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1.
Foods ; 13(11)2024 Jun 04.
Artigo em Inglês | MEDLINE | ID: mdl-38890986

RESUMO

Sulfites play imperative roles in food crops and food products, serving as sulfur nutrients for food crops and as food additives in various foods. It is necessary to develop an effective method for the on-site quantification of sulfites in food samples. Here, 7-(diethylamino) quinoline is used as a fluorescent group and electron donor, alongside the pyridinium salt group as an electron acceptor and the C=C bond as the sulfite-specific recognition group. We present a novel fluorescent sensor based on a mechanism that modulates the efficiency of intramolecular charge transfer (ICT), CY, for on-site quantitative measurement of sulfite in food. The fluorescent sensor itself exhibited fluorescence in the near-infrared light (NIR) region, effectively minimizing the interference of background fluorescence in food samples. Upon exposure to sulfite, the sensor CY displayed a ratiometric fluorescence response (I447/I692) with a high sensitivity (LOD = 0.061 µM), enabling accurate quantitative measurements in complex food environments. Moreover, sensor CY also displayed a colorimetric response to sulfite, making sensor CY measure sulfite in both fluorescence and colorimetric dual-signal modes. Sensor CY has been utilized for quantitatively measuring sulfite in red wine and sugar with recoveries between 99.65% and 101.90%, and the RSD was below 4.0%. The sulfite concentrations in live cells and zebrafish were also monitored via fluorescence imaging. Moreover, the sulfite assimilated by lettuce leaves was monitored, and the results demonstrated that excessive sulfite in leaf tissue could lead to leaf tissue damage. In addition, the sulfate-transformed sulfite in lettuce stem tissue was tracked, providing valuable insights for evaluating sulfur nutrients in food crops. More importantly, to accomplish the on-site quantitative measurement of sulfite in food samples, a portable sensing system was prepared. Sensor CY and the portable sensing system were successfully used for the on-site quantitative measurement of sulfite in food.

2.
Biosens Bioelectron ; 260: 116455, 2024 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-38824702

RESUMO

In this work, a potential-controlled electrochromic visual biosensor was developed for detecting zearalenone (ZEN) using a distance readout strategy. The sensor chip includes a square detection area and a folded signal output area created with laser etching technology. The detection area is modified with graphene oxide and ZEN aptamer, while Prussian blue (PB) is electrodeposited onto the signal output channel. When an appropriate voltage is applied, PB in the signal output area is reduced to colorless Prussian white (PW). The target ZEN molecules have the capability to release aptamers from graphene oxide (GO) surface in the detection area, resulting in a subsequent change in the potential of the visual signal output channel. This change determines the length of the channel that changes from blue to colorless, with the color change distance being proportional to the ZEN concentration. Using this distance readout strategy, ZEN detection within the range of 1 ng/mL to 300 ng/mL was achieved, with a detection limit of 0.29 ng/mL.


Assuntos
Aptâmeros de Nucleotídeos , Técnicas Biossensoriais , Grafite , Limite de Detecção , Zearalenona , Zearalenona/análise , Técnicas Biossensoriais/métodos , Técnicas Biossensoriais/instrumentação , Grafite/química , Aptâmeros de Nucleotídeos/química , Técnicas Eletroquímicas/métodos , Desenho de Equipamento , Ferrocianetos/química , Colorimetria/instrumentação , Colorimetria/métodos
3.
Anal Chem ; 2024 Jun 06.
Artigo em Inglês | MEDLINE | ID: mdl-38844882

RESUMO

DNA-templated silver nanoclusters (AgNCs-DNA) can be synthesized via a one-pot method bypassing the tedious process of biomolecular labeling. Appending an aptamer to DNA templates results in dual-functionalized DNA strands that can be utilized for synthesizing aptamer-modified AgNCs, thereby enabling the development of label-free fluorescence aptasensors. However, a major challenge lies in the necessity to redesign the dual-functionalized DNA strand for each specific target, thus increasing the complexity and hindering widespread application of these aptasensors. To overcome this challenge, we designed six DNA strands (DNA1-DNA6) that incorporate the templates for AgNCs synthesis and A4-linker for further aptamer coupling. Among all the synthesized AgNCs-DNA samples, it was found that both AgNCs-DNA1 and AgNCs-DNA2 stood out for their excellent long-term stability. After capturing the T4-linker that connected with aptamer1 specific for aflatoxin B1 (AFB1), however, we found that only AgNCs-DNA1/aptamer1 maintained excellent long-term stability. This finding highlighted the potential of AgNCs-DNA1 as a versatile label-free fluorescence probe for the development of on-demand fluorescence aptasensors. To emphasize its benefits in aptasensing applications, we utilized AgNCs-DNA1/aptamer1 as the fluorescence probe and MoS2 nanosheets as the quencher to develop a FRET aptasensor for AFB1 detection. This aptasensor demonstrated remarkable sensitivity, enabling the detection of AFB1 within a wide concentration range of 0.03-120 ng/mL, with a limit of detection as low as 3.6 pg/mL (S/N = 3). The versatility of the aptasensor has been validated through the recognition of diverse targets, employing aptamer2 specific for ochratoxin A and aptamer3 specific for zearalenone, thereby showcasing its extensive applicability for on-demand detection. The universal applicability of this aptasensor holds great promise for future applications in diverse fields including food safety, environmental monitoring, and clinical diagnosis.

4.
Anal Chem ; 96(22): 9192-9199, 2024 Jun 04.
Artigo em Inglês | MEDLINE | ID: mdl-38758357

RESUMO

Singlet oxygen (1O2) plays imperative roles in a variety of biotic or abiotic stresses in crops. The change of its concentration within a crop is closely related to the crop growth and development. Accordingly, there is an urgent need to develop an efficient analytical method for on-site quantitative detection of 1O2 in crops. Here, we judiciously constructed a novel ratiometric fluorescent probe, SX-2, for the detection of 1O2 in crops. Upon treating with 1O2, probe SX-2 displayed highly selective ratiometric fluorescence response, which is favorable for the quantitative detection of 1O2. Concurrently, the fluorescence solution color of probe SX-2 was varied, obviously from blue to yellow, indicating that the probe is beneficial for on-site detection by the naked eye. Sensing reaction mechanism studies showed that the 2,3-diphenyl imidazole group in SX-2 could function as a new selective recognition group for 1O2. Probe SX-2 was utilized for the detection of photoirradiation-induced 1O2 and endogenous 1O2 in living cells. The changes in the 1O2 level in zebrafish were also tracked by fluorescence imaging. In addition, the production of 1O2 in crop leaves under a light source of different wavelengths was studied. The results demonstrated more 1O2 were produced under a light source of 365 nm. Furthermore, to achieve on-site quantitative detection, a mobile fluorescence analysis device has been made. Probe SX-2 and mobile fluorescence analysis device were capable of on-site quantitative detecting of 1O2 in crops. The method developed herein will be convenient for the on-site quantitative measurement of 1O2 in distinct crops.


Assuntos
Produtos Agrícolas , Corantes Fluorescentes , Oxigênio Singlete , Peixe-Zebra , Corantes Fluorescentes/química , Oxigênio Singlete/metabolismo , Oxigênio Singlete/química , Produtos Agrícolas/química , Produtos Agrícolas/metabolismo , Animais , Imagem Óptica , Humanos
5.
Anal Chim Acta ; 1282: 341921, 2023 Nov 22.
Artigo em Inglês | MEDLINE | ID: mdl-37923414

RESUMO

BACKGROUND: Coexisting multiple mycotoxins in food poses severe health risks on humans due to the augmented toxicity. Current multiplex detection methods for mycotoxins have evolved from instrumental analyses to rapid methods based on the specific recognition of antibody/aptamer using different signal transducers. However, nearly all of the reported aptasensors for multiple mycotoxins detection require external labels and can only simultaneous detection of two mycotoxins due to the limitation of distinguishable labels. The tedious labeling process definitely increases the operation complexity and the detection cost. Therefore, rapid method for simultaneous label-free detection of multiple mycotoxins in cereals is urgently needed. RESULTS: A disposable aptasensing chip was designed for simultaneous label-free detection of fumonisin B1 (FB1), aflatoxin B1 (AFB1), zearalenone (ZEN), and ochratoxin A (OTA) in one sample. Specifically, ITO conductive glass was divided into a rectangle (35 × 25 mm) and then etched by laser to set aside the required four ITO working electrodes (6 mm in diameter) with respective conductive channels. Gold nanoparticles were electrodeposited on the working electrodes to provide abundant anchoring sites for thiolated aptamers immobilization. On this basis, a disposable aptasensing chip for simultaneous label-free detection of four common coexisting mycotoxins has been developed, which used electrochemical impedance spectroscopy as transducer to measure direct biorecognition of the aptamer and corresponding target. This aptasensing chip provided wide linear ranges of 5-1000, 10-250, 10-1250, 10-1500 ng/mL for FB1, AFB1, ZEN, OTA, respectively, with the respective detection limit of 2.47, 3.19, 5.38, 4.87 ng/mL (S/N = 3). SIGNIFICANCE AND NOVELTY: This aptasensing chip shows fantastic characteristics of great simplicity and portability, easy operation, and multiple mycotoxins recognition. They are easy to produce on a large scale at low cost and the design concept can be easily expanded to screen a large panel of coexisting targets. This work provides a new avenue for multi-target detection and represents a substantial advance toward food quality and safety monitoring or other fields.


Assuntos
Aptâmeros de Nucleotídeos , Nanopartículas Metálicas , Micotoxinas , Zearalenona , Humanos , Micotoxinas/análise , Ouro/química , Limite de Detecção , Nanopartículas Metálicas/química , Zearalenona/análise , Aflatoxina B1/análise , Aptâmeros de Nucleotídeos/química , Contaminação de Alimentos/análise
6.
Biosens Bioelectron ; 240: 115651, 2023 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-37666010

RESUMO

The global spread of environmental biological pollutants, such as antibiotic-resistant bacteria and their antibiotic resistance genes (ARGs), has emerged as a critical public health concern. It is imperative to address this pressing issue due to its potential implications for public health. Herein, a DNA paperclip probe with double-quenching function of target cyclic cleavage was proposed, and an electrochemiluminescence (ECL) biosensing platform was constructed using Ti3C2 MXene in-situ reduction growth of Au NPs (TCM-Au) as a coreactant accelerator, and applied to the sensitive detection of ARGs. Thanks to the excellent catalytic performance, large surface area and Au-S affinity of TCM-Au, the ECL performance of CdS QDs have been significantly improved. By cleverly utilizing the negative charge of the paperclip nucleic acid probe and its modification group, double-quenching of the ECL signal was achieved. This innovative approach, combined with target cyclic amplification, facilitated specific and sensitive detection of the mecA gene. This biosensing platform manifested highly selective and sensitive determination of mecA genes in the range of 10 fM to 100 nM and a low detection limit of 2.7 fM. The credible detectability and anti-interference were demonstrated in Yangtze river and Aeration tank outlet, indicating its promising application toward pollution monitoring of ARGs.


Assuntos
Técnicas Biossensoriais , Poluentes Ambientais , Titânio , Antibacterianos , Resistência Microbiana a Medicamentos
7.
Anal Chim Acta ; 1245: 340845, 2023 Mar 08.
Artigo em Inglês | MEDLINE | ID: mdl-36737133

RESUMO

Long term exposure to hydrogen sulfide (H2S) even in low concentration poses a serious threat to human health and the ecosystem, pointing to the significance for its effective supervision. In this study, we report a sensitive and selective "signal-on" photoelectrochemical (PEC) sensor for the determination of toxic H2S in aqueous solution by in situ growth of AgI semiconductors on tailored three-dimensional (3D) porous Ti3C2 MXene/graphene oxide aerogel (MGA). Our research demonstrated that the resultant MGA with the starting feeding mass ratio of MXene and graphene oxide (GO) of 1:8 (MGA1:8) possessed the most excellent PEC performance after the growth of AgI semiconductors than their monomers (Ti3C2 MXene and GO) and the MGAs with other starting feeding mass ratio. Such designed PEC sensor based on MGA1:8/AgI heterojunction showed dramatically strengthened PEC responses with increasing concentrations of S2-. Correspondingly, a wide linear range of 5 nM-200 µM, a low limit of detection of 1.54 nM (S/N = 3), and exclusively unique selectivity have been achieved. Our research illustrates that the PEC sensor designed with tailored MGA constitutes is an effective pathway to enhance the overall sensing performance, which will envision to boost more efforts for advanced 3D porous aerogel using in PEC sensors.

8.
Food Chem ; 403: 134397, 2023 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-36358096

RESUMO

Sensitive detection for deoxynivalenol (DON) should be developed due to DON as a kind of harmful mycotoxins which can poses health risk to human health even at low concentrations. In this work, an electrochemiluminescence (ECL) DON aptasensor was proposed based on Ti3C2 dots/Ti3C2 nanosheet (TDTN). Compared with Ti3C2 dots and Ti3C2 nanosheet, the ECL intensity of TDTN was 4 times of Ti3C2 dots and 2 times of Ti3C2 nanosheet as emitters. This was attributed to homojunction effect which could provide continuity of band bonding and effectively accelerate charge transfer at the interface. Based on ECL signal changes generated by aptamer and DON fixed on the electrode surface, the ECL aptasensor showed "on-off-on" performances and detected DON specifically in milk, with detection range of 0.001-20 ng/mL and detection limit of 0.3 pg/mL (S/N = 3). Therefore, the constructed ECL aptasensor is a promising detection method for food safety analysis.


Assuntos
Aptâmeros de Nucleotídeos , Técnicas Biossensoriais , Nanopartículas Metálicas , Humanos , Aptâmeros de Nucleotídeos/genética , Técnicas Eletroquímicas/métodos , Técnicas Biossensoriais/métodos , Medições Luminescentes/métodos , Análise de Alimentos
9.
Anal Chem ; 94(6): 2803-2811, 2022 02 15.
Artigo em Inglês | MEDLINE | ID: mdl-35104110

RESUMO

Fluorescence imaging the interplay between lipid droplets (LDs) and protein aggregates (PAs) is extremely valuable for elucidating molecular mechanisms of aging. Here, we describe the first dual-functional fluorescent probe, LW-1, for simultaneously imaging LDs and PAs in distinct fluorescence channels to dissect interplaying roles between LDs and PAs during aging. Notably, based on an intriguing mechanism of hydrogen bonds regulating single bond rotation, LW-1 selectively detected LDs in a red channel. Meanwhile, based on another mechanism of the hydrogen bond regulating intramolecular charge transfer efficiency, probe LW-1 further detected PAs in an NIR channel. Practical applications showed that LW-1 was capable of concurrently detecting LDs and PAs in living cells. Moreover, simultaneously imaging LDs and PAs in intestine tissues of mice at different aging degrees was conducted. The results denoted that the PAs level in the intestine tissue increased dramatically with aging, accompanying the buildup of LDs. Significantly, the interplay between LDs and PAs during aging was observed. These evidences demonstrated that the PAs level was closely related with aging processes in intestine tissues, while LDs were formed correspondingly to interact with PAs, suggesting that excessive PAs can be loaded into LDs and then be removed by lipophagy.


Assuntos
Corantes Fluorescentes , Gotículas Lipídicas , Envelhecimento , Animais , Corantes Fluorescentes/química , Gotículas Lipídicas/química , Camundongos , Imagem Óptica/métodos , Agregados Proteicos
10.
Analyst ; 146(18): 5747-5755, 2021 Sep 13.
Artigo em Inglês | MEDLINE | ID: mdl-34515708

RESUMO

A super simple ratiometric fluorescence nanosensor has been fabricated by controlling the ligands of CdZnTe quantum dots (QDs), allowing the sensitive and visual detection of silver ions (Ag+). The green-emitting L-cysteine-protected CdZnTe QDs (Lcys-CdZnTe QDs) had a specific response to Ag+ and were used as the reporting probe, while the red-emitting N-acetyl-L-cysteine-protected CdZnTe QDs (NAC-CdZnTe QDs) showed no obvious response to all tested metal ions and were selected as the reference probe. Simply mixing them without any encapsulated synthesis ultimately produced a time-saving, low-cost detection method, allowing the sensitive and visual detection of Ag+ in samples. The proposed nanosensor exhibited a linear range of 0.5-4.0 µM along with a detection limit of 0.17 µM, and has been successfully applied in real tap water and lake water samples. This nanosensor also showed obvious color changes in the detection process and has potential in visual semi-quantitative detection. Our approach may provide a general and feasible strategy for designing ratiometric fluorescence nanosensors, which will attract a wide range of interest in sensing-related fields.


Assuntos
Pontos Quânticos , Cádmio , Corantes Fluorescentes , Íons , Ligantes , Prata , Espectrometria de Fluorescência , Telúrio , Zinco
11.
Food Chem ; 331: 127359, 2020 Nov 30.
Artigo em Inglês | MEDLINE | ID: mdl-32580128

RESUMO

Cyanide is a highly toxic anion. Nonetheless, many food plants could produce endogenous cyanide, which causes great danger to human health. Thus, monitoring cyanide in food samples is critically significant. Herein, we rationally developed the first ratiometric near-infrared fluorescent probe for sensing cyanide in food samples. The probe displayed noticeable fluorescence in near-infrared region. Moreover, upon treatment with cyanide, the probe exhibited highly selective and sensitive ratiometric fluorescence response, with limit of detection determined to be 0.075 µM and limit of quantification determined to be 0.25 µM. The ratios of fluorescent intensities at 519 and 688 nm (I519/I688) was linear with added cyanide concentrations from 0 to 80 µM. The relative standard deviations for repeatability and reproducibility varied from 0.55 to 8.94 and from 1.17 to 9.46, respectively. Significantly, probe Hy has been successfully applied for monitoring cyanide in various food samples, such as almonds, sprouting potatoes, and bamboo shoots.


Assuntos
Cianetos/análise , Corantes Fluorescentes/química , Análise de Alimentos/métodos , Contaminação de Alimentos/análise , Limite de Detecção , Prunus dulcis/química , Reprodutibilidade dos Testes , Sasa/química , Sensibilidade e Especificidade , Solanum tuberosum/química , Espectroscopia de Luz Próxima ao Infravermelho/métodos
12.
Anal Biochem ; 602: 113795, 2020 08 01.
Artigo em Inglês | MEDLINE | ID: mdl-32473120

RESUMO

Development of an efficient fluorescent probe for sensing hypochlorite in water samples and biological samples is highly demanded. However, the currently reported fluorescent probes for hypochlorite frequently suffered from the problem of high background fluorescence. Herein, based on the combined effect of two different fluorescence quenching groups, we rationally developed a novel fluorescent probe for hypochlorite with extremely low background fluorescence. Notably, due to the doubly quenching groups, the probe could even keep low background fluorescence in a solution with high viscosity. Furthermore, the probe displayed highly sensitive and selective response to hypochlorite, with the detection limits calculated to be 10.5 nM. Practical application demonstrated that the probe was able to quantitatively detect hypochlorite in various water samples with good recovery. Significantly, the probe showed extremely low background fluorescence in living cells and was capable of detecting minor variation of endogenous hypochlorite in RAW 264.7 cells. Moreover, the fluorescence imaging different concentration of hypochlorite in zebrafish has been successfully conducted. The probe developed herein will be widely used as a reliable tool to accurately monitor the variation of hypochlorite in living organism.


Assuntos
Fluorescência , Corantes Fluorescentes/química , Ácido Hipocloroso/análise , Peixe-Zebra/metabolismo , Animais , Corantes Fluorescentes/síntese química , Camundongos , Estrutura Molecular , Imagem Óptica , Células RAW 264.7 , Viscosidade
13.
Anal Chem ; 92(8): 6072-6080, 2020 04 21.
Artigo em Inglês | MEDLINE | ID: mdl-32216261

RESUMO

Hypochlorite (ClO-) and singlet oxygen (1O2) commonly coexist in living systems and exert important interplaying roles in many diseases. To dissect their complex inter-relationship, it is urgently required to construct a fluorescent probe that can discriminate ClO- and 1O2 in living organisms. Herein, by taking the 3-(aliphaticthio)-propan-1-one group as the unique recognition unit for both ClO- and 1O2, we proposed the first fluorescent probe, Hy-2, to simultaneously discriminate ClO- and 1O2 with high sensitivity and selectivity. Probe Hy-2 itself showed fluorescence in blue channel. After treatment with ClO- and 1O2, respectively, pronounced fluorescence enhancements were observed in the green channel and red channel correspondingly. Moreover, upon development of the probe with aggregation-induced emission (AIE) characteristics, the probe could work well in a solution with high water volume fraction. Probe Hy-2 was also able to accumulate into mitochondria and was utilized as an effective tool to image exogenous and endogenous ClO- and 1O2 in mitochondria. Significantly, as the first trial, probe Hy-2 was employed to simultaneously monitor the variation of ClO- and 1O2 level in cecal tissues of rat in the cecal ligation and puncture (CLP)-induced polymicrobial sepsis model. The results demonstrated that the expressed ClO- and 1O2 levels were tightly correlated with the severity of sepsis, inferring that the overproduction of ClO- and 1O2 is an important factor in the pathogenesis of sepsis. The probe illustrated herein may provide a guide for further exploring the functions of ClO- and 1O2 in various diseases.


Assuntos
Corantes Fluorescentes/química , Ácido Hipocloroso/análise , Imagem Óptica , Oxigênio/análise , Sepse/diagnóstico por imagem , Animais , Modelos Animais de Doenças , Corantes Fluorescentes/síntese química , Ratos , Ratos Sprague-Dawley
14.
ACS Omega ; 4(6): 10784-10790, 2019 Jun 30.
Artigo em Inglês | MEDLINE | ID: mdl-31460176

RESUMO

Monitoring cyanide levels in water and food samples is crucial. Herein, we rationally developed a simple and efficient fluorescent probe for cyanide determination. The probe displayed selective ratiometric fluorescent response to cyanide. In addition, after treatment with cyanide, the fluorescence ratios (I 509/I 466) exhibited a good linearity with cyanide concentration in the range of 0-60 µM, and the detection limit was determined to be 0.23 µM (S/N = 3). Significantly, the practical application demonstrated that the probe was able to quantitatively detect cyanide concentration in natural water samples. Monitoring of endogenous cyanide in cherry nut by the probe was also successfully conducted. Notably, upon fabrication of test strips, the probe could be conveniently utilized for field measurement of cyanide in bitter almond without relying on sophistical instruments. Furthermore, the cyanide in potato tissues was determined for the first time by means of fluorescence imaging.

15.
Adv Mater ; 31(40): e1902365, 2019 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-31389102

RESUMO

The dynamic behavior of a macroscopic adhered hydrogel stabilized through controllable dynamic covalent interactions is reported. These interactions, involving the cross-linked formation of a hydrogel through reaction of a diacylhydrazine precursor with a tetraformyl partner, increase as a function of time. By using a contact time of 24 h and different compounds with recognized aggregation-induced emission features (AIEgens), it proves possible to create six laminated acylhydrazone hydrogels displaying different fluorescent colors. Blocks of these hydrogels are then adhered into a structure resembling a Rubik's Cube, a trademark of Rubik's Brand Limited, (RC) and allowed to anneal for 1 h. This produces a 3 × 3 × 3 block (RC) wherein the individual fluorescent gel blocks are loosely adhered to one another. As a consequence, the 1 × 3 × 3 layers making up the RC can be rotated either horizontally or vertically to produce new patterns. Ex situ modification of the RC or application of a chemical stimulus can be used to produce new color arrangements. The present RC structure highlights how the temporal features, strong versus weak adhesion, may be exploited to create smart macroscopic structures.

16.
Chem Commun (Camb) ; 55(58): 8462-8465, 2019 Jul 25.
Artigo em Inglês | MEDLINE | ID: mdl-31264675

RESUMO

A novel fluorescent probe XQ-1 for selectively detecting 1O2 on the basis of a two-step cascade reaction has been rationally constructed. The probe responded to 1O2 not only showing a high sensitivity, but also displaying a large concentration range, which means that the probe can be used as a powerful tool to monitor the efficacy of PDT toward cancer and concurrently track the adverse effects on healthy cells.

17.
Acc Chem Res ; 52(7): 1915-1927, 2019 07 16.
Artigo em Inglês | MEDLINE | ID: mdl-31184471

RESUMO

Soft materials have received considerable attention from supramolecular chemists and material scientists alike. This interest reflects the advantages provided by their soft, flexible nature and the convenience of the molecular self-assembly that underlies their preparation. Common soft supramolecular materials include polymeric gels, supramolecular polymers, nanoaggregates, and membranes. Polymeric gels are solidlike networks of cross-linked polymer chains. Supramolecular polymers contain repeat units connected through reversible non-covalent bonds. Nanoaggregates are formed as a result of hydrophobic interactions involving amphiphilic building blocks. Because of the presence of non-covalent interactions, supramolecular soft materials typically display stimuli-responsive or adaptive features. Various macrocyclic hosts, such as cyclodextrins, crown ethers, calixarenes, cucurbiturils, and pillararenes, and many classic non-covalent interactions have been harnessed to construct supramolecular soft materials. Only recently has anion binding been used as the underlying recognition motif. Anions are ubiquitous in the natural world. Their importance has inspired efforts to achieve good anion binding and to exploit anion recognition in a number of fields, including extraction, transport, sensing, and catalysis. Most of this effort has involved the use of stand-alone anion receptors. On the other hand, soft materials with anion recognition features could lead to new macromolecular systems of interest in the context of many application areas. In this Account, we summarize the latest efforts from our laboratory to prepare supramolecular soft materials, including polymeric gels, supramolecular polymers, and nanoaggregates, with bona fide anion recognition features. Two anion receptor systems, namely, calix[4]pyrroles (C4Ps) and a tetraimidazolium macrocycle known as the "Texas-sized" molecular box (TxSB), have been used for this purpose. To date, TxSB-based hydrogels have been utilized to capture anions from water and for coded information applications; C4P-based organic polymeric gels have been used to extract dianions from aqueous source phases and for the on-site detection of chloride anions. Polymers containing C4P and TxSB anion recognition subunits typically display responsive features and can be modified through application of appropriately chosen external stimuli. For instance, nanoaggregates may be formed as a result of the hydrophobic interactions of C4P- and TxSB-based amphiphiles. The resulting aggregates were found to mimic the structural evolution of organelles and could be used as effective anion and ion pair extractants. This Account summarizes progress to date while underscoring potential opportunities associated with combining anion recognition and soft materials chemistry. The hope is to stimulate further advances in broad areas, including polymer science, supramolecular chemistry, biology, materials research, and information storage.

18.
J Am Chem Soc ; 141(16): 6468-6472, 2019 04 24.
Artigo em Inglês | MEDLINE | ID: mdl-30957995

RESUMO

We report an expanded "Texas-sized" molecular box (AzoTxSB) that incorporates photoresponsive azobenzene bridging subunits and anion recognition motifs. The shape of this box can be switched through light induced E ↔ Z photoisomerization of the constituent azobenzenes. This allows various anionic substrates to be bound and released by using different forms of the box. Control can also be achieved using other environmental stimuli, such as pH and anion competition.


Assuntos
Compostos Azo/química , Ânions/química , Compostos Azo/síntese química , Concentração de Íons de Hidrogênio , Estrutura Molecular , Termodinâmica
19.
Chem Soc Rev ; 48(10): 2682-2697, 2019 May 20.
Artigo em Inglês | MEDLINE | ID: mdl-31012443

RESUMO

Nature uses the power of non-covalent interactions as the basis for many kinds of adhesion phenomena. Inspired by nature, scientists have prepared various synthetic adhesive materials that rely on a number of non-covalent interactions at the interfaces. Commonly used non-covalent interactions include hydrogen bonding, π-π stacking, charge transfer interactions, electrostatic interactions, hydrophobic interactions, macrocycle-based host-guest interactions, among others. Within this context, macrocycle-based host-guest interactions are of particular interest. Often they give rise to distinct properties, such as multiple combined noncovalent interactions and a diversity of stimuli-based responsiveness. In this tutorial review, we will summarise recent advances in adhesive supramolecular polymeric materials that rely primarily on macrocycle-based host-guest interactions. An overview of future challenges and a perspective of this sub-field are also provided.

20.
Chem Sci ; 9(40): 7746-7752, 2018 Oct 28.
Artigo em Inglês | MEDLINE | ID: mdl-30429983

RESUMO

Reported here is a two-layer gel construct that permits the on-site detection of the chloride anion by means of a hand-held UV-vis lamp and a smart phone "app". To prepare this system, eight fluorescent polymeric gels G1-G8 were synthesized. Gels G1-G4 containing C4P/imidazolium-F- anion recognition motifs were used to construct a fluorescent pattern (Code A) that may be read out by a smart phone as a 3D color code (Info A). Gels G5-G8, which are based on C4P/imidazolium-Br- anion interactions, were used to construct an array (Code B) that may be read as Info B. Code B was then adhered to the surface of Code A to produce an adhered double layer code system stabilized by interfacial C4P/imidazolium-Br- anion interactions. Readout of the top layer (Code B) could be achieved without interference from Code A. Treatment with a Cl- anion source was found to delaminate the top layer and leave intact the more robust bottom layer, allowing the bottom layer (Code A) to be read out. The disparate information content associated with Codes A and B thus permits the on-site recognition of Cl-. The present sensing strategy does not rely on elaborate instrumentation and could provide a new application for elaborated soft materials.

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