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1.
Org Biomol Chem ; 22(13): 2596-2607, 2024 Mar 27.
Artigo em Inglês | MEDLINE | ID: mdl-38450570

RESUMO

Considerable research attention has been devoted to the development of portable and rapid fluorescence sensors that can selectively detect volatile acids, due to the harmful effects of acid vapour on the environment and human health. Although various types of fluorophores have been reported for sensing volatile acid vapours, regulation of the sensory response using aggregation induced emissive (AIE) based gelators has rarely been reported. In this study, we present the design and synthesis of a novel organogelator that is capable of sensing volatile acids through AIE. An acridine-attached poly(aryl ether) dendron molecular system is synthesized through an aldimine coupling reaction, which self-assembles and forms a gel, exhibiting AIE behavior. The synthesized molecule and prepared gel were characterized using NMR, MASS, XRD, HRSEM and rheology techniques. The AIE property of APD was investigated using steady-state absorption and emission spectroscopic techniques. The sensory response of the APD gelator was tested with various analytes, and the results indicated that APD shows rapid response, particularly to acid vapours, where the detection limits (DL) of trifluoroacetic acid (TFA), hydrochloric acid (HCl) and nitric acid (HNO3) vapor were as low as 0.22, 0.9 and 0.30 ppm, respectively. An APD solid film in filter paper shows a visual color change from yellow to red in an aqueous acidic medium, and the effect is reversed in an alkaline medium. These findings suggest that an APD gelator could potentially be utilized to generate a portable acid vapor sensor kit due to its low detection limit and rapid response time, and it could be also be used as a substitute for existing acid indicators.

2.
Langmuir ; 39(13): 4739-4755, 2023 Apr 04.
Artigo em Inglês | MEDLINE | ID: mdl-36940390

RESUMO

A pyrene-based highly emissive low-molecular-weight organogelator, [2-(4-fluorophenyl)-3-(pyren-1-yl)acrylonitrile] (F1), is presented, which divulges thixotropic and thermochromic fluorescence switching via reversible gel-to-sol transition and tremendous superhydrophobicity (mean contact angles: 149-160°), devoid of any gelling and/or hydrophobic units. The rationale for the design strategy reveals that the restricted intramolecular rotation (RIR) in J-type self-assembly promotes F1 for the prolific effects of aggregation- and gelation-induced enhanced emission (AIEE and GIEE). Meanwhile, hindrance in charge transfer via the nucleophilic reaction of cyanide (CN-) on the C═C unit in F1 facilitates the selective fluorescence "turn-on" response in both solution [9:1 (v/v) DMSO/water] and solid state [paper kits] with significantly lower detection limits (DLs) of 37.23 nM and 13.4 pg/cm2, respectively. Subsequently, F1 discloses CN- modulated colorimetric and fluorescence "turn-off" dual-channel response for aqueous 2,4,6-trinitrophenol (PA) and 2,4-dinitrophenol (DNP) in both solution (DL = 49.98 and 44.1 nM) and solid state (DL = 114.5 and 92.05 fg/cm2). Furthermore, the fluorescent nanoaggregates of F1 in water and its xerogel films permit a rapid dual-channel "on-site" detection of PA and DNP, where the DLs ranged from nanomolar (nM) to sub-femtogram (fg) levels. Mechanistic insights reveal that the ground-state electron transfer from the fluorescent [F1-CN] ensemble to the analytes is responsible for anion driven sensory response, whereas the unusual inner filter effect (IFE) driven photoinduced electron transfer (PET) was responsible for self-assembled F1 response toward desired analytes. Additionally, the nanoaggregates and xerogel films also detect PA and DNP in their vapor phase with reasonable percentage of recovery from the soil and river water samples. Therefore, the elegant multifunctionality from a single luminogenic framework allows F1 to provide a smart pathway for achieving environmentally benign real-world applications on multiple platforms.

3.
Phys Chem Chem Phys ; 25(6): 5226-5236, 2023 Feb 08.
Artigo em Inglês | MEDLINE | ID: mdl-36723193

RESUMO

Understanding the dynamics of the back electron transfer (BET) rate of ion pairs from the electronically excited state of donor-acceptor systems is crucial for developing materials for organic electronics. The structure-property relationships in the organic molecular architectures play a key role in controlling the BET rate and have been utilized as a criterion to design systems with a reduced BET rate. Here, we examine the influence of isomerism on the BET rate in anthracene based systems, viz., (E)-2-(2-(anthracen-9-yl)vinyl)benzonitrile (ortho-CN) and (E)-3-(2-(anthracen-9-yl)vinyl)benzonitrile (meta-CN) with N,N-diethylaniline (DEA) in methylcyclohexane using time-resolved spectroscopy. The radical cation (DEA˙+) and the radical anion (ortho-CN˙- or meta-CN˙-) generated after photoexcitation show synchronous decay kinetics, and the rate constant of back electron transfer (kBET) for the DEA/ortho-CN pair was 6.6 × 104 s-1, which is ca. 2 orders of magnitude lower compared with the DEA/meta-CN pair. The role of isomerism in providing resonance stabilization for the organic radicals is expected to have implications for strategies that retard charge recombination in photovoltaics. The role of the molecular structural features that dictate the kinetics for charge recombination has been further identified using quantum calculations.

4.
Phys Chem Chem Phys ; 25(5): 4121-4131, 2023 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-36651827

RESUMO

To push the boundary of the efficiency of perovskite nanocrystal-based photovoltaics, understanding the charge transfer at the interface of these nanocrystals is necessary. In an effort to understand the electronic effects of the substituents in the charge acceptor moiety, three electronically different small molecules (namely, chloranilic acid (CA), p-benzoquinone (BQ), and duroquinone (DQ)) were chosen and their detailed charge transfer dynamics were studied at the CsPbBr3 perovskite nanocrystal-small organic molecule interface using steady state and time-resolved spectroscopic methods. The steady-state absorption and time-resolved emission studies reveal that all three molecules interact with the NCs in the excited state. Femtosecond transient absorption experiments indicate a faster ground-state bleach recovery in the presence of the three acceptors, compared with the pristine NCs. Utilizing band alignment analysis, the faster bleach recovery of the NCs in presence of the acceptors was confirmed to be because of electron transfer from the photo-excited NCs to the acceptor molecules. Moreover, the electron transfer rates fall in the Marcus normal region and can be explained based on the electronic effects of the substituents present on the acceptor molecules.

5.
Langmuir ; 36(35): 10537-10547, 2020 09 08.
Artigo em Inglês | MEDLINE | ID: mdl-32841041

RESUMO

The development of fluorescent probes for selective detection of cyanide has gained considerable attention over the past two decades due to benefits like high selectivity as well as sensitivity, fast response, visual output, accurate quantification, and a simplified sample preparation procedure. However, the propensity of supramolecular gels toward fluorescence sensing of cyanide in aqueous medium is not well explored until now. Herein, we report the design and synthesis of a novel copper based metallogel capable of sensing cyanide in water by fluorescence "turn on". Toward this, a terpyridine attached poly(aryl ether) dendrone derivative (G1) is synthesized which forms gel and exhibits Aggregation Induced Emission (AIE). The addition and diffusion of copper ions to the gel resulted in the formation of a nonluminescent copper metallogel (CuG). The copper metallogel could selectively sense cyanide in water by a fluorescence "turn-on" signal due to the regeneration of the AIE active gel. The mechanistic pathways of the sensing have been studied, and the detection limit for sensing was found to be as low as 1.09 µM. A thin film of CuG was prepared by casting the gel and used as a test strip for the visual detection of cyanide in water.

6.
Soft Matter ; 16(8): 2075-2085, 2020 Feb 26.
Artigo em Inglês | MEDLINE | ID: mdl-32003762

RESUMO

Developing composite hydrogels with excellent self-healing ability and reasonable mechanical strength is extremely challenging. Herein, to overcome this difficulty, we identify the importance of balancing the ratio between the components of a composite hydrogel based on graphene oxide and poly(acrylic acid-acrylamide) [GOxAAM]. The gel exhibits enhanced mechanical strength, excellent self-healing ability, and extraordinary swelling capacity (a swelling ratio of 732) at room temperature and neutral pH. Further, the dye adsorption of the composite hydrogel has been investigated. The hydrogel could selectively adsorb organic cationic dyes (methylene blue vs. rhodamine B) from contaminated water with remarkable efficiency (90-95%). The kinetics investigation suggests that the dye adsorption on this composite hydrogel follows a pseudo-second-order model. The reusability of the hydrogel has been demonstrated by repeating the adsorption-desorption process over 10-14 cycles with almost identical results in the adsorption efficiency. Moreover, the hydrogel is utilized as a solvent-induced slow release source for graphene quantum dots (GQDs). The results taken together suggest that the (GOxAAM) composite gel can be a promising candidate for developing multifunctional gel materials.

7.
Anal Chem ; 91(5): 3533-3538, 2019 03 05.
Artigo em Inglês | MEDLINE | ID: mdl-30712342

RESUMO

Strategies for simultaneous detection and detoxification of Hg2+ using a single sensor from biological and environmental samples are limited and have not been realized in living organisms so far. We report a highly selective, small molecule "turn-on" fluorescent sensor, PYDMSA, based on the cationic dye Pyronin Y (PY) and chelating agent meso-2,3-dimercaptosuccinic acid (DMSA) for the simultaneous detection and detoxification of inorganic mercury (Hg2+). After Hg2+ detection, concomitant detoxification was carried out with sufficient efficacy in living samples, which makes the sensor unique. PYDMSA exhibits high selectivity for Hg2+ over other competing metal ions with an experimental detection limit of ∼300 pM in aqueous buffer solution. When PYDMSA reacts with Hg2+, the CS-C9 bond in the sensor gets cleaved. This results in the "turn-on" response of the fluorescence probe with a concomitant release of one equivalent of water-soluble Hg2+-DMSA complex which leads to a synchronous detoxifying effect. The sensor by itself is nontoxic to cells in culture and has been used to monitor the real-time uptake of Hg2+ in live cells and zebrafish larvae. Thus, PYDMSA is a unique sensor which can be used to detect and detoxify mercury at the same time in living samples.


Assuntos
Corantes Fluorescentes/química , Mercúrio/análise , Pironina/química , Succímero/química , Animais , Células Cultivadas , Embrião não Mamífero , Células HEK293 , Humanos , Estrutura Molecular , Espectrometria de Fluorescência , Peixe-Zebra
8.
Soft Matter ; 15(16): 3407-3417, 2019 Apr 17.
Artigo em Inglês | MEDLINE | ID: mdl-30938746

RESUMO

Fine tuning the optical properties of lanthanide-based gels using low molecular weight gelators has several advantages over the polymeric gelator analogues. Herein, we have prepared a lanthanide-based gel using low molecular weight citric acid as the assembler ligand and the optical properties of the gel were fine-tuned, utilizing a mixed ligand approach, enabling white light emission and environmental sensing (pH and temperature). The coligand utilized in the study was 4'-(4-bromophenyl)-2,2':6',2''-terpyridine. The resultant mixed-ligand gel exhibited green and red emissions in the presence of Tb(iii) ions and Eu(iii) ions, respectively. White light emission was achieved, with CIE coordinates (0.33, 0.32), in the bimetallic Tb/Eu metallogel formed by the precise control over Tb/Eu ratio. The correlated color temperature (CCT) for white-light-emitting gel was calculated, and the value of 5473 K suggests that the system generates cool white light. While most of the reported low molecular weight gelators exhibit on-off responses to stimulus at a particular value, the present system is capable of gradually monitoring changes for stimuli such as pH and temperature over a wide range (pH from 4-11 and temperature from 20 to 70 °C). The unique design strategy of the gel and the characteristic physicochemical properties of the lanthanide ions resulted in the unprecedented ability of the system to monitor changes in environmental stimuli over a considerable range.

9.
Chemistry ; 24(23): 6217-6230, 2018 Apr 20.
Artigo em Inglês | MEDLINE | ID: mdl-29441616

RESUMO

Smart single-component materials with versatile functions require pre-programming of a higher order molecular assembly. An electroactive supergelator (c=0.07 wt %) triphenylamine core-appended poly(aryl ether) dendron (TPAPAE) is described, where substantial dendritic effects improve the order and crystallinity by switching the local minima from self-assembled molecular wires to thermodynamically favorable global minima of ordered crystals, ripened within the fibers. Controlled in situ phase change at room temperature ultimately stabilized the mixed valence states in the single-component supramolecular assembly with photoluminescence and photoinduced charge transport amplified by two orders of magnitude.

10.
Chemistry ; 24(50): 13213-13222, 2018 Sep 06.
Artigo em Inglês | MEDLINE | ID: mdl-29882381

RESUMO

Designing intramolecular charge-transfer (ICT)-based luminogenic ordered assemblies exhibiting significant electrical transport is a challenging task in the field of organic optoelectronics. In this context, a series of novel phenothiazine-based oligo(p-phenylenevinylene) (OPV1-6) derivatives were designed and their structure-property relationship was investigated. Upon examining their photophysical properties, all the OPVs were found to exhibit significant intramolecular charge-transfer characteristics in organic solvents. While inspecting the self-assembly behaviour, the OPV with a long alkyl chain on the central phenyl core (OPV4) underwent gelation in organic solvent mixtures through strong hydrophobic interactions of the long hexadecyl chains and π-interactions from their aromatic counterparts. Computational studies revealed a lamellar packing of molecules in the assembly. Interestingly, the degree of ICT and the gelation abilities of OPVs were significantly influenced by the electronic nature of the substituents appended to the peripheral phenothiazines. Further, the AC impedance results revealed an increase in storage and electronic transport for the fluorescent thin films prepared by an increase in the content of OPV4 in PMMA.

11.
Phys Chem Chem Phys ; 19(10): 7288-7296, 2017 Mar 08.
Artigo em Inglês | MEDLINE | ID: mdl-28239716

RESUMO

Bathochromic and hypsochromic shifts in the photo-luminescent spectra of doped and functionalized carbon nano-dots (CDs) arise due to the complex interaction between CDs and the solvent molecules around them. Nitrogen-functionalized carbon nano-dots (N-CDs) were synthesized from citric acid and urea using microwave assisted hydrothermal methods. Optical studies (absorption and photoluminescence) from the as-synthesized N-CDs were carried out in polar protic, aprotic and non-polar solvents. When excited at 355 nm, blue photoluminescence (PL) was observed from the N-CDs dispersed in polar aprotic solvents while green emission was observed in polar protic solvents. In addition to the general solvent effect, the analysis of the luminescence spectra in protic solvents suggests that hydrogen bonding plays a crucial role in regulating the photophysical characteristics of the system. Temperature dependent PL studies and time correlated single photon counting experiments in various solvent dispersions of N-CDs support the role of hydrogen bonding. This indicates that these results depend on the specific interactions observed from the N-CDs and can be thought of as the primary driving force which is then followed by solvent properties like dipole moments. Both the Lippert-Mataga model and Kamlet-Taft parameters were used to support the photophysical properties observed from N-CDs.

12.
Chemistry ; 22(30): 10558-64, 2016 Jul 18.
Artigo em Inglês | MEDLINE | ID: mdl-27319975

RESUMO

Perylene diimide (PDI) derivatives exhibit a high propensity for aggregation, which causes the aggregation-induced quenching of emission from the system. Host-guest chemistry is one of the best-known methods for preventing aggregation through the encapsulation of guest molecules. Herein we report the use of 18-crown-6 (18-C-6) as a host system to disaggregate suitably substituted PDI derivatives in methanol. 18-C-6 formed complexes with amino-substituted PDIs in methanol, which led to disaggregation and enhanced emission from the systems. Furthermore, the embedding of the PDI⋅18-C-6 complexes in poly(vinyl alcohol) (PVA) films generated remarkably high emission quantum yields (60-70 %) from the PDI derivatives. More importantly, the host-guest systems were tested for their ability to conduct electricity in PVA films. The electrical conductivities of the self-assembled systems in PVA were measured by electrochemical impedance spectroscopy (EIS) and the highest conductivity observed was 2.42×10(-5)  S cm(-1) .

13.
Chemistry ; 21(13): 5093-100, 2015 Mar 23.
Artigo em Inglês | MEDLINE | ID: mdl-25689678

RESUMO

Self-assembly of AB2 and AB3 type low molecular weight poly(aryl ether) dendrons that contain hydrazide units were used to investigate mechanistic aspects of helical structure formation during self-assembly. The results suggest that there are three important aspects that control helical structure formation in such systems with acyl hydrazide/hydrazone linkage: i) J-type aggregation, ii) the hydrogen-bond donor/acceptor ability of the solvent, and iii) the dielectric constant of the solvent. The monomer units self-assemble to form dimer structures through hydrogen-bonding and further assembly of the hydrogen-bonded dimers leads to macroscopic chirality in the present case. Dimer formation was confirmed by NMR spectroscopy and by mass spectrometry. The self-assembly in the system was driven by hydrogen-bonding and π-π stacking interactions. The morphology of the aggregates formed was examined by scanning electron microscopy, and the analysis suggests that aprotic solvent systems facilitate helical fibre formation, whereas introduction of protic solvents results in the formation of flat ribbons. This detailed mechanistic study suggests that the self-assembly follows a nucleation-elongation model to form helical structures, rather than the isodesmic model.


Assuntos
Dendrímeros/química , Éter/química , Géis/química , Polímeros/química , Espectroscopia de Ressonância Magnética , Estrutura Molecular
14.
Chemistry ; 21(34): 11972-5, 2015 Aug 17.
Artigo em Inglês | MEDLINE | ID: mdl-26189871

RESUMO

Self-assembly of pyrene butyric acid (PBA) and 2,4,7-trinitro-9H-fluoren-9-one (TNF) directed by a pyridine-linked cholesterol unit resulted in the formation of a conducting material (1.9472×10(-4)  S Cm(-1) ) due to the formation of 1 D nanofibers. X-ray diffraction, IR, and atomic force microscopic (AFM) techniques were used to establish the mechanism of the self-assembly of the multicomponent gels. Results indicate efficient charge transfer in the 1 D nanofibers, assisted by hydrogen bonding.

15.
J Phys Chem A ; 119(49): 11783-90, 2015 Dec 10.
Artigo em Inglês | MEDLINE | ID: mdl-26580460

RESUMO

The present study utilizes the luminescence nature of the graphene quantum dots (GQDs) to analyze the mechanistic aspects of the photoinduced electron transfer (PET) processes between GQDs and aniline derivatives. A systematic investigation of PET from various aniline derivatives to GQDs has been presented. Solution-processable GQDs have been synthesized from graphene oxide (GO) at 200 °C. The as-synthesized GQDs exhibit a strong green luminescence at 510 nm, upon photoexcitation at 440 nm. Various aniline derivatives (aniline, N-methylaniline, N,N'-dimethylaniline, N-ethylaniline, N,N'-diethylaniline, and N,N'-diphenylaniline) have been utilized as electron donors to probe the PET process. Results from UV-visible absorption and steady-state and time-resolve luminescence spectroscopy suggest that the GQDs interact with the aniline derivatives in the excited state, which results in a significant luminescence quenching of the GQDs. The bimolecular rate constants of the dynamic quenching have been deduced for various donor-acceptor systems, and the values are in the range of (1.06-2.68) × 10(9) M(-1) s(-1). The negative values of the free energy change of the electron transfer process suggest that PET from aniline derivatives to GQDs is feasible and could be responsible for the luminescence quenching. The PET has been confirmed by detecting radical cations for certain aniline derivatives, using a nanosecond laser flash photolysis setup. The present study shows that among the various types of graphene systems, GQDs are better candidates for understanding the mechanism of PET in graphene-based donor-acceptor systems.

16.
Chemistry ; 20(29): 9002-11, 2014 Jul 14.
Artigo em Inglês | MEDLINE | ID: mdl-24898180

RESUMO

We describe the design, synthesis, and "stimuli-responsive" study of ferrocene-linked Fréchet-type [poly(aryl ether)]-dendron-based organometallic gels, in which the ferrocene moiety is attached to the dendron framework through an acyl hydrazone linkage. The low-molecular-weight gelators (LMWGs) form robust gels in both polar and non-polar solvent/solvent mixtures. The organometallic gels undergo stimuli-responsive behavior through 1) thermal, 2) chemical, and 3) electrochemical methods. Among them, conditions 1 and 3 lead to seamlessly reversible with repeated cycles of identical efficiency. Results indicate that the flexible nature of the poly(aryl ether) dendron framework plays a key role in retaining the reversible electrochemical behavior of ferrocene moiety in the LMWGs. Further, the organometallic gelators have exhibited unique selectivity towards Pb(2+) ions (detection limit ≈10(-8) M). The metal ion-sensing results in a gel-sol phase transition associated with a color change visible to the naked eye. Most importantly, decomplexing the metal ion from the system leads to the regeneration of the initial gel morphology, indicating the restoring ability of the organometallic gel. The metal-ligand binding nature has been analyzed by using (1)H NMR spectroscopy, mass spectrometry, and DFT calculations.


Assuntos
Antracenos/química , Compostos Ferrosos/química , Géis/química , Chumbo/análise , Cátions Bivalentes/análise , Colorimetria , Cristalografia por Raios X , Éter/química , Hidrazonas/química , Limite de Detecção , Metalocenos , Modelos Moleculares , Oxirredução , Transição de Fase
17.
Langmuir ; 29(5): 1609-17, 2013 Feb 05.
Artigo em Inglês | MEDLINE | ID: mdl-23297831

RESUMO

Novel poly(aryl ether) dendron-based low-molecular-weight organogelaters (LMWG) containing naphthalene units at the core have been synthesized, and the self-assembly of the system has been examined in a variety of solvents and solvent mixtures. The compounds readily form gels with attractive critical gel concentration values associated with gelation-induced enhanced emission (GIEE). In addition to the remarkable properties of the previously reported anthracene and pyrene analogues (Rajamalli, P.; Prasad, E. Org. Lett.2011, 13, 3714 and Rajamalli, P.; Prasad, E. Soft Matter2012, 8, 8896), the self-assembled systems exhibit distinctly different structure-property relationships. Unlike the reported ones, the present system forms sheetlike morphology in nonpolar solvent mixtures, giant vesicles in polar solvent mixtures, and lamellar or hexagonal columnar phases in single solvents. The unique properties of the self-assembled systems, which were analyzed through electron microscopic (SEM, TEM, AFM) and spectroscopic techniques (POM, fluorescence), are attributed to the replacement of anthracene/pyrene units by naphthalene units. The present work unravels the subtle role of minute structural change in altering the properties of LMWGs based on poly(aryl ether) dendrons.


Assuntos
Éteres/química , Corantes Fluorescentes/química , Naftalenos/química , Polímeros/química , Dendrímeros/química , Corantes Fluorescentes/síntese química , Géis/síntese química , Géis/química , Estrutura Molecular , Peso Molecular , Tamanho da Partícula , Propriedades de Superfície
18.
J Phys Chem A ; 116(9): 2154-60, 2012 Mar 08.
Artigo em Inglês | MEDLINE | ID: mdl-22313188

RESUMO

Electron transfer from the ground and excited states of Sm[15-crown-5](2)I(2) complex to a series of electron acceptors (benzaldehyde, acetophenone, benzophenone, nitrobenzene, benzyl bromide, benzyl chloride, 1-iodohexane, and 1,4-dinitrobenzene) was investigated in acetonitrile. Electron transfer from the ground state of the Sm(II)-crown system to aldehydes and ketones has a significant inner sphere component indicating that the oxophilic nature of Sm(II) prevails in the system even in the presence of bulky ligands such as 15-crown-5 ether. Activation parameters for the ground state electron transfer were determined, and the values were consistent with the proposed mechanistic models. Since crown ethers stabilize the photoexcited states of Sm(II), the photochemistry of Sm[15-crown-5](2)I(2) system in solution state has been investigated in detail. The results suggest that photoinduced electron transfer from Sm(II)-crown systems to a wide variety of substrates is feasible with rate constant values as high as 10(7) M(-1) s(-1). The results described herein imply that the present difficulty of manipulating the extremely reactive excited state of Sm(II) in solution phase can be overcome through stabilizing the excited state of the divalent metal ion by careful design of the ligand systems.

19.
ACS Phys Chem Au ; 2(1): 3-15, 2022 Jan 26.
Artigo em Inglês | MEDLINE | ID: mdl-36855576

RESUMO

Inclusion complexation is one of the best strategies for developing a controlled release of a toxic drug without unexpected side effects from the very beginning of the administration to the target site. In this study, three benzimidazolium based ionic liquids (ILs) having bromide anion and cation bearing long alkyl chains, hexyl- ([C6CFBim]Br), octyl- ([C8CFBim]Br), and decyl- ([C10CFBim]Br) were designed and synthesized as antibacterial drugs. Inclusion complexes (ICs) of studied ILs have been prepared by the combination of ß-cyclodextrin (ß-CD), considering these conjugations should enhance the benignity of ILs and make them potential candidates for the controlled drug release. Characterizations and structural analysis of studied ICs have been performed by 1H NMR, 2D-ROESY NMR, FT-IR, HRMS, TGA, DSC, surface tension, ionic conductivity, dynamic light scattering (DLS), and isothermal titration calorimetry (ITC). Further, the morphology of the ICs has been analyzed by SEM and TEM. Furthermore, neat ILs and ICs have been treated against Escherichia coli and Bacillus subtilis to investigate their antibacterial activity, which confirms the prevention of bacterium growth and the shrinkage of the bacterial cell wall. The findings of this work provide the proof of concept that studied benzimidazolium based ILs-ß-CD host-guest complexes should act as a potential candidate in controlled drug delivery and other biomedical applications.

20.
Chemistry ; 17(31): 8609-17, 2011 Jul 25.
Artigo em Inglês | MEDLINE | ID: mdl-21681838

RESUMO

Significant aggregation is observed in pyrene-modified zero- and first-generation polyamidoamine (PAMAM) dendrimers above their critical aggregation concentration (CAC, >10(-6) M). The pyrene units are attached to the dendrimer skeleton through imine bonds, which play a pivotal role in enhancing the aggregation propensity of the PAMAM dendrimers. Scanning electron microscopy studies suggest that pyrene-modified PAMAM dendrimers aggregate into doughnut-shaped assemblies. As a result of aggregation, the pyrene chromophores are pre-arranged in a face-to-face geometry in the ground state, and readily generate pyrene "static excimer" on photoexcitation. The static pyrene excimer emits with an unprecedented quantum yield of 0.62 ± 0.01 in dichloromethane, and also exhibits remarkable positive solvatochromism from 498 to 638 nm, which leads to the highest bathochromic shift for pyrene excimer emission in solution reported so far. Lippert-Mataga analysis of the system suggests that general and specific solvent effects play a crucial role in the positive solvatochromism exhibited by the system. Luminescence quenching studies on both monomer and aggregate systems were carried out in the presence of various metal ions, and the results imply that pyrene-modified PAMAM dendrimer can be utilized for selective detection of Hg ions in the presence of a wide variety of transition, alkali, and alkaline earth metal ions. This report presents the first dendrimer-based chromophoric system exhibiting positive solvatochromism over a range of 140 nm, and shows that pyrene-modified PAMAM dendrimers can be effectively utilized to generate wavelength-tunable emitting systems displaying bluish green, greenish yellow, and orange-red colors at room temperatures.


Assuntos
Dendrímeros/química , Pirenos/química , Dendrímeros/síntese química , Fluorescência , Mercúrio/análise , Microscopia Eletrônica de Varredura , Modelos Químicos , Estrutura Molecular , Pirenos/síntese química
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