Susmita Das

Tunable Cytotoxicity of Rhodamine 6G via Anion Variations

Chemotherapeutic agents with low toxicity to normal tissues are a major goal in cancer research. In this regard, the therapeutic activities of cationic dyes, such as rhodamine 6G, toward cancer cells have been studied for decades with observed toxicities toward normal and cancer cells. Herein, we report rhodamine 6G-based organic salts with varying counteranions that are stable under physiological conditions, display excellent fluorescence photostability, and more importantly have tunable chemotherapeutic properties. Our in vitro studies indicate that the hydrophobic compounds of this series allow production of nanoparticles which are nontoxic to normal cells and toxic to cancer cells. Furthermore, the anions, in combination with cations such as sodium, were observed to be nontoxic to both normal and cancer cells. To the best of our knowledge, this is the first demonstration that both the cation and anion play an extremely important and cooperative role in the antitumor properties of these compounds.

Lanthanide-based luminescent NanoGUMBOS.

Lanthanide photochemistry has been frequently studied for its high luminescence intensity, narrow emission band, and stable luminescent lifetime decay. In the work presented here, nanoparticles prepared using an aerosolization process were derived from europium-based GUMBOS (Group of Uniform Material Based on Organic Salts). These nanoparticles were characterized using electron microscopy, X-ray photoelectron spectroscopy (XPS), absorbance, and photoluminescence spectroscopy. An average diameter of 39.5 ± 8.4 nm for our nanoparticles was estimated by use of electron microscopy. Absorbance, luminescence, and luminescence lifetime decay measurements indicate intense and steady luminescence, which suggests a multitude of possible applications for lanthanide-based GUMBOS, especially in sensory devices, OLEDs, and photovoltaic devices.

Ionic liquid-based optoelectronic sensor arrays for chemical detection

Development of ionic liquid (IL)-based colorimetric sensor arrays for detection and identification of chemicals in both the aqueous and vapor phases is reported. These facile and inexpensive optoelectronic sensors were fabricated by using ionic liquids (ILs) derived from readily available pH indicator dyes. A series of 12 different chemosensory ILs were synthesized by pairing anionic pH indicator dyes with trihexyl(tetradecyl)phosphonium ([P66614]) cation via an ion exchange reaction. The incorporation of the [P66614] cation imparted hydrophobic characteristics to these ILs, and this induced hydrophobicity led to their desired low solubility in aqueous solutions, as well as eliminated the need for a specialized hydrophobic matrix/substrate for immobilization. In this manuscript, four different matrices, i.e. glass microfiber filter papers, cotton threads, silica thin layer chromatography (TLC) plates, and alumina TLC plates, were employed for fabrication of sensor arrays. These sensor arrays were used to analyze pH values of aqueous solutions as well as for detection of acidic and basic vapors. To further prove the applicability of these IL sensor arrays as tools to sense closely related complex materials, the arrays were applied to successful discrimination of aqueous solutions of smoke from three commercially available cigarettes. The digital data generated from these sensor arrays were used in developing predictive models for accurately identifying various analytes. Two approaches were used for developing the models, and two methods were applied for assessing the predictive accuracy of the models. Use of cotton threads as a matrix led to development of a more flexible, low volume, and lightweight array to estimate pH and detect a variety of vapors. These wearable arrays may possibly be incorporated into bandages, sweatbands, diapers, and similar systems. Overall, these IL-based sensor arrays should provide a new research direction in the development of advanced colorimetric sensor arrays for detection and identification of a range of analytes relevant to many different applications.

Fluorescence, Phosphorescence, and Chemiluminescence

Noureen Siraj,† Bilal El-Zahab,‡ Suzana Hamdan,† Tony E. Karam,† Louis H. Haber,† Min Li, Sayo O. Fakayode, Susmita Das, Bertha Valle, Robert M. Strongin, Gabor Patonay, Herman O. Sintim, Gary A. Baker, Aleeta Powe, Mark Lowry, Jan O. Karolin, Chris D. Geddes, and Isiah M. Warner*,† †Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana 70803, United States ‡Department of Mechanical and Materials Engineering, Florida International University, Miami, Florida 33174, United States Process Development Center, Albemarle Corporation, Baton Rouge, Louisiana 70805, United States Department of Chemistry, Winston-Salem State University, Winston-Salem, North Carolina 27110, United States Department of Civil Engineering, Adamas Institute of Technology, Barasat, Kolkata 700126, West Bengal India Department of Chemistry, Texas Southern University, Houston, Texas 77004, United States Department of Chemistry, Portland State University, Portland, Oregon 97207, United States Department of Chemistry, Georgia State University, Atlanta, Georgia 30302-4098, United States Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742, United States Department of Chemistry, University of Missouri Columbia, Columbia, Missouri 65211-7600, United States Department of Chemistry, University of Louisville, Louisville, Kentucky 40208, United States Institute of Fluorescence, University of Maryland Baltimore County, Baltimore, Maryland 21202, United States

Fluorescent one-dimensional nanostructures from a group of uniform materials based on organic salts

Herein we report the synthesis of a fluorescent organic salt through anion exchange and the subsequent fabrication of 1D-nanostructures via a facile templating method.

A novel composite film for detection and molecular weight determination of organic vapors

A novel vapor-sensitive composite film comprising cellulose acetate and a representative compound (1-n-butyl-2,3-dimethylimidazolium hexafluorophosphate) from a Group of Uniform Materials Based on Organic Salts (GUMBOS) has been developed and characterized. The vapor sensing characteristics of the film is investigated using a quartz crystal microbalance (QCM) transducer. The material exhibited greatly improved performance characteristics toward a number of organic vapors. It is demonstrated that the ratio of the change in resonance frequency (Δf) to the change in motional resistance (ΔR) is a concentration-independent quantity proportional to the molecular weight of the absorbed chemical species. To the best of our knowledge, this is the first study to show a direct relationship between Δf/ΔR and the molecular weight of analytes. This unique finding should prove extremely useful for easy identification and molecular weight determination of a broad range of chemical vapors.

Tunable Size and Spectral Properties of Fluorescent NanoGUMBOS in Modified Sodium Deoxycholate Hydrogels

Microstructures of sodium deoxycholate hydrogels were altered considerably in the presence of variable tris(hydroxymethyl)aminomethane (TRIS) concentrations. These observations were confirmed by use of X-ray diffraction, polarized optical microscopy, rheology, and differential scanning calorimetry measurements. Our studies reveal enhanced gel crystallinity and rigidity with increasing TRIS concentrations. The tunable hydrogel microstructures obtained under various conditions have been successfully utilized as templates to synthesize cyanine-based fluorescent nanoGUMBOS (nanoparticles from a group of uniform materials based on organic salts). A systematic variation in size (70-200 nm), with relatively low polydispersity and tunable spectral properties of [HMT][AOT] nanoGUMBOS, was achieved by use of these modified hydrogels. The gel microstructures are observed to direct the size as well as molecular self-assembly of the nanomaterials, thereby tuning their spectral properties. These modified hydrogels were also found to possess other interesting properties such as variable morphologies ranging from fibrous to spherulitic, variable degrees of crystallinity, rigidity, optical activity, and release profiles which can be exploited for a multitude of applications. Hence, this study demonstrates a novel method for modification of sodium deoxycholate hydrogels, their applications as templates for nanomaterials synthesis, as well as their potential applications in biotechnology and drug delivery.

Irradiation Induced Fluorescence Enhancement in PEGylated Cyanine-Based NIR Nano- and Mesoscale GUMBOS

We report on the synthesis and characterization of a PEGylated IR786 GUMBOS (Group of Uniform Materials Based on Organic Salts). The synthesis of this material was accomplished using a three step protocol: (1) substitution of chloride on the cyclohexenyl ring in the heptamethine chain of IR786 by 6-aminohexanoic acid, (2) grafting of methoxy polyethylene glycol (MeOPEG) onto the 6-aminohexanoic acid via an esterification reaction, and (3) anion exchange between [PEG786][I] and lithium bis(trifluoromethylsulfonyl)imide (LiNTf(2)) or sodium bis(2-ethylhexyl)sulfosuccinate (AOT) in order to obtain PEG786 GUMBOS. Examination of spectroscopic data for this PEG786 GUMBOS indicates a large stokes shift (122 nm). It was observed that this PEG786 GUMBOS associates in aqueous solution to form nano- and mesoscale self-assemblies with sizes ranging from 100 to 220 nm. These nano- and mesoscale GUMBOS are also able to resist nonspecific binding to proteins. PEGylation of the original IR786 leads to reduced cytotoxicity. In addition, it was noted that anions, such as NTf(2) and AOT, play a significant role in improving the photostability of PEG786 GUMBOS. Irradiation-induced J-aggregation in [PEG786][NTf(2)] and to some extent in [PEG786][AOT] produced enhanced photostability. This observation was supported by use of both steady state and time-resolved fluorescence measurements.

Molecular weight sensing properties of ionic liquid-polymer composite films: theory and experiment

Ionic liquids (ILs) are rapidly emerging as important coating materials for highly sensitive chemical sensing devices. In this regard, we have previously demonstrated that a quartz crystal microbalance (QCM) coated with a binary mixture of an IL and cellulose acetate can be employed for detection and molecular weight estimation of organic vapors (J. Mater. Chem. 2012, 22, 13732). Herein, we report follow-up studies aimed at formulating the theoretical basis for our previously observed relationship between molecular weight and changes in the QCM parameters. In the current work, we have investigated the vapor sensing characteristics of a series of binary blends of ILs and polymers over a wider concentration range of analytes, and a quadratic equation for estimating the approximate molecular weight of an organic vapor is proposed. Additionally, the frequency (f) and dissipation factor (D) at multiple harmonics were measured by use of a quartz crystal microbalance with dissipation monitoring (QCM-D). These QCM-D data were then analyzed by fitting to various models. It is observed that the behavior of these films can be best described by use of the Maxwell viscoelastic model. In light of these observations, a plausible explanation for the correlation between the molecular weight of absorbed vapors and the QCM parameters is presented. Our previous findings appear to be a special case of this more general observation. Overall, these results underscore the true potential of IL-based composite materials for discrimination and molecular weight estimation of a broad range of chemical vapors.

Ionic liquid-based fluorescein colorimetric pH nanosensors

A novel pH sensitive, colorimetric ionic liquid nanosensor based on phosphonium salts of fluorescein is reported. Herein, fluorescein salts of various stoichiometries were synthesized by use of a trihexyltetradecylphosphonium cation [TTP]+ in combination with dianionic [FL]2- and monoanionic [FL]- fluorescein. Nanomaterials derived from these two compounds yielded contrasting colorimetric responses in neutral and acidic environments. Variations in fluorescence spectra as a function of pH were also observed. Examination of TEM and DLS data revealed significant expansion in the diameter of [TTP]2[FL] nanodroplets in acidic environments of variable pHs. A similar trend was also observed for [TTP][FL] nanoparticles. The pH dependent colorimetric and other optical properties of these nanomaterials are attributed to alterations in molecular orientations and stacking as suggested by measuring the absorption, fluorescence, and zeta potential. Since the pH is an important indicator for many diseases, including cancer, these nanosensors are considered to be potential candidates for biomedical applications.