Dual‐Modal Magnetic Resonance/Fluorescent Zinc Probes for Pancreatic β‐Cell Mass Imaging

Despite the contribution of changes in pancreatic β‐cell mass to the development of all forms of diabetes mellitus, few robust approaches currently exist to monitor these changes prospectively in vivo. Although magnetic‐resonance imaging (MRI) provides a potentially useful technique, targeting MRI‐active probes to the β cell has proved challenging. Zinc ions are highly concentrated in the secretory granule, but they are relatively less abundant in the exocrine pancreas and in other tissues. We have therefore developed functional dual‐modal probes based on transition‐metal chelates capable of binding zinc. The first of these, Gd ?1 , binds Zn^II directly by means of an amidoquinoline moiety (AQA), thus causing a large ratiometric Stokes shift in the fluorescence from λ_em=410 to 500 nm with an increase in relaxivity from r₁=4.2 up to 4.9 mM ^?1 s^?1. The probe is efficiently accumulated into secretory granules in β‐cell‐derived lines and isolated islets, but more poorly by non‐endocrine cells, and leads to a reduction in T₁ in human islets. In vivo murine studies of Gd ?1 have shown accumulation of the probe in the pancreas with increased signal intensity over 140 minutes.     

Recent Progress towards Transition‐Metal‐Catalyzed Synthesis of Fluorenes

Fluorenes are a commonly encountered structural motif in materials science, pharmaceutical chemistry, and organic synthesis. Among various strategies towards the synthesis of this unique structure, transition metal‐catalyzed functionalization has emerged as one of the most efficient methods. This Minireview presents an overview of the recent advances in this emerging area by highlighting the reactions’ specificity and applicability and, where possible, provides a mechanistic rationale.     

Discrete Rectangles,Prisms, and Heterometallic Cages from a Conjugated Cp*Rh‐Based Building Block

By carefully selecting an existing synthetic strategy and suitable coordination subunits, constructing desired coordination geometries is no longer that difficult to accomplish. Herein, a new strategy to construct a series of unprecedented structures by using conjugated Cp*Rh‐based complex BN‐OTf (Cp*=η⁵‐C₅Me₅) as the building block is proposed. DFT calculations revealed extensive delocalized π bonds in the subunit. With BN‐OTf , rectangular macrocycles TN‐bpy and TN‐bpe were controllably synthesized. Single‐crystal XRD studies confirmed one‐dimensional stacking channels for the tetranuclear structure. Notably, the starting ligand imidazole‐4,5‐dicarboxylate was found to act not only as a tetradentate but also as a hexadentate ligand that can coordinate to further metal ions. Subsequently, [4 Rh+1 M] heterometallic complexes HMZ (M=Cu and Zn) were accessed by chelating borderline hard/soft Lewis acids. With TN‐Linker or HMZ , two routes resulted in the [8 Rh+2 M] heterometallic cages HMC (M=Cu and Zn) with excellent crystallinity and stability. Surprisingly, when BN‐OTf bonded to rhodium itself, triangular prisms TP‐Linker were obtained with high solubility after being linked by bipyridine linkers. Both the X‐ray structure and ¹H NMR spectrum confirmed the novel isomerization of the triangular structures. All of the compounds were obtained in high yields and were fully characterized by ¹H NMR spectroscopy, elemental analysis, IR spectroscopy, and in most cases single‐crystal X‐ray structure determination.     

TODGA/[C_2mim][NTf_2]萃取Th~(4+)

研究了N,N,N′,N′-四辛基-3-氧戊二酰胺(TODGA)溶于疏水性离子液体咪唑类离子液体1-乙基-3-甲基咪唑双三氟甲磺酰亚胺盐([C2mim][NTf2])中对硝酸水溶液体系中四价钍离子(Th4+)的萃取行为。详细考察了接触时间、酸度、Th4+浓度、TODGA浓度、温度对TODGA/[C2mim][NTf2]体系萃取性能的影响。作为对比,我们还考察了TODGA在传统有机溶剂异辛烷中对Th4+的萃取。结果表明:TODGA/[C2mim][NTf2]体系对Th4+的萃取是吸热反应,且在50℃下,能在5 min内达到平衡。萃取体系随着酸度对Th4+的萃取性能先降后增大;Th4+浓度的增大,TODGA浓度的降低,对Th4+的萃取性能下降。TODGA在离子液体萃取体系中比在有机体系中有更好的Th4+萃取效果,特别是在低酸条件下。通过萃取机理研究,推测出在低酸下萃取反应是离子交换且TODGA与Th4+配比为2∶1,在高酸下萃取是中性配位。     

Microphase Separation within Disk Shaped Aggregates of Triblock Bottlebrushes

Well‐defined AbBA triblock bottlebrush with poly(N,N‐dimethyl acrylamide) (PAm) as A block and polyacrylate, densely grafted with poly(tert‐butyl acrylate)‐block‐polystyrene (PBA‐b‐PS), as brush bB block is prepared by controlled radical polymerization and click chemistry. The triblock copolymer with a composition of PAm₂₀₀‐b‐b(PBA₁₄‐b‐PS₄₇)₁₆₇‐b‐PAm₂₀₀ is obtained and is further transformed into PAm₂₀₀‐b‐b(PAA₁₄‐b‐PS₄₇)₁₆₇‐b‐PAm₂₀₀ by hydrolysis of the PBA segment into poly(acrylic acid) (PAA). In a mixture of N,N‐dimethylformamide (DMF) and methanol, a poor solvent of bB block, PAm₂₀₀‐b‐b(PAA₁₄‐b‐PS₄₇)₁₆₇‐b‐PAm₂₀₀ self‐assembled into disk‐like platelets, which have an internal lamellar structure by further microphase‐separation of PAA‐b‐PS branches in 2D. Moreover, Ag nanoparticles are aligned by PAA segments along the disk to form a pattern.

     

A review of transition metal chalcogenide/graphene nanocomposites for energy storage and conversion

Recent advances in the applications of transition metal chalcogenides/graphene (TMC/graphene) nanocomposites in future energy storage and conversion are reviewed. The synthesis processes and structures of TMC/graphene, workingpriciple of evergy energy device, and the electrochemical performances are summarized.     

Synergistic effect of functional carbon nanotubes and graphene oxide on the anti‐corrosion performance of epoxy coating

In this work, we reported the synergistic effect of functional carbon nanotubes (CNTs) and graphene oxide (GO) on the anticorrosion performance of epoxy coating. For this purpose, the GO and CNTs were firstly modified by the 3‐aminophenoxyphthalonitrile to realize the nitrile functionalized graphene oxides (GO‐CN) and carbon nanotubes (CNTs‐CN). As modified GO‐CN and CNTs‐CN were characterized and confirmed by Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, and gravimetric analyzer. It was found that about 19 and 24 wt% of 3‐aminophenoxyphthalonitrile were grafted onto the surface of the GO and CNTs, respectively. The electrochemical impedance spectroscopy results showed that the GO‐CN&CNTs‐CN hybrid materials exhibit a remarkable superiority in enhancing the anticorrosion performance of epoxy coatings. Significant synergistic effect of the lamellar structural GO‐CN and CNTs‐CN on the anticorrosion performance of epoxy composite coatings was designed. Besides, the epoxy coating with 1 wt% of the GO‐CN&CNTs‐CN hybrid exhibited the best anticorrosion performance, in which the impedance showed the largest one (immersion in 3.5 wt% of NaCl solution for 168 hr). Copyright © 2016 John Wiley & Sons, Ltd.     

一步乳液聚合法制备高溶解性导电聚苯胺

报道了一种高溶解性导电聚苯胺(PANI)的制备方法,以聚2-丙烯酰胺-2-甲基丙磺酸(PAMPS)作为掺杂酸和乳化剂,利用其特有的长链、亲水性及强酸性基团效应,通过乳液聚合法一步合成出具有较高溶解性的导电聚苯胺。利用核磁共振光谱仪(NMR)、傅里叶红外光谱仪(FT-IR)和扫描电子显微镜(SEM)等技术手段对产物结构和性能进行了表征分析。结果表明,在m(苯胺)∶m(AMPS)∶m(APS)=1∶2∶1.5;AMPS质量分数为20%;APS质量分数为30%;反应时间为5 h;反应温度为5℃的条件下,聚苯胺的产率高达86%,在有机溶剂二甲基甲酰胺(DMF)中的溶解度可达0.3814 g/g,在水中的溶解度可达0.2123 g/g,电导率达5.9 S/cm。     

Enhancement of SrTiO<Subscript>3</Subscript>/BiPO<Subscript>4</Subscript> heterostructure for simulated organic wastewater degradation under UV light irradiation

A novel SrTiO₃/BiPO₄ heterostructure with different amounts of SrTiO₃ have been successfully prepared through the hydrothermal process. The photocatalysts were characterized by X-ray powder diffraction, UV–Vis diffuse reflectance spectroscopy, scanning electron microscopy, energy dispersive X-ray spectroscopy, transmission electron microscopy, high-resolution transmission electron microscopy, and X-ray photoelectron spectroscopy. The photocatalytic performance was evaluated by degrading the methylene blue dye solution under UV light. Results showed that the samples displayed excellent photocatalytic degradation efficiency due to the highly efficient suppression of the recombination of electron–hole pairs. A possible mechanism of SrTiO₃/BiPO₄ heterojunctions was discussed. The research indicated that the as-prepared SrTiO₃/BiPO₄ heterogeneous photocatalyst can be used as an effective material for degrading industrial organic wastewater.     

纳米自组装γ-Al_2O_3孔隙结构的核磁共振表征

纳米自组装γ-Al_2O_3具有两种纳米级孔道,可作为适合于大分子扩散的催化剂载体,也可用于页岩气藏模型。表征纳米材料孔隙结构的方法有扫描电镜、氮吸附法及压汞法等,各有局限。本文利用核磁共振弛豫测量对纳米自组装γ-Al_2O_3孔隙结构进行研究和定量表征,并通过核磁共振实验和数值模拟对纳米自组装γ-Al_2O_3表面弛豫强度及孔径分布进行探索。结果表明,数值模拟核磁弛豫表征的纳米自组装γ-Al_2O_3的主体孔径为5-7 nm和30-42 nm,核磁弛豫实验通过误差函数法表征的主体孔径为5-9 nm和29-47 nm。相比于氮吸附仅表征微孔介孔及部分大孔,不能表征大于100 nm孔径,压汞法描述小于10 nm孔径相对不准确等问题,核磁弛豫能够全面表征2.8-315 nm纳米自组装γ-Al_2O_3的双峰孔隙系统。三个样品S-1、S-2、S-3的横向弛豫时间T_2谱小孔大孔波峰的信号幅度比0.603、1.15、1.84直接反映各自的化学小孔大孔氧化铝投料比0.85、1.38、1.7的变化。建立的表征方法可以应用于页岩气微观结构和机理研究中,前景广阔。