Rationale: Multiple primary cancer is common in clinical practice, but its diagnosis process is complicated, and relevant genetic testing is required to assist in diagnosis when necessary. The formulation of treatment strategies for multiple primary cancer is a highly personalized process. In this article, we introduce a case of a patient with rectal cancer and gastric cancer who was diagnosed with multiple primary cancers, to investigate and explore the clinical application value of next-generation sequencing (NGS) testing in patients with multiple primary gastric and colorectal cancers.
View Article and Find Full Text PDFAchieving high enantioselectivity with synthetic receptors, particularly in water, remains a significant challenge despite the success seen in natural biological systems. In this study, we introduce a facile synthesis of Tröger's base (TB)-containing macrocyclic arenes (TBn), where TB units are linked via methylene bridges, providing the macrocycles with a rigid framework. Oxidation of enantiopure TBn yields corresponding chiral nitrogen oxides (TBnNO) with excellent water solubility, attributed to the high polarity of the N-O bond, surpassing the pH limitations of traditional ion-functionalized approaches.
View Article and Find Full Text PDFBiochim Biophys Acta Mol Basis Dis
October 2024
A practical synthesis of -1,4-dialdehydes based on the oxidative cleavage of cyclobutanediol derivatives using polymer-supported periodate was developed. The -1,4-dialdehydes were obtained in up to >99% yield and subsequently employed in Ir-catalyzed asymmetric Tishchenko reactions to give the corresponding chiral lactones, which are versatile synthetic intermediates, in good yield with moderate enantiomeric excess. The catalytically active species was identified by means of cold-spray ionization mass spectrometry and H NMR spectroscopy.
View Article and Find Full Text PDFBiomed Pharmacother
November 2023
With the improvement of genetic testing technology in diseases in recent years, researchers have a more detailed and clear understanding of the source of cancers. Succinate dehydrogenase B (SDHB), a mitochondrial gene, is related to the metabolic activities of cells and tissues throughout the body. The mutations of SDHB have been found in pheochromocytoma, paraganglioma and other cancers, and is proved to affect the occurrence and progress of those cancers due to the important structural functions.
View Article and Find Full Text PDFSqualene is a triterpenoid compound and widely used in various industries such as medicine and cosmetics due to its strong antioxidant and anticancer properties. The purpose of this study is to increase the accumulation of squalene in filamentous fungi using exogeneous butenafine hydrochloride, which is an inhibitor for squalene epoxidase. The detailed settings achieved that the filamentous fungi, Trichoderma virens PS1-7, produced squalene up to 429.
View Article and Find Full Text PDFPlatinum-containing macrocycles (platinacycles) have gained attention due to their unique photoelectric properties. In the present study, a novel conjugated platinacycle was synthesized by the dehydrochlorination coupling reaction of a bipyridine dichloroplatinum(II) complex and a 3,6-diethynylcarbazol derivative. The structure of the platinacycle was confirmed by H/C, H-H COSY, HMQC, HMBC, DEPT NMR spectroscopies in conjunction with DFT calculations, IR spectroscopy and MALDI-TOF mass spectrometry.
View Article and Find Full Text PDFThe complexation of prism[5]arenes with amino acid derivatives showed association constants of up to 10 M, significant CD with of up to 0.8 × 10 and CPL with of 2 × 10. The absolute configuration-CD signal correlation was established.
View Article and Find Full Text PDFThe first successful example of a catalytic enantioselective intramolecular Tishchenko reaction of a -dialdehyde in the presence of a chiral iridium complex is described. Chiral lactones were obtained in good yields with up to 91% ee. The obtained enantioenriched lactones were utilized for the first synthesis of ()-cedarmycins A and B.
View Article and Find Full Text PDFIn the context of asymmetric synthesis, epimerization is usually problematic. Here, we describe the use of the epimerization of -2,3-bis(hydroxymethyl)-γ-butyrolactone for the synthesis of enterolactones with anti-carcinogenic, anti-inflammatory, anti-angiogenic, and antioxidant activity. Selective α- or β-epimerization of a γ-butyrolactone was used to selectively synthesize both enantiomers of enterolactone.
View Article and Find Full Text PDFSelf-inhibition has been observed widely in hierarchical biochemical processes but has yet to be demonstrated in pure molecular physical rather than chemical or biological processes. Herein, we report an unprecedented example of self-inhibition during the supramolecular chirality induction, memory, erasure, and inversion processes of pillar[5]arene (P[5]) derivatives. The addition of chiral alanine ethyl ester to bulky substituent-modified P[5]s led to time-dependent chirality induction due to the shift in the equilibrium of the and conformers P[5].
View Article and Find Full Text PDFUnprecedented interheteromacrocyclic hosts charge transfer (CT) crystals were generated by cooling organic solutions containing -dimethoxybenzene-constituted pillar[5]arene () and -benzoquinone-constituted pillar[5]quinone (). Despite the weak CT interaction known between -dimethoxybenzene and -benzoquinone and the lack of formation of CT complexes between and in the solution phase, CT cocrystals between and were formed with solvent molecules included into the hosts' cavities. Such a cocrystallization arises from an elegant synergy between the CT interaction and solvent-binding-promoted crystallization.
View Article and Find Full Text PDFThe design and development of specific recognition and sensing systems for biologically important anionic species has received growing attention in recent years, as they play significant roles in biology, pharmacy, and environmental sciences. Herein, a new supramolecular sensing probe L1 was developed for highly selective differentiation of nucleotides. L1 displayed extremely marked absorption and emission differentiation upon binding with nucleotide homologs of AMP, ADP, and ATP, due to the divergent spatial orientations of guests upon binding, which allowed for a naked-eye colorimetric differentiation for nucleotides.
View Article and Find Full Text PDFA chiral electrochemically responsive molecular universal joint (EMUJ) was synthesized by fusing a macrocyclic pillar[6]arene (P[6]) to a ferrocene-based side ring. A single crystal of an enantiopure EMUJ was successfully obtained, which allowed, for the first time, the definitive correlation between the absolute configuration and the circular dichroism spectrum of a P[6] derivative to be determined. The self-inclusion and self-exclusion conformational change of the EMUJ led to a chiroptical inversion of the P[6] moiety, which could be manipulated by both solvents and changes in temperature.
View Article and Find Full Text PDFComplexation of achiral pillar[5]arenes with chiral amines induced strong circular dichroism (CD) signals. The CD responses differed drastically depending on the nature of the amino acid guest, and they significantly varied and part of them even inverted, upon increasing the length of the alkyl chains of the pillar[5]arenes guests. Accordingly, this tactic allowed for the unprecedented simultaneous enantiomeric and structural differentiation of α-amino esters with homologous molecular hosts.
View Article and Find Full Text PDFThree chiral bicyclic pillar[5]arene derivatives termed as molecular universal joints (MUJs), were synthesized and separated enantiomerically. These MUJs showed temperature-driven chirality switching in certain solvents. Herein, it is demonstrated that temperature-driven chirality switching could also be realized by mixing two miscible organic solvents, in each of which chirality inversion is not accomplishable.
View Article and Find Full Text PDFReaction of chiral amines with benzaldehydes 3,5-disubstituted by two pyrenes or perylenes afforded corresponding double winged chiral imines, which aggregated to show significantly enhanced circular dichroism spectra at the transition bands of the chromophores in the mixture solutions of DMF and H2O.
View Article and Find Full Text PDFChiral slipped 5,8:9',10'-cyclodimers were preferentially produced over classical 9,10:9',10'-cyclodimers upon supramolecular photocyclodimerization of 2-anthracenecarboxylate (AC) mediated by β-cyclodextrin (β-CD). This photochirogenic route to the slipped cyclodimers, exclusively head-to-tail (HT) and highly enantioselective, has long been overlooked in foregoing studies but is dominant in reality and is absolutely supramolecularly activated by 2:2 complexation of AC with β-CD. The intricate structural and photophysical aspects of this higher-order complexation-triggered process have been comprehensively elucidated, while the absolute configurations of the slipped cyclodimers have been unambiguously assigned by comparing the experimental and theoretical circular dichroism spectra.
View Article and Find Full Text PDFThe synthesis and optical resolution of helically chiral 5,6,9,10-tetrahydro-1-[6]helicenethiol and its subsequent transformations to enantiopure 1-sulfur-functionalized [6]helicenes are reported. A novel enantiopure [7]thiahelicene having a thiophene ring at the terminal position of the [6]helicene skeleton was synthesized.
View Article and Find Full Text PDFThe study of an enantiopure bicyclic pillar[5]arene-based molecular universal joint (MUJ) by single-crystal X-ray diffraction allowed for the first time the unequivocal assignment of the absolute configuration of a planar chiral pillar[5]arene by circular dichroism spectroscopy. Crucially, the absolute configuration of the MUJ was switched reversibly by temperature, with an accompanying sign inversion of the anisotropy factor that varied by as much as 0.03, which is the largest value ever reported.
View Article and Find Full Text PDFA biphenyl photosensitizer axle was implanted into the cavities of native and capped γ-cyclodextrins through rotaxanation using a cucubit[6]uril-templated azide-alkyne 1,3-dipolar cycloaddition, resulting in the construction of highly defined chiral binding/sensitizing sites. The orientation and interaction of the axle and capping moieties at the ground and excited states were interrogated by NMR, UV-vis, circular dichroism, and fluorescence spectroscopic studies. In situ photoisomerization of (Z,Z)-1,3-cyclooctadiene sensitized in the cavity of these [4]rotaxanes afforded (Z,E)-1,3-cyclooctadiene in up to 15.
View Article and Find Full Text PDFTandem asymmetric hydrogen transfer oxidation/aldol condensation under relay catalysis of a chiral iridium complex/achiral Brønsted base binary system is described for the synthesis of α-benzylidene-γ-hydroxytetralones with high ee's. A two-step synthesis of catalponol was achieved using this sequential methodology together with regio- and stereoselective hydroboration.
View Article and Find Full Text PDFWavelength effects on the enantiodifferentiating photocyclodimerization of 2-anthracenecarboxylate (AC) mediated by native and modified γ-cyclodextrins (CDs) were examined in different solvents at varying temperatures to manipulate the photochirogenic outcomes beyond the thermodynamically determined re/si-enantiotopic face selectivity upon 2 : 1 complexation of AC with CD in the ground state. Indeed, the stereochemical outcomes, i.e.
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