The Cu(I)-catalyzed annulation–halotrifluoromethylation and cyanotrifluoromethylation of enynones have been established, enabling multibond formations of the synthesis of quaternary carbon-centered ...1-indanones in moderate to good chemical yields. The reaction of enynones with Togni’s reagent and chloro- or bromotrimethylsilane afforded halo- and CF3-containing 1-indenones. However, the addition of K3PO4 as a base into the catalytic system led to forming cyano-anchored (Z)-1-indanones as major stereoisomeric products. This strategy exhibits remarkable compatibility with a wide range of enynones.
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Summary
Introduction
Gliomas are the most common primary brain tumors in adults and a significant cause of cancer‐related mortality. A 9‐gene signature was identified as a novel prognostic model ...reflecting survival situation obviously in gliomas.
Aims
To identify an mRNA expression signature to improve outcome prediction for patients with different glioma grades.
Results
We used whole‐genome mRNA expression microarray data of 220 glioma samples of all grades from the Chinese Glioma Genome Atlas (CGGA) database (http://www.cgga.org.cn) as a discovery set and data from Rembrandt and GSE16011 for validation sets. Data from every single grade were analyzed by the Kaplan–Meier method with a two‐sided log‐rank test. Univariate Cox regression and linear risk score formula were applied to derive a gene signature with better prognostic performance. We found that patients who had high risk score according to the signature had poor overall survival compared with patients who had low risk score. Highly expressed genes in the high‐risk group were analyzed by gene ontology (GO) and gene set variation analysis (GSVA). As a result, the reason for the divisibility of gliomas was likely due to cell life processes and adhesion.
Conclusion
This 9‐gene‐signature prediction model provided a more accurate predictor of prognosis that denoted patients with high risk score have poor outcome. Moreover, these risk models based on defined molecular profiles showed the considerable prospect in personalized cancer management.
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BFBNIB, FZAB, GIS, IJS, IZUM, KILJ, NLZOH, NUK, OILJ, PILJ, PNG, SAZU, SBCE, SBMB, UL, UM, UPUK
A new Pd(II)-catalyzed annulation/iododifluoromethylation of enynones has been developed for the synthesis of versatile 1-indanones with moderate to good yields (26 examples). The present strategy ...enabled the concomitant incorporation of two important difluoroalkyl and iodo functionalities into 1-indenone skeletons with (E)-stereoselectivity. The mechanistic pathway was proposed, consisting of the difluoroalkyl radical-triggered α,β-conjugated addition/5-exo-dig cyclization/metal radical cross-coupling/reductive elimination cascade.
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Objective To analyze the correlations between platelet-related parameters and the incidence of anxiety and depression in the patients undergoing peritoneal dialysis(PD),and evaluate the efficacy of ...the parameters in the diagnosis of anxiety and depression in PD patients. Methods A total of 245 patients undergoing PD in the First Affiliated Hospital of Hebei North University from September 2022 to February 2023 were enrolled.The generalized anxiety scale(GAD-7) and the patient health questionnaire(PHQ-9) were used to evaluate the anxiety and depression of the patients,respectively.The personal information and biochemical indicators of the patients were collected,and the platelet count(PLT),mean platelet volume(MPV),and platelet distribution width(PDW) were measured.Logistic regression was adopted to analyze the relationships of platelet-related parameters with anxiety and depression in PD patients. Results Among the 245 patients undergoing PD,the incidences of anxiety and depression were 15.9% and 38.0%,respec
Exercise preconditioning (EP) can alleviate myocardial ischemic/hypoxic injury by inducing endogenous cardioprotection. Hematoxylin–eosin (HE), hematoxylin-basic fuchsin-picric acid (HBFP), and ...chromotrope-2R brilliant green (C-2R BG) staining have been used to visualize myocardial ischemic/hypoxic changes in previous EP studies, but comprehensive evaluation and comparisons of these methods are lacking. This study evaluated ischemic/hypoxic changes in adjacent myocardial sections by HE, HBFP, and C-2R BG and compared the characteristics of sections stained by these three methods to show changes associated with exercise-induced myocardial ischemic/hypoxic injury. Rats were randomly divided into four groups: control (C), exercise preconditioning (EP), exhaustive exercise (EE), and exercise preconditioning + exhaustive exercise (EP + EE). Adjacent myocardial sections were stained as described above and compared to evaluate the effects of exercise-induced myocardial ischemic/hypoxic injury. The three staining methods revealed consistent localization patterns of myocardial ischemic/hypoxic injury in all groups. Results suggest that EP can alleviate exhaustive exercise-induced myocardial ischemic/hypoxic injury, and the three staining methods are suitable for the histological study of exercise-induced myocardial ischemic/hypoxic injury and protection. HE staining is a simple procedure but is not specific for myocardial ischemic/hypoxic injury. HBFP and C-2R BG staining can be used to specifically visualize myocardial ischemic/hypoxic injury.
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EMUNI, FIS, FZAB, GEOZS, GIS, IJS, IMTLJ, KILJ, KISLJ, MFDPS, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, SBMB, SBNM, UKNU, UL, UM, UPUK, VKSCE, ZAGLJ
The phenomenon of aggregation-induced polarization (AIP) was observed showing optical rotation amplification and adjustment. The relationship between optical rotations of chiral aggregates of ...multilayered chiral folding oligomers and polymers with water% in THF (
f
w
) has been established accordingly. New multilayered chiral oligomers were synthesized under the asymmetric catalytic systems established by our laboratory recently. These products were well-characterized by UV-vis, NMR, and MALDI-TOF spectra. Absolute stereochemistry (enantio- and diastereochemistry) was assigned by comparison with similar asymmetric induction by the same catalyst in our previous reactions. The present AIP work can serve as a new tool to determine chiral aggregates, especially for those that cannot display emission. AIP would also complement AIE-based CPL since AIP serves as a new tool providing enhanced right- or left-hand polarized lights with individual wavelengths. It will find many applications in chemical and materials science in the future.
Flexible luminescent metal–organic frameworks (MOFs) sensitive to physical and chemical variation demonstrate potential application in sensing, but are commonly limited to ones incorporating ...specialized chromophores, so that the design, preparation, and reversible well-defined crystallographic transitions of such materials remain a great challenge. Here, an easily prepared flexible luminescent silver-chalcogenolate cluster-based metal–organic framework (SCC-MOF), Ag 10 bpy, exceptionally distinguishes chloromethanes CH2Cl2, CHCl3, and CCl4 by different fluorescent responsive signals, which originated from its crystalline dipole moment orientation relative to chromophores. Moreover, “glass-to-fluid” transition of the distinctly responsive species in the crystalline pore is demonstrated to modulate striking chromism with scarce segmented emission among MOFs, resulting from subtle dynamic solvation of chromophores. Retention of single crystallinity enables elucidation of the relationship between distinct fluorescent response and complicated structural variation at the molecular level. This new type of flexible emissive SCC-MOF is potentially useful for the development of versatile sensing and switching fluorescent materials.
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A novel class of polymers and oligomers of chiral folding chirality has been designed and synthesized, showing structurally compacted triple-column/multiple-layer frameworks. Both uniformed and ...differentiated aromatic chromophoric units were successfully constructed between naphthyl piers of this framework. Screening monomers, catalysts, and catalytic systems led to the success of asymmetric catalytic Suzuki-Miyaura polycouplings. Enantio- and diastereochemistry were unambiguously determined by X-ray structural analysis and concurrently by comparison with a similar asymmetric induction by the same catalyst in the asymmetric synthesis of a chiral three-layered product. The resulting chiral polymers exhibit intense fluorescence activity in a solid form and solution under specific wavelength irradiation.
A new type of chirality, orientational chirality, consisting of a tetrahedron center and a remotely anchored blocker, has been discovered. The key structural element of this chirality is ...characterized by multiple orientations directed by a through-space functional group. The multi-step synthesis of orientational chiral targets was conducted by taking advantage of asymmetric nucleophilic addition, Suzuki-Miyaura cross-coupling and Sonogashira coupling. An unprecedented catalytic species showing a five-membered ring consisting of C (sp
)-Br-Pd-C (sp
) bonds was isolated during performing Suzuki-Miyaura cross-coupling. X-ray diffraction analysis confirmed the species structure and absolute configuration of chiral orientation products. Based on X-ray structures, a model was proposed for the new chirality phenomenon to differentiate the present molecular framework from previous others. DFT computational study presented the relative stability of individual orientatiomers. This discovery would be anticipated to result in a new stereochemistry branch and to have a broad impact on chemical, biomedical, and material sciences in the future.
A new asymmetric catalytic conjugate reduction of yne-allenones to synthesize enantioenriched cyclobuta
naphthalen-4(2
)-ones has been established that uses copper-bisphosphine complexes as catalysts ...and gives excellent regio- and enantioselectivities (≥99% ee) in most cases. This protocol tolerates a broad scope of substrates, exhibits high compatibility with various substituents, and gives excellent stereoselectivity, providing a catalytic and efficient entry to fabrication of synthetically important chiral 6-6-4 tricarbocyclic scaffolds.
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