BiOCl/蒙脱土复合光催化剂的制备及其光催化活性

为优化BiOCl光催化剂的结构,改善其对有机污染物的吸附性能,进而提高光催化反应活性,采用超声辅助化学沉淀法制备了BiOCl/蒙脱土(MMT)复合光催化剂,并考察了MMT质量分数(w(MMT))对复合光催化剂结构及光催化反应活性的影响。 X射线粉末衍射(XRD)、扫描电子显微镜(SEM)、傅里叶红外光谱(FTIR)和紫外-可见漫反射光谱(DRS)等的表征结果表明,所得催化剂呈微球状结构,禁带宽度为3.24 eV。 随着w(MMT)的增加,催化剂的微球状结构逐渐被破坏,但带隙能未发生明显变化。 以8-羟基喹啉为目标物考察了复合催化剂的吸附及光催化反应活性。 结果表明,随着w(MMT)增加,催化剂对8-羟基喹啉的吸附和光催化氧化活性逐渐增加,这可归因于与MMT的复合增大了比表面积并降低了光生载流子复合效率。 当w(MMT)为15%时,催化剂的吸附及光催化性能达到最佳,光照50 min后,8-羟基喹啉的降解率达到85.6%,矿化率达到51.0%。 光生空穴和超氧自由基负离子为主要的氧化活性物种。 复合催化剂还可高效降解邻苯二酚和对氨基苯甲酸。 同时,复合光催化剂表现出较强的化学稳定性,表明其具有较强的实际应用价值,可用于处理含有机酚类污染物的工业废水。     

I2O5 promoted iodosulfenylation of indoles under metal-free conditions

A mild, efficient, and metal-free strategy to construct 2-iodo-3-arylthioindoles was developed via I₂O₅-promoted iodosulfenylation of indoles utilizing simple, cheap and easily available thiophenols as sulfur sources. It is the first time that the iodothiolation difunctionalization of indoles at C-2 and C-3 positions was accomplished with the formation of 2-iodo-3-arylthioindoles in moderate to good yields.     

Pseudapenes A–C,sesquiterpenoids from the marine-derived fungus Pseudallescheria apiosperma F52-1

Three sesquiterpenoids pseudapenes A–C (1–3) were isolated from the marine-derived fungus Pseudallescheria apiosperma F52-1. Pseudapene A (1) has an unprecedented 2-methyl-5-methylene-3-(2-methylbut-2-ene)-dicyclo(3, 3, 0)-octane carbon skeleton and pseudapenes B (2) and C (3) possess an unique 2-methyl-4-methylene-2-(2-methylpent-2-ene)-dicyclo(3, 2, 0)-heptane chemical scaffold. Their structures were determined by use of MS and NMR spectroscopic data, and ECD, optical rotation and ¹³C NMR calculations.     

Hyphenone A,the first 3,3-diisoprenylated bicyclic polyprenylated acylphloroglucinols as Cav3.1 T-type calcium channel inhibitor from Hypericum henryi

Hyphenone A (1), a new type of bicyclic polyprenylated acylphloroglucinols (BPAPs) featured with an unprecedented 3,3-diisoprenylated 1,3,5-trione core, were characterized from the roots of Hypericum henryi together with two new congeners (hyphenones B–C, 2–3) and five known biosynthetic related PPAPs. Biogenetically, 1 should be derived from a novel 3,3,5,5-tetraisoprenylated MPAPs precursor. Their structures were elucidated by comprehensive spectroscopic data and X-ray diffraction. Moreover, 1–3 were identified as the first PPAPs type Ca_v3.1 T-type calcium channel (TTCC) inhibitors, with IC₅₀ values of 7.07, 6.19, and 5.47 μM, respectively.     

Organic Room‐Temperature Phosphorescence with Strong Circularly Polarized Luminescence Based on Paracyclophanes

Pure organic materials with intrinsic room‐temperature phosphorescence typically rely on heavy atoms or heteroatoms. Two different strategies towards constructing organic room‐temperature phosphorescence (RTP) species based upon the through‐space charge transfer (TSCT) unit of [2.2]paracyclophane (PCP) were demonstrated. Materials with bromine atoms, PCP‐BrCz and PPCP‐BrCz, exhibit RTP lifetime of around 100 ms. Modulating the PCP core with non‐halogen‐containing electron‐withdrawing units, PCP‐TNTCz and PCP‐PyCNCz, successfully elongate the RTP lifetime to 313.59 and 528.00 ms, respectively, the afterglow of which is visible for several seconds under ambient conditions. The PCP‐TNTCz and PCP‐PyCNCz enantiomers display excellent circular polarized luminescence with dissymmetry factors as high as ?1.2×10^?2 in toluene solutions, and decent RTP lifetime of around 300 ms for PCP‐TNTCz enantiomers in crystalline state.     

A Photolabile Semiconducting Polymer Nanotransducer for Near‐Infrared Regulation of CRISPR/Cas9 Gene Editing

Noninvasive regulation of CRISPR/Cas9 gene editing is conducive to understanding of gene function and development of gene therapy; however, it remains challenging. Herein, a photolabile semiconducting polymer nanotransducer (pSPN) is synthesized to act as the gene vector to deliver CRISPR/Cas9 plasmids into cells and also as the photoregulator to remotely activate gene editing. pSPN comprises a ¹O₂‐generating backbone grafted with polyethylenimine brushes through ¹O₂‐cleavable linkers. NIR photoirradiation spontaneously triggers the cleavage of gene vectors from pSPN, resulting in the release of CRISPR/Cas9 plasmids and subsequently initiating gene editing. This system affords 15‐ and 1.8‐fold enhancement in repaired gene expression relative to the nonirradiated controls in living cells and mice, respectively. As this approach does not require any specific modifications on biomolecular components, pSPN represents the first generic nanotransducer for in vivo regulation of CRISPR/Cas9 gene editing.     

Consecutive Intermolecular Reductive Amination/Asymmetric Hydrogenation: Facile Access to Sterically Tunable Chiral Vicinal Diamines and N‐Heterocyclic Carbenes

A highly enantioselective iridium‐ or ruthenium‐catalyzed intermolecular reductive amination/asymmetric hydrogenation relay with 2‐quinoline aldehydes and aromatic amines has been developed. A broad range of sterically tunable chiral N,N′‐diaryl vicinal diamines were obtained in high yields (up to 95 %) with excellent enantioselectivity (up to >99 % ee). The resulting chiral diamines could be readily transformed into sterically hindered chiral N‐heterocyclic carbene (NHC) precursors, which are otherwise difficult to access. The usefulness of this synthetic approach was further demonstrated by the successful application of one of the chiral vicinal diamines and chiral NHC ligands in a transition‐metal‐catalyzed asymmetric Suzuki–Miyaura cross‐coupling reaction and asymmetric ring‐opening cross‐metathesis, respectively.     

A microchip electrophoretic assay for DNA methyltransferase activity based on methylation‐sensitive endonuclease DpnⅡ

DNA methylation is a significant epigenetic modification and the methods for the detection of DNA methyltransferase (MTase) activity are important due to aberrant methylation closely related to the occurrence of cancer. In this study, a simple and rapid microchip electrophoresis (ME) coupled with LED‐induced fluorescence (LEDIF) method was presented for the detection of Dam MTase activity. This strategy was based on methylation‐sensitive endonuclease DpnⅡ which could recognize the same specific site 5′‐GATC‐3′ with Dam MTase in double‐stranded DNA (dsDNA). The adenines in the specific site could be methylated by Dam MTase, then the special site could not be digested by DpnⅡ. Both methylated dsDNA and unmethylated dsDNA could be analyzed by ME‐LEDIF after stained by SYBR gold. The results showed the fluorescence intensities of methylated dsDNA were directly proportional to Dam MTase activities in the range of 0.5–20 U/mL with a detection limit of 0.12 U/mL. Furthermore, the method could successfully be applied to evaluation experiments of Dam MTase inhibitors. The results confirmed the ME‐LEDIF method is a promising approach for inhibitors screening of DNA MTase and development of anticancer drugs     

A Renal‐Clearable Duplex Optical Reporter for Real‐Time Imaging of Contrast‐Induced Acute Kidney Injury

Despite its high morbidity and mortality, contrast‐induced acute kidney injury (CIAKI) remains a diagnostic dilemma because it relies on in vitro detection of insensitive late‐stage blood and urinary biomarkers. We report the synthesis of an activatable duplex reporter (ADR) for real‐time in vivo imaging of CIAKI. ADR is equipped with chemiluminescence and near‐infrared fluorescence (NIRF) signaling channels that can be activated by oxidative stress (superoxide anion, O₂^.?) and lysosomal damage (N‐acetyl‐β‐d ‐glucosaminidase, NAG), respectively. By virtue of its high renal clearance efficiency (80 % injected doses after 24 h injection), ADR detects sequential upregulation of O₂^.? and NAG in the kidneys of living mice prior to a significant decrease in glomerular filtration rate (GFR) and tissue damage in the course of CIAKI. ADR outperforms the typical clinical assays and detects CIAKI at least 8 h (NIRF) and up to 16 h (chemiluminescence) earlier.     

Inverting the Triiodide Formation Reaction by the Synergy between Strong Electrolyte Solvation and Cathode Adsorption for Lithium–Oxygen Batteries

An exceptionally strong solvation effect of dimethyl sulfoxide (DMSO) on I₂ is identified by the largest shift observed so far of the I₂ Raman peak with respect to I₂ vapor and by elongated I?I bond lengths in first‐principles molecular‐dynamics simulations. This effect together with strong binding by an RuO₂ surface to I₂ is found to invert the direction of the reaction I^?+I₂?I₃^? to the left‐hand side. Inspired by this finding, we prepared a Li–O₂ battery with the Li/DMSO+LiI/RuO₂ structure. The synergic action of DMSO and RuO₂ on I₂ is found to suppress the shuttle effect of the redox mediator (RM) by anchoring I₂ molecules, the oxidation product of the RM. Significantly enhanced stability is demonstrated over 100 cycles at charging voltage below 3.65 V.