Stereochemistry of cercosporin

The absolute configuration of the asymmetric carbons and the axial chirality of the natural mold metabolite cercosporin (from $\text{Cercospora sp}$.) have been established on the basis of X-ray analysis and chemical reactions. The results confirm the inherent dissymmetry of the perylenequinone ring, the twisting of which gives rise to the diastereoisomer isocercosporin. The energy barrier for the conversion of cercosporin into isocercosporin has been evaluated.     

Synthesis and structure of a 1:1 complex of a chiral methyl 4,6-0-benzylidene-2 , 3-0 (1 ,2-bis (ethoxyethoxy) -benzenediyl) - α,d-glucopyranoside and potassium iodide

The chiral crown ether was prepared according to the method described in the literature and its complex with potassium iodide was obtained. The crystal data are as follows: a = 10.315(4), b = 9.265(4), c = 15.88(2) Å, β = 100.70(7)°. V = 1494 Å,³ Z = 2, D₀ = 1.55 Mg m^?3 space group symmetry P2₁.The structure was determined by the heavy atom method using 2214 independent observed reflections. The conformation of the macrocyclic ring is discussed.     

Crystal structures of two substituted biphenyl derivatives: 5,5′-di t-butyl-2-2′-biphenyldiol and 5,5′-dimethyl-2,2′-biphenyldiol

5,5-Di t-butyl-2,2-biphenyldiol (I), C₂₀H₂₆O₂, crystallizes in the orthorhombic space group P2₁2₁2₁ with a = 18.243(2), b = 9.947(2), c = 9.685(3) Å, and Z = 4; 5,5-dimethyl-2,2-biphenyldiol (II), C₁₄H₁₄O₂, crystallizes in the monoclinic space group P2₁/c with a = 9.959(2), b = 7.932(3), c = 15.392(2) Å, = 105.43(2)°, and Z = 4. The aromatic rings are tilted by 52.7(1) and 43.8(1)° to each other in compounds (I) and (II), respectively. Strong intra- and inter-molecular H-bonds connect the molecules in the crystals.     

X-ray structural investigation of 1,3,6,8-tetramethyl-10-(4-m.xilenyl-2,6-pyridyl diketone) anthracene

The structure of the compound obtained by reaction of AlCl₃-promotedm-xilene with 2,6-pyridine dicarbonyldichloride in dichloromethane has been investigated by X-ray diffraction methods. The compound is monoclinic, space groupP2₁/c,a=13.907(2),b=17.247(3),c=12.042(2) Å,=109.75(4)°. The structure was solved by direct methods and refined by full matrix least-squares to a finalR=6.37 for 3718 independent observed reflections [I>2(I)]. The structure of the compound enables an understanding of the chemical pathway of the synthesis process.     

Crystal structure of 1,1-diphenyl-2,4-dimethyl-5-(N-benzamide)-1,3-pentadiene

Crystals of the title compound are monoclinic (C₂₆H₂₅NO): space groupP2₁/c,a=16.565(3),b=10.328(2),c=12.621(3) Å,=104.02(3)°. The structure was solved by direct methods and refined by block-matrix least-squares to giveR=0.056 andR _w =0.061 for 1613 reflections above 2(I). The amide moiety is tilted by 19.3(2)° with respect to the mean aromatic ring plane. The two othergem phenyl rings subtend a dihedral angle of 112.2(4)° to each other. The molecules are joined in the solid by N-HO hydrogen bonds.     

Crystal structure of the complex between 7,7,8,8-tetracyanoquinodimethane and 1-oxide-2-phenyl-quinoline

A series of complexes between 1-oxide quinolines and 7,7,8,8-tetracyanoquinodimethane has been synthesized and one of them has been analyzed by x-ray diffraction methods. Crystals of the title compound are monoclinic (C₁₅H₁₁NO·C₁₂H₄N₄), space groupP2₁/n,a=44.525(4),b=7.326(2),c=6.531(2) Å,=90.23(3)°. The structure was solved by direct methods and refined by block-matrix least-squares to giveR=0.047 for 1865 reflections above 2(I). Molecular dimensions, interplanar distances, empirical method and IR spectra suggest a -^* interaction with very low charge-transfer in the complex.     

Modern automated microextraction procedures for bioanalytical,environmental, and food analyses

Sample preparation frequently is considered the most critical stage of the analytical workflow. It affects the analytical throughput and costs; moreover, it is the primary source of error and possible sample contamination. To increase efficiency, productivity, and reliability, while minimizing costs and environmental impacts, miniaturization and automation of sample preparation are necessary. Nowadays, several types of liquid-phase and solid-phase microextractions are available, as well as different automatization strategies. Thus, this review summarizes recent developments in automated microextractions coupled with liquid chromatography, from 2016 to 2022. Therefore, outstanding technologies and their main outcomes, as well as miniaturization and automation of sample preparation, are critically analyzed. Focus is given to main microextraction automation strategies, such as flow techniques, robotic systems, and column-switching approaches, reviewing their applications to the determination of small organic molecules in biological, environmental, and food/beverage samples.