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1.
Spectrochim Acta A Mol Biomol Spectrosc ; 303: 123166, 2023 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-37481841

RESUMO

In this study, a highly fluorescent and receptor-free phenothiazine derivative (PDAB) was developed to detect picric acid. A combination of steady-state and time-resolved fluorescence studies was conducted to examine the excited state behavior of PDAB with picric acid in solution. The PDAB probe displayed a significant degree of selectivity and was highly sensitive to picric acid, with an extremely low detection limit of 9.82 nM. Time-resolved fluorescence quenching studies exhibit direct evidence of an inner filter effect-based sensing mechanism. Using the Parker equation, a thorough analysis was done to correct the inner filter effect on the sensing of picric acid. Overall, these studies provide critical information on the sensing mechanism for picric acid detection.

2.
J Mol Model ; 29(3): 79, 2023 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-36856937

RESUMO

BACKGROUND: In the present work, DFT and time-dependent DFT calculations were performed to investigate the role of anchoring groups on the photophysical properties and reveal structure-property correlations of triphenylamine (TPA) derivatives. The selected anchoring groups are tetrazole, acrylamide, hydantoin, and rhodanine. RESULTS: Our results show that the different anchoring groups employed alter the planarity, intramolecular charge transfer properties, and HOMO-LUMO gap and hence influence the optoelectronic properties of the dyes. Although all molecules fulfill the basic requirements with suitable energy levels, band gap, absorption, and charge transfer properties, the dye with rhodanine acceptor (TPA4) was the most promising candidate due to its lowest HOMO-LUMO gap, red-shifted highest λmax absorption value, better ICT pattern, low total reorganization energy, and good electron injection properties. Overall, it is anticipated that the results of this investigation will point to new avenues for the experimental fabrication of remarkably effective metal-free organic dyes for solar cell applications.

3.
Analyst ; 148(1): 137-145, 2022 Dec 20.
Artigo em Inglês | MEDLINE | ID: mdl-36468752

RESUMO

In this work, we have meticulously tuned the carcinogenic Congo red dye to environmentally benign fluorescent carbon dots (CDs) by adopting a typical hydrothermal method without any additives. The as-synthesized CDs were extremely water soluble, exhibited an excitation wavelength independent emission with a high fluorescence quantum yield (46%) and were biocompatible. The microscopy results revealed that the CDs were quasi-spherical with a particle diameter of ∼5 nm. The structure and functional groups of the CDs were comprehensively investigated using Fourier-transform infrared, X-ray photoelectron and Raman spectroscopy analyses. These studies show that the CDs were intrinsically functionalized with -OH, N-H and CO groups. In the sensing experiments, the CDs selectively responded to Fe3+ ions over other analytes with a detection limit of 12 nM. The time-resolved fluorescence quenching measurements were used to decipher the sensing mechanism. For the onsite 'equipment-free' detection of iron, we have developed a CD adsorbed paper-based analytical tool. Furthermore, the selective nature of CDs was highly beneficial for detecting Fe3+ in non-heme metalloprotein (ferritin) and real water samples. Thus, the CDs produced from the Congo red dye could be a prospective asset to the bio-imaging and biosensing research fields.


Assuntos
Ferritinas , Pontos Quânticos , Vermelho Congo , Pontos Quânticos/química , Carbono/química , Estudos Prospectivos , Corantes Fluorescentes/química , Água/química , Espectrometria de Fluorescência
4.
J Phys Chem B ; 126(21): 3831-3843, 2022 06 02.
Artigo em Inglês | MEDLINE | ID: mdl-35583491

RESUMO

This work aimed to investigate the interaction of bovine serum albumin with newly synthesized potent new pyrene derivatives (PS1 and PS2), which might prove useful to have a better antibacterial character as found for similar compounds in the previous report [Low et al. Bioconjugate Chemistry 2014, 12, 2269-2284]. However, to date, binding studies with plasma protein are still unknown. Steady-state fluorescence spectroscopy and lifetime fluorescence studies show that the static interaction binding mode and binding constants of PS1 and PS2 are 7.39 and 7.81 [Kb × 105 (M-1)], respectively. The experimental results suggest that hydrophobic forces play a crucial role in interacting pyrene derivatives with BSA protein. To verify this, molecular docking and molecular dynamics simulations were performed to predict the nature of the interaction and the dynamic behavior of the two compounds in the BSA complex, PS1 and PS2, under physiological conditions of pH = 7.1. In addition, the free energies of binding for the BSA-PS1 and BSA-PS2 complexes were estimated at 300 K based on the molecular mechanics of the Poisson-Boltzmann surface (MMPBSA) with the Gromacs package. PS2 was found to have a higher binding affinity than PS1. To determine the behavior of the orbital transitions in the ground state geometry, we found that both compounds have similar orbital transitions from HOMO-LUMO via π → π* and HOMO-1-LUMO+1 via n → π*, which was included in the FMO analysis. A cytotoxicity study was performed to determine the toxicity of the compounds. Based on the MD study, the stability of the compounds with BSA and the dynamic binding modes were further revealed, as well as the nature of the binding force components involved and the important residues involved in the binding process. From the binding energy analysis, it can be assumed that PS2 may be more active than PS1.


Assuntos
Simulação de Dinâmica Molecular , Soroalbumina Bovina , Sítios de Ligação , Simulação de Acoplamento Molecular , Ligação Proteica , Pirenos , Soroalbumina Bovina/química , Espectrometria de Fluorescência , Termodinâmica
5.
Anal Methods ; 14(5): 518-525, 2022 02 03.
Artigo em Inglês | MEDLINE | ID: mdl-35029617

RESUMO

In this work, we have employed an intramolecular charge transfer-based DMN colorimetric probe for the rapid naked-eye detection of cyanide ions in solution as well as real water samples. The intermolecular interaction between the DMN probe and cyanide ions in solution was investigated using a combination of spectroscopic and computational methods in this study. The DMN probe exhibited a selective colorimetric response for cyanide ions over the other anions exposed. The cyanide sensing mechanism of the probe has been investigated by 1H NMR titration and density functional theory calculations. The results reveal that the colorimetric response of the DMN probe is due to the Michael adduct formation in the ß-conjugated position of the dicyanovinyl group with cyanide, which blocks intramolecular charge transfer transition. Under optimized experimental conditions, the DMN probe showed a linear plot in the concentration range of 0.01-0.25 µM, with a detection limit of 23 nM. Further, a 3D printed portable accessory for the smartphone and an open-source android application is developed to suit the DMN probe for on-site work. In addition, we have developed the microfluidic paper-based analytical device that could selectively detect cyanide ions at very low concentration using a colorimetric DMN probe. In addition, the DMN probe was effectively used to determine the cyanide ion in a variety of water samples.


Assuntos
Colorimetria , Cianetos , Ânions/química , Colorimetria/métodos , Cianetos/química , Espectroscopia de Ressonância Magnética
6.
Talanta ; 235: 122733, 2021 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-34517601

RESUMO

The microfluidic paper-based analytical devices (µPADs) have grown-up swiftly over the decade due to its low cost, simple fabrication procedure, resource-limitedness, non-toxicity and their environmentally benign nature. The µPADs, also identified as point-of-care devices or health care devices have successfully applied in several fields such as diagnostics, biological, food safety, environmental, electrochemical and most importantly colorimetric/fluorimetric sensors, owing to the attractive passive motions of analyte without any external forces. In recent years, a large number of colorimetric and fluorimetric probes have been reported that can selectively recognize the analytes in µPADs. However, there is no organized review on its structure-activity relationship. In this review, we have focused to summarize the colorimetric and fluorimetric probes utilized in µPADs. This review discuss about the relationships between the structure and functions of various probes as signaling units of the efficient µPADs. The probes including nanomaterials, nanozymes, polymers and organic molecules, their structural activity with regard to sensing performances along with their limit of detection are also discussed. This review is expected to assist readers for better understanding of the sensing mechanisms of various chemo and bio-probes utilized in µPADs, as well as promote their advancement in the field. On the other hand, this review also helps the researchers for enhancement of µPADs and paves way for synergistic application of existing molecular probes as an effective diagnostic tool for the worldwide pandemic novel corona virus COVID-19.


Assuntos
COVID-19 , Técnicas Analíticas Microfluídicas , Humanos , Dispositivos Lab-On-A-Chip , Microfluídica , Papel , SARS-CoV-2
7.
Food Funct ; 12(11): 5038-5050, 2021 Jun 08.
Artigo em Inglês | MEDLINE | ID: mdl-33960359

RESUMO

Rheumatoid Arthritis (RA) is an autoimmune disease that commences as inflammation and progressively destroys the articular joint. In this study, we assess the anti-rheumatic potential of the monoterpenoid class of thymol conjugated with Carbon Dots (CDs). Waste biomass in the form of dried rose petals was chosen as a precursor for the synthesis of CDs via a one-step hydrothermal bottom-up methodology. The prepared CDs exhibited absorption in the near-visible region, and unique excitation-dependent emission behaviour was confirmed from UV-Visible and fluorescence measurements. The surface morphology of CDs was confirmed by SEM and HR-TEM analysis to be quasi-spherical particles with an average size of ∼5-6 nm. The presence of various functional moieties (hydroxyl, carbonyl, and amino) was confirmed via FT-IR measurement. The graphitization of CDs was confirmed by the D and G bands for sp2 and sp3 hybridization, respectively, through Raman analysis. Esterification methodology was adopted to prepare the CDs-thymol conjugate and confirmed via FT-IR analysis. CDs play the role of a nanocarrier for thymol, an anti-arthritic agent. The bioactive compound of thymol showed potent anti-arthritic activity against RA targets through in silico docking studies. Further, the in vivo studies revealed that CDs-thymol conjugates (10 mg per kg body weight) showed a significant reduction in rat paw volume along with reduced levels of RF and CRP (2.23 ± 0.42 IU ml-1 and 16.96 ± 0.22 mg ml-1) when compared to the disease control rats. X-ray radiography and ultrasonic imaging revealed less bone destruction, joint derangement, and swelling in arthritis-induced Wistar rats. They could also potentially improve the Hb (14.14 ± 0.19), RBC (6.01 ± 0.11), PCV (6.01 ± 0.11) levels and elevate the status of antioxidant enzymes (GPx, SOD, MDA), and the activity was comparable to the standard drug, ibuprofen (10 mg kg-1), suggesting that the CDs-thymol conjugate at 10 mg kg-1 could act as a strong anti-arthritic agent. This work is evidence for the utilization of waste biomass as a value-added product such as a nanocarrier for biomedical applications.


Assuntos
Antirreumáticos/química , Antirreumáticos/farmacologia , Carbono/química , Pontos Quânticos , Timol/química , Animais , Antioxidantes , Artrite Reumatoide/tratamento farmacológico , Feminino , Interleucinas/química , Metaloproteinase 1 da Matriz/química , Metaloproteinase 3 da Matriz/química , Simulação de Acoplamento Molecular , Ratos , Ratos Wistar , Receptor Tipo 1 de Fator de Crescimento de Fibroblastos/química , Espectroscopia de Infravermelho com Transformada de Fourier , Fator de Crescimento Transformador beta/química
8.
J Chem Inf Model ; 61(4): 1825-1839, 2021 04 26.
Artigo em Inglês | MEDLINE | ID: mdl-33843222

RESUMO

Excited-state intramolecular proton transfer (ESIPT) and intramolecular charge transfer (ICT) processes are widely exploited in the designing of organic materials for multifarious applications. This work explores the aftereffects of combining both ESIPT and ICT events in a single molecule, namely, N,N'-bis(salicylidene)-p-phenylenediamine (BSP) exploiting DFT and TD-DFT formalisms. The PBE0 functional employed in the present study is found to yield results with better accuracy for excited-state calculations. The results reveal that introduction of electron donor (-NH2) and electron acceptor (-NO2) substituents on BSP produces a strikingly red-shifted emission with respect to the corresponding emission from the unsubstituted analogue in polar solvents. This red-shifted emission originated due to the coupled effect of ESIPT and planar-ICT (PICT) processes from the coplanar geometry adopted by the substituted molecule (s-BSP). Based on the computed potential energy curves, the ground-state intramolecular proton transfer (GSIPT) was found to take place more favorably in s-BSP than in BSP under all solvent conditions. In the case of ESIPT, the barrier and relative energies of the phototautomers of s-BSP were slightly higher than BSP, which shows that simultaneous substitution of -NH2 and -NO2 groups causes slight perturbation to the ESIPT process. Overall, the computed results show that simultaneous substitution of suitable electron donor and acceptor substituents provides profitable changes in the photophysical properties of ESIPT molecules like BSP. These molecular-level insights will pave way for designing better materials for diverse applications.


Assuntos
Fenilenodiaminas , Prótons , Teoria da Densidade Funcional , Modelos Moleculares
9.
ACS Omega ; 5(50): 32761-32768, 2020 Dec 22.
Artigo em Inglês | MEDLINE | ID: mdl-33376914

RESUMO

Herein, we have developed a novel aggregation-induced emission (AIE) probe and three-dimensional (3D) printed portable device for copper (Cu2+) sensing in an aqueous medium. A ubiquitous synthetic route has been employed to devise the anthracene-conjugated imidazo[1,5-a]pyridine (TL19) probe as a unique anchor for Cu2+ ions. The TL19 is meticulously characterized through pivotal spectroscopic techniques, and the satisfactory results were obtained. The solvatochromic analysis and density functional theory calculations cohesively reveal that the TL19 exhibits the intramolecular charge transfer transition upon photoexcitation. Intriguingly, the TL19 exhibits spherically shaped nanoaggregates and enhanced fluorescence in DMSO/water (10:90) mixtures. This fluorescent nanoaggregate instantaneously responded toward the detection of Cu2+ via a deaggregation mechanism. The detection limit is found to be 9 pM in an aqueous medium. Further, the detection of Cu2+ in the HeLa cells has also been achieved due to bright green fluorescence, photostability, and biocompatibility nature of TL19 aggregates. On the other hand, an internet of things (IoT)-embedded 3D printed portable device is constructed for the detection of Cu2+ ions in real water samples. The Cu2+ detection is achieved through an IoT device, and results were acknowledged through an android application in 3.32 s round-trip time. Thus, the IoT-enabled AIE probe could be a prospective device for Cu2+ detection in a constrained environment.

10.
Analyst ; 145(13): 4532-4539, 2020 Jul 07.
Artigo em Inglês | MEDLINE | ID: mdl-32420579

RESUMO

This work addresses the synthetic optimization of carbon dots (CDs) and their application in sensing picric acid from latent fingerprints by exploiting a smartphone-based RGB tool. The optimization of the synthesis of CDs is investigated towards achieving shorter reaction time, better product yield and fluorescence quantum efficiency. Precursors such as citric acid and thiourea were chosen for the synthesis of CDs. Among the various synthetic methodologies, it is found that the pyrolysis method offers ∼50% product yield within 15 min. The morphology and optical properties of the prepared CDs are characterized using the typical microscopic and spectroscopic techniques, respectively. The synthesized CDs exhibit quasi-spherical shape with an average particle size of 1.7 nm. The excitation dependent emissive properties of CDs are investigated by time resolved fluorescence spectroscopy. Furthermore, the excellent fluorescence properties (φ = 11%) of CDs are explored as a fluorescent fingerprint powder for the identification of latent fingerprints on various substrates. In addition, the presence of picric acid in latent fingerprints was detected. Furthermore, this study is extended to perform real time detection of fingerprints and harmful contaminants in fingerprints by utilizing a smartphone-based RGB color analysis tool. Based on these investigations, the prepared CDs could be a prospective fluorescent material in the field of forensics.

11.
ACS Omega ; 5(12): 7025-7031, 2020 Mar 31.
Artigo em Inglês | MEDLINE | ID: mdl-32258938

RESUMO

Recycling of waste into valuable products plays a significant role in sustainable development. Herein, we report the conversion of vehicle exhaust waste soot into water-soluble fluorescent carbon dots via a simple acid refluxion method. The obtained carbon dots were characterized using microscopic and spectroscopic techniques. Microscopic techniques reveal that the prepared carbon material is spherical in shape with an average particle size of ∼4 nm. Spectroscopic studies exhibited that the carbon dots are emissive in nature, and the emission is excitation-dependent. Further, the prepared carbon dots were successfully utilized as a fluorescent probe for the detection of tartrazine with a limit of detection of 26 nM. The sensitivity of carbon dots has also been realized by the detection of trace amounts of tartrazine in commercial soft drinks. Overall, this work demonstrates the conversion air pollutant soot into value-added fluorescent nanomaterials toward sensing applications.

12.
RSC Adv ; 10(59): 35787-35791, 2020 Sep 28.
Artigo em Inglês | MEDLINE | ID: mdl-35517061

RESUMO

Herein, we have developed a tool for monitoring the outdoor performance of dye-sensitized solar cells. In this regard, a new dye consisting of an N-aryl-substituted imidazole with N-alkylated carbazole as the donor and cyanoacrylic acid as the acceptor has been designed. The overall power conversion efficiency of the designed dye reached ∼50%, with respect to that of the N719-based device (4%) under similar experimental conditions. Further, the device was interfaced with an IoT system, which measured the voltage and transmitted the device parameters to the user's mobile phone through a cloud channel. The developed IoT tool provides a resolution of 0.0315 mV and a round-trip delay time of <0.32 s for transmitting the information to the user's mobile phone.

13.
Anal Chem ; 91(20): 13244-13250, 2019 10 15.
Artigo em Inglês | MEDLINE | ID: mdl-31542920

RESUMO

Developing a fluorescent probe for the selective and sensitive detection of explosives is a topic of continuous research interest. Additionally, underlying the principles behind the detection mechanism is indeed providing substantial information about the design of an efficient fluorescence probe. In this context, a pyrene-tethered 1-(pyridin-2-yl)imidazo[1,5-a]pyridine-based fluorescent probe (TL18) was developed and employed as a fluorescent chemosensor for nitro explosives. The molecular structure of TL18 was well-characterized by NMR and EI-MS spectrometric techniques. UV-visible absorption, steady-state, and time-resolved fluorescence spectroscopic techniques have been employed to explicate the photophysical properties of TL18. The fluorescent nature of the TL18 probe was explored for detection of nitro explosives. Intriguingly, the TL18 probe was selectively responsive to picric acid over other explosives. The quantitative analysis of the fluorescence titration studies of TL18 with picric acid proved that the probe achieved a detection limit of 63 nM. Further, DFT and QTAIM studies were used to establish the nature of the sensing mechanism of TL18. The hydrogen-bonding interactions are the reason for the imperative sensing property of TL18 for picric acid. Thus, our experimental and theoretical studies provide an adequate and appropriate prerequisite for an efficient fluorescent probe. Furthermore, a smartphone-interfaced portable fluorimeter module is developed to facilitate sensitive and real-time sensing of picric acid. This portable module was capable of detecting picric acid down to 99 nM. Eventually, these studies will have a significant impact on development and application of a new class of chemosensors for detection of explosives.


Assuntos
Substâncias Explosivas/análise , Corantes Fluorescentes/química , Picratos/análise , Pirenos/química , Smartphone , Corantes Fluorescentes/síntese química , Modelos Químicos , Pirenos/síntese química , Teoria Quântica , Espectrometria de Fluorescência
14.
Spectrochim Acta A Mol Biomol Spectrosc ; 221: 117150, 2019 Oct 05.
Artigo em Inglês | MEDLINE | ID: mdl-31176291

RESUMO

Herein, we have meticulously derived the nanosized fluorescent aggregates from pyrene Schiff base (PS) in DMSO:water (10:90) ratio. The aggregation property of PS molecule was characterized by SEM and TEM measurements, revealed the aggregated particles are in spherical shape with ~3 nm in size. Moreover, aggregates exhibit a high fluorescence quantum yield (48%) which was effectively used for the in vitro bioimaging of two different cancer cells such as A549 and MCF-7 cells in which it exhibiting excellent biocompatibility. Further, it was estimated the capability of twofold acridine orange/ethidium bromide (AO/EB) staining to identify the apoptotic associated changes in cancer cells. Additionally, the aggregates were successfully demonstrated as a luminescent probe for the perceptive biomolecule detection of bilirubin. On the other hand, the PS molecule was successfully utilized for protein binding and metal ion sensing studies. The interaction of bovine serum albumin (BSA) with PS molecule in DMSO was using fluorescence spectroscopic method and nature of interaction was also confirmed through molecular docking analysis. The PS molecule also acts as an excellent sensor for biologically important Fe3+ ion with detection limit of 336 nM. Overall, PS molecule can be a prospective material in biological field both in solution as well as aggregated forms.


Assuntos
Bilirrubina/análise , Corantes Fluorescentes/química , Ferro/análise , Pirenos/química , Soroalbumina Bovina/metabolismo , Células A549 , Laranja de Acridina , Sobrevivência Celular/efeitos dos fármacos , Etídio , Corantes Fluorescentes/toxicidade , Humanos , Limite de Detecção , Células MCF-7 , Simulação de Acoplamento Molecular , Imagem Molecular/métodos , Nanoestruturas/química , Nanoestruturas/toxicidade , Tamanho da Partícula , Bases de Schiff/química , Soroalbumina Bovina/química , Espectrometria de Fluorescência
15.
Spectrochim Acta A Mol Biomol Spectrosc ; 220: 117144, 2019 Sep 05.
Artigo em Inglês | MEDLINE | ID: mdl-31141777

RESUMO

In this work, a new anthracene Schiff base derivative (AS) was successfully synthesized and characterized by pivotal analytical techniques. Based on the contented results, the AS molecule was employed for photophysical investigation using UV-Visible absorption, steady state and time resolved fluorescence techniques. The photophysical studies reveal that the AS possesses modest molar absorption coefficient (104) and weak fluorescence (ϕ = 0.006). The weak fluorescence of AS is due to intramolecular photoinduced electron transfer (PET). Intriguingly, the weak fluorescence intensity of AS is enhanced dramatically by the gradual addition of water up to 90% as well as appearance of long lived fluorescence decay. The enhancement in the fluorescence intensity and lifetime clearly indicates that this molecule has aggregation-induced emission (AIE) property. Further, the AIE property of AS is utilized for sensitive detection of picric acid (PA). The fluorescence of aggregated AS is quenched regularly with the sequential addition of PA concentration. The higher Stern-Volmer constant (2.61 × 105 M-1) and excellent detection limit of 93 nM designate the AS aggregates as potential candidate for explosive detection. The mechanism behind the quenching of fluorescence can be ascribed to inner filter effect, which is supported by spectral overlap analysis and fluorescence lifetime measurements. The suitability of AS aggregates for practical applications is realized by the detection of trace amounts of PA in real water samples.

16.
Spectrochim Acta A Mol Biomol Spectrosc ; 196: 295-302, 2018 May 05.
Artigo em Inglês | MEDLINE | ID: mdl-29459160

RESUMO

In recent years, quantum dots (QDs) are one of the most promising nanomaterials in life sciences community due to their unexploited potential in biomedical applications; particularly in bio-labeling and sensing. In the advanced nanomaterials, carbon dots (CDs) have shown promise in next generation bioimaging and drug delivery studies. Therefore the knowledge of the exact nature of interaction with biomolecules is of great interest to designing better biosensors. In this study, the interaction between CDs derived from tamarind and calf thymus DNA (ct-DNA) has been studied by vital spectroscopic techniques, which revealed that the CDs could interact with DNA via intercalation. The apparent association constant has been deduced from the absorption spectral changes of ct-DNA-CDs using the Benesi-Hildebrand equation. From the DNA induced emission quenching experiments the apparent DNA binding constant of the CDs (Kapp) have also been evaluated. Furthermore, we have analyzed the antibacterial and antifungal activity of CDs using disc diffusion assay method which exhibited excellent activity against E. coli and C. albicans with inhibition zone in the range of 7-12mm. The biocompatible nature of CDs was confirmed by an in vitro cytotoxicity test on L6 normal rat myoblast cells by using MTT assay. The cell viability is not affected till the high dosage of CDs (200µg/mL) for >48h. As a consequence of the work, future development of CDs for microbial control and DNA sensing among the various biomolecules is possible in view of emerging biofields.


Assuntos
Anti-Infecciosos , Carbono , Nanopartículas , Animais , Anti-Infecciosos/química , Anti-Infecciosos/metabolismo , Anti-Infecciosos/farmacologia , Anti-Infecciosos/toxicidade , Bactérias/efeitos dos fármacos , Carbono/química , Carbono/metabolismo , Carbono/farmacologia , Carbono/toxicidade , Linhagem Celular , Sobrevivência Celular/efeitos dos fármacos , DNA/química , DNA/metabolismo , Estabilidade de Medicamentos , Corantes Fluorescentes/química , Corantes Fluorescentes/metabolismo , Corantes Fluorescentes/farmacologia , Corantes Fluorescentes/toxicidade , Humanos , Células MCF-7 , Testes de Sensibilidade Microbiana , Nanopartículas/química , Nanopartículas/metabolismo , Nanopartículas/toxicidade , Ratos
17.
Phys Chem Chem Phys ; 20(9): 6264-6273, 2018 Feb 28.
Artigo em Inglês | MEDLINE | ID: mdl-29431799

RESUMO

The geometry (twist vs. planar) of a dye is one of the most pivotal factors for determining intramolecular charge transfer (ICT), light harvesting and photovoltaic properties of dye-sensitized solar cells. In order to comprehend the role of dye geometry on the above properties, we have devised the pyrene based D-π-A dyes namely 2-cyano-3-(5-pyren-1-yl-furan-2-yl)-acrylic acid (PFCC) and 2-cyano-3-(5-pyren-1-ylethynyl-furan-2-yl)-acrylic acid (PEFCC). The synthesized pyrene dyes were well characterized by NMR and EI-MS spectrometry. In both the dyes, the donor (pyrene) and acceptor (cyanoacrylic acid) segments remained the same. The varied π-spacers were furan and ethynyl furan. The influences of the ethynyl spacer on the energy levels, light absorption, dynamics of excited states and photovoltaic properties of the DSCs were systematically investigated via theoretical calculations and spectroscopic measurements. UV-visible absorption spectral measurements indicated that the introduction of the ethynyl spacer enhances the molar absorptivity of a dye (PEFCC) in the order of 2, but does not shift the absorption range, which is consistent with the results obtained from density functional theory (DFT) calculations. The theoretical analysis indicated that the charge transfer transition is mainly constituted of the HOMO to the LUMO that were found to be located on donor and acceptor segments, respectively, which is supportive for efficient charge separation and electron injection processes. TDDFT calculations highlighted that the LUMO of the PEFCC dye is more stabilized by the incorporation of the ethynyl group between the pyrene and furan moieties that aid to inject electrons efficiently into TiO2 thereby resulting in an enhanced power conversion efficiency of 2.47% when compared to the PFCC dye. Notably, the overall conversion efficiency of the PEFCC dye reached 60% with respect to that of an N719-based device (4.12%) fabricated under similar conditions. Transient absorption kinetic studies demonstrated that a slower charge recombination rate is an essential factor behind enhanced efficiencies in PEFCC based cells.

18.
Phys Chem Chem Phys ; 20(7): 5117-5127, 2018 Feb 14.
Artigo em Inglês | MEDLINE | ID: mdl-29392257

RESUMO

In this work, Zn-porphyrin with a hydantoin anchor (ZnPHy) was designed and synthesized for dye-sensitized solar cell (DSC) applications. The synthesized ZnPHy was well characterized using IR, NMR and mass spectral techniques, and satisfactory results were obtained. Cyclic voltammetry, UV-visible absorption, steady-state fluorescence, time-resolved fluorescence and transient absorption spectroscopic techniques were employed to elucidate the electrochemical and photophysical properties of ZnPHy. The obtained properties revealed that the synthesized ZnPHy can be used as a photosensitizer for DSC applications. The nature of ZnPHy binding onto the TiO2 surface was investigated using ATR-FTIR and UV-Vis absorption measurements. The amount of adsorbed ZnPHy on TiO2 surface was reasonably fit using the Langmuir adsorption isotherm, with a binding constant value of 1.03 × 105 M-1. Time-resolved measurements were used to elucidate the rate of electron injection and the regeneration and recombination kinetics for ZnPHy/TiO2 film. The ZnPHy showed a high electron injection rate with a ϕinj of 99%. Intriguingly, the rate of electron recombination is much slower than the rates reported for carboxyl-based Zn-porphyrins. Such a high electron injection and slow electron recombination rate are beneficial to produce long-lived electrical current in a photovoltaic device. Thus, the ZnPHy-sensitized TiO2 electrode showed the best photovoltaic performance, with the short-circuit photocurrent density (JSC), open-circuit voltage (VOC) and fill factor (ff) of 3.49 mA cm-2, 0.6 V and 0.52, respectively, yielding an overall conversion efficiency (η) of 1.01%. For comparison, the ZnCOOH-sensitized electrode was also fabricated under the same conditions and yielded the η value of 0.84%. Hence, the hydantoin moiety could be a potential alternative anchoring group for DSC applications.

19.
ACS Omega ; 3(8): 9096-9104, 2018 Aug 31.
Artigo em Inglês | MEDLINE | ID: mdl-31459044

RESUMO

Herein, we report the preparation of graphene oxide dots (GO dots) by fine-tuning the carbonization degree of citric acid. The structure of GO dots was characterized by absorption spectroscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, as well as high-resolution scanning electron microscopy and transmission electron microscopy analyses. The typical particle size of the GO dots was 42 nm. The fluorescent characteristics of the GO dots were analyzed by fluorescence spectroscopy. Once excited at 360 nm, the GO dots were fluorescent in the range of 450-550 nm, which was dependent on the excitation wavelength. Further, GO dots were effectively utilized for multifarious applications such as photoinduced electron transfer and detection of explosives and biomolecules. The emission property of GO dots was competently quenched by viologens, picric acid (PA), and bilirubin (BR). The mechanism of quenching by viologens and explosives/biomolecules was found to be due to photoinduced electron transfer and the internal filter effect, respectively. Intriguingly, the detection minimum of PA is in the nanomolar level. Toward commercialization, the economic test strips have also been introduced for the identification of PA. Furthermore, the GO dots have been applied as an efficient luminescent bioprobe for a selective and perceptive finding of BR.

20.
ACS Appl Bio Mater ; 1(5): 1705-1716, 2018 Nov 19.
Artigo em Inglês | MEDLINE | ID: mdl-34996219

RESUMO

Tin(IV) porphyrin scaffolds having long-chain (C8 and C16) alkoxyphenyl group at one meso position were synthesized with axial dichloro and dihydroxo ligands. Modifications with respect to the alkoxy chain length and the axial ligands were investigated using UV-vis and fluorescence spectroscopy as well as cyclic voltammetry. Significantly higher molar absorption coefficients were noted with dichloro axial ligands whereas higher fluorescence quantum yields were observed for C8 alkoxy chain substituents. Electrochemical redox data revealed that the porphyrin ring became difficult to reduce consequent to the presence of electron donating alkoxy chain. Evaluation of the aggregation behavior in different organic solvents and DMF-water mixture has been carried out. The singlet oxygen production and photostability data are supportive of their suitability for antibacterial photodynamic therapy. The antibacterial studies carried out in Gram negative (E. coli) and Gram positive (B. subtilis) bacteria using agar well diffusion and LB broth assay revealed selective toxicity in B. Subtilis cells. Fluorescence microscopy and competitive DNA binding studies with Hoechst 33342 revealed DNA binding at the minor groove which was further substantiated with molecular docking studies.

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