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51.
Brahmananda?Ghosh David A.?LightnerEmail author Antony F.?McDonaghEmail author 《Monatshefte für Chemie / Chemical Monthly》2004,135(9):1189-1199
Summary. A symmetrical C(10)-selena-bilirubin analog, 8,12-bis(2-carboxyethyl)-7,13-dimethyl-2,3,17,18-tetraethyl-10-selenabiladiene-ac-1,19(21H,24H)-dione was synthesized from 8-(2-carboxyethyl)-2,3-diethyl-7-methyl-(10H)-dipyrrin-1-one in one step by reaction with diselenyl dichloride. The selena-rubin exhibited UV-vis and NMR spectroscopic properties similar to those of the parent mesobilirubin, and like bilirubin and mesobilirubin, it adopts an intramolecularly hydrogen-bonded conformation, shaped like a ridge-tile but with a steeper pitch. The longer C–Se bond lengths (2.2Å) and smaller bond angles at C–Se–C (88°), as compared to C–CH2–C (1.5Å, 106°), lead to an interplanar angle between the two dipyrrinones of only 72°, which is considerably less than that of bilirubin (100°) and close to that (74°) of its 10-thia-rubin analog. Despite the conformational distortion, the sensitivity of Se toward oxidation and the typically weak C–Se bond, the selena-rubin is metabolized in normal rats, like bilirubin, to acyl glucuronides, which are secreted into bile. In mutant (Gunn) rats lacking bilirubin glucuronosyl transferase (UGT1A1), glucuronide or other metabolites of the selena-rubin were not detected in bile, demonstrating the importance of hepatic glucuronidation for its biliary excretion. 相似文献
52.
Philpott's theory of vibronic transitions of substitutional impurities in molecular crystals has been examined. The lowest energy guest transition in a number of mixed crystals has been calculated and compared with experiment. Satisfactory agreement is achieved. In some cases consideration of charge overlap of the guest and nearest host gives better agreement. 相似文献
53.
Intramolecular [2 + 2] photocycloaddition of alkenes with a furano sugar placed between them have been investigated under both copper(I)-catalyzed and sensitized conditions. The copper(I)-catalyzed photocycloaddition of the dienes 4a, 4b, and 4c led to unexpected formation of the thermodynamically less stable cis-syn-cis 4-5-5 tricyclic adducts 5a, 5b, and 5c, respectively. The sensitized photocycloaddition of the diene 14 also gave the cis-syn-cis adduct 15 showing that the copper(I) catalyst does not have any influence on the stereochemical course through coordination with the anomeric ring oxygen of the furano sugar. The identical stereochemical course observed under both catalyzed and sensitized photoaddition reactions have been attributed to be of steric origin. Bis(dienes) 25a and 25b, which gave an intractable mixture on copper(I)-catalyzed irradiation, underwent smooth photocycloaddition in the presence of benzophenone, and the resulting 1,2-divinyl cyclobutanes underwent spontaneous [3.3]-rearrangement at room temperature to produce bicyclo[6.3.0]undecanes 30a and 30b, respectively. This investigation provides an approach for the construction of enantiopure bicyclo[3.2.0]heptanes and -[6.3.0]undecanes. 相似文献
54.
P. Ramachandra T. Siva Rama Krishna Gautam R. Desiraju 《Journal of Chemical Sciences》1989,101(4):327-334
The compound 3-hydroxy-6-(4′-nitro)phenylazopyridine (1) was observed to incorporate several organic solvents of crystallisation, forming stable clathrates. These clathrates decompose
upon heating and the host material is chemically transformed. Single crystal X-ray diffraction studies on the ethanol clathrate
lead to a reasonable model for the host structure. But the guest molecules are severely disordered. Alternatively, the compound
forms twinned crystals. The chemically closely related compound2 does not form clathrates. 相似文献
55.
Using a very simple trial function and unperturbed electron densities calculated by a new procedure, the frequency-dependent dipole polarizability () of Ne, Ar, Kr and Xe has been calculated in the range 0 0.45 a.u., by a Karplus-Kolker-type variation-perturbation method. Results progressively worsen for larger systems so that, for Xe, (0) is only 75% of the experimental value. Probable reasons for this are discussed. 相似文献
56.
Landa Purushottam Unnikrishnan V. B. Dattatraya Gautam Rawale Mansi Gujrati Surya Dev Mishra Sajeev T. K. Neelesh C. Reddy Srinivasa Rao Adusumalli Ram Kumar Mishra Vishal Rai 《Chemical science》2020,11(48):13137
Analytically pure proteins are indispensable for diverse applications, including therapeutics. Here, we report a methodology where a single amino acid, glycine, enables metal-free protein purification. This robust platform is enabled by a Gly-tag resin for site-specific capture, enrichment, and release through chemically triggered C–C bond dissociation by resonance-assisted electron density polarization.Gly-tag resin precisely captures and releases a protein with one glycine at the N-terminus. The user-friendly protocol delivers analytically pure protein free of metal contaminants. 相似文献
57.
[reaction: see text] (-)-Doliculide, a potent antitumor agent, is synthesized stereoselectively in a convergent manner. The key strategy involves a stereoselective synthesis of the polyketide unit and synthesis of the D-tyrosine derivative, followed by assembly of the fragments by an esterification and cycloamidation reaction sequence. The synthesis of the polyketide fragment was achieved by an iterative asymmetric synthesis to install stereoselectively both 1,3-dimethyl groups and the 1,3-diol unit by utilizing asymmetric cyclopropanations and Sharpless asymmetric epoxidations as the key steps. 相似文献
58.
Piperine, an alkaloid derived from the fruits of Piper nigrum, has been tested as an extracting bioreagent for gold. It has been observed that piperine as well as the fruits of Piper nigrum itself can act as an efficient exchanger for gold both in trace and macro scale. The accumulation of gold by these bioreagents
is highly pH dependent. 相似文献
59.
Novel bilirubin analogues with dipyrrinones conjoined to an acetylene rather than a methylene group were synthesized and examined spectroscopically. Despite the increased separation of the dipyrrinones forced by replacing a -CH(2)- by a -C(triple bond)C- unit, molecular dynamics calculations show that, like bilirubin, they may still engage in intramolecular hydrogen bonding to carboxylic acid groups when the propionic acid chains are slightly lengthened, e.g., butanoic acids. Unlike bilirubin, however, which is bent in the middle and has a ridge-tile shape, the acetylene orients the attached dipyrrinones along a linear path, and intramolecular hydrogen bonding preserves a twisted linear molecular shape. The extended planes of the dipyrrinones intersect along the -C(triple bond)C- axis at an angle of 136 degrees for the conformation stabilized by intramolecular hydrogen bonding in the bis-butyric acid rubin (1b). With shorter acid chains (propionic), only one CO(2)H can engage an opposing dipyrrinone in intramolecular hydrogen bonding, and in this energy-minimum conformation of the linear pigment 1a, the intersection of the extended planes of the dipyrrinones has an angle of 171 degrees. Spectroscopic evidence for such linearized and twisted structures was found in the pigments' NMR spectral data and their exciton UV-vis and induced circular dichroism spectra. 相似文献
60.
Summary [NiL2X2] (L =N,N-dimethyl-1,2-ethanediamine; X = Cl–, CF3CO
2
–
, CC13CO
2
–
and CBr3CO
2
–
), [NiL2C2O4] · H2O and [NiL2X2] · 2 H2O (X = Br–, 0.5 SO
4
2–
and 0.5 SeO
4
–
) have been synthesised and their thermal studies carried out. Thermally induced phase transition phenomena are noticed in [NiL2X2] (X = CF3CO
2
–
and CCl3CO
2
–
) and their probable mechanisms are described. [NiL2X2] (X = Br–, 0.5 SO
4
2–
and 0.5 SeO
4
2–
) and [NiLX2] (X = Cl–, 0.5 C2O
4
2–
and 0.5 SO
4
2–
) have been prepared by solid state pyrolysis from the respective parent diamine complexes. [NiL2X2] have been made in solid state by temperature arrest technique from [NiL2(CX3CO2)2] (X = Cl– and Br–). 相似文献