Research on Chemical Intermediates - Enzymatic transesterification of dl-menthol with vinyl acetate in tert-Butyl methyl ether (TBME) catalyzed by Candida cylindracea lipase (CCL) was carried out... 相似文献
Transfer Factors (Fv) of 238U, 226Ra, 234Th, 210Po and 210Pb from five different agricultural soils in semi-arid region (Syria) to four different barley genotypes were studied in an agricultural potted experiment. The geometric mean of the Fv values were (0.08) for 210Pb, and (0.02) for 210Po, while it ranged from 0.18 to 0.42 ,from 0.08 to 0.15 and from 0.22 to 0.4 for 238U, 234Th and 226Ra, respectevily. The Fv values of 238U and 226Ra were within the recommended global medians, while the Fv values of 234Th, 210Pb and 210Po were higher. There is no clear relationship between the soil properties and Fv of all studied radionuclides to barley genotypes. Moreover, the expression of glutathione (GSH) gene, which is belived to be involoved in heavy metal removal was generally low in all studied varieties grown in all soil types.
A detailed investigation of the influence of counterions on the [N–I–N]+ halogen bond in solution, in the solid state and in silico is presented. Translational diffusion coefficients indicate close attachment of counterions to the cationic, three-center halogen bond in dichloromethane solution. Isotopic perturbation of equilibrium NMR studies performed on isotopologue mixtures of regioselectively deuterated and nondeuterated analogues of the model system showed that the counterion is incapable of altering the symmetry of the [N–I–N]+ halogen bond. This symmetry remains even in the presence of an unfavorable geometric restraint. A high preference for the symmetric geometry was found also in the solid state by single crystal X-ray crystallography. Molecular systems encompassing weakly coordinating counterions behave similarly to the corresponding silver(i) centered coordination complexes. In contrast, systems possessing moderately or strongly coordinating anions show a distinctly different behavior. Such silver(i) complexes are converted into multi-coordinate geometries with strong Ag–O bonds, whereas the iodine centered systems remain linear and lack direct charge transfer interaction with the counterion, as verified by 15N NMR and DFT computation. This suggests that the [N–I–N]+ halogen bond may not be satisfactorily described in terms of a pure coordination bond typical of transition metal complexes, but as a secondary bond with a substantial charge-transfer character. 相似文献
Polynitrile anions are important in both coordination chemistry and molecular materials chemistry, and are interesting for their extensive electronic delocalization. The title compound crystallizes with two symmetry‐independent half 4,4′‐bipyridine‐1,1′‐diium (bpyH22+) cations and two symmetry‐independent 1,1,3,3‐tetracyano‐2‐ethoxypropenide (tcnoet−) anions in the asymmetric unit. One of the bpyH22+ ions is located on a crystallographic twofold rotation axis (canted pyridine rings) and the other is located on a crystallographic inversion center (coplanar pyridine rings). The ethyl group of one of the tcnoet− anions is disordered over two sites with equal populations. The extended structure exhibits two separate N—H...NC hydrogen‐bonding motifs, which result in a sheet structure parallel to (010), and weak C—H...NC hydrogen bonds form joined rings. Two types of multicenter CN...π interactions are observed between the bpyH22+ rings and tcnoet− anions. An additonal CN...π interaction between adjacent tcnoet− anions is observed. Using density functional theory, the calculated attractive energy between cation and anion pairs in the tcnoet−...π(bipyridinediium) interactions were found to be 557 and 612 kJ mol−1 for coplanar and canted bpyH22+ cations, respectively. 相似文献
This review focuses on new families of spin crossover (SCO) complexes based on polynitrile anions as new anionic ligands or on polyazamacrocycles as neutral macrocyclic ligands. We have shown that the structural and electronic characteristics (original coordination modes and high electronic delocalization) of the polynitrile anions can be tuned by slight chemical modifications such as substitution of functional groups or variation of the negative charge to design new discrete or polymeric SCO systems.In our ongoing work on the design of new molecular systems based on new ligands that can be fine-tuned via chemical modifications, another promising way which has been recently developed in our group concerns the use of new neutral polydentate ligands which are able to tune the ligand field energy around the metal centre. Here we report some recent original Fe(II) SCO complexes based on such polydentate ligands. 相似文献
The use of polynitrile anions as ligands (L) either alone or in combination with neutral co-ligands (L′) is a very promising and appealing strategy to get molecular architectures with different topologies and dimensionalities thanks to their ability to coordinate and bridge metal ions in many different ways. The presence of several potentially coordinating nitrile groups (or even other donor groups as –OH, –SH or –NH2), their rigidity and their electronic delocalization allow the synthesis of original magnetic high dimensional coordination polymers with transition metals ions. Furthermore, these ligands have shown coordinating and bridging capabilities in novel discrete and polymeric bistable materials (materials showing original magnetic behaviours or spin crossover (SCO) transitions). Here we report an overview of the results obtained with some of these modified polynitrile ligands, showing their rich coordination chemistry and their crucial role in new molecular materials exhibiting unusual magnetic transitions. 相似文献
Highly efficient removal of endocrine‐disrupting compounds (EDCs) such as 17β‐estradiol (E2), 4‐nonylphenol (NP) and atrazine from water was achieved using a novel macroporous adsorption medium. The medium consisted of a macroporous poly(vinyl alcohol) (PVA) cryogel with molecularly imprinted polymer (MIP) particles embedded in it. The MIP was prepared using E2, NP and atrazine as templates. The macroporous composite molecularly imprinted cryogels were formed inside the open‐ended protective shells, known as Kaldnes carriers. These adsorbents (defined as Macroporous Gel Particles, MGPs) were evaluated on the removal of E2, NP and atrazine from water using different column configurations, namely column filled with the MGPs (packed‐bed column) and in moving‐bed reactors (defined here as moving‐bed MGPs reactor). Complete binding (> 99%) of E2 from a spiked aqueous solution (1 mg/L) was achieved using E2‐MIP/MGPs in a moving‐bed MGPs reactor at the retention time in the reactor of 4 min, while only 77% was bound to the nonimprinted medium (NIP/MGPs). Similar results were also obtained for the adsorption medium imprinted with atrazine. All contaminants studied (E2, atrazine and NP) were effectively removed from water at low (environmentally relevant) concentrations by the respective adsorption medium. 相似文献