Conformational change-modulated spin transport at single-molecule level in carbon systems

Controlling the spin transport at the single-molecule level, especially without the use of ferromagnetic contacts, becomes a focus of research in spintronics. Inspired by the progress on atomic-level molecular synthesis, through first-principles calculations, we investigate the spin-dependent electronic transport of graphene nanoflakes with side-bonded functional groups, contacted by atomic carbon chain electrodes. It is found that, by rotating the functional group, the spin polarization of the transmission at the Fermi level could be switched between completely polarized and unpolarized states. Moreover, the transition between spin-up and spin-down polarized states can also be achieved, operating as a dual-spin filter. Further analysis shows that, it is the spin-dependent shift of density of states, caused by the rotation, that triggers the shift of transmission peaks, and then results in the variation of spin polarization. Such a feature is found to be robust to the length of the nanoflake and the electrode material, showing great application potential. Those findings may throw light on the development of spintronic devices.     

盐酸伊达比星杂质A的合成工艺优化及其高效液相分析

通过对盐酸伊达比星脱羟基杂质A的合成研究，为盐酸伊达比星的质控标准提供参考。以盐酸伊达比星为起始原料，经过4步反应得到脱羟基杂质A。本文提供了盐酸伊达比星杂质A的制备方法以及高效液相色谱分析方法，为杂质含量控制提供了依据。该工艺可以稳定、快速制备高纯度脱羟基杂质A，制备总收率为57.20%，纯度为57.20%，其结构经¹H NMR， ¹³C NMR和MS(ESI)表征。     

A Facile and Universal Top‐Down Method for Preparation of Monodisperse Transition‐Metal Dichalcogenide Nanodots

Despite unique properties of layered transition‐metal dichalcogenide (TMD) nanosheets, there is still lack of a facile and general strategy for the preparation of TMD nanodots (NDs). Reported herein is the preparation of a series of TMD NDs, including TMD quantum dots (e.g. MoS₂, WS₂, ReS₂, TaS₂, MoSe₂ and WSe₂) and NbSe₂ NDs, from their bulk crystals by using a combination of grinding and sonication techniques. These NDs could be easily separated from the N‐methyl‐2‐pyrrolidone when post‐treated with n‐hexane and then chloroform. All the TMD NDs with sizes of less than 10 nm show a narrow size distribution with high dispersity in solution. As a proof‐of‐concept application, memory devices using TMD NDs, for example, MoSe₂, WS₂, or NbSe₂, mixed with polyvinylpyrrolidone as active layers, have been fabricated, which exhibit a nonvolatile write‐once‐read‐many behavior. These high‐quality TMD NDs should have various applications in optoelectronics, solar cells, catalysis, and biomedicine.     

Design and application of feedback-sustained target waves in excitable medium

In this paper, we present a formulas of rational ratios between the frequency of external stimulus and its paced target waves, considering the existence of the absolute refractory period and the relative refractory period. Based on this, we design a self-sustained high-frequency target waves by feeding back few periphery field points to the center to responsibly play the role of source for pacemaker. Such constructed target waves, to all appearances, are shown as a repetition of their initial condition. We explore further in application that those feedback-sustained targets can eliminate both a freely rotating spiral waves and a pinned ones only if frequencies, feedback lengths and radius of obstacles are appropriately chosen. After feedback stimuli are removed, the system eventually returns to the rest state.     

Rational Design of an “OFF–ON” Phosphorescent Chemodosimeter Based on an Iridium(III) Complex and Its Application for Time‐Resolved Luminescent Detection and Bioimaging of Cysteine and Homocysteine

Biothiols, such as cysteine (Cys) and homocysteine (Hcy), play very crucial roles in biological systems. Abnormal levels of these biothiols are often associated with many types of diseases. Therefore, the detection of Cys (or Hcy) is of great importance. In this work, we have synthesized an excellent “OFF‐ON” phosphorescent chemodosimeter 1 for sensing Cys and Hcy with high selectivity and naked‐eye detection based on an Ir^III complex containing a 2,4‐dinitrobenzenesulfonyl (DNBS) group within its ligand. The “OFF‐ON” phosphorescent response can be assigned to the electron‐transfer process from Ir^III center and C^N ligands to the DNBS group as the strong electron‐acceptor, which can quench the phosphorescence of probe 1 completely. The DNBS group can be cleaved by thiols of Cys or Hcy, and both the ³M LCT and ³LC states are responsible for the excited‐state properties of the reaction product of probe 1 and Cys (or Hcy). Thus, the phosphorescence is switched on. Based on these results, a general principle for designing “OFF‐ON” phosphorescent chemodosimeters based on heavy‐metal complexes has been provided. Importantly, utilizing the long emission‐lifetime of phosphorescence signal, the time‐resolved luminescent assay of 1 in sensing Cys was realized successfully, which can eliminate the interference from the short‐lived background fluorescence and improve the signal‐to‐noise ratio. As far as we know, this is the first report about the time‐resolved luminescent detection of biothiols. Finally, probe 1 has been used successfully for bioimaging the changes of Cys/Hcy concentration in living cells.     

Terbinafine hydrochloride intercalated in montmorillonite: synthesis and characterization

The novel antifungal hybrid of terbinafine hydrochloride (TER-HCl)/montmorillonite was synthesized by the intercalation method under mechanical stirring. Intercalation of TER-HCl in the MMT galleries was characterized by X-ray diffraction (XRD), Fourier transform infrared spectra, elemental analysis (EA). and thermogravimetric analysis (TGA). The results from IR, TGA, and EA showed a difference in chemical composition of the MMT and the TER-HCl/MMT. XRD analysis showed that the basal spacing of montmorillonite significantly expanded from 1.53 to 2.79 nm. TER-HCl was successfully intercalated into the interlayer of MMT, and 28 % of TER-HCl was released after 48 h in 0.9 % (w/v) NaCl aqueous solution (pH 7) at 37 ± 0.5 °C. The antifungal activity of the hybrid against Candida albicans was evaluated using the inhibitory zone method and the minimum inhibitory concentration. The TER-HCl/MMT strongly inhibited C. albicans. These results show that TER-HCl/MMT can be useful in biomedical applications.     

系列含4，5-二氮杂-9，9’-螺二芴配体的钌配合物的合成及其性能研究

本文合成了3个新钌（Ⅱ）配合物,[Ru（bpy）₂（SB）]（PF₆）₂、[Ru（bpy）（SB）₂]（PF₆）₂和[Ru（SB）₃]（PF₆）₂（bpy=2,2’-bipyridine,SB=4,5-diaza-9,9’-spirobifluorene）,通过核磁和元素分析对配合物的结构进行了确定。[Ru（bpy）₂（SB）]（PF₆）₂通过X射线单晶衍射确认了结构。研究了配合物的光物理性能。结果表明[Ru（bpy）₂（SB）]（PF₆）₂在乙腈中的发桔红光,波长为606nm,量子产率约为0.0012。在同样条件下[Ru（bpy）（SB）₂]（PF₆）₂和[Ru（SB）₃]（PF₆）₂的发光非常微弱甚至几乎没有发光。还研究了这些配合物的电致化学发光性能。随着配体中SB含量的增加,发光的峰电压从1.36V增加到1.58V,相对发光强度从731降低到52。     

Highly porous PEEK and PEEK/HA scaffolds with Escherichia coli-derived recombinant BMP-2 and erythropoietin for enhanced osteogenesis and angiogenesis

The present study reports the results of structural and mechanical analysis, as well as proteins release kinetics and osteointegration in mice craniotomy model of highly porous PEEK (PolyEther Ether Ketone) and PEEK/HA (PolyEther Ether Ketone/HydroxyApatite) biomimetic scaffolds loaded with Escherichia coli-derived recombinant Bone Morphogenetic Protein-2 (BMP-2) and ErythroPOietin (EPO). Porous scaffolds were obtained by thermopressing with NaCl as a pore-forming filler. Two fractions of pore-forming filler were used to imitate natural trabecular bone tissue by making a preferential porosity using large fraction and creating an extended surface and special microrelief using small fraction. Hydroxyapatite (HA) was added up to 20% to activate bioinert PEEK providing loading of recombinant growth factors and osteointegration as well as sufficient level of mechanical properties imitating human trabecular bone. Unexpectedly, the non-activated PEEK produced by our technology was also able to spontaneously bind both BMP-2 and EPO. Loading of both BMP-2 and EPO to both types of implants resulted in enhanced neoosteogenesis and angiogenesis in a critical-size cranial defect model in mice in 3–6 weeks. Considering good mechanical characteristics and excellent osteoinductive and angiogenic properties, both materials in combination with BMP-2 and EPO can find their application in regenerative medicine.