Synthesis and characterization of double hydrophilic block copolymers containing semi-rigid and flexible segments

3-Methyl-(E)-stilbene (3MSti) and 4-(diethylamino)-(E)-stilbene (DEASti) monomers are synthesized and polymerized separately with maleic anhydride (MAn) in a strictly alternating fashion using reversible addition-fragmentation chain transfer (RAFT) polymerization techniques. The optimal RAFT chain transfer agents (CTAs) for each copolymerization affect the reaction kinetics and CTA compatibilities. Psuedo-first order polymerization kinetics are demonstrated for the synthesis of poly((3-methyl-(E)-stilbene)-alt-maleic anhydride) (3MSti-alt-MAn) with a thiocarbonylthio CTA (methyl 2-(dodecylthiocarbonothioylthio)−2-methylpropionate, TTCMe). In contrast, a dithioester CTA (cumyl dithiobenzoate, CDB) controls the synthesis of poly((4-(diethylamino)-(E)-stilbene)-alt-maleic anhydride) (DEASti-alt-MAn) with pseudo-first order polymerization kinetics. DEASti-alt-MAn is chain extended with 4-acryloylmorpholine (ACMO) to synthesize diblock copolymers and subsequently converted to a double hydrophilic polyampholyte block copolymers (poly((4-(diethylamino)-(E)-stilbene)-alt-maleic acid))-b-acryloylmorpholine) (DEASti-alt-MA)-b-ACMO) via acid hydrolysis. The isoelectric point and dissociation behavior of these maleic acid-containing copolymers are determined using ζ-potential and acid–base titrations, respectively. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 219–227     

Water‐Soluble Luminescent Hybrid Composites Consisting of Oligosilsesquioxanes and Lanthanide Complexes and their Sensing Ability for Cu2+

Water‐soluble hybrid composites with great potential for selective and sensitive sensing and that are obtained through simple, rapid, and environmentally friendly methods are highly desirable and remain a challenging task. Herein, we present luminescent hybrid composites that were realized by linking Na₃[Ln(dpa)₃] (dpa=2,6‐pyridinedicarboxylic acid) to octa‐amino functionalized polyhedral oligomeric silsesquioxane (POSS‐NH₂) through hydrogen‐bonding interactions between the oxygen atoms of the carboxylate groups of dpa and the hydrogen‐bond‐donor amino groups. The resulting hybrid composites Ln(dpa)₃@POSS‐NH₂ are highly soluble in aqueous solutions and the quantum yield of Eu(dpa)₃@POSS‐NH₂ is as high as 56.5 % or 46.3 % in the solid state and in aqueous solution, respectively, as determined by using the integrating sphere method. The novel water‐soluble luminescent hybrid composites exhibit high thermal and photostability, and the emitted colors of the resulting hybrid composite can be finely tuned by changing the Eu³⁺/Tb³⁺ ratio. Interestingly, Eu(dpa)₃@POSS‐NH₂ hybrid composites exhibited an effective switch‐off fluorescence response to Cu²⁺ over other common metal ions in aqueous media.     

Anionic water-soluble sulfonated phthalocyanines: microwave-assisted synthesis,aggregation behaviours,electrochemical and in-situ spectroelectrochemical characterisation

In this work, a phthalonitrile derivative bearing p-sulfonylphenoxy group at the 3-position has been synthesised. The water-soluble non-peripherally tetrasubstituted zinc (3) and cobalt (4) phthalocyanines were obtained by cyclotetramerisation of this phthalonitrile derivative in the presence of anhydrous metal salts by microwave irradiation. The compounds have been characterised by using FT-IR, ¹H NMR, UV–Vis and Mass spectrometry (MS) data. The aggregation behaviours of these compounds were investigated in methanol, DMSO, DMF, and water. We have also studied the aggregation behaviours of the phthalocyanine complex 3 in various DMSO/water mixtures. Additionally, the redox properties of the phthalocyanine complexes were examined in dimethylsulfoxide by voltammetry and in situ spectroelectrochemistry. Redox behaviours of the complexes supported the structures of the complexes. Metal and ring-based reductions were observed for 4 and only ring-based electron transfer processes were observed with 3.     

Aggregation Mode,Host-Guest Chemistry in Water,and Extraction Capability of an Uncharged,Water-Soluble,Liquid Pillar[5]arene Derivative

An uncharged, water-soluble per-ethylene-glycol pillar[5]arene derivative ( 1 ) was synthesized and its aggregation mode, host-guest chemistry in water and extraction ability was explored. Compound 1 is a liquid at room temperature; in water, limited self-aggregation occurred at high concentrations as deduced from diffusion NMR and dynamic light scattering. Compound 1 forms pseudo-rotaxane-like 1 : 1 host-guest complexes with 1,ω-di-substituted alkanes with association constants on the order of 10³–10⁴ m ⁻¹. Interestingly, NMR experiments showed that the guest location relative to the host ring system differs among the different complexes. In proof-of-concept experiments, compound 1 was shown to extract structurally related organic compounds from benzene into water with significant selectivity. Compound 1 , which is a liquid at room temperature and has only limited interactions with its side arms, can, in principle, be regarded as a complement to or as a kind of type I porous liquid.     

Photoswitchable Composite Polymer Electrolytes Using Spiropyran-Immobilized Nanoporous Templates

Composite polymer electrolytes (CPEs) with smart, stimuli-responsive characteristics have gained considerable attention owing to their noninvasive manipulation and applications in future technologies. To address this potential, in this work, we demonstrate photoresponsive composite polymer electrolytes, consisting of gel polymer electrolyte (GPE) and spiropyran-immobilized nanoporous anodic aluminum oxide (SP-AAO) templates. Under UV irradiation, the close SP form isomerizes to the open merocyanine (MC) form, creating extremely polarized AAO surfaces; whereas, under visible light irradiation, the MC form reverts to the SP form, creating neutral surface conditions. The electrostatic interactions between ions and AAO surfaces are investigated by attenuated total reflection Fourier-transform infrared (ATR-FTIR) spectroscopy. Moreover, the behavior of ionic conductivity of the GPE@SP-AAO is found to be consistent with the kinetics of isomerization tracked by UV-Vis spectroscopy. This work provides a promising platform for developing next-generation photoelectronic smart devices.     

具有双荧光发射的螺吡喃的合成与性质研究

设计合成了未见文献报道的含有双官能团的螺吡喃类化合物1,通过红外光谱、核磁共振氢谱、碳谱和高分辨质谱对其结构进行了确证。紫外可见吸收光谱表明化合物在有机溶剂中的光致变色性良好;化合物的乙醇溶液在365 nm光激发时产生双荧光发射,分别为闭环体和开环体所对应的的荧光峰。本文首次从场效应角度推测了螺吡喃吲哚林N原子上含有极性基团时开环体稳定的原因。     

Adsorption of thorium(IV) on magnetic multi-walled carbon nanotubes

The influences of pH, contact time, solid-liquid ratio, temperature and C60(C(COOH)2)n on Th(IV) adsorption onto the magnetic multi-walled carbon nanotubes(MMWCNTs) were studied by batch technique. The dynamic process showed that the adsorption of Th(IV) onto MMWCNTs could reach equilibrium in 40 h and matched the pseudo-second-order kinetics model. The adsorption of Th(IV) onto MMWCNTs was significantly dependent on pH values, the adsorption ratio increased markedly at pH 3.0–5.0, and then maintained a steady state as pH values increased. At low pH, different C60(C(COOH)2)n content could enhance the adsorption content of Th(IV) onto MMWCNTs, but restrained it at higher pH. Through simulating the adsorption isotherms by Langmuir, Freundlich and Dubini-Radushkevich models, it could be seen respectively that the adsorption pattern of Th(IV) onto MMWCNTs was mainly surface complexation, and that the adsorption process was endothermic and irreversible.     

Zinc(II)-poly(urea-formaldehyde) supported on magnetic nanoparticles: A hybrid nanocatalyst for green synthesis of spiropyrans,spiroxanthenes, and spiropyrimidines

Immobilization of metal ions onto inorganic supports has very interesting biological, industrial, and catalysis applications. In this study, CoFe₂O₄@SiO₂@PUF@Zn(OAc)₂ nanostructure was successfully fabricated by immobilization of zinc acetate on the surface of poly(urea-formaldehyde) supported on magnetic CoFe₂O₄@SiO₂ nanoparticles through a layer-by-layer assembly. The structure of hybrid nanoparticles was characterized by Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, energy-dispersive X-ray spectroscopy, inductively coupled plasma atomic emission spectroscopy, vibrating sample magnetometry, Brunauer–Emmett–Teller surface area analysis, scanning electron microscopy, and transmission electron microscopy. Zinc-poly(urea-formaldehyde) supported on magnetic nanoparticles (MNPs@SiO₂@PUF@Zn) was successfully used for the synthesis of spirooxindolopyran and spirooxindoloxanthene derivatives in aqueous medium as an environmentally benign condition. High yields, short reaction times, green solvent, reusability without significant reduction in catalytic activity, and simple separation of the catalyst using an external magnet along with environmental compatibility are some benefits of this procedure.     

Reversibly light‐responsive biodegradable poly(carbonate) micelles constructed via CuAAC reaction

Light‐responsive poly(carbonate)s PEG₁₁₃‐b‐PMPC_n‐SP were synthesized via copper catalyzed azide‐alkyne cycloaddition reaction between azide‐modified spiropyran (SP‐N₃) and amphiphilic copolymer PEG₁₁₃‐b‐PMPC_n. PEG₁₁₃‐b‐PMPC₂₅‐SP can self‐assemble to biocompatible micelles with an average diameter of ～96 nm and a critical aggregation concentration of 0.0148 mg mL^?1. Under 365 nm UV light irradiation, the characteristic absorption intensity of merocyanine (MC) progressively increased and most of the micellar aggregations were disrupted within 10 min, suggesting the completion of the transformation of hydrophobic SP to hydrophilic MC. Subsequent exposuring the micelles to 620 nm visible light, spherical micelles aggregated again. The light‐controlled release and re‐encapsulation behaviors of coumarin 102‐loaded micelles were further investigated by fluorescence spectroscopy. This study provides a convenient way to construct smart poly(carbonate)s nanocarriers for controlled release and re‐encapsulation of hydrophobic drugs. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 750–760     

Adsorption of a cationic water-soluble dye onto cationic Langmuir–Blodgett films via nano clay platelets: An efficient approach to control the H-dimer

This communication reports the successful adsorption of a water-soluble cationic fluorescent dye Acridine Orange (AO) onto Langmuir–Blodgett (LB) films of a cationic amphiphile octadecylamine (ODA) in the presence of nano-clay platelets hectorite. Acridine orange (AO) has been widely used as a stainer for the characterization of biopolymers. But AO has a tendency to form non-florescent H-dimer even in the aqueous solution. Anionic nano-clay platelets hectorite played an important role in controlling the H-dimer formation of AO in the hybrid film. Effects of various parameters in the adsorption process were investigated in detail.