Molecular crystals with moving parts: synthesis, characterization, and crystal packing of molecular gyroscopes with methyl-substituted triptycyl frames

We report a highly convergent synthesis for the preparation of molecular gyroscopes consisting of para-phenylene rotors linked by triple bonds to methyl-substituted triptycenes acting as pivots and encapsulating frames. The desired 1,4-bis[2-(2,3,6,7,12,13-hexamethyl-10-alkyl-9-triptycyl)ethynyl]benzenes were prepared from 2,3-dimethyl-1,3-butadiene using Diels-Alder cycloadditions and Pd(0)-catalyzed coupling as the key reactions. The main challenge in the synthesis came about in the preparation of 9-alkynyl-triptycenes by Diels-Alder reaction of benzynes and 9-alkynyl-2,3,6,7-tetramethylanthracenes. These reactions occurred with chemical yields and regioselectivities that were strongly influenced by steric and electronic effects of substituents at C10 of the anthracene core. Anthracenes with methyl, propyl, and phenyl substituents were utilized to complete the synthesis of their corresponding molecular gyroscopes, and their solid-state structures were determined by single-crystal X-ray diffraction analysis. Examination of these results indicated that, as expected, the bulky triptycyl groups encourage crystallization motifs that create more free volume around the phenylene rotor, as needed to facilitate fast gyroscopic motion in the solid state.     

Asteriscanolide. A sesquiterpene lactone with a new natural skeleton.

A sesquiterpene lactone was isolated from the hexane extract of $\text{Asteriscus aquaticus}$. Its constitution and stereochemistry were determined by spectroscopic techniques, principally two-dimensional NMR correlations (COSY, HCCORR, RELAY) and with the interpretation of certain chemical transformations. The results were confirmed by X-ray diffraction and the name asteriscane is proposed for the new natural skeleton.     

Understanding of the mode of action of Fe(III)-EDDHA as iron chlorosis corrector based on its photochemical and redox behavior

The very low reduction potential of the chelate Fe(III)-EDDHA (EDDHA = ethylenediamine N,N'-bis(2-hydroxy)phenylacetic acid) makes it unreactive in photochemically or chemically induced electron transfer processes. The lack of reactivity of this complex toward light invalidates photodegradation as an alternative mechanism for environmental elimination. However, in spite of its low reduction potential, the biological reduction of Fe(III)-EDDHA is very effective. Based on electrochemical measurements, it is proposed that Fe(III)-EDDHA itself is not the substrate of the enzyme ferric chelate reductase. Likely, at the more acidic pH in the vicinity of the roots, the ferric chelate in a closed form (FeL-) could generate a vacant coordination site that leads to an open hexacoordinate species (FeHL) where the reduction of the metal by the enzyme takes place.     

Intramolecular interactions in the triplet excited states of benzophenone-thymine dyads

Time-resolved and product studies on the synthesized dyads 1 and 2 have provided evidence that the benzophenone-to-thymine orientation strongly influences intramolecular photophysical and photochemical processes. The prevailing reaction mechanism has been established as a Paterno-Büchi cycloaddition to give oxetanes 3-6; however, the ability of benzophenone to achieve a formal hydrogen abstraction from the methyl group of thymidine has also been evidenced by the formation of photoproducts 7 and 8. These processes have been observed only in the case of the cisoid dyad 1. Adiabatic photochemical cycloreversion of the oxetane ring is achieved upon direct photolysis to give the starting dyad 1 in its excited triplet state. The photobiological implications of the above results are discussed with respect to benzophenone-photosensitized damage of thymidine.     

Synthesis, characterization, and structural study of K2FeZrP3O12 with the langbeinite structure

A potassium iron zirconium phosphate, K₂FeZrP₃O₁₂, was synthesized by thermal treatment of a material obtained by the sol-gel method, mixing two aqueous solutions, the first containing KCl, FeCl₃ and ZrOCl₂, and the second, H₃PO₄. The crystal structure was refined using powder X-ray diffraction data. The unit cell is cubic, a=10.0554(3) Å, space group P2₁3. This compound is the first iron zirconium phosphate described with a langbeinite-type structure.     

Photochemical access to tetra- and pentacyclic terpene-like products from R-(+)-sclareolide

Fused tetracyclic oxetanes 4, highly substituted cyclobutenes 6, and the pentacyclic derivatives 7 and 8 were obtained by irradiation of derivatives 3 that were prepared from commercial R-(+)-sclareolide (1) in three steps. Compounds 4 are formed through a Paterno-Büchi reaction, while tricyclic derivatives 6 are the fragmentation products of the first formed oxetanes. In clear contrast, cyclopentenyl and 3-furyl derivatives, 3e and 3f, gave the [2+2] adducts, namely pentacyclic derivatives 7 and 8. All the reported reactions are totally regio- and stereoselective, with the exception of the cyclization of furyl derivative 3f, which gave the mixture of both the crossed (7b) and the right (8) isomers.     

Chemical constituents,in vitro antioxidant and antimicrobial properties of ethyl acetate extract obtained from Cytisus triflorus l’Her

Abstract

The present study investigates the phenolic composition, antioxidant and antimicrobial activities of an ethyl acetate extract from C. triflorus L’Her. The phytochemical study on the aerial parts of C. triflorus belonging to the Fabaceae family led to the isolation and structural elucidation of 5-Hydroxy-7-O-glucosylflavone (P1), 5-Hydroxy-7-O-galactosylflavone (P2), 5,7-Dihydroxy-flavone (P3), 5,7,3’-Trihydroxy,4’-methoxy-flavone (P4). These compounds were identified by 1D and 2D NMR combined analysis as well as by UV.

Ethyl acetate extract of C. triflorus showed a significant and dose-dependent antioxidant activity in vitro, related to the presence of phenolics (180.33?±?12.22?µg GAE/mg) and flavonoids (16.78?± 1.54?µg QE/mg). The antimicrobial activity was evaluated in vitro against Staphylococcus aureus CECT 240 and Escherichia coli CECT 4099, by agar-diffusion method. The most active antibacterial activity was expressed by ethyl acetate extract of C. triflorus against Gram-positive bacteria S. aureus. The gathered results suggest that C. triflorus polyphenols and flavonoids are closely associated to its antioxidant and antimicrobial properties.     

Synthesis and biological evaluation of analogues of butyrolactone I and molecular model of its interaction with CDK2

A series of analogues of butyrolactone I, a natural product isolated from Aspergillus terreus that selectively inhibits the CDK2 and CDK1 kinases and that has been found to exhibit an interesting antiproliferative activity, have been synthesized. Its antitumor activity has been tested. Molecular models of the complex between butyrolactone I and the CDK2 active site have been built using a combination of conformational search and automated docking techniques. The stability of the resulting complexes has been assessed by molecular dynamics simulations and the experimental results obtained for the synthesized analogues are rationalized based on the molecular models.     

Determination of mineral balances in sheep offered feed with added cadmium and zinc

The optimum conditions for microwave digestion of herbage and faeces to determine mineral concentrations were obtained by varying sample mass, reagent and heating programme, and it was confirmed that the resulting element concentrations were the same as for certified reference material. The effects of feeding cadmium to sheep at a level that is typical of polluted regions (1 mg/kg) for ten days were investigated, as well as the possible amelioration of cadmium effects by adding 30 mg/kg Zn to the diet. Cadmium in the feed increased the cadmium balance and produced several mineral disturbances, in particular a reduction in sodium balance which is typical of renal tubular disorders. Including zinc in the diet as well as cadmium reduced the cadmium balance to a level similar to that of sheep that did not receive cadmium or zinc, which suggests that the zinc status is critical in determining whether cadmium in feed increases the cadmium balance in sheep.