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91.
Lydia A. Panther Dr. Daniel P. Guest Dr. Andrew McGown Hugo Emerit Dr. Raysa Khan Tareque Dr. Arathy Jose Mr. Chris M. Dadswell Dr. Simon J. Coles Dr. Graham J. Tizzard Dr. Ramón González-Méndez Dr. Charles A. I. Goodall Prof. Mark C. Bagley Prof. John Spencer Dr. Barnaby W. Greenland 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(49):e202201444
Solvent-free synthesis by using a vibratory ball mill (VBM) offers the chance to access new chemical reactivity, whilst reducing solvent waste and minimising reaction times. Herein, we report the core functionalisation of N,N’-bis(2-ethylhexyl)-2,6-dibromo-1,4,5,8-naphthalenetetracarboxylic acid (Br2-NDI) by using Suzuki, Sonogashira and Buchwald–Hartwig coupling reactions. The products of these reactions are important building blocks in many areas of organic electronics including organic light-emitting diodes (OLEDs), organic field-effect transistors (OFETs) and organic photovoltaic cells (OPVCs). The reactions proceed in as little as 1 h, use commercially available palladium sources (frequently Pd(OAc)2) and are tolerant to air and atmospheric moisture. Furthermore, the real-world potential of this green VBM protocol is demonstrated by the double Suzuki coupling of a monobromo(NDI) residue to a bis(thiophene) pinacol ester. The resulting dimeric NDI species has been demonstrated to behave as an electron acceptor in functioning OPVCs. 相似文献
92.
Christina C. Roggatz Mercedes González-Wangüemert Hugo Pereira Maria João Rodrigues Manuela Moreira da Silva Luísa Barreira 《Natural product research》2016,30(18):2034-2040
This work reports for the first time the nutritional profile and antioxidant potential of the edible sea cucumber Holothuria arguinensis from the North-eastern Atlantic. H. arguinensis has high levels of protein, with the amino acids profile dominated by alanine, glycine and proline and low lysine/arginine ratios. Its carbohydrate and energetic contents are also low as well as the total lipid levels, although its lipid profile is rich in polyunsaturated fatty acids (PUFA), especially arachidonic, eicosapentaenoic and docosahexaenoic acids. In addition, H. arguinensis has high levels of calcium. The water and ethanol extracts show ability to scavenge free radicals and to chelate copper and iron ions. Our results indicate that H. arguinensis has a balanced nutritional quality suitable for human consumption. In addition, it contains compounds with antioxidant potential; thus its intake can contribute for a healthy and well-balanced diet. 相似文献
93.
94.
We prove Russo‐Seymour‐Welsh‐type uniform bounds on crossing probabilities for the FK Ising (FK percolation with cluster weight q = 2) model at criticality, independent of the boundary conditions. Our proof relies mainly on Smirnov's fermionic observable for the FK Ising model [24], which allows us to get precise estimates on boundary connection probabilities. We stay in a discrete setting; in particular, we do not make use of any continuum limit, and our result can be used to derive directly several noteworthy properties—including some new ones—among which are the fact that there is no infinite cluster at criticality, tightness properties for the interfaces, and the existence of several critical exponents, in particular the half‐plane, one‐arm exponent. Such crossing bounds are also instrumental for important applications such as constructing the scaling limit of the Ising spin field [6] and deriving polynomial bounds for the mixing time of the Glauber dynamics at criticality [17]. © 2011 Wiley Periodicals, Inc. 相似文献
95.
Butylated hydroxytoluene (BHT) is an antioxidant utilized as additive in foods and packaging plastic. Its presence in drinking water is possible if it is used as an antioxidant in the packaging plastic because it may migrate into the package's contents. A method for the determination of BHT in water by means of solid-phase microextraction and gas chromatography-mass spectrometry has been developed and evaluated with respect to the time of fiber exposure, limits of detection and quantitation, linearity and precision. Finally, the method was applied to evaluate the presence of this substance in samples of mineral and mineralized bottled drinking water, and it appeared to be present in seven out of a total of fifteen commercial brands. 相似文献
96.
The hitherto unsolved problem of the origin of the unusually high nitrogen inversion-rotation (NIR) barriers in 7-azabicyclo[2.2.1]heptanes (the bicyclic effect) was examined using the natural bond orbital (NBO) approach. Reinvestigating the NIR barrier for tropane by DNMR, we found that NIR barriers increase smoothly on going from nitrogen-bridged bicyclic systems of a larger ring size to the smaller ring homologous systems. The experimental NIR barriers are reproduced with good accuracy using the MP2/6-31G level of theory. The NBO analysis for these and other azabicycles led to the conclusion that the height of these barriers is mostly determined by the energy of the sigma-orbitals of the C(alpha)(-)C(beta) bonds as well as the nitrogen lone pair. Thus, the bicyclic effect is actually an extreme case of a common C(alpha-)N-C(alpha) tripyramid geometry-NIR barrier dependence for N-bridged bicyclic amines. By establishing the rate-determining role of the C(alpha-)N-C(alpha) tripyramid fragment for NIR, we have derived the first sufficiently accurate quantitative correlations amine geometry-NIR barrier for monocyclic as well as bicyclic N-H and N-Me amines (i.e., for an amine set which also includes the bicyclic effect systems). 相似文献
97.
Bacteriochlorophyll (BChl) derivatives (with central Mg replaced by metal "M") ([M]-BChl with M = 2H, Mg, Zn, Pd, Cu) have been investigated for their photodynamic capacity and stability toward photodegradation in organic solvents and aqueous micellar solution. A protocol has been developed for screening new sensitizers. BChl and [Zn]-BChl are efficient sensitizers, but they are also quickly degraded by the reactive oxygen species (ROS) produced by autosensitization, as well as by hetero-sensitization with 17(4)-methyl-13(2)-demethoxycarbonyl-pheophorbide a (MPP). Photostable [Cu]-BChl is a poor sensitizer, whereas [Pd]-BChl and bacteriopheophytin a are not only very efficient sensitizers but are also very stable toward ROS. beta-Carotene is no efficient physical quencher of ROS in the system; rather, it acts as a photochemical quencher that competes with [M]-BChl and undergoes photooxygenation at high rates. Photolability seems to depend on the pigment oxidation potential and, in parallel, on the presence of central metals preferring coordination numbers higher than 4, whereas photodynamic capacity depends on long excited state life-times of the pigment or efficient intersystem crossing (or both). 相似文献
98.
A series of derivatisation reactions between p-t-butyl calix[4]arene and ethyl bromoacetate were carried out in order to prepare 1,3 diester substituted calix[4]arene. Mass spectral data, obtained from direct injection of samples, indicated that the reactions were rich in the desired product. Since the ultra violet (UV) spectra of the desired product and possible impurities are very similar, liquid chromatography (LC) chromatographic data seemed to corroborate these results. However, when on-line LC-UV-MS was carried out and each LC peak subjected to MS analysis as it eluted, a very different picture emerged. It was found that many of these reactions actually contained high levels of the monoester product which, having less affinity for sodium in the MS, is therefore seriously underestimated in any direct injection assay. LC-diode array detection (DAD) methods were also used to help successfully identify and characterise the compounds being formed in these complex reactions. The overall results obtained in this paper allowed the optimal reaction conditions to be determined for this reaction. LC-MS analysis of the chromatographic peaks also identified the presence of two isomers of the diester substituted calix[4]arene (1,3 and 1,2 diesters). The combination of LC and UV/MS detection is required for accurate analysis of the products of such reactions. 相似文献
99.
Gaynor D Starikova ZA Ostrovsky S Haase W Nolan KB 《Chemical communications (Cambridge, England)》2002,(5):506-507
The reaction of 2-(dimethylamino)phenylhydroxamic acid (2-dmAphaH) with NiSO(4).6H2O gives the complex [Ni7(2-dmAphaH-1)2(2-dmApha)8(H2O)2]SO(4).15H2O uniquely exhibiting four distinct hydroxamate binding modes, two of which are novel, and showing both antiferromagnetic and ferromagnetic interactions in contrast to [Cu5(2-dmAphaH-1)4(HSO4)2(MeOH)2].2MeOH, a strongly antiferromagnetic metallacrown formed with CuSO(4).5H2O. 相似文献
100.
[reaction: see text] The copper metallomicellar hydrolysis of O-methyl O-4-nitrophenyl phenylphosphonothioate to O-methyl phenylphosphonothioic acid takes place with effectively complete inversion at phosphorus. 相似文献