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1.
Dr. Joaquim Torra Dr. Felipe Viela Dr. Diego Megías Dr. Begoña Sot Prof. Cristina Flors 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(19):e202200026
CRANAD-2 is a fluorogenic curcumin derivative used for near-infrared detection and imaging in vivo of amyloid aggregates, which are involved in neurodegenerative diseases. We explore the performance of CRANAD-2 in two super-resolution imaging techniques, namely stimulated emission depletion (STED) and single-molecule localization microscopy (SMLM), with markedly different fluorophore requirements. By conveniently adapting the concentration of CRANAD-2, which transiently binds to amyloid fibrils, we show that it performs well in both techniques, achieving a resolution in the range of 45–55 nm. Correlation of SMLM with atomic force microscopy (AFM) validates the resolution of fine features in the reconstructed super-resolved image. The good performance and versatility of CRANAD-2 provides a powerful tool for near-infrared nanoscopic imaging of amyloids in vitro and in vivo. 相似文献
2.
Experimental and Theoretical Studies on the Rearrangement of 2‐Oxoazepane α,α‐Amino Acids into 2′‐Oxopiperidine β2,3,3‐Amino Acids: An Example of Intramolecular Catalysis 下载免费PDF全文
Dr. Diego Núñez‐Villanueva Dr. M. Ángeles Bonache Laura Lozano Dr. Lourdes Infantes Prof. José Elguero Prof. Ibon Alkorta Prof. M. Teresa García‐López Dr. Rosario González‐Muñiz Dr. Mercedes Martín‐Martínez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2489-2500
Enantiopure β‐amino acids represent interesting scaffolds for peptidomimetics, foldamers and bioactive compounds. However, the synthesis of highly substituted analogues is still a major challenge. Herein, we describe the spontaneous rearrangement of 4‐carboxy‐2‐oxoazepane α,α‐amino acids to lead to 2′‐oxopiperidine‐containing β2,3,3‐amino acids, upon basic or acid hydrolysis of the 2‐oxoazepane α,α‐amino acid ester. Under acidic conditions, a totally stereoselective synthetic route has been developed. The reordering process involved the spontaneous breakdown of an amide bond, which typically requires strong conditions, and the formation of a new bond leading to the six‐membered heterocycle. A quantum mechanical study was carried out to obtain insight into the remarkable ease of this rearrangement, which occurs at room temperature, either in solution or upon storage of the 4‐carboxylic acid substituted 2‐oxoazepane derivatives. This theoretical study suggests that the rearrangement process occurs through a concerted mechanism, in which the energy of the transition states can be lowered by the participation of a catalytic water molecule. Interestingly, it also suggested a role for the carboxylic acid at position 4 of the 2‐oxoazepane ring, which facilitates this rearrangement, participating directly in the intramolecular catalysis. 相似文献
3.
Condeixa Lucas Dias Silva Pierry Moah Diego Farias Brenda Leiras Adriana 《Central European Journal of Operations Research》2022,30(3):921-940
Central European Journal of Operations Research - Societal awareness and legislation changes concerning sustainability have affected how organizations generate value for stakeholders, as well as... 相似文献
4.
Design and development of a two‐dimensional system based on hydrophilic and reversed‐phase liquid chromatography with on‐line sample treatment for the simultaneous separation of excreted xenobiotics and endogenous metabolites in urine 下载免费PDF全文
Diego García‐Gómez Encarnación Rodríguez‐Gonzalo Rita Carabias‐Martínez 《Biomedical chromatography : BMC》2015,29(8):1190-1196
In the present work we describe a two‐dimensional liquid chromatographic system (2D‐LC) with detection by mass spectrometry (MS) for the simultaneous separation of endogenous metabolites of clinical interest and excreted xenobiotics deriving from exposure to toxic compounds. The 2D‐LC system involves two orthogonal chromatographic modes, hydrophilic interaction liquid chromatography (HILIC) to separate polar endogenous metabolites and reversed‐phase (RP) chromatography to separate excreted xenobiotics of low and intermediate polarity. Additionally, the present proposal has the novelty of incorporating an on‐line sample treatment based on the use of restricted access materials (RAMs), which permits the direct injection of urine samples into the system. The work is focused on the instrumental coupling, studying all possible options and attempting to circumvent the problems of solvent incompatibility between the RAM device and the two chromatographic columns, HILIC and RP. The instrumental configuration developed, RAM‐HILIC‐RPLC‐MS/MS, allows the simultaneous assessment of urinary metabolites of clinical interest and excreted compounds derived from exposure to toxic agents with minimal sample manipulation. Thus, it may be of interest in areas such as occupational and environmental toxicology in order to explore the possible relationship between the two types of compounds. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
5.
René Meziat Diego Patiño Pablo Pedregal 《Computational Optimization and Applications》2007,38(1):147-171
We propose an alternative method for computing effectively the solution of non-linear, fixed-terminal-time, optimal control
problems when they are given in Lagrange, Bolza or Mayer forms. This method works well when the nonlinearities in the control
variable can be expressed as polynomials. The essential of this proposal is the transformation of a non-linear, non-convex
optimal control problem into an equivalent optimal control problem with linear and convex structure. The method is based on
global optimization of polynomials by the method of moments. With this method we can determine either the existence or lacking
of minimizers. In addition, we can calculate generalized solutions when the original problem lacks of minimizers. We also
present the numerical schemes to solve several examples arising in science and technology. 相似文献
6.
This paper deals with two mixed nonlinear boundary value problems depending on a parameter λ. For each of them we prove the existence of at least three generalized solutions when λ lies in an exactly determined open interval. Usefulness of this information on the interval is then emphasized by means of some consequences. Our main tool is a very recent three critical points theorem stated in [Topol. Methods Nonlinear Anal. 22 (2003) 93-104]. 相似文献
7.
This Letter considers the generalized second law of gravitational thermodynamics in two scenarios featuring a phantom dominated expansion plus a black hole. The law is violated in both scenarios. 相似文献
8.
The determination of polar and nonpolar organophosphorus compounds, triazines and their metabolites, molinate and chlorothalonil in 1 l water samples was investigated using off-line solid-phase extraction followed by gas chromatography with nitrogen-phosphorus and flame photometric detection. The ethylvinylbenzene-divinylbenzene copolymer (LiChrolut EN) and the commercial graphitized carbon black (GCB) of Envi-Carb were tested as solid-phase sorbents. The matrix effect was studied by extracting the compounds spiked in water samples of different types (Milli-Q, tap, salted tap water, river and sea water). The polymeric sorbent LiChrolut EN allowed the determination at low ng/l of all 40 compounds tested, except the very polar atrazine-desethyl-deisopropyl (DDA). Recoveries of compounds from the Envi-Carb sorbent are comparable to those obtained for LiChrolut EN with the exception of chlorothalonil and the more hydrophobic organophosphorus compounds (coumaphos, leptophos), which were strongly sorbed in the Envi-Carb cartridges. Envi-Carb, however, enabled the determination of DDA with a limit of detection of 14 ng/l. 相似文献
9.
A study of the viability of three derivatizing reagents for obtaining amino acid profiles in honey through high performance liquid chromatography (HPLC) is presented. A method using diode array detection based on a reaction with diethyl ethoxymethylene malonate (DEMM) and two other methods using fluorescence detection based on derivatization with fluorenylmethyl chloroformate (FMOC-Cl) and 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate (AQC) have been developed. The three methods yield detection limits close to the ppb level, but vary in relation to other analytical characteristics. The use of methyl chloroformate derivatives allows the profile to be obtained with the greatest sensitivity within a short time frame. On applying such methods to honey samples of diverse botanical origin, we observe that the proline values obtained are always lower than those found using the official spectrophotometric method, thereby underlining the advisability of using HPLC methods to reduce uncertainty in these results. 相似文献
10.
Guido Galliani Diego Monti Giovanna Speranza Paolo Manitto 《Tetrahedron letters》1984,25(52):6037-6040
Bilin-1,19(21H,24H)-diones interact with O2·- in DMSO giving rise to adducts showing charge-transfer character. This reaction can be reversed by addition of O2·- consuming compounds. The O2·-biliverdin dimethyl ester adduct collapses partially to 10-oxobilirubin dimethyl ester when treated with thiourea and 2-mercaptoethanol. 相似文献