Metal–organic frameworks (MOFs) have evolved as an exciting class of materials in the domain of porous materials. The unique features of these materials arise from the combined properties of metal ions/clusters and organic struts which form the building blocks of these fascinating architectures. Among other multifarious applications, MOFs have shown tremendous applications as sensory materials for a wide variety of species. The signal transduction induced mechanism in these confined nanospaces generate optical output in response to a particular analyte which can be detected by wide variety of detection techniques. Fluorometric methods of sensing is one of widely studied method over past few decades. MOF‐based fluorometric detection is a key research theme developed over the past few years. In this review, we give a brief overview of the recent developments of MOFs as “turn‐on” sensors for a wide range of analytes (viz. cations, anions, volatile organic compounds (VOCs), etc.). 相似文献
A rigid, covalently linked perylene‐3,4:9,10‐tetracarboxylic acid bisimide (PBI) cyclophane was synthesized by imidization of a bay‐substituted perylene bisanhydride with p‐xylylenediamine. The interchromophoric distance of approximately 6.5 Å establishes an ideal rigid cavity for the encapsulation of large aromatic compounds such as perylene and anthracene with binding constants up to 4.6×104 M ?1 (in CHCl3). For electron‐poor guest molecules, the complexation process is accompanied by a significantly increased fluorescence, whereas the emission intensity is dramatically quenched by more electron‐rich guests because of the formation of charge‐transfer complexes. Furthermore, the influence of the PBI core twist on the binding constant results in a remarkable selectivity towards more flexible aromatic guest molecules. 相似文献
An easily available naphthalimide‐based fluorescent probe NPA for Pb2+ detection was successfully developed. NPA exhibited an obvious fluorescence turn‐on response toward Pb2+ in aqueous solution and in living cells. Moreover, a series of model compounds were rationally designed and synthesized in order to explore the sensing mechanism and binding mode of NPA with Pb2+. 相似文献
The doping of π‐conjugated organic compounds with trivalent boron atoms produces materials with intriguing properties and functions that result from the interaction of the π‐electron system with the vacant p orbital on boron. This offers unique opportunities in various applications such as organic (opto)electronics, biomedical imaging, and sensors for physiologically relevant anions or amines, as demonstrated by numerous examples on the molecular scale. Recently, the B‐doping strategy has been expanded to polymer chemistry with a view to benefit from the best of both worlds. Herein, recent advances in the synthesis of π‐conjugated polymers doped with tricoordinate boron in the backbone are reviewed. Selected applications are described where these functional materials have already been successfully implemented. 相似文献
The ability of multiple CF3‐substituted arenes to act as acceptors for anions is investigated. The results of quantum‐chemical calculations show that a high degree of trifluoromethyl substitution at the aromatic ring results in a positive quadrupole moment. However, depending on the polarizability of the anion and on the substitution at the arene, three different modes of interaction, namely Meisenheimer complex, side‐on hydrogen bonding, or anion–π interaction, can occur. Experimentally, the side‐on as well as a η2‐type π‐complex are observed in the crystal, whereas in solution only side‐on binding is found. 相似文献
Tetraphenylethylene (TPE)‐based glycoconjugates were easily synthesized by copper(I)‐catalyzed “click reactions” between propargyl‐attached TPE and azido‐functionalized sugars. The TPE compound bearing lactosyl moieties ( Lac‐TPE ) was found to be a fluorescence “turn‐on” sensor for cholera toxin by virtue of aggregation‐induced emission characteristics of the TPE motif owing to the specific interaction of lactose with the cholera toxin B subunit, whilst a cellobiose‐functionalized TPE derivative did not show any response to the toxin. Therefore, Lac‐TPE shows promising applications in the detection of cholera toxin, as well as in the investigation of carbohydrate–protein interaction. 相似文献
Summary: A new class of poly(arylene ethynylene)s (PAEs) containing an electron‐deficient N‐alkylphthalimide unit was prepared by means of a Sonogashira reaction. Complete solubility of the PAEs was observed by utilizing a 2,6‐diisopropylphenyl side chain. The chemical structure of the novel soluble polymer 3c was confirmed by NMR spectra, whereas the insoluble polymers were characterized by elemental analysis and IR spectra. Fluorescence measurements of 3c indicate a rigid structure and high symmetry in the excited state.
The development of inexpensive and highly efficient enzyme‐responsive polymers has significantly contributed to targeted drug delivery systems. Here, a superamphiphile with a capability of fluorescent dissociation sensing is designed. It is constructed with negatively charged adenosine 5′‐triphosphate (ATP) and negatively charged fluorescein diphosphate (FDP), which are used as fluorescence detection, and a cationic diblock copolymer methoxy‐poly(ethylene glycol)113‐b‐poly(2‐dimethyl‐aminoethyl methacrylate)70. Upon addition of calf intestinal alkaline phosphatase, the superamphiphile disintegrates, presumably due to the enzymatic hydrolysis of ATP. This process is accompanied by an increase in the fluorescence emission intensity of fluorescein owing to the hydrolysis of FDP. The in vitro application of the superamphiphile is also proven. Thus, the “turn‐on” fluorescence of the superamphiphile serves as a real‐time module for detection of the disintegration of superamphiphile. 相似文献
A new methodology for creating patterned fluorescence images was developed based on acrylate polymers that have pendant triphenylmethane derivatives as precursor fluorophores. Photoinduced oxidation of the substituted nonfluorescent triphenylmethane substituents on the polymers results in the generation of fluorescent cationic species. Patterned fluorescence images were obtained when the polymer film was subjected to photomasked UV‐irradiation. The rate of formation and quality of the patterned images were found to be dependent on the nature of substituents on the methane carbon of the triphenylmethane group. Inefficient image formation takes place with the polymer derived from the H‐substituted derivative owing to the inefficient oxidation of the triphenylmethane group. In contrast, photomasked UV‐irradiation of a thin polymer film derived from the CN‐substituted triphenylmethane derivative leads to fast (1 s irradiation, 12 mW · cm−2) and finely resolved patterned fluorescence images.
Amphiphilic hybrid π‐conjugated polymers that have polyhedral oligomeric silsesquioxanes on their side chains have been successfully synthesized by the Sonogashira–Hagihara polycondensation reaction. The obtained polymers were studied with ultraviolet‐visible absorption and photoluminescence spectra. In these polymers, the π‐conjugation length was extended along the poly(p‐phenylene‐ethynylene) backbone. Furthermore, the content of the POSS substituents can influence the aggregation behavior of the polymers and subsequent luminescent properties.
A series of π‐conjugated polymers linked by benzocarborane (1,2‐(buta‐1′,3′‐diene‐1′,4′‐diyl)‐1,2‐dicarbadodecaborane) were synthesized via Sonogashira–Hagihara polycondensation reaction. The opened molecular structure of diiodo monomer containing benzocarborane resulted in fast polymerization and high molecular weights. The obtained polymers were fully characterized by 1H, 13C, and 11B NMR spectroscopies. UV‐vis absorption and photoluminescence studies revealed the acceptor‐profile of benzocarborane. Unlike the polymers linked by o‐carborane, these polymers exhibited strong luminescence in the solution state, presumably because the inductive effect of carborane is dominant, rather than cage‐π interactions.
A new chemodosimeter based on pyridinium‐fused pyridinone iodide ( PI ) has been obtained through a “clean reaction” method. This compound can detect CN? in aqueous solution with a high selectivity and rapid response. The detection of CN? occurs through the nucleophilic attack of CN? on the C?N bond, which induces the destruction of the π‐conjugation on the pyridinium ring. Support of this detection mechanism was obtained by 1H NMR titration, HR‐MS, and DFT calculations. Upon the addition of 10 equivalents CN? to a solution of PI in THF/H2O (1:1, v/v), a 57‐fold enhancement in fluorescence intensity was observed at the maximum emission wavelength of 457 nm. Meanwhile, the maximum absorption wavelength was also blue‐shifted from 447 nm to 355 nm. Other common anions such as BF4?, PF6?, F?, Cl?, Br?, I?, H2PO4?, ClO4?, CH3COO?, NO2?, N3?, and SCN? had little effect on the detection of CN?. The response time of PI for CN? was less than 5 seconds. The detection limit was calculated to be 5.4×10?8 M , which is lower than the maximum permission concentration in drinking water (1.9 μM ) set by the World Health Organization (WHO). 相似文献
A simple, highly selective and sensitive colorimetric system for the detection of fluoride ion in an aqueous medium has been developed using 2‐(2‐hydroxyphenyl)‐2,3‐dihydroquinolin‐4(1 H)‐one. This system allows selective “turn‐on” fluorescence detection of fluoride ion, which is found to be dependent upon guest basicity. An excited‐state proton transfer is proposed to be the signaling mechanism, which is rationalized by DFT and TD‐DFT calculations. The present sensor can also be applied to detect fluoride levels in real water samples. 相似文献
tBu3 PPd(Ph)Br ( 1 )‐catalyzed Suzuki‐Miyaura coupling polymerization of 2‐(4‐hexyl‐5‐iodo‐2‐thienyl)‐4,4,5,5‐tetramethyl‐1,3,2‐dioxaborolane ( 2 ) was investigated. Monomer 2 was polymerized with 1 at 0 °C in the presence of CsF and 18‐crown‐6 in THF containing a small amount of water to yield P3HT with a narrow molecular weight distribution and almost perfect head‐to‐tail regioregularity. The values increased up to 11 400 g · mol−1 in proportion to the feed ratio of 2 to 1 . The MALDI‐TOF mass spectra showed that P3HT with moderate molecular weight uniformly had a phenyl group at one end and a hydrogen atom at the other, indicating involvement of a catalyst‐transfer mechanism. Successive 1 ‐catalyzed polymerization of fluorene monomer 3 and then 2 yielded a well‐defined block copolymer of polyfluorene and P3HT.
Anionic conjugated polymer (PFP‐SO) was assembled with a novel enzymatic substrate 6‐O‐modified PNP‐β‐galactoside ( 1 ) for sensitive multiplex enzyme detections. The PFP‐SO/ 1 /lipase/β‐galactosidase system has two chemical input signals which are Input 1 (lipase) and Input 2 (β‐galactosidase), and output optical signals such as fluorescence emission at 416 nm or 450 nm. Four types of logic gates, including YES, INH, NAND and AND, were successfully constructed and utilized for multiplex detections of lipase and β‐galactosidase in one tube.
We have demonstrated that giant polymer micelles with a uniform diameter (ca. 200 nm) can be fabricated by “supramolecular wrapping” of poly(styrene) (PS) with the β‐1,3‐glucan polysaccharide, with the β‐1,3‐glucan fastening the PS chains together in a noncovalent fashion to facilitate the formation of a supramolecular polymer network on the O/W emulsion surface. Various spectroscopic and microscopic investigations have revealed that the inner cores of the micelles are comprised of a hydrophobic PS network, whereas the surfaces consist of a hydrophilic β‐1,3‐glucan layer. Accordingly, functional guest molecules can easily be encapsulated inside the cavity through hydrophobic interactions. The encapsulated molecules can simply be released from the micelle cores by peeling off the β‐1,3‐glucan shell in a supramolecular manner. As functional groups can be introduced into the glucose side‐chain unit in a straightforward manner by chemical modification, the micellar surface can acquire further functions useful for molecular recognition. These results show that the micelles obtained could have applications as novel soft nanoparticles, which would be indispensable not only for nanotechnologies, but also for biotechnologies aimed at gene or drug delivery systems. 相似文献