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701.
Giovanni Di Nicola Mariano Pierantozzi 《Journal of Thermal Analysis and Calorimetry》2014,116(1):129-134
This work presents a new formula to calculate the surface tension of ketones. As a first step, an analysis of the available data of the experimental surface tension data for ketones was made. Experimental data were collected for the following pure fluids: acetone, 2-butanone, 2-pentanone, 3-pentanone, 2-hexanone, 3-heptanone, 4-heptanone, 2-octanone, and 6-undecanone. The data were then regressed with the most reliable semi-empirical correlation methods in the literature based on the corresponding states theory. The final equation proposed is very simple and gives noticeable improvement with respect to existing equations. 相似文献
702.
Masked Rhodamine Dyes of Five Principal Colors Revealed by Photolysis of a 2‐Diazo‐1‐Indanone Caging Group: Synthesis,Photophysics, and Light Microscopy Applications 下载免费PDF全文
Dr. Vladimir N. Belov Dr. Gyuzel Yu. Mitronova Prof. Mariano L. Bossi Prof. Vadim P. Boyarskiy Elke Hebisch Dr. Claudia Geisler Dr. Kirill Kolmakov Dr. Christian A. Wurm Dr. Katrin I. Willig Prof. Stefan W. Hell 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(41):13162-13173
Caged rhodamine dyes (Rhodamines NN) of five basic colors were synthesized and used as “hidden” markers in subdiffractional and conventional light microscopy. These masked fluorophores with a 2‐diazo‐1‐indanone group can be irreversibly photoactivated, either by irradiation with UV‐ or violet light (one‐photon process), or by exposure to intense red light (λ~750 nm; two‐photon mode). All dyes possess a very small 2‐diazoketone caging group incorporated into the 2‐diazo‐1‐indanone residue with a quaternary carbon atom (C‐3) and a spiro‐9H‐xanthene fragment. Initially they are non‐colored (pale yellow), non‐fluorescent, and absorb at λ=330–350 nm (molar extinction coefficient (ε)≈104 M?1 cm?1) with a band edge that extends to about λ=440 nm. The absorption and emission bands of the uncaged derivatives are tunable over a wide range (λ=511–633 and 525–653 nm, respectively). The unmasked dyes are highly colored and fluorescent (ε= 3–8×104 M?1 cm?1 and fluorescence quantum yields (?)=40–85 % in the unbound state and in methanol). By stepwise and orthogonal protection of carboxylic and sulfonic acid groups a highly water‐soluble caged red‐emitting dye with two sulfonic acid residues was prepared. Rhodamines NN were decorated with amino‐reactive N‐hydroxysuccinimidyl ester groups, applied in aqueous buffers, easily conjugated with proteins, and readily photoactivated (uncaged) with λ=375–420 nm light or intense red light (λ=775 nm). Protein conjugates with optimal degrees of labeling (3–6) were prepared and uncaged with λ=405 nm light in aqueous buffer solutions (?=20–38 %). The photochemical cleavage of the masking group generates only molecular nitrogen. Some 10–40 % of the non‐fluorescent (dark) byproducts are also formed. However, they have low absorbance and do not quench the fluorescence of the uncaged dyes. Photoactivation of the individual molecules of Rhodamines NN (e.g., due to reversible or irreversible transition to a “dark” non‐emitting state or photobleaching) provides multicolor images with subdiffractional optical resolution. The applicability of these novel caged fluorophores in super‐resolution optical microscopy is exemplified. 相似文献
703.
Vezzaro A Boschetti A Dell'Anna R Canteri R Dimauro M Ramina A Ferasin M Giulivo C Ruperti B 《Analytical and bioanalytical chemistry》2011,399(7):2571-2582
Volatile organic compounds of extra virgin olive oils obtained from the local Italian cultivar Grignano were measured by proton
transfer reaction–mass spectrometry (PTR-MS). Oils were extracted by olives harvested at different ripening stages across
veraison, performing each extraction step and the whole extraction process in nitrogen atmosphere to observe the changes in the volatile
profiles of the oils. Principal component analysis carried out on the full spectral signature of the PTR-MS measurements showed
that the stage of ripening has a stronger effect on the global definition of volatile profiles than the use of nitrogen during
oil extraction. The fingerprint-like chemical information provided by the spectra were used to construct a heat map, which
allowed the dynamical representation of the multivariate nature of mass evolution during the ripening process. This provided
the first evidence that some groups of volatile organic compounds displayed a time course of regulation with coordinated increasing
or decreasing trends in association with specific stages of fruit ripening. 相似文献
704.
Canevali C Mattoni M Morazzoni F Scotti R Casu M Musinu A Krsmanovic R Polizzi S Speghini A Bettinelli M 《Journal of the American Chemical Society》2005,127(42):14681-14691
Ce-doped borosilicate (BSG), phosphosilicate (PSG), and borophosphosilicate (BPSG) glasses (B:P:Si molar ratios 8:0:92, 0:8:92, and 8:8:84; Ce:Si molar ratio 1 x 10(-)(4) to 1 x 10(-)(2)) were prepared by the sol-gel method. High-resolution transmission electron microscopy (HRTEM), (31)P, (29)Si, and (11)B magic angle spinning nuclear magnetic resonance (MAS NMR), electron paramagnetic resonance (EPR), and UV-vis absorption investigations demonstrated that, in PSG and BPSG, Ce(3+) ions interact with phosphoryl, [O=PO(3/2)], metaphosphate, [O=PO(2/ 2)O](-), and pyrophosphate, [O=PO(1/2)O(2)](2)(-), groups, linked to a silica network. This inhibits both CeO(2) segregation and oxidation of isolated Ce(3+) ions to Ce(4+), up to Ce:Si = 5 x 10(-)(3). In BSG, neither trigonal [BO(3/2)] nor tetrahedral [BO(4/2)](-) boron units coordinate cerium; thus, Ce(3+) oxidation occurs even at Ce:Si = 1 x 10(-)(4), as in pure silica glass (SG). The homogeneous rare-earth dispersion in the host matrix and the stabilization of the Ce(3+) oxidation state enhanced the intensity of the photoluminescence emission in PSG and BPSG with respect to BSG and SG. The energy of the Ce(3+) emission band in PSG and BPSG matrixes agrees with the phosphate environment of the rare earth. 相似文献
705.
706.
Real-time PCR for quantitative detection of chamois (Rupicapra rupicapra) and pyrenean ibex (Capra pyrenaica) in meat mixtures 总被引:2,自引:0,他引:2
Fajardo V González I Martín I Rojas M Hernández PE García T Martín R 《Journal of AOAC International》2008,91(1):103-111
A real-time quantitative polymerase chain reaction (PCR) technique was developed for the quantification of chamois and pyrenean ibex DNAs in meat mixtures by using a SYBR green detection platform. Two species-specific systems and a eukaryotic endogenous system were combined in the real-time PCR approach to quantify the target species. In the specific systems, a 133 base pair (bp) fragment of the 12S rRNA gene was amplified from chamois DNA, and an 88 bp fragment from the D-loop region was amplified from pyrenean ibex DNA. In the endogenous system, universal primers amplified a 141 bp fragment on the nuclear 18S rRNA gene from eukaryotic DNA. The threshold cycle values obtained with the 18S rRNA primers were used to normalize those obtained from chamois- or pyrenean ibex-specific systems, serving as endogenous control for the total content of PCR-amplifiable DNA in the sample. Analysis of experimental raw and heat-treated binary mixtures of chamois and pyrenean ibex meat in a swine meat matrix demonstrated the suitability of the assay for the detection and quantification of the target DNAs in the range of 0.1-0.8%, depending on the species and treatment of the meat samples. 相似文献
707.
Li L Li Z Chen D Lu X Feng X Wright EC Solberg NO Dunaway-Mariano D Mariano PS Galkin A Kulakova L Herzberg O Green-Church KB Zhang L 《Journal of the American Chemical Society》2008,130(6):1918-1931
Arginine deiminase (ADI) catalyzes the hydrolytic conversion of L-arginine to ammonia and L-citrulline as part of the energy-producing L-arginine degradation pathway. The chemical mechanism for ADI catalysis involves initial formation and subsequent hydrolysis of a Cys-alkylthiouronium ion intermediate. The structure of the Pseudomonas aeruginosa ADI-(L-arginine) complex guided the design of arginine analogs that might react with the ADIs to form inactive covalent adducts during catalytic turnover. One such candidate is L-canavanine, in which an N-methylene of L-arginine is replaced by an N-O. This substance was shown to be a slow substrate-producing O-ureido-L-homoserine. An in depth kinetic and mass spectrometric analysis of P. aeruginosa ADI inhibition by L-canavanine showed that two competing pathways are followed that branch at the Cys-alkylthiouronium ion intermediate. One pathway leads to direct formation of O-ureido-L-homoserine via a reactive thiouronium intermediate. The other pathway leads to an inactive form of the enzyme, which was shown by chemical model and mass spectrometric studies to be a Cys-alkylisothiourea adduct. This adduct undergoes slow hydrolysis to form O-ureido-L-homoserine and regenerated enzyme. In contrast, kinetic and mass spectrometric investigations demonstrate that the Cys-alkylthiouronium ion intermediate formed in the reaction of L-canavanine with Bacillus cereus ADI partitions between the product forming pathway (O-ureido-L-homoserine and free enzyme) and an inactivation pathway that leads to a stable Cys-alkylthiocarbamate adduct. The ADIs from Escherichia coli, Burkholderia mallei, and Giardia intestinalis were examined in order to demonstrate the generality of the L-canavanine slow substrate inhibition and to distinguish the kinetic behavior that defines the irreversible inhibition observed with the B. cereus ADI from the time controlled inhibition observed with the P. aeruginosa, E. coli, B. mallei, and G. intestinalis ADIs. 相似文献
708.
We present a study of crystalline CCl(4) spanning up to 10 orders of magnitude in time at temperatures ranging from 160 K to 190 K using molecular dynamics simulations. The relaxation process is studied using angular self correlation functions. The results show that each of the four nonequivalent molecules of the monoclinic phase have a particular relaxation time. Two of the molecules relax in an exponential way and the two other molecules have a more complex behavior, especially at the lower temperatures. In all cases, the molecular rotations correspond to quick jumps between equivalent tetrahedral equilibrium positions. Most of these rotations are about the C(3) symmetry axes, however at high temperatures, rotations about the C(2) symmetry axes are observed as well. The waiting time between rotations follows a Poisson distribution. The calculated relaxation times show an Arrhenius behavior with different activation energy for different nonequivalent molecules, in line with recently published findings of nuclear quadrupole resonance experiments. 相似文献
709.
Blach D Correa NM Silber JJ Falcone RD 《Journal of colloid and interface science》2011,353(1):124-130
The long-time behavior of the hydrolysis and condensation reaction of the tetraethoxysilane (TEOS) pre-solution at different pH values with and without addition of polyethyleneglycol (PEG) for various aging times was characterized by liquid (1)H, (13)C, and (29)Si NMR spectroscopy. After aging, the alcohol is released in the TEOS pre-solution without addition of PEG at pH 3 and 9. On the other hand, the hydrolysis and condensation rates of the TEOS pre-solutions with addition of PEG at pH 3 and 9 increase except for the TEOS pre-solution with addition of PEG 2000 at pH 9. However, the hydrolysis and condensation rates of the TEOS pre-solutions with and without addition of PEG at pH 5 and 7 are almost the same before and after aging. The effects of the pH values, polymer size and aging times on the hydrolysis and condensation reaction of the TEOS pre-solutions are discussed. 相似文献
710.
Carlos E. Rodríguez Javier Palacios Ignacio Fajardo José Luis Urdiales Xavier Le Guével José Lozano Francisca Sánchez-Jiménez 《Journal of the American Society for Mass Spectrometry》2016,27(2):366-369
This is the first study where graphene is used as a MALDI adjuvant in combination with the traditional matrix α-cyano-4-hydroxycinnamic acid (CHCA) to improve the signal intensity of peptide samples. Use of this amended matrix not only leads to increased signals but also to a higher number of peaks detected in complex samples. Additionally, the use of graphene has a stabilizing effect that can also be exploited to improve the detection of easily cleavable molecules. 相似文献