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81.
Potential of prodendronic polyamines with modulated segmental charge density as novel coating for fast and efficient analysis of peptides and basic proteins by CE and CE‐MS 下载免费PDF全文
Tanize Acunha Clara Ibáñez María Isabel Pascual Reguera Mariagiovanna Sarò Rodrigo Navarro Juan Alfonso Redondo Helmut Reinecke Alberto Gallardo Carolina Simó Alejandro Cifuentes 《Electrophoresis》2015,36(14):1564-1571
In this work, the suitability of a new polymer family has been investigated as capillary coatings for the analysis of peptides and basic proteins by CE. This polymer family has been designed to minimize or completely prevent protein–capillary wall interactions and to modify the EOF. These coating materials are linear polymeric chains bearing as side cationizable moiety a dentronic triamine derived from N,N,N’,N’‐tetraethyldiethylenetriamine (TEDETA), which is linked to the backbone through a spacer (unit labeled as TEDETAMA). Four different polymers have been prepared and evaluated: a homopolymer which comprised only of those cationizable repetitive units of TEDETAMA, and three copolymers that randomly incorporate TEDETAMA together with neutral hydrosoluble units of N‐(2‐hydroxypropyl) methacrylamide (HPMA) at different molar percentages (25:75, 50:50 and 75:25). It has been demonstrated that the composition of the copolymers influences the EOF and therefore the separation of the investigated biopolymers. Among the novel polymers studied, poly‐(TEDETAMA‐co‐HPMA) 50:50 copolymer was successfully applied as coating material of the inner capillary surface in CE‐UV and CE‐MS, providing EOF reversing together with fast and efficient baseline separation of peptides and basic proteins. Finally, the feasibility of the polymer‐coated capillary was shown through the analysis of lysozyme in a cheese sample. 相似文献
82.
The results of a (1)H nuclear magnetic relaxation dispersion (NMRD) and EPR study on aqueous suspensions of Gd(3+)-loaded NaY nanozeolites and AlTUD-1 mesoporous material are described. Upon increase of the Si/Al ratio from 1.7 to 4.0 in the Gd(3+)-loaded zeolites, the relaxation rate per mM Gd(3+) (r1) at 40 MHz and 25 degrees C increases from 14 to 27 s(-)1 mM(-1). The NMRD and EPR data were fitted with a previously developed two-step model that considers the system as a concentrated aqueous solution of Gd(3+) in the interior of the zeolite that is in exchange with the bulk water outside the zeolite. The results show that the observed increase in relaxivity can mainly be attributed to the residence lifetime of the water protons in the interior of the material, which decreased from 0.3 to 0.2 micros, upon the increase of the Si/Al ratio. This can be explained by the decreased interaction of water with the zeolite walls as a result of the increased hydrophobicity. The importance of the exchange rate of water between the inside and the outside of the material was further demonstrated by the relatively high relaxivity (33 s(-1) mM(-1) at 40 MHz, 25 degrees C) observed for a suspension of the Gd(3+)-loaded mesoporous material AlTUD-1. Unfortunately, Gd(3+) leaches rather easily from that material, but not from the Gd(3+)-loaded NaY zeolites, which may have potential as contrast agents for magnetic resonance imaging. 相似文献
83.
A theoretical study of the possible protonation sites of simple molecules formed by C, N, Si, P, B and Al that present a triple
bond between those atoms has been carried out. The calculations performed include MP2 and CCSD(T) methods with the aug-cc-pVTZ
basis set. The nature of the protonated species has been analyzed with the Atoms In Molecules methodology.
To Serafin, a free spirit and a good friend.
Contribution to the Serafin Fraga Memorial Issue. 相似文献
84.
This work presents a numerical simulation of an ultrafiltration process of bovine serum albumin in solution, using hollow-fiber membranes. Such membranes are constituted of tiny polymer cylinders disposed in a tube-and-shell arrangement. The concentrate flows through the interior of the fibers and the pure solvent is recovered in the shell, assuming perfect solute rejection. In modeling the process, the flow of concentrate inside the fibers was considered to be laminar, with constant density, viscosity and solute diffusivity. Axial diffusion and angular effects were ignored. The model combines the effect of concentration polarization and adsorption, which are the two main limiting phenomena in ultrafiltration processes. The pressure on the shell side was considered constant and inside the fibers a linear pressure profile, dependent on the axial position, was adopted. The solution of the problem was achieved with the method of orthogonal collocation, with adequate choice of the weight function in the radial direction. In the axial direction, a finite-difference method was used. The numerical results were compared with experimental data available in the literature. 相似文献
85.
L. Morales A. Caneiro D. VegaR. Zysler H. LanzaR.C. Mercader 《Journal of solid state chemistry》2002,168(1):100-109
The incorporation of Sn into LaMnO3 perovskite and its influence on magnetotransport properties were studied in samples synthesized at low temperature. Single-phase materials for two series of samples with La/(Sn+Mn)=1 and La/(Sn+Mn)<1 ratios were obtained by substitution of up to 10% of the Mn ions by Sn4+. The effect of Sn substitution was monitored through measurements of thermal, “M(T)”, and magnetic field, “M(H)”, dependences of magnetization, as well as of resistivity, “ρ(T)”, at 0 and 70 kOe. These showed that this effect depends strongly on the perovskite cation site ratio (A/B). For La/(Sn+Mn)=1, M and TC were depressed as Sn content was increased. The magnetization data suggest the presence of magnetic clusters with superparamagnetic behavior. No evidence of magnetoresistance (MR) was found. For La/(Sn+Mn)<1 ratio, the samples showed ferromagnetic behavior and MR and both M and TC raised as Sn content increased. The results are discussed in terms of A site vacancies. 相似文献
86.
Palma E Correia JD Oliveira BL Gano L Santos IC Santos I 《Dalton transactions (Cambridge, England : 2003)》2011,40(12):2787-2796
Bone scintigraphy with (99m)Technetium-methylenediphosphonate ((99m)Tc-MDP) or (99m)Technetium-hydroxymethylenediphosphonate ((99m)Tc-HMDP) presents several limitations, namely low specificity, uncertainty in the radiopharmaceutical's molecular structure and long acquisition time after injection. Aiming to find bone-seeking radiotracers based on the core fac-[(99m)Tc(CO)(3)](+) with improved chemical and biological properties, we synthesized new conjugates (pz-PAM and pz-ALN), comprising a pyrazolyl-diamine chelating unit (pz: N,N,N donor atom set) for metal stabilization and a pendant pamidronate (PAM) or alendronate (ALN) moiety for bone targeting. The reaction of the conjugates with fac-[(99m)Tc(CO)(3)](+) yielded (> 95%) the stable complexes fac-[(99m)Tc(CO)(3)(pz-PAM)](-) (2a) and fac-[(99m)Tc(CO)(3)(pz-ALN)](-) (3a), which have been characterized by comparing their HPLC gamma-traces with the UV-vis traces of the Re surrogates 2 and 3, respectively. 2a and 3a bind strongly onto hydroxyapatite. The biodistribution studies in Balb-c mice have shown that 2a and 3a presented an high bone uptake (2a 18.3 ± 0.6% I.D./g, 3a 17.3 ± 6.1% I.D./g, at 1 h post injection), similar to (99m)Tc-MDP (17.1 ± 2.4% I.D./g, at 1 h post injection), with comparable clearance from most tissues and increased total excretion (2a 66% I.D., 3a 67% I.D. and (99m)Tc-MDP 49% I.D., at 1 h post injection). The bone-to-blood (2a 86.2, 3a 74.7) and the bone-to-muscle ratios (2a 77.7, 3a 79.0) are higher than the ones found for (99m)Tc-MDP (70.9, 47.9), at 4 h post injection. Planar whole-body gamma camera images of the rats injected with the (99m)Tc(CO)(3)-labeled pamidronate (2a) and alendronate (3a) confirmed the overall adequate biological profile of the new radiotracers for bone imaging. 相似文献
87.
Isabel V. L. Wilkinson Kelly J. Perkins Hannah Dugdale Lee Moir Aini Vuorinen Maria Chatzopoulou Sarah E. Squire Sebastian Monecke Alexander Lomow Marcus Geese Philip D. Charles Peter Burch Jonathan M. Tinsley Graham M. Wynne Stephen G. Davies Francis X. Wilson Fraydoon Rastinejad Shabaz Mohammed Kay E. Davies Angela J. Russell 《Angewandte Chemie (International ed. in English)》2020,59(6):2420-2428
Duchenne muscular dystrophy (DMD) is a fatal muscle‐wasting disease arising from mutations in the dystrophin gene. Upregulation of utrophin to compensate for the missing dystrophin offers a potential therapy independent of patient genotype. The first‐in‐class utrophin modulator ezutromid/SMT C1100 was developed from a phenotypic screen through to a Phase 2 clinical trial. Promising efficacy and evidence of target engagement was observed in DMD patients after 24 weeks of treatment, however trial endpoints were not met after 48 weeks. The objective of this study was to understand the mechanism of action of ezutromid which could explain the lack of sustained efficacy and help development of new generations of utrophin modulators. Using chemical proteomics and phenotypic profiling we show that the aryl hydrocarbon receptor (AhR) is a target of ezutromid. Several lines of evidence demonstrate that ezutromid binds AhR with an apparent KD of 50 nm and behaves as an AhR antagonist. Furthermore, other reported AhR antagonists also upregulate utrophin, showing that this pathway, which is currently being explored in other clinical applications including oncology and rheumatoid arthritis, could also be exploited in future DMD therapies. 相似文献
88.
89.
Marcelino Maneiro Manuel R. Bermejo M. Isabel Fernndez Ana M. Gonzlez‐Noya Alexei M. Tyryshkin Robin G. Pritchard 《无机化学与普通化学杂志》2003,629(2):285-290
A new MnIII‐Schiff base complex, [MnL(OH2)](ClO4) ( 1 ) (H2L = N, N′‐bis‐(3‐Br‐5‐Cl‐salicylidene)‐1, 2‐diimino‐2‐methylethane), an inorganic model of the catalytic center (OEC, Oxygen Evolving Complex) in photosystem II (PSII), has been synthesized and characterized by elemental analysis, IR and EPR spectroscopy, mass spectrometry, magnetic susceptibility measurement and the study of its redox properties by cyclic and normal pulse voltammetry. This complex mimics reactivity (showing a relevant photolytic activity), and also some structural characteristics (parallel‐mode MnIII EPR signal from partially assembled OEC cluster) of the natural OEC. The complex 1 was found to rearrange in solution into a crystallographically solved square‐pyramidal complex, [MnLL′] ( 2 ) (HL′ = 6‐bromo‐4‐chloro‐2‐cyanophenol), through a process, which probably liberates radical species (detected by EPR), and provokes a C—N bond cleavage in the ligand. A photo‐radical mechanism is discussed to explain this rearrangement. 相似文献
90.
A method for the direct determination of volatile and non-volatile nickel and vanadium compounds in crude oil without previous treatment using direct solid sampling graphite furnace atomic absorption spectrometry is proposed. The crude oil samples were weighed directly onto solid sampling platforms using a microbalance and introduced into a transversely heated solid sampling graphite tube. In previous work of our group losses of volatile nickel and vanadium compounds have been detected, whereas other nickel and vanadium compounds were thermally stable up to 1300 and 1600 °C, respectively. In order to avoid this problem different chemical modifiers (conventional and permanent) have been investigated. With 400 μg of iridium as permanent modifier, the signal started to drop already after two atomization cycles, possibly because of an interaction of nickel (which is a catalyst poison) with iridium. Twenty micrograms of palladium applied in each determination was found to be optimum for both elements. The palladium was deposited on the platform and submitted to a drying step at 150 °C for 75 s. After that the sample was added onto the platform and submitted to the furnace program. The influence of sample mass on the linearity of the response and on potential measurement errors was also investigated using four samples with different nickel content. For the sample with the lowest nickel concentration the relationship between mass and integrated absorbance was found to be non-linear when a high sample mass was introduced. It was suspected that the modifier had not covered the entire platform surface, which resulted in analyte losses. This problem could be avoided by using 40 μL of 0.5 g L−1 Pd with 0.05% Triton X-100. Calibration curves were established with and without modifier, with aqueous standards, oil-in-water emulsions and the certified reference material NIST SRM 1634c (trace metals in residual fuel oil). The sensitivity for aqueous standards and emulsions was close to that for SRM 1634c, making possible the use of aqueous standards for calibration. The limits of detection and quantification obtained for nickel and vanadium under this condition were found to be 0.02 and 0.06 μg g−1, respectively, for both elements, based on 10 mg of sample. Nickel and vanadium were determined in the samples with (total Ni and V) and without the use of Pd (thermally stable compounds), and the concentration of volatile compounds was calculated by difference. The results were compared with those obtained by high-resolution continuum source graphite furnace atomic absorption spectrometry by emulsion technique; no significant differences were found for total Ni and V at the 95% confidence level according to a Student's t-test. 相似文献