A highly selective and sensitive fluorescent chemosensor for Hg2+ in neutral buffer aqueous solution

A selective and sensitive fluorescent chemosensor for Hg2+, which was composed of two aminonaphthalimide fluorophores and a receptor of 2,6-bis(aminomethyl)pyridine, was synthesized through the reaction of 2,6-bis(chloromethyl)pyridine and N-[2-(2-hydroxyethoxy)ethyl]-4-piperazino-1,8-naphthalimide. The chemosensor showed an about 17-fold increase in fluorescence quantum yield upon addition of 1 equiv of Hg2+ in neutral buffer aqueous solution, and the other common metal ions did not notably disturb the detection of Hg2+.     

β-Cyclodextrin modified filter paper based solid phase extraction–room temperature phosphorimetry for preconcentration and determination of nitrogen heterocyclic compounds in water samples

A highly selective method for the preconcentration and the determination of nitrogen heterocyclic compounds (NHCs) by solid phase extraction–room temperature phosphorimetry (SPE–RTP) was described. The β-cyclodextrin (β-CD) coated filter paper was synthesized and used as the SPE membrane and the substrate for the measurement of RTP emission of NHCs in water samples. The RTP characteristics of NHCs on the coated filter paper were studied. The conditions for the measurement of RTP intensities of NPAHs were discussed and optimized in detail. Several experimental parameters related to the preconcentration of NHCs on the coated filter paper were also examined. The experimental results showed that the β-CD coated filter paper could selectively extract NHCs containing three benzene rings with a high enrichment efficiency. The limit of detections of carbazole, 7,8-benzoquinoline and phenanthridine were found to be 9.1 × 10⁻¹⁴, 8.3 × 10⁻¹³ and 7.8 × 10⁻¹³ mol mL⁻¹, respectively. The proposed method was applied to the analysis of NHCs in water samples. The recoveries of carbazole, 7,8-benzoquinoline and phenanthridine in water samples was in the range of 86.1–109.3%.     

高抗冲聚苯乙烯/蒙脱土复合材料的阻燃性研究

用经十六烷基三甲基溴化铵有机化改性的蒙脱土 (OMMT)与高抗冲聚苯乙烯 (HIPS)通过熔融插层法制备了HIPS OMMT复合材料 ,用X ray衍射技术对材料结构进行了表征 ,发现钠基蒙脱土 (Na+ MMT)和有机蒙脱土的层间距分别为 1 5 1nm和 2 18nm ,HIPS OMMT(5phr)复合材料中蒙脱土的层间距因聚合物大分子的插入扩大为 3 4 4nm ;而HIPS与Na+ MMT形成的复合材料的层间距与Na+ MMT的层间距相比却没有变化 ,表明未有机化处理土没有形成插层结构 .锥形量热仪的研究结果表明HIPS OMMT复合材料的热释放速率、质量损失速率以及生烟速率等燃烧特性参数均显著降低 ,具有较明显的阻燃性和抑烟性 ,而HIPS Na+ MMT非插层型复合材料只有在Na+ MMT很高填充量下 (>2 0phr)才有一定阻燃效果 .比较了铵盐对HIPS阻燃性的影响 ,结果表明铵盐自身的阻燃作用很小 ,主要是插层复合结构起阻燃作用 .     

Progress of the key materials for organic solar cells

Organic solar cells have attracted academic and industrial interests due to the advantages like lightweight, flexibility and roll-to-roll fabrication. Nowadays, 18% power conversion efficiency has been achieved in the state-of-the-art organic solar cells. The recent rapid progress in organic solar cells relies on the continuously emerging new materials and device fabrication technologies, and the deep understanding on film morphology, molecular packing and device physics. Donor and acceptor materials are the key materials for organic solar cells since they determine the device performance. The past 25 years have witnessed an odyssey in developing high-performance donors and acceptors. In this review, we focus on those star materials and milestone work, and introduce the molecular structure evolution of key materials. These key materials include homopolymer donors, D-A copolymer donors, A-D-A small molecular donors, fullerene acceptors and nonfullerene acceptors. At last, we outlook the challenges and very important directions in key materials development.     

π-烯丙基氯化铁三吡啶配合物与丁烯醛反应的研究

丁烯醛在π-烯丙基氯化铁三吡啶配合物作用下,会生成自缩合产物,经色谱-质谱、红外光谱、核磁等手段表征,确认产物为6-甲基-1,3环已二烯基甲醛。推测反应机理是丁烯醛与π-烯丙基氯化铁三吡啶配合物进行配位体交换,然后与另一丁烯醛分子加成环化而成。由于配合物中配位体的定位作用,大大提高了反应的选择性而未见其它副反应发生。     

Two routes to vesicle formation: metal-ligand complexation and ionic interactions

Two routes to vesicle formation were designed to prepare uni- and multilamellar vesicles in salt-free aqueous solutions of surfactants. The formation of a surfactant complex between a double-chain anionic surfactant with a divalent-metal ion as the counterion and a single-chain zwitterionic surfactant with the polar group of amine-oxide group is described for the first time as a powerful driving force for vesicle-phases constructed from salt-free mixtures of aqueous surfactant solutions. As a typical example, a Zn(2+)-induced charged complex fluid, vesicle-phase has been studied in aqueous mixtures of tetradecyldimethylamine oxide (C(14)DMAO) and zinc 2,2-dihydroperfluorooctanoate [Zn(OOCCH(2)C(6)F(13))(2)]. This ionically charged vesicle-phase formed due to surfactant complexation has interesting rheological properties and is not shielded by excess salts because there are no counterions in the solution. Such a vesicle-phase of surfactant complex is important for many applications; for example, the vesicle-phase was further used to produce in situ the vesicle-phase of the salt-free cationic/anionic (catanionic) surfactants, C(14)DMAOH(+)-(-)OOCCH(2)C(6)F(13). The salt-free catanionic vesicle-phase could be produced through injecting H(2)S gas into the C(14)DMAO/Zn(OOCCH(2)C(6)F(13))(2) vesicle-phase, because the zwitterionic surfactant C(14)DMAO can be charged by the H(+) released from H(2)S to become a cationic surfactant and Zn(2+) was precipitated as ZnS. After the ZnS precipitates were removed from C(14)DMAO/Zn(OOCCH(2)C(6)F(13))(2) solutions, the final mixed solution does not contain excess salts as do other cationic/anionic surfactant systems. Both the C(14)DMAO-Zn(OOCCH(2)C(6)F(13))(2) complex and the resulting catanionic C(14)DMAOH(+)-(-)OOCCH(2)C(6)F(13) solution are birefringent Lalpha-phase solutions that consist of uni- and multilamellar vesicles. Ring-shaped semiconductor ZnS materials with encapsulated ZnS precipitates and regular spherical ZnS particles were prepared, which resulted in a transition from vesicles composed of metal-ligand complexes to vesicles held together by ionic interactions in the salt-free aqueous systems. This strategy should provide a new method to prepare inorganic materials. The present routes to form vesicles solve a problem: how to prepare nanomaterials using surfactant self-assembly, with structure controlled not by the growing material, but by the phase behavior of the surfactants.     

Electron Redistribution Enables Redox-Resistible Li6PS5Cl towards High-Performance All-Solid-State Lithium Batteries

Sulfide electrolytes with high ionic conductivity hold great promise for all-solid-state lithium batteries. However, the parasitic redox reactions between sulfide electrolyte and Li metal result in interfacial instability and rapid decline of the battery performance. Herein, a redox-resistible Li₆PS₅Cl (LPSC) electrolyte is created by regulating the electron distribution in LPSC with Mg and F incorporation. The introduction of Mg triggers the electron agglomeration around S atom, inhibiting the electron acceptance from Li, and F generates the self-limiting interface, which hinders the redox reactions between LPSC and Li metal. This redox-resistible Li₆PS₅Cl-MgF₂ electrolyte therefore presents a high critical current density (2.3 times that of pristine electrolyte). The LiCoO₂/Li₆PS₅Cl-MgF₂/Li cell shows an outstanding cycling stability (93.3 %@100 cycles at 0.2 C). This study highlights the electronic structure modulation to address redox issues on sulfide-based lithium batteries.     

Doping Sumanene with Both Chalcogens and Phosphorus(V): One‐Step Synthesis,Coordination, and Selective Response Toward AgI

Heterasumanenes 4 – 6 containing chalcogen (S, Se, and Te) and phosphorus atoms have been synthesized in a one‐pot reaction from trichalcogenasumanenes 1 – 3 by replacing one chalcogen atom with a P=S unit. The P=S unit makes 4 – 6 almost planar and shrinks the HOMO–LUMO gap as compared to 1 – 3 . The bonding between Ag⁺ and S atom on P=S brings about a distinct change to the optical properties of 4 – 6 ; 4 in particular shows a selective fluorescence response toward Ag⁺ with LOD of 0.21 μm . Compounds 4 – 6 form complexes with AgNO₃ to be ( 4 )₂?AgNO₃, ( 5 )₂?AgNO₃, and ( 6 )₂?(AgNO₃)₃. In complexes, the coordination between Ag⁺ and P=S is observed, which leads to shrinkage of C?P and C?X (X=S, Se, Te) bond lengths. As a result, 4 , 5 , and 6 are all bowl‐shaped in complexes with bowl‐depths reaching to 0.66 Å, 0.42 Å, and 0.40 Å, respectively. There are Ag?Te dative bonds between Ag⁺ and Te atom on telluorophene in ( 6 )₂?(AgNO₃)₃.     

In situ endpoint detection of reactive ion-beam etching of dielectric gratings with an etch-stop layer using downstream mass spectrometry

Downstream mass spectrometry is successfully used in the reactive ion-beam etching of dielectric diffraction gratings of deep grooves with vertical sidewalls to achieve in situ endpoint detection. Silica (SiO₂) gratings with a Sc₂O₃ etch-stop layer are fabricated by reactive ion-beam etching with CHF₃ as etchant, and the mass spectrometric signal of SiF₃⁺ produced by the reactive etching of the SiO₂ grating material is monitored. When the etch-stop layer is reached, a drop of this signal occurs. By comparing the monitoring curves and resulting gratings of different etching methods, we find that the decrease of the monitored signal is strongly influenced by the sidewall steepness of the etched grating grooves. All conditions being equal, the greater sidewall steepness renders the faster decrease of the signal. Consequently, the proposed approach of endpoint detection applies well to the gratings with steep sidewalls. With the help of two previously developed methods, the sidewall steepness of grating grooves is increased, and the optimal endpoint is detected. Employing the proposed technique, we have reproducibly fabricated dielectric gratings with proper groove depth and even groove bottom.     

提高离子束刻蚀亚微米光栅侧壁陡直度的方法

现代亚微米光栅的应用通常要求栅脊侧壁陡直。通过比较两种配备不同离子源的刻蚀机的反应离子束刻蚀结果,认为影响亚微米光栅侧壁陡直度的一个重要因素是离子束发散角(束散角),且小束散角有利于获得陡直的光栅侧壁。国内应用最广泛的双栅考夫曼刻蚀机束散角较大(大于13°),致使用常规方法获得的熔石英光栅的侧壁倾角仅为77°。针对此刻蚀机,尝试了三种提高侧壁陡直度的方法:旋转倾斜刻蚀法、交替倾斜刻蚀法和二次金属掩模法,分别把侧壁倾角提高到86°、86°和82°。最后从掩模侧壁收缩速率和槽底部与顶部离子通量的差异对束散角对侧壁陡直度的影响给予解释,并说明了上述三种方法的工作机理。