they are birationally equivalent either to double covers of Enriques surfaces or to double planes of two different types: the branch curve either has degree 10 and suitable singularities, originally suggested by Campedelli, or is the union of two lines and a curve of degree 12 with certain singularities. The latter type of double planes are degenerations of examples described by Du Val, and their existence was previously unknown; we show some examples of this new type, also computing their torsion group.
115.
Mulchande J Martins L Moreira R Archer M Oliveira TF Iley J 《Organic & biomolecular chemistry》2007,5(16):2617-2626
The presence of a leaving group at C-4 of monobactams is usually considered to be a requirement for mechanism-based inhibition of human leukocyte elastase by these acylating agents. We report that second-order rate constants for the alkaline hydrolysis and elastase inactivation by N-carbamoyl monobactams are independent of the pKa of the leaving group at C-4. Indeed, the effect exerted by these substituents is purely inductive: electron-withdrawing substituents at C-4 of N-carbamoyl-3,3-diethylmonobactams increase the rate of alkaline hydrolysis and elastase inactivation, with Hammett pI values of 3.4 and 2.5, respectively, which indicate the development of a negative charge in the transition-states. The difference in magnitude between these pI values is consistent with an earlier transition-state for the enzymatic reaction when compared with that for the chemical process. These results suggest that the rate-limiting step in elastase inactivation is the formation of the tetrahedral intermediate, and that beta-lactam ring-opening is not concerted with the departure of a leaving group from C-4. Monobactam sulfones emerged as potent elastase inhibitors even when the ethyl groups at C-3, required for interaction with the primary recognition site, are absent. For one such compound, a 1 : 1 enzyme-inhibitor complex involving porcine pancreatic elastase has been examined by X-ray crystallography and shown to result from serine acylation and sulfinate departure from the beta-lactam C-4. 相似文献
116.
Maria L Cunha S Videira M Gano L Paulo A Santos IC Santos I 《Dalton transactions (Cambridge, England : 2003)》2007,(28):3010-3019
This report describes the synthesis and biological evaluation of cationic (99m)Tc-tricarbonyl complexes anchored by ether-containing tris(pyrazolyl)methane or bis(pyrazolyl)ethanamine ligands to be applied in the design of radiopharmaceuticals for myocardial imaging: fac-[(99m)Tc(CO)(3){RC(pz)(3)}](+) (R = H (1a), MeOCH(2) (2a), EtOCH(2) (3a), (n)PrOCH(2) (4a)) and fac-[(99m)Tc(CO)(3){RNHCH(2)CH(pz)(2)}](+) (R = H (5a), MeO(CH(2))(2) (6a)) (pz = pyrazolyl). At the no carrier added level, complexes 1a-6a were obtained in high radiochemical yield (> 98%) by reaction of fac-[(99m)Tc(CO)(3)(H(2)O)(3)](+) with the corresponding tripod chelator in aqueous medium. All these complexes display a high in vitro and in vivo stability, except 6a which metabolizes in vivo yielding fac-[(99m)Tc(CO)(3){HO(CH(2))(2)NHCH(2)CH(pz)(2)}](+) (7a). Biological studies in mice have shown that among the radiotracers evaluated in this work, 3a, anchored by a tris(pyrazolyl)methane chelator bearing an ethyl methyl ether substituent, has the highest heart uptake (3.6 +/- 0.5%ID g(-1) at 60 min p.i.). Complex 3a presents also the best heart: blood, heart: liver and heart: lung ratios, appearing as the most promising as a potential myocardial imaging agent. The chemical identity of 1a-7a was ascertained by HPLC comparison with the previously reported fac-[Re(CO)(3){HC(pz)(3)}]Br (1) and with the novel fac-[Re(CO)(3){RC(pz)(3)}]Br (R = MeOCH(2) (2), EtOCH(2) (3), (n)PrOCH(2)(4)) and fac-[Re(CO)(3){RNHCH(2)CH(pz)(2)}]Br (R = H (5), MeO(CH(2))(2) (6) HO(CH(2))(2) (7)). The novel Re(I) tricarbonyl complexes, 2-7, were characterized by the common analytical techniques, including single crystal X-ray diffraction analysis. The solid state structure confirmed the presence of facial and tridentate (kappa(3)-N(3)) anchor ligands. Solution NMR studies have also shown that this kappa(3)-N(3) coordination mode is retained in solution for all complexes (2-7). 相似文献
117.
Alves G Figueiredo I Castel-Branco M Loureiro A Fortuna A Falcão A Caramona M 《Biomedical chromatography : BMC》2007,21(11):1127-1134
Eslicarbazepine acetate (BIA 2-093) is a novel central nervous system drug undergoing clinical phase III trials for epilepsy and phase II trials for bipolar disorder. A simple and reliable chiral reversed-phase HPLC-UV method was developed and validated for the simultaneous determination of eslicarbazepine acetate, oxcarbazepine, S-licarbazepine and R-licarbazepine in human plasma. The analytes and internal standard were extracted from plasma by a solid-phase extraction using Waters Oasis HLB cartridges. Chromatographic separation was achieved by isocratic elution with water-methanol (88:12, v/v), at a flow rate of 0.7 mL/min, on a LichroCART 250-4 ChiraDex (beta-cyclodextrin, 5 microm) column at 30 degrees C. All compounds were detected at 225 nm. Calibration curves were linear over the range 0.4-8 microg/mL for eslicarbazepine acetate and oxcarbazepine, and 0.4-80 microg/mL for each licarbazepine enantiomer. The overall intra- and interday precision and accuracy did not exceed 15%. Mean relative recoveries varied from 94.00 to 102.23% and the limit of quantification of the assay was 0.4 microg/mL for all compounds. This method seems to be a useful tool for clinical research and therapeutic drug monitoring of eslicarbazepine acetate and its metabolites S-licarbazepine, R-licarbazepine and oxcarbazepine. 相似文献
118.
Carmen Aguilar Marta Alves da Silva Margarida Saraiva Mastura Neyazi I. Anna S. Olsson Sina Bartfeld 《Experimental & molecular medicine》2021,53(10):1471
Infectious diseases are a major threat worldwide. With the alarming rise of antimicrobial resistance and emergence of new potential pathogens, a better understanding of the infection process is urgently needed. Over the last century, the development of in vitro and in vivo models has led to remarkable contributions to the current knowledge in the field of infection biology. However, applying recent advances in organoid culture technology to research infectious diseases is now taking the field to a higher level of complexity. Here, we describe the current methods available for the study of infectious diseases using organoid cultures.Subject terms: Biological models, Adult stem cells 相似文献
119.
Mario F. S. Ferreira Margarida M. V. Facao Sofia C. V. Latas 《Fiber and Integrated Optics》2000,19(1):31-41
Stable soliton propagation in a system with linear and nonlinear gain and spectral filtering is investigated. Different types of exact analytical solutions of the cubic and the quintic complex Ginzburg-Landau equation (CGLE) are reviewed. The conditions to achieve stable soliton propagation are analyzed within the domain of validity of soliton perturbation theory. We derive an analytical expression defining the region in the parameter space where stable pulselike solutions exist, which agrees with the numerical results obtained by other authors. An analytical expression for the soliton amplitude corresponding to the quintic CGLE is also obtained. We show that the minimum value of this amplitude depends only on the ratio between the linear gain and the quintic gain saturating term. 相似文献
120.
Filipe Rollo Patricia T. Borges Clia M. Silveira Margarida T. G. Rosa Smilja Todorovic Elin Moe 《Molecules (Basel, Switzerland)》2022,27(13)
Endonuclease III (EndoIII) is a bifunctional DNA glycosylase with specificity for a broad range of oxidized DNA lesions. The genome of an extremely radiation- and desiccation-resistant bacterium, Deinococcus radiodurans, possesses three genes encoding for EndoIII-like enzymes (DrEndoIII1, DrEndoIII2 and DrEndoIII3), which reveal different types of catalytic activities. DrEndoIII2 acts as the main EndoIII in this organism, while DrEndoIII1 and 3 demonstrate unusual and no EndoIII activity, respectively. In order to understand the role of DrEndoIII1 and DrEndoIII3 in D. radiodurans, we have generated mutants which target non-conserved residues in positions considered essential for classic EndoIII activity. In parallel, we have substituted residues coordinating the iron atoms in the [4Fe-4S] cluster in DrEndoIII2, aiming at elucidating the role of the cluster in these enzymes. Our results demonstrate that the amino acid substitutions in DrEndoIII1 reduce the enzyme activity without altering the overall structure, revealing that the residues found in the wild-type enzyme are essential for its unusual activity. The attempt to generate catalytic activity of DrEndoIII3 by re-designing its catalytic pocket was unsuccessful. A mutation of the iron-coordinating cysteine 199 in DrEndoIII2 appears to compromise the structural integrity and induce the formation of a [3Fe-4S] cluster, but apparently without affecting the activity. Taken together, we provide important structural and mechanistic insights into the three EndoIIIs, which will help us disentangle the open questions related to their presence in D. radiodurans and their particularities. 相似文献