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.     

A new iterative algorithm for equilibrium and fixed point problems of nonexpansive mapping

In this paper, a new iterative algorithm involving nonexpansive mapping in Hilbert space is proposed and proved to be strongly convergent to a point which is simultaneously a fixed point of a nonexpansive mapping and a solution of an equilibrium problem. The results of the paper extend previous results, see, for instance, Takahashi and Takahashi (J Math Anal Appl 331:506–515, 2007), and other results in this field. Moreover, this algorithm is applied to find zeros of a maximal monotone operator and solve an optimization problem.     

Teacher preparation for a problem-solving curriculum in Singapore

Problem solving is at the heart of the Singapore Mathematics curriculum. However, it remains a challenge for teachers to realise this curricular goal in practice. Here, we review the efforts of Singapore mathematics teacher educators in incorporating problem-solving (teaching) competency in teacher education and PD programmes. We discuss conceptual and practical issues, actions taken and changes made in building teachers?? capacity to enact a problem-solving curriculum in a school-based design experiment project. In the project, teachers learnt problem solving, observed and then carried out lessons, using the ??Mathematics Practical????akin to the science practical??as key to instruction and assessment.     

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.     

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.     

Room-temperature ferromagnetism of diamagnetically-doped ZnO aligned nanorods fabricated by vapor reaction

Large-scale monocrystalline oxide-diluted magnetic semiconductor (ODMS) Zn_1−x Bi _x O nanorods arrays (NAs) were prepared within a large doping concentration range from 5% to 20% by a simple chemical vapor deposition. X-ray diffraction and high-resolution transmission electron microscopy reveal the monotonous expansion of the lattice constants with increasing Bi content, due to the effective Bi doping. In particular, room-temperature ferromagnetic (RTFM) behavior with Curie temperature over 363.7 K has been observed based on Bi-doped ZnO nanoarrays, whereas undoped ZnO NAs disappear. The RTFM origin is suggested, in which vacancies can be controlled to tune the FM. The as-formed RTFM NAs would have potential applications in many areas of advanced nanotechnology, such as new spintronic devices and magneto-optic components.     

Practical and Highly Selective C?H Functionalization of Structurally Diverse Ethers

A trityl ion mediated C H functionalization of ethers with a wide range of nucleophiles at ambient temperature has been developed. The reaction displays high chemoselectivity and good functional group tolerance. The protocol also exhibits excellent regio‐ and diastereoselectivities for the unsymmetric ethers, thus stereoselectively generating highly functionalized disubstituted 2,5‐trans tetrahydrofurans (THF), 2,6‐trans tetrahydropyrans (THP), 2,6‐trans dihydropyrans (DHP), and 1,3‐trans isochromans, and highlighting the capacity of the protocol in complex molecule synthesis.     

Frontispiz: Mild and Versatile Nitrate‐Promoted C?H Bond Fluorination

A novel and facile C H bond fluorination proceeds under remarkably mild conditions (close to room temperature in most cases). Both aromatic and olefinic C(sp²) H bonds with a wide range of electronic properties are selectively fluorinated in the presence of a catalytic amount of simple, cheap, and nontoxic nitrate as the promoter. A Pd^II/Pd^IV catalytic cycle that is initiated by an in situ generated cationic [Pd(NO₃)]⁺ species was proposed based on preliminary mechanistic studies.     

Catalytic epoxidation of alkenes over supported manganese oxide with hydrogen peroxide: effect of supports and manganese loading

Manganese oxides supported on γ-Al₂O₃, amorphous SiO₂, MCM-41, and TiO₂ prepared by an impregnation method were used as heterogeneous catalysts for epoxidation of alkenes with 30 % H₂O₂ in the presence of NaHCO₃ aqueous solution. The effect of support and manganese loading on their activity was studied. The 1.3-MnO _x /γ-Al₂O₃ exhibited superior epoxidazing activity of styrene, compared with other supported MnO _x . Hydrogen temperature-programmed reduction, UV–vis and ESR analyses suggested that Mn²⁺ (catalytic activity species) dominated in 1.3 % MnO _x /γ-Al₂O₃ due to a strong interaction between MnO _x and γ-Al₂O₃. Recycling studies showed the catalyst was a heterogeneous one and retained its activity after recycling four times.