求解离散不适定问题的正则化GMERR方法

迭代极小残差方法是求解大型线性方程组的常用方法, 通常用残差范数控制迭代过程.但对于不适定问题, 即使残差范数下降, 误差范数未必下降. 对大型离散不适定问题,组合广义最小误差(GMERR)方法和截断奇异值分解(TSVD)正则化方法, 并利用广义交叉校验准则(GCV)确定正则化参数,提出了求解大型不适定问题的正则化GMERR方法.数值结果表明, 正则化GMERR方法优于正则化GMRES方法.     

Versatile Nitro-Fluorophore as Highly Effective Sensor for Hypoxic Tumor Cells: Design, Imaging and Evaluation

Based on the characteristics of a nitro-group, which can be partially or totally reduced to an amino-group in hypoxic cells, two series of hypoxic sensors containing 7H-Benzimidazole [2,1-a]benz[de]isoquinolin-7-one cores with nitro groups in different positions were designed, synthesized and evaluated. The target compounds exhibited significantly different fluorescence characteristics (fluorescence enhancement or quenching). The strong fluorescences of some partially reduced compounds could be explained through the examination of their infrared spectra, which showed a restriction of the nitro-group vibration. These compounds exhibited significant hypoxic–oxic fluorescence differences not only in numerical values but also in their fluorescent imaging properties as reported for the first time.      

Synthesis and Antitumor Effect of Sophoridine Derivatives Bearing an Acyclic Aryloxy Phosphoramidate Mustard Functionality

To elevate the potency of sophoridine, phosphoramidate mustard motif was incorporated to D‐ring opened sophoridine scaffold. A series of acyclic aryloxy phosphoramidate mustard functionalized sophoridine derivatives were synthesized and screened for cytostatic activity in a range of different tumor cell lines (S180, H22, K562, MCF‐7, SMMC‐7721, and LoVo). All these compounds were shown to be more sensitive to S180 and H22 cells with IC₅₀ values ranging from 2.10 to 7.21 μM. In addition, all targeted derivatives distinctly are more cytotoxic to cancer cells than normal cell L929. Compounds 8b , 8c , 8d , and 8e displayed moderate tumor suppression without apparent organ toxicity in vivo against mice bearing H22 liver tumors. Their potential binding modes with DNA topoisomerase I complex have also been investigated.     

An Efficient Five‐Component Reaction for the Synthesis of 4,4′‐((2‐Oxoindoline‐3,3‐diyl)bis(methylene))bis(2‐aryl‐1H‐pyrrolo[3,4‐c]quinoline‐1,3(2H)‐dione) Derivatives

An efficient cascade process five‐component reaction of isatins and 3‐oxo‐N‐arylbutanamide for the synthesis of 4,4′‐((2‐oxoindoline‐3,3‐diyl)bis(methylene))bis(2‐aryl‐1H‐pyrrolo[3,4‐c]quinoline‐1,3(2H)‐dione) derivatives was reported under mild condition. The advantages of this strategy are easy to obtain raw materials, convenient one‐pot procedure, and simple operation.     

Unified reciprocity of dithiophosphate by dichalcogenophosph(in)ate ligands on copper hydride nanoclusters via ligand exchange reaction

A structural study of ligand exchange on chalcogen‐passivated copper nanoclusters is far less developed. Herein, we report the synthesis of polyhydrido copper nanoclusters [Cu₂₀H₁₁{Se₂P(O ⁱBu)₂}₉] ( 2 ) passivated by Se‐donor ligands via ligand replacement reaction on [Cu₂₀H₁₁{S₂P(O ⁱPr)₂}₉] ( 1 ) with NH₄[Se₂P(O ⁱBu)₂]. In parallel to the synthesis of 2 , cluster [Cu₂₀H₁₁{S₂P(CH₂CH₂Ph)₂}₉] ( 4 ) was produced by the ligand exchange reaction on a new derivative of 1 , that is [Cu₂₀H₁₁{S₂P(O ⁿPr)₂}₉] ( 3 ). Solid state structures of both clusters 2 and 4 were unequivocally established by single‐crystal X‐ray diffraction studies and cluster 4 epitomizes exceptional case to preserve both the shape and size of the nanocluster during the course of ligand exchange. Structurally precise cluster 2 is the second example where the copper hydride nanocluster is stabilized by Se‐donor ligands. The anatomy of 2 can be visualized as a twisted cuboctahedral Cu₁₃ core, two triangular faces of which are capped by a Cu₆ cupola and a single Cu atom along the C₃ rotational axis.     

NH4I/1,10-phenanthroline catalyzed direct sulfenylation of N-heteroarenes with ethyl arylsulfinates

An efficient synthesis of N-heterocyclic aryl sulfides via NH₄I/1,10-phenanthroline-catalyzed direct sulfenylation reactions was reported. In this reaction, heteroarenes such as indoles, and pyrroles serve as nucleophiles by installing a arylthio group at the C3 and C2 position of heterocycles, respectively. With readily accessible and free of unpleasant odor ethyl arylsulfinates as sulfur reagents, the metal-free-catalyzed direct sulfenylation of N-heteroarenes has been developed. 3-Arylthio-indoles and 2-arylthio-pyrroles derivatives were obtained in moderate to excellent yields, even on gram scale. The reaction was general for a broad scope of substrates and demonstrated good tolerance to a variety of functional groups.     

Identification and Directed Development of Non‐Organic Catalysts with Apparent Pan‐Enzymatic Mimicry into Nanozymes for Efficient Prodrug Conversion

Nanozymes, nanoparticles that mimic the natural activity of enzymes, are intriguing academically and are important in the context of the Origin of Life. However, current nanozymes offer mimicry of a narrow range of mammalian enzymes, near‐exclusively performing redox reactions. We present an unexpected discovery of non‐proteinaceous enzymes based on metals, metal oxides, 1D/2D‐materials, and non‐metallic nanomaterials. The specific novelty of these findings lies in the identification of nanozymes with apparent mimicry of diverse mammalian enzymes, including unique pan‐glycosidases. Further novelty lies in the identification of the substrate scope for the lead candidates, specifically in the context of bioconversion of glucuronides, that is, human metabolites and privileged prodrugs in the field of enzyme‐prodrug therapies. Lastly, nanozymes are employed for conversion of glucuronide prodrugs into marketed anti‐inflammatory and antibacterial agents, as well as “nanozyme prodrug therapy” to mediate antibacterial measures.     

Catalytic Asymmetric Synthesis of α‐Arylpyrrolidines and Benzo‐fused Nitrogen Heterocycles

Herein, we report a practical two‐step synthetic route to α‐arylpyrrolidines through Suzuki–Miyaura cross‐coupling and enantioselective copper‐catalyzed intramolecular hydroamination reactions. The excellent stereoselectivity and broad scope for the transformation of substrates with pharmaceutically relevant heteroarenes render this method a practical and versatile approach for pyrrolidine synthesis. Additionally, this intramolecular hydroamination strategy facilitates the asymmetric synthesis of tetrahydroisoquinolines and medium‐ring dibenzo‐fused nitrogen heterocycles.     

Assembled Vitamin B2 Nanocrystals with Optical Waveguiding and Photosensitizing Properties for Potential Biomedical Application

Great success has been achieved in recent years in the development of synthetic or assembled nanobiomaterials. Among these, biomolecule‐based nanoarchitectures with special optical property are of particular interest. Here, we demonstrate that vitamin B₂ nanocrystals assembled as nanorods can be obtained with precise control. Excitingly, such one‐dimensional nanostructures not only exhibit intrinsic optical waveguiding properties but also the ability to sensitize oxygen to produce reactive oxygen species. With these properties, we applied the obtained vitamin B₂ nanorods under remotely localized light illumination into single tumour cells in vitro for anticancer photodynamic therapy. Further, vitamin B₂ nanorods were explored for in vivo photodynamic therapy by using a tumour model. With such bionanostructures, new features and functions of vitamin B₂ and its derivatives have been developed.     

Structure Switching and Modulation of the Magnetic Properties in Diarylethene‐Bridged Metallosupramolecular Compounds by Controlled Coordination‐Driven Self‐Assembly

We report three self‐assembled iron complexes that comprised an anti‐parallel open form (o‐ L _anti), a parallel open form (o‐ L _syn), and a closed form (c‐ L ) of diarylethene conformers. Under kinetic control, Fe^II₂(o‐ L _anti)₃ was isolated, which exhibited a dinuclear structure with diamagnetic properties. Under light‐irradiation control, Fe^II₂(c‐ L )₃ was prepared and exhibited paramagnetism and spin‐crossover behaviour. Under thermodynamic control and in the presence of indispensable [Fe^III(Tp*)(CN)₃]^?, Fe^II₂(o‐ L _anti)₃ and Fe^II₂(c‐ L )₃ transformed into tetranuclear Fe^III₂Fe^II₂(o‐ L _syn)₂, which exhibited complete spin‐crossover behaviour at T_1/2=353 K.