Latest ArticlesA novel diterpenoid with an unprecedented 5/6/5/7 tetracyclic system, rhodauricanol A (1), five new grayanane-derived diterpenoids, dauricanols A−E (2−6), and five known ones (7−11) were isolated from the flowers of Rhododendron dauricum. Rhodauricanol A (1) possesses a unique 5/6/5/7 tetracyclic ring system featuring a 16-oxa-tetracyclo[11.2.1.01,5.07,13]hexadecane core. Dauricanols A−C (2−4) are the first 1,3-dioxolane conjugates of grayanane diterpenoids and 5-hydroxymethylfurfural and vanillin, respectively, and dauricanols D (5) and E (6) represent the first examples of 6-deoxy-1,5-seco-grayanane diterpenoids. Their structures were determined by spectroscopic methods, quantum chemical calculation including 13C NMR-DP4+ analysis and ECD calculation, and single-crystal X-ray diffraction analysis. Plausible biosynthetic pathways for 1−4 were proposed. All the isolates showed significant analgesic activities, and dauricanols B (3) and C (4) showed more potent analgesic activities than the positive control, morphine.
In this paper, cucurbit[7]uril (CB[7])-mediated three-dimensional gold nanoassemblies were successfully prepared to increase the loaded amount of CB[7] and enhance the electrochemical detection of amino acids. Particle sizes of gold nanoparticles (AuNPs) significantly affect stability and detection sensitivity of nanoassemblies. The volume of gold nanoassemblies first increased and then decreased with the increase of CB[7] concentration. The 3D gold nanoassemblies composed of 16 nm AuNPs and 100 µmol/L CB[7] had excellent stability and maximum volume, exhibiting more sensitive detection for a variety of amino acids. And the detection limits of aromatic amino acids are lower in virtue of the higher binding constant between aromatic amino acids and CB[7]. This study will develop and deepen our understanding of molecular recognition in amino acids detection.
Computed tomography (CT) is one of the most commonly used non-invasive clinical imaging modalities to predict, diagnose and treat the disease. Iodinated contrast media (ICM) is a form of intravenous radiocontrast agent containing iodine, which enhances the visibility of hollow tissue structures in medical CT imaging. ICM may cause allergic reactions, contrast-induced nephropathy, hyperthyroidism and possibly metformin accumulation. It is significant to find out the risk factors, pathogenesis, diagnosis, prevention, and treatment of adverse reactions caused by ICM. Revealing the changes of the lipid droplets (LDs) viscosity in pathophysiological processes such as cancer and iodined contrast media induced adverse reaction is not only important for monitoring the occurrence and development of some pathophysiological processes but also vital for the deep insight of the biological effects of LDs in these pathophysiological processes. A lipid droplets targeted fluorescent probe DN-1 was devised to sense cellular viscosity alteration with high selectivity and sensitivity, which was applied to distinguish cancer cells and normal cells and reveal viscosity changes during iodined CT contrast media treatment.
A label-free lactic acid sensor has been successfully developed by using a Dysprosium single crystal-based photoelectric potential technique via Dy-SCN/FTO electrode. Interestingly, the proposed sensor demonstrated excellent performance for L-lactic acid analysis with a wide linear range of 0.0196~16.31 mmol/L, the detection limit of as low as 3.20 µmol/L as well as an advisable stability. The feasibility of this strategy was also verified by practical application towards human sweat samples. The mechanism studies indicated that lactic acid molecules specifically bind to the surface of semiconductor materials, which alters the charge distribution of the electrode surface and subsequently results in band bending/photoelectric potential changes. The theoretical formula for this photoelectric chemistry (PEC) strategy was then derived according to charge balance theory. We believe that the proposed Dy-SCN/FTO sensor would open a new way for rapid, non-invasive L-lactic acid level evaluation during human physical condition monitoring.
Control of self-assembly is significant to the preparation of supramolecular materials, but the control of hydration, responsiveness, dimension, catalysis of macrocyclic amphiphiles in an atom-economic manner is still a great challenge. The herein presented 527 Da low-molecular-weight macrocyclic amphiphile was fabricated by utilizing the selenium-containing crown ether as a hydrophobic motif together with guanidinium group as the hydrophilic moiety. The resulting benzo[21]crown-7 based macrocyclic amphiphile readily forms a redox-responsive solid nanoparticles in water, which can further interconnect into wrinkled pattern on-surface, as well as exhibits as a nanozyme for catalyzing disulfid bond formation. The present work highlights the great potential of guanidinium- and selenium-containing crown ethers for the control of functional assemblies.
A highly efficient asymmetric (3 + 2) cycloaddition of α-diazo pyrazoleamides with silyl enol ethers was realized by employing a chiral N, N'-dioxide-Ni(Ⅱ) complex catalyst. The process includes the formation of chiral nickel carbenoid intermediate and the following enantioselective cycloaddition reaction. The desired dihydrofuran O, O-acetal derivatives were obtained in good yields (up to 90%) with high enantioselectivity (up to 99% ee) under mild reaction conditions within short reaction time. On the basis of the determination of the catalyst structure, a possible transition state mode was proposed.
Fatty acid photodecarboxylase of Chlorella variabilis NC64A (CvFAP) is a novel photoenzyme with great potential in the treatment of waste lipids and production of sustainable aviation fuel. However, the fragile nature of CvFAP to blue light is an urgent challenge. Herein, we demonstrated anaerobic environment could significantly improve the photostability of CvFAP for the first time. The decarboxylation of palmitic acid by CvFAP for 3 h under anaerobic environment increased pentadecane yield by 44.7% as compared to that under aerobic environment. The residual activity of CvFAP after blue-light preillumination in the absence of palmitic acid for 0.5 h under anaerobic environment was 80.4%, which was 258.7 times higher than that under aerobic environment. Remarkable accumulation of superoxide radical and singlet oxygen in CvFAP under aerobic environment led to the poor photostability of CvFAP. Anaerobic environment helped to mitigate the production of superoxide radical and singlet oxygen in CvFAP, improving the photostability of CvFAP.
Stimuli-responsive macrocycles are of importance for synthetic chemistry and smart materials. In this manuscript, we report two novel organoborane cyclophanes, which were successfully synthesized by ruthenium-catalyzed olefin metathesis. They are composed of one/two boron-doped helicene π-skeletons and flexible alkyl chain linkers, thus representing a new kind of non-conjugated organoborane macrocycles. Their cyclic structures and photophysical properties, as well as Lewis acidity were theoretically and experimentally investigated. Notably, two enantiomers in one single crystal are observed for one organoborane cyclophane, owning to the presence of helical π-framework in its cyclic structure. Moreover, their Lewis acid-base adducts may dissociate in the excited state and thus display intriguing photo-responsive fluorescence properties, which can be further modulated by temperature. This study thus provides a novel design strategy for non-conjugated organoborane macrocycles, which may promote the development of stimuli-responsive macrocyclic materials with fascinating properties.
Removal and recovery of phosphorus (P) from wastewater is of great importance to addressing the challenges of eutrophication and phosphorus shortage. The P removal and recovery performance of conventional electrochemical precipitation approach was constrained by the limited mass transfer rate. Herein, a cathodic membrane filtration (CMF) reactor was developed using Ti/SnO2-Sb anode and titanium mesh cathodic membrane module to achieve efficient removal and recovery of P in wastewater. Compared with the flow-by mode, the CMF system in the flow-through mode exhibited excellent P removal performance due to the markedly enhanced mass transfer. At the current density of 4 A/m2, membrane flux of 16.6 L m−2 h−1, and Ca/P molar ratio of 1.67, the removal efficiency of P was 96.2% and the energy consumption was only 45.7 kWh/kg P. The local high pH of cathode surface played a vital role in P removal, which substantially accelerated the nucleation of calcium phosphate (CaP). Based on the crystalline and morphological characterization of the precipitates, the hydroxyapatite was the most stable crystalline phase of CaP, which was transformed from intermediate phases (such as dicalcium phosphate and amorphous calcium phosphate). This study paves the way for applying electrochemical membrane filtration system for P removal and recovery from wastewater.
Cyclin-dependent kinases (CDKs) have become potential targets for treating various diseases, especially cancer. Compound iCDK9 is an excellent and selective CDK9 inhibitor, but its major limitation is the potential toxicity and poor understanding of the underlying mechanism. The PROTAC (proteolysis targeting chimera) degraders of bioactive molecules can significantly induce in vitro and in vivo degradation of their target protein with high selectivity and effectively reduce the dose-limiting toxicity of small molecule drugs. Therefore, we designed and synthesized the bifunctional PROTAC molecules of iCDK9, being used for identifying its previously unknown target and revealing the underlying pharmacological mechanism. The PROTAC bifunctional molecule CD-5 could selectively and significantly degrade CDK9 with low cell toxicity. Therefore, we selected CD-5 as a chemical prober in the SILAC quantitative proteomic analysis, which disclosed that CD-5 could enormously lessen the lysine acetyltransferase KAT6A. Furthermore, KAT6A degradation induced by CD-5 repressed the levels of H3K14Ac and H3K23Ac. Lastly, the streptavidin immunoprecipitation (IP) assay confirmed a direct interaction between KAT6A and iCDK9. Collectively, our results uncover that KAT6A is a potential non-kinase target of iCDK9. Notably, this study also demonstrates that the PROTAC-SILAC strategy is an alternative approach for cellular target identification of bioactive molecules.
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