Design and preparation of a novel fluorescent naphthalimide derivative supramolecular self-assembly system and its bioimaging application

ABSTRACT

A novel fluorescent naphthalimide derivative gelator (N-18) was designed and characterised which could form a stable gel in 1,4-dioxane/H₂O (2/1, v/v), methyl sulfoxide (DMSO), ethanol/H₂O (4/1, v/v), acetone/H₂O (2/1, v/v) and methanol. The self-assembly process of molecule N-18 in the five solvents was carefully investigated by the field emission scanning electron microscope, UV-vis absorption spectra, fluorescence emission spectra, fourier transform infrared spectroscopy (FTIR), X-ray powder diffraction (XRD) and water contact angle experiments. Different structures from microbelts to helical nanofibers were formed in the self-assembly process. Hydrogen bonding and π–π stacking interaction were the mainly driving forces for the formation of gel. At the same time, the hydrophobic surface with the contact angles of 133°–142° was observed on the xerogel films N-18 from the above five solvents. Interestingly, molecule N-18 could be applied in bioimaging in a living cell.     

A novel self-assembly based on double-layer zinc porphyrin sensitizers in supramolecular solar cell

Two new self-assemblies based on zinc porphyrin dyes ZnPx-ZnPA (x?=?1, 2) were synthesized and used for dye-sensitized solar cells. Capping layer dyes consist of zinc porphyrin (ZnP) as core unit and carbazole (P1), phenothiazine (P2) as electron-donating group. The dye ZnPA contains carboxylic group as an anchor porphyrin with upper dyes (denoted as ZnP1 and ZnP2) formed dyads by coordination bonds of Zn-to-ligand self-assembled devices. The assembly modes were also verified by transmission electron microscopy (TEM). The influence of the upper porphyrins on molecular structure as well as photovoltaic performance was investigated via photophysical and electrochemical studies and calculations. With addition of the phenothiazine unit, the ZnP2-ZnPA possesses better light-harvesting capability with a significantly red-shifted Q-band. The photoelectrochemical efficiencies for ZnP2-ZnPA are better than those of ZnP1-ZnPA ascribed to larger J_sc and V_oc.

     

Chirality manipulation of supramolecular self-assembly based on the host-guest chemistry of cyclodextrin

Chiral materials have been of the interests of scientists for nearly a century. People have endeavored a great effort to manipulate the chirality of various self-assembled materials. Among these efforts, cyclodextrins are used only in recent years, although it has long been recognized that the chirality of cyclodextrin can be transferred to the guest. In this review, we for the first time summarize the recent advancement of the supramolecular chirality manipulation on the basis of the host-guest chemistry of cyclodextrins. By using the simple Harata-Kodaka's rule, natural cyclodextrins can be exploited in a dynamic manner to create chirality inversion materials through crystalline self-assembly, which is facile and environment-friendly. What is more, we also discussed the remarks on future outlooks at the end of this article and expect it to stimulate a rapid development on both the theory and application level.     

Fabrication of photoluminescent liquid crystal device using an in situ self-assembled molecular layer of a pyrene derivative

An in situ self-assembled molecular layer of 1-pyrenesulfonic acid sodium salt as an alignment agent was formed on indium tin oxide substrates for vertically aligning liquid crystals (LCs). The thus-aligned LCs exhibited uniform vertical alignment under crossed polarisers. The electro-optical characteristic of the LC cell fabricated using this method exhibited better performance than those of conventional LC cells with a polyimide alignment layer. Because the proposed alignment method is a simple one and involves low concentrations of the alignment agent (0.05 wt%), it is highly cost-effective. Further, the pyrene derivative, when mixed with LCs, exhibited photoluminescence (PL) under ultraviolet light. Given that the proposed method resulted in highly vertically aligned LCs and the alignment agent exhibited PL, the method should find wide use in the fabrication of colour-filter-free LC displays.     

Self-assembly of an alkylated guanosine derivative into ordered supramolecular nanoribbons in solution and on solid surfaces

We report on the synthesis and self-assembly of a guanosine derivative bearing an alkyloxy side group under different environmental conditions. This derivative was found to spontaneously form ordered supramolecular nanoribbons in which the individual nucleobases are interacting through H-bonds. In toluene and chloroform solutions the formation of gel-like liquid-crystalline phases was observed. Sub-molecularly resolved scanning tunneling microscopic imaging of monolayers physisorbed at the graphite-solution interface revealed highly ordered two-dimensional networks. The recorded intramolecular contrast can be ascribed to the electronic properties of the different moieties composing the molecule, as proven by quantum-chemical calculations. This self-assembly behavior is in excellent agreement with that of 5'-O-acylated guanosines, which are also characterized by a self-assembled motif of guanosines that resembles parallel ribbons. Therefore, for guanosine derivatives (without sterically demanding groups on the guanine base) the formation of supramolecular nanoribbons in solution, in the solid state, and on flat surfaces is universal. This result is truly important in view of the electronic properties of these supramolecular anisotropic architectures and thus for potential applications in the fields of nano- and opto-electronics.     

Synthesis and optical behaviour of hydrogen-bonded liquid crystals based on a chiral pyridine derivative

Three series of cholesteryl-containing supramolecular hydrogen-bonded (H-bonded) liquid crystal (LC) complexes with different number of fluoro-substituent were synthesised and characterised. Cholesteryl isonicotinate as proton acceptor and 4-n-alkoxybenzoic acids with or without fluoro-substituent as proton donor had been mixed in tetrahydrofuran to obtain H-bonded LC complexes. The effect of lateral substitution and the length of terminal chain in the H-bonded precursors on the formation of the supramolecular complexes had been examined. It was found that the introduction of fluoro substituent on the induced mesogens could widen the molecular width and thus reduce the molecular aspect ratio of the complexes, therefore it could lead to compress the formation of the LCs. However, the fluoro substituent played a positive role in enhancing the intermolecular interactions and stabilising the H-bond structure of the complexes. The influence of terminal length on the mesogenic behaviours is also discussed. On increasing the spacer length, the clear point and the thermal range of induced mesophase-like cholesteric phase decreased, and an induced chiral smectic phase began to appear in some complexes with long terminal tails.     

Studies directed toward the fabrication of a synthetic cation-conducting channel based on lariat ethers: The feeble forces concept for self-assembly

The work described here derives from our observation that while Nature certainly utilizes covalent interactions and other forces of great strength in the construction of biomolecules, many feeble forces are involved as well. We have used feeble forces in model studies directed eventually to the synthesis of a self-assembling, cation-conducting channel. Specifically, we have prepared three models for portions of such a cation-conducting channel. The first is based on the steroidal lariat ethers that clearly self-assemble. This process involvesinter alia entropy as a feeble force of cumulative importance. Second, we have prepared threetris(macrocyclic) systems that are simplified versions of the proposed channel-former. Third, we have demonstrated the strength of carefully-conceived hydrogen bonding interactions by constructing a molecular box based on the interaction between adenine and thymine.     

一个苯并咪唑衍生物的基于晶态-晶态转变的余辉刺激响应行为

通过苯并咪唑-5,6-二羧酸和间氨基苯磺酸的缩合得到有机物3-(5,7-dioxoimidazo[4,5-f]isoindol-6(1H,5H,7H)-yl) benzenesulfonic acid (DIBS),进而通过在不同温度下重结晶获得2种固态相： DIBS (10℃)和DIBS (60℃)。DIBS (10℃)具有寿命为721.55 ms的绿色室温磷光,而DIBS (60℃)的黄绿色余辉由寿命分别为259.78和336.33 ms的延迟荧光和室温磷光组成。2种相的不同发光行为可归因于DIBS分子在2种相中不同的构型及堆积结构。有趣的是,在研磨或加热刺激下,DIBS (10℃)可转变为DIBS (60℃),显示出罕见的余辉刺激响应行为。     

A reversible chemosensor for nitrite based on the fluorescence quenching of a carbazole derivative

The carbazole derivative, with an amino group in 9-position (9-methylacryloylamino carbazole (MAC), has been utilized to prepare a fluorescent sensor and used for the determination of NO₂⁻ based on the reaction between nitrite (NO₂⁻) and excess I⁻ to form I₃⁻, which can quench the fluorescence of carbazole derivative. MAC, as a fluorescent carrier, has a terminal double bond and is covalently immobilized on a quartz glass plate surface by photo-polymerization to prevent the leakage of the dye. The sensor shows sufficient repeatability, selectivity, operational lifetime of 8 weeks, and a fast response of less then 30 s. NO₂⁻ can be determined in the range between 1.0×10⁻⁶ and 1.0×10⁻⁴ mol l⁻¹ with a detection limit of 8.0×10⁻⁷ mol l⁻¹ at pH of 2.0. The quenching mechanism is discussed. Most commonly coexisting ions do not interfer with the NO₂⁻ assay.     

多功能氨基酸衍生物钝化的高性能钙钛矿太阳能电池

采用含有羧基、氨基和苯基等多官能团的氨基酸衍生物分子(Fmoc-L-异亮氨酸,Fmoc-Ile-OH)钝化钙钛矿薄膜表面缺陷。首先,该氨基酸衍生物可降低钙钛矿薄膜中PbI₂杂质含量,并提高钙钛矿薄膜的颗粒尺寸。其次,氨基酸衍生物的引入可有效改善钙钛矿薄膜的光学特性和钙钛矿/电荷传输层界面载流子输运性能。另外,经钝化处理的钙钛矿太阳能电池表现出更优的器件二极管理想因子、更低的陷阱填充极限电压和更高的载流子复合电阻,这些结果证实了Fmoc-Ile-OH可有效钝化钙钛矿薄膜表面缺陷。最后,通过工艺条件优化,制得了转化效率为21.09%的高效钙钛矿太阳能电池器件,其性能远优于对照组器件的效率(18.00%)。     

交联度对原位聚合法制备聚合物胶束性质的影响及相应的空心球制备

用原位聚合法成功地制备出不同响应温度的温敏性聚乳酸/聚(异丙基丙烯酰胺-co-丙烯酰胺)[P(D,L-LA)/P(NIPAM-co-AM)]核壳胶束. 实验中发现, 壳层的交联剂含量对粒子的尺寸有很大的影响, 当交联剂的摩尔分数从5%提高到15%时, 粒子在25 ℃时的流体力学直径从170.2 nm增加到886.5 nm. 通过对胶束粒子的核进行生物降解, 方便地得到了相应的空心球. 用FTIR监测核的降解过程, 用SEM和AFM检测核降解完全后粒子的外在形貌和内在结构变化. DLS结果表明, 空心球粒子同样具有良好的温度响应性, 其响应温度可通过改变原位聚合时单体AM的含量加以调节.     

A fluorescent chemical sensor for Fe based on blocking of intramolecular proton transfer of a quinazolinone derivative

In this paper, 2-(2′-hydroxy-phenyl)-4(3H)-quinazolinone (HPQ), a typical compound that exhibits excited state intramolecular proton transfer (ESIPT) reaction and possesses good photophysical properties, is synthesized and used as fluoroionophore for Fe³⁺ sensitive optochemical sensor. The decrease of fluorescence intensity of HPQ membrane upon the addition of Fe³⁺ was attributed to the blocking of ESIPT reactions of HPQ and quenching its fluorescence. The effect of the composition of the sensing membrane was studied, and experimental conditions were optimized. The sensor shows a linear response toward Fe³⁺ in the concentration range of 7.1 × 10⁻⁷ M to 1.4 × 10⁻⁴ M with a limit of detection of 8.0 × 10⁻⁸ M, and a working pH range from 2.5 to 4.5. It shows excellent selectivity for Fe³⁺ over a large number of cations such as alkali, alkaline earth and transitional metal ions. The proposed sensor is applied to the determination of the content of iron ions in pharmaceutical preparations samples with satisfactory results.     

一类Fmoc保护二肽醇类凝胶因子的合成与凝胶化研究

合成了一类Fmoc保护二肽凝胶因子(Fmoc-Lys(Fmoc)-Tyr-OR, R=＝Me, Et, Hex),, 并通过加热溶解-冷却静置方法测试了其凝胶性能。. 它们可在多种脂肪醇类溶剂中形成有机凝胶,, 并且具有热可逆性。. 通过透射电镜发现,, R为Me的凝胶因子在正己醇中可自组装成纳米级纤维状结构,, 相互交织使溶剂得以固定形成半透明凝胶,, 而在正丙醇中则倾向自组装成多刺球状,, 形成不透明白色凝胶。. IR及荧光光谱分析结果表明氢键与π-π stacking作用参与了其凝胶化自组装,, 同时氢键在凝胶态的强度较其固态时降低。. 该结果也从XRD数据中得以进一步证实。     

Catalytic effect of supramolecular system based on cationic surfactant and monopodands in nucleophilic substitution of phosphorus esters

The data are presented on the synthesis of podands with terminal quinoxaline fragments of rings and their influence on both the micellization properties of cetyltrimethylammonium bromide in a water—DMF solution and kinetics of basic hydrolysis of O-p-nitrophenyl O-ethyl chloromethylphosphonate and O-p-nitrophenyl O-hexyl chloromethylphosphonate in the absence and presence of surfactants. The mechanism of the podand effect on the reaction rate depends on the structures of phosphonate and podand. 1,8-Bis(3-ethyl-1,2-dihydro-2-oxoquinoxalin-1-yl)-3,6-dioxaoctane inhibits the basic hydrolysis of the substrates to 3—4 times. In a micellar solution of the surfactant, an approximately 20-fold acceleration of the reaction rate constant is observed. The observed rate constant decreases when podand is added to a micellar solution. The catalytic effect of the polycomponent system is due to concentrating of the reactants. The micellar microenvironment can exert both positive and negative effects on the reactivity of phosphonates.     

Development of a mobile system based on laser-induced breakdown spectroscopy and dedicated to in situ analysis of polluted soils

Principal Components Analysis (PCA) is successfully applied to the full laser-induced breakdown spectroscopy (LIBS) spectra of soil samples, defining classes according to the concentrations of the major elements. The large variability of the LIBS data is related to the heterogeneity of the samples and the representativeness of the data is finally discussed.     

An unprecedented 3-D supramolecular framework of {CuCN} coordination polymer based on anhydride: in situ formation of ligand by intramolecular dehydration

Hydrothermal reactions of K₄[Fe(CN)₆]?3H₂O with H₂bimdc (H₂bimdc = benzimidazole-5,6-dicarboxylic acid) afforded a coordination polymer (CP), [Cu(CN)(bimdca)] (1) (bimdca = benzimidazole-5,6-dicarboxylic anhydride), as the first example of the {CuCN}-based CP modified by anhydride. The polymer is characterized by elemental analysis, IR, TG, XRD, and single-crystal X-ray diffraction. In 1, horizontal and vertical parallel chains based on {Cu₂(CN)₄(bimdca)₂} dimer units crisscross resulting in a 2-D network with a (4⁴6²) topology, which is further connected to adjacent 2-D layers generating a 3-D supramolecular framework through intermolecular force between oxygens of anhydride. In addition, 1 exhibits interesting fluorescence and good degradation ability for MB under UV light.