Synthesis of stimuli-responsive pillararene-based supramolecular polymer materials for the detection and separation of metal ions

A stimuli-responsive supramolecular polymer network(G-(CN)_(2)⊂BXDSP5)with aggregation-induced emission(AIE)properties has been efficiently constructed by host-guest interactions between pillar[5]arene derivative BXDSP5 and a homoditopic guest G-(CN)_(2),which shows not only excellent fluorescence properties due to the AIE effect but also desirable ion-sensing abilities in both solution and solid states,holding great potential in the applicable fluorescence detection for Fe^(3+).The resultant G-(CN)_(2)⊂BXDSP5 can be transformed into supramolecular polymer gel at high concentration via multiple noncovalent interactions,showing multi-stimuli-responsiveness in response to temperature change,mechanical force,and competitive agent.Meanwhile,the xerogel of supramolecular polymer material has been successfully used to remove Fe^(3+)from water with high adsorption efficiency.In addition,an ionresponsive film based on supramolecular polymer has also been developed,which can serve as a practical and convenient fluorescence test kit for detecting Fe^(3+).

Effects of Electron Donating Ability of Substituents and Molecular Conjugation on the Electronic Structures of Organic Radicals

The geometries and electronic structures of a series of electron donor-acceptor radical molecules have been studied theoretically.The computational results show that the introduction of substituents with strong electron donating ability into tri-(2,4,6-trichlorophenyl)methyl(TTM)radicals enables the radical molecules to form the non-Aufbau electronic structure.The difficulty of forming the non-Aufbau electronic structure decreases with the enhancement of the electron donating ability of the substituent,but the expansion of the molecular conjugated system is not conducive to the formation.The hybridization of different fragments in molecular orbitals results in the disproportionation of orbital energy level and forms a staggered energy level structure.The electronic structure of radical molecules can be adjusted by substituents and molecular skeleton profoundly,which is a very effective means for molecular design.

具有自组装纳米结构的AIE光敏剂用于增强光动力治疗（英文）

基于具有聚集诱导发光(AIE)性质的2,3-双(4’-(二苯基)-[1,1’-联苯]-4-基]富甲腈(BDBF)分子,制备了三种纳米结构并用于图像引导光动力学治疗(PDT).普兰尼克F127可包封BDBF形成常见的球形纳米粒子(F127@BDBF NPs),该纳米粒子可发射红色荧光,荧光量子效率(FQY)为9.8%.此外, BDBF也可在水中自组装成纳米棒(BDBF NRs).与F127@BDBF NPs相比, BDBF NRs呈现出较强的橙色荧光,具有较高的荧光量子产率(23.3%),以及基本相同的单线态氧(1O2)产生能力.利用F127对BDBF NRs进行进一步修饰可得到BDBF@F127 NRs,该纳米粒子仍然保持了棒状形貌和较好的1O2产生能力.同时,与溶解态的BDBF相比,三种纳米结构的单线态氧产生效率增强.这些纳米结构在水溶液和生理条件下具有良好的稳定性.细胞的光毒性实验表明,三种纳米结构均能有效抑制肿瘤细胞增殖.因此,通过简单的自组装方法制备高荧光量子效率和较强单线态氧产生能力的纳米结构可作为一种有效的途径来增强光动力.

Applications of covalent organic frameworks(COFs)：From gas storage and separation to drug delivery

Covalent organic frameworks（COFs） are an emerging class of porous covalent organic structures whose backbones were composed of light elements（B,C,N,O,Si） and linked by robust covalent bonds to endow such material with desirable properties,i.e.,inherent porosity,well-defined pore aperture,ordered channel structure,large surface area,high stability,and multi-dimension.As expected,the abovementioned properties of COFs broaden the applications of this class of materials in various fields such as gas storage and separation,catalysis,optoelectronics,sensing,small molecules adsorption,and drug delivery.In this review,we outlined the synthesis of COFs and highlighted their applications ranging from the initial gas storage and separation to drug delivery.

Stimuli-responsive fluorescent supramolecular polymer network based on a monofunctionalized leaning tower[6]arene

A fluorescent supramolecular polymer network with an excellent triple-stimuli responsive property based on metal-ligand coordination and host-guest interactions has been constructed from a terpyridine-monofunctionalized leaning tower[6]arene,a tetraphenylethylene AIEgen,and a bridging coordination ion(Zn^2+).Addition of competitive binding agents,trifluoroacetic acid,and/or pillar[5]arene can break the metal coordination and/or host-guest inclusion complexation,and thermal heating can weaken the non-covalent interactions in the supramolecular polymer gel,all leading to the gel-to-sol transition.

Controlled drug delivery systems based on calixarenes

In recent years, cancer has become the number two cause of death around the world, and scientists have exploited various treatment maps. Calixarenes, with diversified features, have been widely applied into drug delivery systems, which can respond to multi-stimuli and exhibit excellent performance. In this mini-review, we summarize the recent advances on controlled drug delivery systems based on calixarenes, in the form of inclusion complexes, amphiphilic self-assembly nanocarriers including micelles, hydrogels, vesicles and liposomes, and supramolecular nanovalves on mesoporous silica nanomaterials.

Electrochemical determination of paraquat using a glassy carbon electrode decorated with pillararene-coated nitrogen-doped carbon dots

An electrochemical sensor(carboxylatopillar[5]arene-coated nitrogen-doped carbon dots,namely CCDs)based on carboxylatopillar[5]arene(CP[5])functionalized nitrogen-doped carbon dots(N-CDs)has been developed in a facile and economic manner.To improve the performance of this electrochemical sensor in pesticide detection,the optimal solution pH(pH 7)and loading amount of CCDs on the electrode(0.50 mg/mL)have been determined.By virtue of the good conductivity of N-CDs and the molecular recognition property of CP[5],CCDs modified glassy carbon electrode,namely CCDs/GCE,shows excellent anti-interference capability,selectivity,stability,and reproducibility in the sensitive detection of paraquat.The peak currents are proportional to the paraquat concentration(from 0.1μmol/L to 10μmol/L)with a detection limit of 6.4 nmol/L(S/N=3),indicating a great potential in pesticide detection.In comparison with the electrochemical sensors that require expensive metal nanoparticles and complex preparation processes,CCDs/GCE exhibits excellent detection capability of paraquat with lower cost and simpler preparation processes.

Synthesis and facet-dependent photocatalytic activity of strontium titanate polyhedron nanocrystals

Cubic-perovskite （SrTiO3） has a great potential to be utilized in a wide range of applications. However, currently very little is known about the shape and facet effects of SrTiO3 on their physicochemical properties. This is largely owing to the difficulties in controlling the morphology of facets during synthesis. Herein, we describe a facile route for the facet- and size-controlled fabrication of single- crystalline SrTiO3 triangular prisms with highly exposed {101} side faces and {111} end faces. Theoretical and experimental studies of their photocatalytic performance have shown that triangular prisms exhibit superior photocatalytic activities than nanocubes with exposed （001） faces for the degradation of organic contaminants, which may be primarily attributed to the much higher surface energy of {101} facets （2.97 J/m^2） and {111} facets （2.80 J/m^2） than of that of {001} facets （0.98 J/m^2）.

Temperature-sensitive polypeptide brushes-coated mesoporous silica nanoparticles for dual-responsive drug release

A biopolymer-inorganic hybrid system(MSN@PBLGF) is designed and fabricated from mesoporous silica nanoparticles(MSNs) and folic acid(FA)-terminated temperature-sensitive synthetic polypeptide,i.e.,poly(γ-benzyl-L-glutamate)(PBLG) derivative,through a thiol-disulfide exchange reaction,where MSNs with high drug loading capacity serve as drug nanocarriers and the biocompatible PBLG biopolymer brushes installed on MSN surface through disulfide bonds endow the system with tumor-specific recognition ability and GSH/temperature dual-stimuli responsiveness.Controlled drug release experiments indicate that DOX can be tightly hosted in the system with limited premature release,but efficiently released in response to an increased concentration of GSH and/or an elevated temperature.Intracellular experiments demonstrate that the DOX-loaded MSN@PBLGF nanohybrid shows outstanding cellular uptake and cell-growth inhibition effects on human lung cancer cell line A549 in comparison with healthy human cells such as hepatocyte cells LO2.

Deep eutectic solvent assisted facile synthesis of low-dimensional hierarchical porous high-entropy oxides

High-entropy-oxides(HEOs),a new class of solids that contain five or more elemental species,have attracted increasing interests owing to their unique structures and fascinating physicochemical properties.However,it is a huge challenge to construct various nanostructured,especially low-dimensional nanostructured HEOs under the high temperature synthetic conditions.Herein,a facile strategy using glucose-urea deep eutectic solvent(DES)as both a solvent and the carbon source of structure-directed template is proposed for the synthesis of various HEOs with two-dimentional(2D)nanonets and one-dimentional(1D)nanowires,including rock-salt(Co,Cu,Mg,Ni,Zn)O,spinel(Co,Cr,Fe,Mn,Ni)_(3)O_(4),and perovskite La(Co,Cr,Fe,Mn,Ni)O_(3).The as-prepared HEOs possessed five or more uniformly dispersed metal elements,large specific surface areas(more than 25 m^(2)·g^(−1)),and a pure single-phase structure.In addition,high cooling rate(cooling in air or liq-N_(2)-quenching)was indispensable to obtain a single-phase rock-salt(Co,Cu,Mg,Ni,Zn)O because of phase separation caused by copper.By taking advantage of unique features of HEOs,rock-salt(Co,Cu,Mg,Ni,Zn)O can function as a promising candidate for lithium-ion batteries(LIBs)anode material,which achieved excellent cycling stability.This work provides a feasible synthetic strategy for low-dimensional hierarchical HEOs,which creates new opportunities for the stable HEOs being highly active functional materials.

A Binary Supramolecular Assembly with Intense Fluorescence Emission, High pH Stability, and Cation Selectivity: Supramolecular Assembly-Induced Emission Materials

We construct a fuorescent supramolecular system(TPE-Q_(4)⊂DSP5)of excellent tolerance to a wide range of pH by the facile selfassembly of a new pillar[5]arene bearing disulfonated arms(DSP5)with an AIE-active tetraphenylethene-based tetratopic guest bearing four quaternary ammonium binding sites(TPE-Q_(4)),which exhibits strong blue emission even in dilute aqueous solutions along with much higher quantum yield and longer fuorescence lifetime than TPE-Q_(4) itself.Tis appreciable property can be attributed to the supramolecular assembly-induced emission(SAIE)mechanism endowed by the host-guest inclusion complexation based on synthetic macrocycles.Remarkably,the enhanced fuorescence of the supramolecular assembly is quenched efciently and exclusively by ferric ions in water with a high Stern–Volmer formula constant of 1.3×10^(5) mol^(−1),demonstrating the excellent cation selectivity and visualized responsiveness in ion sensing and detection.

Aggregation-induced emission systems involving supramolecular assembly

Aggregation-induced emission(AIE),as an exciting photophysical phenomenon,has been regarded as one frontier research topic within both ranges of molecular luminescence and materials science over the last two decades.Since controllable molecular ensembles with particular morphologies and tunable functions can be elegantly constructed in the realm of supramolecular chemistry,the integration of supramolecular assembly and AIE systems can expectedly bring about luminescent materials with tunable emission and tailorable well-ordered architectures.In this review,we will provide a summary of the creation and working mechanisms of AIE systems involving supramolecular systems that are driven by different supramolecular driving forces including hydrogen bonding,host−guest interactions,metal coordination,and π-π interactions.The morphological and photoluminescent features of these AIE-active supramolecular assemblies will be elucidated,and the regulated fluorescence properties of the AIEgens induced by the assembling-disassembling processes will be discussed in detail.

A one-pot synthesis of a self-included bisester-functionalized copillar[5]arene

We report here a one-pot synthetic method for the synthesis of a bisester-functionalized copillar[5]arene(BECP5A) with yield up to 20%. The properties of BECP5A in solution and in solid state were deeply investigated with the aid of 1D and 2D NMR spectra and X-ray diffraction, showing that this molecule has a fully self-included conformation in chloroform and partial self-inclusion in DMSO, and the compound has an asymmetrical structure with only one self-included side in the cavity of pillar[5]arene in the solid state. This compound will be used as the precursor of complex systems such as polymers and mechanically interlocked molecules.

Design and synthesis of self-included pillar[5]arene-based bis-[1]rotaxanes

Two strategies for the design of new pillar[5]arene-based mechanically self-interlocked molecules (MSMs) are reported here. The first strategy is based on the construction of an intermediate pseudo[1]rotaxane followed by the desired bis-[l]rotaxane. The other one is based on the construction of the desired bis-[1]rotaxane directly via a condensation reaction through host-guest interactions between a mono-functionalized pillar[5]arene and the axle. The newly synthesized bis-[1]rotaxane BR was characterized by ~1H NMR, ^(13)C NMR, 2D NMRs (~1H-^(13)C HSQC,~1H-~1H COSY and NOESY) and LC-ESI-MS,which indicated compound BR displayed an self-interlocked structure in CDCl_3. Surprisingly, the results of SEM, TEM and DLS showed that the compound BR could assemble into spherical nanoparticles in MeOH.

Accurate Control of Deuterated Locations and Amount of Deep Blue Ir（dfpypy）epic for Phosphorescent Efficiency Enhancement： Evaluations from Theoretical Aspect

A well-known deep-blue emitting iridium（III） complex was selected for deuterium isotope effect evalua- tion, both on deuterated locations and numbers, through theoretical investigation. It was revealed that the containment of the d site deuteriation of ancillary ligand picolinate enabled the non-radiative deactivation process to be repessed, and thereby improving the quantum efficiency through such a simple and controllable approach.

Chemotransformation of Bacterial Cells Without Heat-shock

Transformation of DNA into microbial cells via heat-shock approach has been well established in the fieldof molecular biology for decades. Herein we described an unexpected finding that heat-shock may not play an essen-tial role in the transformation process. This observation was verified via UV-Vis and fluorescence spectroscopies, andconfocal microscopy images for various DNAs and bacterial cells. The non-heat-shock approach proposed in thisstudy can be a convenient and beneficial modification for DNA transformation, especially for those laboratorieslacking ice machine and heat-shock equipment.

Porous Organic Polymer Nanoparticles for Sensing of Unsaturated Hydrocarbons

The design and synthesis of porous organic polymers for the potential application in chemical sensors remains a huge challenge nowadays. Herein, a porous organic polymer possessing tetrazole groups（TTZ-3） was synthe-sized via simple Schiff base chemical reaction. Thermogravimetric analysis（TGA）, Fourier transform infrared spec- trometer（FTIR）, solid-state 13C cross polarization/magic angle spinning nuclear magnetic resonance（CP/MAS NMR）, transmission electron microscopies（TEM） and field-scanning electron microscopies（FE-SEM） were adopted to cha- racterize the structure and morphology in detail. Significantly, the formed polymers exhibited special detection of unsaturated hydrocarbons through fluorescence enhancement based on photoactivatable 1,3-dipolar cycloaddition reactions. Furthermore, the reaction activity of different unsaturated hydrocarbons towards the polymers was investigated. This work highlights the great potential of porous organic polymers as chemical sensors in realizing environmental pollution monitoring and reducing the incidence of disease, such as chronic obstructive pulmonary disease.

Ethynyl Substitution Effect on the Electronic Excitation Spectra of Aniline

We made an extended study on the structure and properties of the low-lying electronic states of ethynyl substituted aniline and their cations. We performed these calculations using density functional theory method（B3LYP and CAM-B3LYP DFT） and the complete active space self-consistent field（CASSCF） approach in connection with the aug-cc-pVZ Dunning＇s basis sets and concerted ANO-L-VDZP basis sets. Our results included their equilibrium geometries, the vertical excitation spectra and the vertical and adiabatic ionization energies. The effect of ethynyl substitution on the electronic structure and the spectroscopy of aniline was probed.

High-Performance n-Hexane Purification by Nonporous Adaptive Crystals of Leaning Pillar[6]arene

The production of high-purity n-hexane under mild conditions is of great significance in both the petrochemical industry and synthetic chemistry.Here,we report an easy-to-operate and energy-efficient n-hexane purification strategy using nonporous adaptive crystals of perethylated leaning pillar[6]arene(EtLP6).Adaptive EtLP6 crystals preferentially absorb n-hexane over other branched or cyclic C6 alkanes with similar boiling points.This selectivity arises from the different thermodynamic stabilities and variabilities of EtLP6 crystalloids loaded with n-hexane and other C6 alkanes.Moreover,the reversible transformations between the nonporous guest-free and n-hexane-containing structures make the EtLP6 crystals highly recyclable.

Patterned surfaces for biological applications:A new platform using two dimensional structures as biomaterials

With the highly interdisciplinary of research and great development of microfabrication techniques,patterned surfaces have attracted great attention of researchers since they possess specific regularity and orderness of structures.In recent years,series of two dimensional patterned structures have been successfully fabricated,and widely used in anti-reflection,anti-fogging,self-cleaning,and sensing,etc.In the meantime,patterned structures have been gradually used in biologically relative fields such as biomaterials,aiming to deepen the perception of organism and understand the vital movements of human body.In this review,we provide a brief introduction on current status of techniques for two dimensional patterns fabrication,the applications of patterned surfaces in biologically related fields,and give out a prospective on the development of these patterned surfaces in the future.