Chemistry of Natural Compounds - A new chamigrane sesquiterpene, antroalbol F (1), along with one known compound, acaciicolinol C (2), were isolated from cultures of the fungus Antrodiella... 相似文献
The one-pot catalytic conversion of cellulose into ethylene glycol (EG) is an attractive way of biomass utilization. However, low-cost, efficient, and stable catalysts are the premise and research challenges of industrial application. Herein, the magnetic recyclable W–Ni@C catalyst was synthesized by in-situ pyrolysis of Ni-MOFs impregnated with ammonium metatungstate. Compared with the Ni-W bimetallic catalysts prepared by the impregnation method and the sol–gel method, the W–Ni@C catalyst for cellulose hydrogenolysis reaction can achieve a higher ethylene glycol yield (67.1% vs 43.3% and 42.6%) and 100% of cellulose conversion rate. The uniformly dispersed Ni nanoparticles and abundant defective WOx were formed in a reductive atmosphere generated in pyrolysis of Ni-MOFs, which was indispensable for the hydrogenolysis of cellulose into EG. Besides, the hierarchical porous carbon derived from organic ligands in Ni-MOFs reduces the mass transfer resistance while confining Ni nanoparticles and WOx to prevent their leaching, effectively enhancing the stability of the W–Ni@C catalyst. Therefore, the remarkable catalytic performance, the simple and effective recovery method as well as satisfying stability would make W–Ni@C become a promising catalyst for the conversion of cellulose to EG.
Elaboration of enantioenriched complex acyclic stereotriads represents a challenge for modern synthesis even more when fluorinated tetrasubstituted stereocenters are targeted. We have been able to develop a simple strategy in a sequence of two unprecedented steps combining a diastereoselective aldol-Tishchenko reaction and an enantioselective organocatalyzed kinetic resolution. The aldol-Tishchenko reaction directly generates a large panel of acyclic 1,3-diols possessing a fluorinated tetrasubstituted stereocenter by condensation of fluorinated ketones with aldehydes under very mild basic conditions. The anti 1,3-diols featuring three contiguous stereogenic centers are generated with excellent diastereocontrol (typically >99 : 1 dr). Depending upon the precursors both diastereomers of stereotriads are accessible through this flexible reaction. Furthermore, from the obtained racemic scaffolds, development of an organocatalyzed kinetic resolution enabled to generate the desired enantioenriched stereotriads with excellent selectivity (typically er >95 : 5). 相似文献
Naphthalene endoperoxides are known as convenient sources of singlet oxygen (O2, 1Δg), which is the major product of endoperoxide cycloreversion reaction. However, their potential as carriers of ground-state molecular oxygen (O2, 3Σg) similar to artificial oxygen carriers remains largely unexplored. This is due to the extreme reactivity and cytotoxic effects of the released singlet oxygen. We now report that a compound with a bimodular design, which incorporates an endoperoxide and an efficient physical quencher of singlet oxygen, 1,4-diazabicyclo[2.2.2]octane (DABCO), produces exclusively ground-state molecular oxygen. This result, coupled with the fact that oxygen release rates from endoperoxides are highly amenable to fine-tuning in a very broad range, and open to targeting by ligand attachment, raises the potential of these compounds far above any comparable chemical, or even biochemical sources. In cell culture experiments, we showed that the addition of the endoperoxide-quencher conjugate can enhance and sustain cell proliferation. 相似文献
Adsorptive separation of C2H6 from C2H4 by adsorbents is an energy-efficient and promising method to boost the polymer grades C2H4 production. However, that C2H6 and C2H4 display very similar physical properties, making their separation extremely challenging. In this work, by regulating the pore environment in a family of chitosan-based carbon materials (C-CTS-1, C-CTS-2, C-CTS-4, and C-CTS-6)- we target ultrahigh C2H6 uptake and C2H6/C2H4 separation, which exceeds most benchmark carbon materials. Explicitly, the C2H6 uptake of C-CTS-2 (166 cm3/g at 100 kPa and 298 K) has the second-highest adsorption capacity among all the porous materials. In addition, C-CTS-2 gives C2H6/C2H4 selectivity of 1.75 toward a 1:15 mixture of C2H6/C2H4. Notably, the adsorption enthalpies for C2H6 in C-CTS-2 are low (21.3 kJ/mol), which will facilitate regeneration in mild conditions. Furthermore, C2H6/C2H4 separation performance was confirmed by binary breakthrough experiments. Under different ethane/ethylene ratios, C-CTS-X extracts a low ethane concentration from an ethane/ethylene mixture and produces high-purity C2H4 in one step. Spectroscopic measurement and diffraction analysis provide critical insight into the adsorption/separation mechanism. The nitrogen functional groups on the surface play a vital role in improving C2H6/C2H4 selectivity, and the adsorption capacities depend on the pore size and micropore volume. Moreover, these robust porous materials exhibit outstanding stability (up to 800 °C) and can be easily prepared on a large scale (kg) at a low cost (~$26 per kg), which is very significant for potential industrial applications. 相似文献
卤代醌是一类卤代芳烃类环境污染物的致癌中间体,也是在饮用水中新发现的氯化消毒副产物。我们最近发现卤代醌和 H2O2 或有机氢过氧化物体系可以不依赖过渡金属离子,而产生高活性的羟基/烷氧自由基和醌氧/醌碳自由基。目前尚不清楚这些卤代醌类致癌物和氢过氧化物共存能否诱导 DNA 产生氧化损伤和修饰,以及其潜在的分子机制是什么。我们的研究发现 DNA 在四氯-1,4-苯醌/H2O2体系中可被氧化产生 8-氧脱氧鸟苷、DNA 链断裂和三种甲基氧化产物,这些反应不依赖过渡金属离子,且由于卤代醌与 DNA 的嵌入作用而导致其氧化作用增强。其他卤代醌也观察到了类似的现象,而且通常比经典的 Fenton 体系更有效。我们进一步将研究从纯化的 DNA 扩展到了活细胞的基因组 DNA。同时还发现卤代醌和有机氢过氧化物(如叔丁基过氧化氢或在正常生理条件下产生的 13S-过氧羟基-9Z,11E-十八碳二烯酸(13-HPODE))共存时,可通过独特的醌氧自由基介导机制诱导 DNA 氧化生成致突变性更强的咪唑啉酮类产物 dIz。这些发现为解释普遍存在的卤代醌类致癌中间体和消毒副产物的潜在基因毒性、致突变性和致癌性提供了新思路。 相似文献
Temperature-dependent near-infrared (NIR) spectroscopy has been developed and taken as a powerful technique for analyzing the structure of water and the interactions in aqueous systems. Due to the overlapping of the peaks in NIR spectra, it is difficult to obtain the spectral features showing the structures and interactions. Chemometrics, therefore, is adopted to improve the spectral resolution and extract spectral information from the temperature-dependent NIR spectra for structural and quantitative analysis. In this review, works on chemometric studies for analyzing temperature-dependent NIR spectra were summarized. The temperature-induced spectral features of water structures can be extracted from the spectra with the help of chemometrics. Using the spectral variation of water with the temperature, the structural changes of small molecules, proteins, thermo-responsive polymers, and their interactions with water in aqueous solutions can be demonstrated. Furthermore, quantitative models between the spectra and the temperature or concentration can be established using the spectral variations of water and applied to determine the compositions in aqueous mixtures. 相似文献