Divergent Total Synthesis of Euphoranginol C,Euphoranginone D,ent-Trachyloban-3β-ol,ent-Trachyloban-3-one,Excoecarin E,and ent-16α-Hydroxy-atisane-3-one

A divergent synthetic approach to biogenetically related diterpenoids such as ent-kauranes, ent-trachylobanes, ent-beyerane, and ent-atisane has been developed. The unified synthetic route involves the De Mayo reaction to rapidly generate the bicyclo[3.2.1]-octane moiety of ent-kaurane. The key reactions also include bioinspired nucleophilic cyclopropanation generating the [3.2.1.0^2,7]-tricyclic core of ent-trachylobane and regioselective cyclopropane fragmentation furnishing ent-beyerane and ent-atisane through the nucleophilic attack and protonation of the cyclopropane ring. This strategy enables the asymmetric total syntheses of six diterpenoids from the commercially available geraniol.     

Bioorthogonal Ligation and Cleavage by Reactions of Chloroquinoxalines with ortho-Dithiophenols

A bioorthogonal ligation and cleavage method via reactions of chloroquinoxalines (CQ) and ortho-dithiophenols (DT) is presented. Double nucleophilic substitutions of ortho-dithiophenols to chloroquinoxalines provide conjugates containing tetracyclic benzo[5,6][1,4]dithiino[2,3-b]quinoxaline with strong built-in fluorescence together with release of the other functional molecules. Three cleavable linkers were designed and successfully used in release of the molecules containing biotin from the protein conjugates. The CQ-DT bioorthogonal reactions can be applied for the bioorthogonal ligations, bioorthogonal cleavages, and trans-tagging of proteins, and show advantages of readily accessible unnatural orthogonal groups, appealing reaction kinetics (k₂≈1.3 m ⁻¹ s⁻¹), excellent biocompatibility of orthogonal groups, and high stability of conjugates. This complements previous bioorthogonal reactions and is a new route for protein-fishing applications and in-gel fluorescence analysis.     

Rationally Designed Three-Layered Cu2S@Carbon@MoS2 Hierarchical Nanoboxes for Efficient Sodium Storage

Hybrid materials, integrating the merits of individual components, are ideal structures for efficient sodium storage. However, the construction of hybrid structures with decent physical/electrochemical properties is still challenging. Now, the elaborate design and synthesis of hierarchical nanoboxes composed of three-layered Cu₂S@carbon@MoS₂ as anode materials for sodium-ion batteries is reported. Through a facile multistep template-engaged strategy, ultrathin MoS₂ nanosheets are grown on nitrogen-doped carbon-coated Cu₂S nanoboxes to realize the Cu₂S@carbon@MoS₂ configuration. The design shortens the diffusion path of electrons/Na⁺ ions, accommodates the volume change of electrodes during cycling, enhances the electric conductivity of the hybrids, and offers abundant active sites for sodium uptake. By virtue of these advantages, these three-layered Cu₂S@carbon@MoS₂ hierarchical nanoboxes show excellent electrochemical properties in terms of decent rate capability and stable cycle life.     

用于细胞和组织中弗林蛋白酶特异性成像的双光子荧光探针研究

弗林蛋白酶是前体蛋白转化酶家族中最具特色的酶之一,具有重要的生物学功能,其表达量水平与许多疾病有密切的关系,如癌症的发生和发展与弗林蛋白酶表达水平有着密切关联.目前文献中报道了一些单光子荧光探针用于弗林蛋白酶的检测,但这些探针不能应用于深层组织成像,且弗林蛋白酶在肿瘤发展过程的作用仍没有得到很好地研究.针对这些问题,本工作构建了一种新型双光子荧光探针Nap-F用于细胞和肿瘤组织内弗林蛋白酶的检测与双光子成像.Nap-F是由经典双光子荧光染料1,8-萘酰亚胺、弗林蛋白酶特异性多肽序列RVRR和自消除连接体整合而成.实验结果表明Nap-F对弗林蛋白酶具有很好的特异性,能够定量检测弗林蛋白酶的活性.在飞秒激光820 nm激发下,Nap-F能有效降低生物背景,并提高组织穿透深度,适用于细胞和组织的双光子成像.Nap-F成功地实现了几种活细胞中弗林蛋白酶的双光子成像,揭示了癌细胞和表达缺陷细胞中弗林蛋白酶含量的差异.更重要的是,我们将该探针用于CoCl₂固定HIF-1构建的肿瘤细胞缺氧模型成像,实验结果表明弗林蛋白酶的表达与肿瘤细胞缺氧程度存在正相关性.     

Fabrication of Heterostructured Fe2TiO5–TiO2 Nanocages with Enhanced Photoelectrochemical Performance for Solar Energy Conversion

Photocatalysts with well‐designed compositions and structures are desirable for achieving highly efficient solar‐to‐chemical energy conversion. Heterostructured semiconductor photocatalysts with advanced hollow structures possess beneficial features for promoting the activity towards photocatalytic reactions. Here we develop a facile synthetic strategy for the fabrication of Fe₂TiO₅–TiO₂ nanocages (NCs) as anode materials in photoelectrochemical (PEC) water splitting cells. A hydrothermal reaction is performed to transform MIL‐125(Ti) nanodisks (NDs) to Ti–Fe–O NCs, which are further converted to Fe₂TiO₅–TiO₂ NCs through a post annealing process. Owing to the compositional and structural advantages, the heterostructured Fe₂TiO₅–TiO₂ NCs show enhanced performance for PEC water oxidation compared with TiO₂ NDs, Fe₂TiO₅ nanoparticles (NPs) and Fe₂TiO₅–TiO₂ NPs.     

On Symmetric Cayley Graphs of Valency Eleven

A Cayley graph Γ=Cay(G,S)is said to be normal if G is normal in Aut Γ.In this paper,we investigate the normality problem of the connected 11-valent symmetric Cayley graphs Γ of finite nonabelian simple groups G,where the vertex stabilizer Av is soluble for A=Aut Γ and v ∈ VΓ.We prove that either Γ is normal or G=A5,A10,A54,A274,A549 or A1099.Further,11-valent symmetric nonnormal Cayley graphs of A5,A54 and A274 are constructed.This provides some more examples of nonnormal 11-valent symmetric Cayley graphs of finite nonabelian simple groups after the first graph of this kind(of valency 11)was constructed by Fang,Ma and Wang in 2011.     

Quantification of Venetoclax for Therapeutic Drug Monitoring in Chinese Acute Myeloid Leukemia Patients by a Validated UPLC-MS/MS Method

Venetoclax has emerged as a breakthrough for treatment of leukemia with a wide interindividual variability in pharmacokinetics. Herein, a rapid, sensitive, and reliable UPLC-MS/MS method for quantification of venetoclax in plasma was developed and validated. The method was operated in the multiple-reaction monitoring (MRM) mode to detect venetoclax at m/z transition 868.5 > 321.0 and IS at 875.5 > 321.0, respectively. Protein precipitation prior to injection into the LC-MS/MS and the analyte was separated on an ACQUITY UPLC BEH C18 column by gradient elution with acetonitrile and 0.1% formic acid in water. Linear calibration curves were obtained in the range of 25–8000 ng/mL. The specificity, recovery, matrix effect, and stability also met the acceptance criteria of FDA guidance. The method was successfully applied to analyze plasma in acute myeloid leukemia (AML) patients. The peak plasma concentration (C_max) of venetoclax in Chinese AML patient was 2966.0 ± 1595.0 ng/mL while the trough concentration (C_min) was 1018.0 ± 729.4 ng/mL. Additionally, C_max and C_min showed a positive correlation with AST levels. Furthermore, C_max was significantly higher in the older patients. The present method can be applied for TDM of venetoclax in treatment of hematological cancers.     

PPLT倍频宽线宽掺镱双包层光纤放大激光

分别通过理论和实验研究了周期性极化的钽酸锂（PPLT）倍频宽线宽准连续掺镱双包层光纤放大激光.PPLT样品长为40 mm,极化周期为7.67 μm.基频光的中心波长为1064 nm,线宽约为6 nm.从基频光的光谱特性出发,利用超晶格倍频理论,解释了实验中获得的倍频温度与二次谐波功率之间的关系.在基频光的功率为2.2 W时,获得的宽线宽光纤激光倍频效率为1.8%.     

环境监测实验室管理系统的开发与应用

基于2005版《计量认证/审查认可(验收)评审准则》要求,为满足环境监测实验室业务流程而设计开发了信息管理系统。该系统主要用于环境监测实验室的资源管理和日常自动化办公。系统采用B/S架构,实现全球化办公运作,能对监测样品的受理、分发、分析、原始记录、监测报告、数据三级审核、报告签发实现全程自动流转,并运用工作流和智能表单设计实现实验室程序文件中各类程序和日常办公事务流程的执行;原始记录和监测报告全部实现自动归档及智能查询;同时根据2005版准则中的要求,对人员、设备、材料、环境要素、记录、质量控制等所有要素全面实施网络化管理。     

Anisotropy of hole structures in oriented polycarbonate probed by two-dimensional angular correlation of annihilation radiation

Two-dimensional angular correlation of annihilation radiation (2D-ACAR) experiments have been performed on an uniaxially oriented polymer, bisphenol-A polycarbonate. The two-dimensional hole structures of unoriented and oriented polymers, determined from the momentum distributions, are found to be spherical and ellipsoidal, respectively. The average hole radii are determined to be 2.9 Å in the unoriented sample and between 2.3 and 3.8 Å in the oriented sample. Applications of the 2D-ACAR method to image the three-dimensional hole structures of polymeric materials are discussed. © 1996 John Wiley & Sons, Inc.