Soft Matter
·
2013
·Vol. 9
·期 24
·5807-5814
·
IF 3.909
Xiuqin Cai,Ying Wu,Liya Wang,Ni Yan,Jing Liu,Xiaohua Fang,Yu Fang
Two novel cholesteryl derivatives of calix[4]arene with L- or D-phenylalanine residues in the linkers (1 and 2, respectively) were designed and synthesized. The gelation behaviors of the compounds in 30 organic solvents were tested. It was demonstrated that 1 gels n-butanol and n-pentanol at room temperature, but 2 gels isopropanol only under the treatment of heating–cooling cycling or energy supplementing via sonication, vortex or agitation at room temperature. AFM and SEM measurements revealed that the structures of the gel networks are greatly affected by the spatial configurations of the linkers contained in the calix[4]arene derivatives. Furthermore, mechanical treatment not only promotes the gelation of the system of 2–isopropanol, but also enhances the strength of the gel. Specifically, 18 min of agitation at room temperature makes the storage modulus and the yield stress of the gel (3.5%, w/v) exceed 1 × 106 Pa and 6 × 103 Pa, respectively, which are second only to the mechanically strongest low molecular mass gelator-based molecular gel reported until now. XRD analysis revealed the hexagonal packing structure of 1 in its n-pentanol gel.
研究领域:
化学
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材料科学
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高影响因子
Soft Matter
·
2012
·Vol. 8
·期 14
·3756-3761
·
IF 4.39
Xiuqin Cai,Kaiqiang Liu,Junlin Yan,Helan Zhang,Xiaoyu Hou,Zhang Liu,Yu Fang
A novel calix[4]arene-based dimeric-cholesteryl derivative was synthesized, and its gelation behaviour in thirty organic solvents was investigated. It has been shown that the compound cannot gel any of the pure solvents tested. However, it gels a mixture of solvents n-decane and acetonitrile efficiently, provided the volume ratio of the two solvents in a mixture is within 9 : 1 and 3 : 2. AFM and SEM measurements revealed that the molecules of the compound aggregate into micro-/nano-rods first, then fine fibers, and then thick fibers, and finally networked structures in the mixture solvents. Interestingly, the gel with a composition of 1 to 1 (Vn-Decane:VAcetonitrile) and 2.5% (w/v) of the compound exhibits super-smart and fully reversible thixotropic properties, a phenomenon never reported before. Furthermore, the mechanical strength of the gel could be easily adjusted by altering the concentration of the gelator and the composition of the mixture solvents. Further interrogation of the gel revealed that structurally the gel is a gel-emulsion with acetonitrile dispersed in n-decane, a rarely found O/O (oil in oil) gel-emulsion which may find uses in the templated preparation of low-density materials with complicated internal structures.
研究领域:
化学
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材料科学
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超分子化学
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高影响因子
Journal of Water Process Engineering
·
2022
·
IF 7.34
Xiying Zhu,Lijia Liu,Yudan Wang,Fuqiu Ma,Yao Tian,Hongxing Dong,Chunhong Zhang
Seawater contains abundant uranium, which could provide a long–term supply for developing the nuclear power industry. Developing an efficient uranium–selective adsorbent is therefore an urgent requirement. In this work, we used a simple Friedel–Crafts alkylation reaction and a subsequent phosphorylation reaction to prepare porous phosphorylated hyper-crosslinked calix[4]arene (C4HP) for potential use in the recovery of uranium from seawater. The effect of the initial pH, adsorbent composition, sorbent dose and contact time on the sorption of uranyl ions was investigated. Because of the introduction of the phosphate groups , C4HP shows an excellent adsorption capacity of 336.4 mg·g −1 for uranium, which is much higher than that of hyper-crosslinked calix[4]arene (C4H) without phosphorylation. Meanwhile, C4HP functioned as a promising adsorbent for uranyl extraction with fast capture kinetics (the adsorption equilibrium can be reached in 150 min). After 6 cycles, C4HP maintained its original adsorption capacity of 76.2 % (255.4 mg·g −1 ). Furthermore, C4HP possesses excellent adsorption selectivity for uranium in artificial seawater, with a K d U of ~4.1 × 10 4 mL·g −1 , much higher than that of other metals. This makes it useful for broad applications and capturing uranium from natural seawater. The effective extraction of uranyl was primarily attributed to the chelation of uranyl ions with phosphate groups .
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RSC Advances
·
2017
·Vol. 7
·期 45
·28476-28482
·
IF 3.108
Xiuqin Cai,Yunhua Xu,Rong Yang,Hui Yang
A novel calix[4]arene-based tetracholesteryl derivative was synthesized, and its gelation behaviours in 30 organic solvents were studied. It showed that 1 gelled long chain alkane, some of alcohol, kerosene, ethyl acetate benzene and toluene. Interestingly the gel of 1/kerosene possessed special property, which was that the mixture solution of the compound 1/kerosene heating for a while was put on the flat contact heater and formed a gel film at 25 °C and 65 °C. Unlike ordinary film, gel film had higher strength and toughness at 65 °C, by contrast other was fragile and broken easily at 25 °C, this phenomenon was few reported before. In order to explore the phenomenon, the mechanism of the gel of 1/kerosene was discussed by Scanning Electron Microscope (SEM), High Nuclear Magnetic Resonance (H NMR), Fourier Transform Infrared Spectrometer (IR) and micro-rheology. SEM revealed that the xerogel of 1/kerosene assembled network through some long and thick fibers at 65 °C, with concentration reducing fibers become thin and its networks were clearly observed. In contrast the morphology of xerogel was porous at low concentration and was a bulk at high temperature system. According to EI data in micro-rheology, the gelation process could be divided into three stages at 65 °C and they could be that some cholesterol segments in the gelator interacting with each other formed some small aggregation in the first stage, and other cholesterol section of the gelator sufficiently were cross-linked with time and assembled into large assembly in the second plateau. In the final moment the large assembly build gel network and the system of gel tended to stable. But there are two stages at low temperature and could be some cholesterol segments that didn't take part in assembly, which may be the cause that the performance of gel was fragile.
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HYDROMETALLURGY
·
2016
·
IF 2.29
Zhang Peng,Dong Linfei,Zhang Dongxiang,Lei Shi,Hongmei Yang,Jinying Li,Wang Yaling,V.V. Tarasov
Calix[4]arene derivatives including diethyl phosphite groups were used for the first time for separating Nd(III) from nitrate media. Calix[4]arene derivatives were synthesized and characterized by infrared spectroscopy (IR), mass spectroscopy (MS), and 1 H NMR. Four calix[4]arene derivatives, CalixF (①), DCalixF (②), PCalixF (⑤), and POCalixF (⑥), were used in a solvent extraction method. The effects of aqueous acidity, diluent, temperature, shaking time, and Nd(III) concentration were investigated. The results showed that the extraction ability of ⑤ and ⑥ with a phosphate functional group at the upper rim were best for the extraction of Nd(III). Derivative ⑥ had better complexing capacities than ⑤ for the generation of a phenolic hydroxyl group at the lower rim. The enthalpy (∆ H O ), Gibbs free energy (∆ G O ), and entropy (∆ S O ) changes for the extraction were obtained from a thermodynamic study. The results showed that the extraction of Nd(III) from a nitric acid system might be an endothermic reaction since the process was naturally spontaneous and increasing the temperature during extraction was determined to be thermodynamically feasible. The extraction of Nd(III) was governed by a two-stage chemical reaction and diffusion process. In the first stage, the process was controlled by a fast chemical reaction at the liquid-liquid interface. The composition of the Nd(III)-calix[4]arene derivative complex was determined to be [Nd(NO 3 ) 3 ] 2 [L]. The second stage was the diffusion of extracted products towards equilibrium. Calix[4]arene derivative ⑥ was found to be an efficient extractant for the separation of Nd(III) and would be a potential extractant for the disposal of radioactive waste in spent fuel .
研究领域:
化学
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核能科学
·
环境科学
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高影响因子
Journal of Materials Chemistry C
·
2023
·Vol. 11
·期 31
·10509-10519
·
IF 6.4
Chengcheng Zhou,Ding Shen,Xingpeng Chai,Boyang Shi,Wenya Zhu,Guowei Wang
The rapid development of the semiconductor industry puts forward higher requirements on the properties of insulating dielectrics. As a supramolecular compound, calix[4]arene has a unique cavity structure, showing potential for a low-k material. We herein reported a novel strategy to functionalize the 4-tert-butylcalix[4]arene with different numbers of benzocyclobutene (BCB) units (2 or 4) and spacers (–(CH2)3– or –(CH2)6–) by sequential substitution and hydrosilylation reactions. These precursors can be cured under heating to form a crosslinked film. The optimized curation condition was screened by differential scanning calorimetry (DSC) measurement. Combining with a comparison experiment using a precursor with calix[4]arene but without BCB units, the wide-angle X-ray scattering (WAXS) pattern and thermal analysis provided solid evidence that the high thermal stability of the film (glass transition temperature (Tg) > 110 °C, 5 wt% loss temperature >367 °C, and the coefficient of the thermal expansion < 87.88 ppm °C−1) was majorly contributed by calix[4]arene, while the excellent dielectric properties (the lowest dielectric constant Dk = 2.23 and the average dielectric loss Df < 1.5 × 10−3) were synergistically affected by both calix[4]arene and BCB units. The static water contact angle was mostly higher than 100° and high hydrophobicity was confirmed, which can meet the additional requirements in practical application. The low dielectric constant synergized by calix[4]arene and the BCB unit is hoped to aid in developing a novel strategy for low-k materials.
研究领域:
材料科学
·
化学工程
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高影响因子
MACROMOLECULAR RAPID COMMUNICATIONS
·
2025
·
IF 4.3
Ying Zhao,Min Wang,Guangming Liao,Yezhen Chen,Yukun Hu,Longyu Tian,Zaijun Lu
With the rapid development of communication technologies, there is an urgent need for materials that simultaneously possess excellent dielectric properties and high thermal stability to ensure efficient signal transmission. In this study, a molecular-level microphase structure modulation strategy is proposed, in which vinyl-functionalized calix[4]arene-modified polysulfone oligomers are used to prepare a series of novel polysulfone-based crosslinked networks (VPSU-VC4As). This method demonstrates remarkable efficiency in enhancing the thermal stability and dielectric properties of the materials. After incorporating 4-tert-Butylcalix[4]arene, the glass transition temperature (T g ) of the thermosets increases from 193°C to 231°C, with T d5 exceeding 350°C and an increased char yield. Meanwhile, the dielectric constant (D k ) and dielectric loss (D f ) of the thermosets are significantly reduced (D k = 2.61 and D f = 4.6 × 10 −3 at 1 GHz). Studies reveal that this improvement is attributed to the nanoporous structure of VC4A and the presence of bulky tert-butyl groups, which increase the free volume of the polymer, reduce its density, and enhance hydrophobicity. The material also exhibits a dielectric breakdown strength of 6.97–7.77 kV/mm and a tensile strength of 27–64 MPa. This work not only confirms the unique advantages of calix[4]arene in developing low-k materials but also further optimizes the dielectric properties of polysulfone through molecular design, providing a new strategy for the development of low-dielectric materials.
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PubMed
高影响因子
Frontiers in Chemistry
·
2022
·
IF 5.545
Fang Shanfang,Dang Yuan-Ye,Li Haizhou,Li Hongxia,Liu Jiayong,Zhong Rongcui,Chen Yongzhi,Liu Shouping,Lin Shuimu
Bacteria have developed increasing resistance to currently used antimicrobial agents. New classes of antimicrobial drugs are urgently required to fight drug-resistant pathogens. Here, we designed and synthesized a series of calix[4]arene derivatives as antibacterial agents by biomimicking the structural properties and biological functions of antibacterial peptides. After introducing cationic hydrophilic moieties and preliminary structural optimization, we obtained a lead compound (16) that exhibited excellent antibacterial activity against Gram-positive bacteria, low toxicity toward mammalian cells and poor hemolytic activity. The antibacterial mechanism studies showed that compound 16 can destroy bacterial cell membrane directly, leading to bacterial death and a low tendency to develop bacterial resistance.
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PubMed
高影响因子
NEW JOURNAL OF CHEMISTRY
·
2014
·Vol. 39
·期 1
·639-649
·
IF 3.159
Ying Wu,Kaiqiang Liu,Xiangli Chen,Yongping Chen,Shaofei Zhang,Junxia Peng,Yu Fang
A calix[4]arene-based dimeric-cholesteryl derivative with naphthalene in the linkers (C2N2C) was designed and synthesized. The gelation behaviors of the compound in 36 liquids were evaluated. It was demonstrated that C2N2C could gel 16 of the liquids tested, which include both polar and apolar liquids. SEM and AFM studies revealed that the morphologies of the gel networks are dependent on the concentrations of C2N2C and the nature of the liquids under study. Importantly, rheological studies revealed that the gel of the compound in benzene possesses sensitive, fast and fully reversible thixotropic property. More importantly, the Tgel of the C2N2C/benzene gel could be at least more than 60 degrees higher than the boiling point of benzene when the gelator concentration is greater than 6% (w/v), a result never reported before. CD measurements revealed the chiral nature of the assemblies of the gel networks. Further investigation by AFM measurements confirmed the right-hand helical structures of the gel networks of C2N2C/benzene gel. As anticipated, hydrogen bonding and π–π stacking are the two main driving forces for the formation of the gels.
研究领域:
化学
·
材料科学
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高影响因子
MATERIALS CHEMISTRY AND PHYSICS
·
2021
·
IF 4.094
Hanxue Li,Haoliang Huang,Xianguang Yan,Chuanxiang Liu,Liang Li
Dyes are indispensable in the textile industry and are very difficult to degrade due to the presence of two or more benzene rings in their structures. However, the purification of water resources is currently an urgent issue. In this study, a trichlorotriazine-derived calix[4]arene and 1,3,5-tris(4-aminophenyl) benzene were crosslinked to generate a calix[4]arene crosslinked polymer that can serve as a highly efficient adsorbent for separating cationic dyes from water. This research provides evidence for the efficiency of the polymer to adsorb various organic micropollutants in water via batch adsorption experiments. In particular, this polymer exhibited a removal efficiency over 99.6% and 99.4% for methylene blue and toluidine blue within 5 min, respectively. The kinetic results showed that the adsorption process of this polymer for organic dyes could be described with quasi-second-order models, and Langmuir isotherm adsorption models demonstrated that the maximum equilibrium adsorption capacity for methylene blue and toluidine blue was reached to 1806.82 and 2161.32 mg g −1 , respectively. These observations suggest that the adsorption is mainly dependent on the electrostatic interactions, π−π interactions, and hydrogen bonding between the polymer and the organic dyes. Furthermore, the adsorption capacities of the adsorbent were maintained at high levels after five cycles. Its excellent adsorption capability and recyclability make this polymer a promising candidate for potential applications in water purification.
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JOURNAL OF SEPARATION SCIENCE
·
2014
·Vol. 37
·期 22
·3268-3275
·
IF 2.594
Zhifen Deng,Junwei Liu,Chenchen Hu,Liu Yang,Huifang Du,Kai Hu,Yanjie Huang,Xiaoqing Yang,Qiong Jiang,Shusheng Zhang
Two new kinds of alanine-substituted calix[4]arene stationary phases of 5,11,17,23- p-tert- butyl-25,27-bis( l -alanine-methylester- N -carbonyl-methoxy)-26,28-dihyroxycalix[4]arene-bonded silica gel stationary phase (BABS4) and 5, 11, 17, 23- p-tert -butyl-25,26,27,28-tetra( l -alanine-methylester- N -carbonyl-methoxy)-calix[4]arene-bonded silica gel stationary phase (TABS4) were prepared and characterized in the present study. They were compared with each other and investigated in terms of their chromatographic performance by using polycyclic aromatic hydrocarbons, disubstituted benzene isomers, and mono-substituted benzenes as solute probes. The results indicated that both BABS4 and TABS4 exhibited multiple interactions with analytes. In addition, the commonly used Tanaka characterization protocol for the evaluation of commercially available stationary phases was applied to evaluate the properties of these two new functionalized calixarene stationary phases. The Tanaka test results were compared with Zorbax Eclipse XDB C 18 and Kromasil phenyl columns, respectively. BABS4 has stronger hydrogen-bonding capacity and ion-exchange capacity than TABS4, and features weaker hydrophobicity and hydrophobic selectivity. Both of them behave similarly in stereoselectivity. Both BABS4 and TABS4 are weaker than C 18 and phenyl stationary phases in hydrophobicity and hydrophobic selectivity.
研究领域:
分析化学
·
色谱学
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高影响因子
JOURNAL OF MEMBRANE SCIENCE
·
2021
·
IF 8.742
Wanting Chen,Xiaozhou Wang,Tiantian Li,Xiaoming Yan,Xuemei Wu,Yang Zhang,Fan Zhang,Shouhai Zhang,Gaohong He
A novel amphiphilic cone-shaped inducer, tetra-quaternized tetraoctyloxycalix[4]arene (TQCX), is proposed to create continuous ionic channels in an anion exchange membrane (AEM). Via molecular dynamics simulation, it was found that four upper-rim cationic groups induce ionic aggregation via electrostatic interactions , while four lower-rim hydrophobic octyl side chains promote the clustering of hydrophobic domains via van der Waals interactions with the polymer backbone. The core cavity in TQCX introduces additional free volume to connect hydrophilic domains. At the optimal TQCX content of 3 wt%, the ionic clusters with a diameter of ∼12 nm are induced, and even linearly arranged to construct continuous ionic channels with a length up to ∼300 nm. Besides, TQCX also aggregates to form the ion-rich nanoparticles with the size of ∼500 nm, which also assist in the construction of interconnected hydroxide-conducting pathways. Consequently, hydroxide conductivity of the composite membrane yields a 70% improvement at 3 wt% TQCX over that of the pristine membrane, achieving the top level among the reported main-chain-type AEMs based on the polysulfone backbone.
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