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Ramachandram Badugu

Publications and source records attributed to Ramachandram Badugu.

15 recordsLinked to original sources
PubMed2006

Distance-dependent metal-enhanced fluorescence from Langmuir-Blodgett monolayers of alkyl-NBD derivatives on silver island films.

We described the effect of fluorophore distance from the silver island films (SIFs) on the metal-enhanced fluorescence (MEF) from two newly developed long-chain nitrobenzoxadiazole derivatives (NBD-C16 and NBD-C18). The well-established Langmuir-Blodgett technique is used to deposit the fluorophores at defined distances from the SIFs surface, and an inert amphiphilic stearic acid is used to control the distance. NBD probes deposited directly on the SIFs surface show the highest metal-enhanced fluorescence of approximately 32-fold, and both of the probes that were studied show a consistent decrease in metal-enhanced fluorescence when increasing the distance from the fluorophore to the SIFs surface. The lowest fluorescence enhancement of approximately 4-fold is observed for the probes located 90 nm from the SIFs surface. Additionally, we also have noticed the shortest fluorescence lifetimes for the NBD probes deposited directly onto the SIFs surface, and the lifetimes are consistently increased when increasing the distances between the fluorophore and SIFs surfaces. These contrasting spectral changes, enhanced fluorescence, and decreased fluorescence lifetimes are in accordance with an increase in the rate of radiative decay for fluorophores near the silver particles. The present study provides significant information on the effect of fluorophore distance on the metal-enhanced fluorescence phenomenon.

4-Chloro-7-nitrobenzofurazan↗
PubMed2006

Metal-enhanced fluorescence from CdTe nanocrystals: a single-molecule fluorescence study.

We described, for the first time, the metal-enhanced fluorescence from the CdTe nanocrystals spin coated on silver island films (SIFs). CdTe nanocrystals show approximately 5-fold increase in fluorescence intensity, 3-fold decrease in lifetimes, and reduction in blinking on SIF surfaces that can be observed by ensemble and single-molecule fluorescence studies. The single-molecule study also provides further insight on the heterogeneity in the fluorescence enhancement and lifetimes of the CdTe nanocrystals on both glass and SIF surfaces, which is otherwise not possible to observe using ensemble measurements.

Cadmium Compounds↗
PubMed2006

Langmuir-Blodgett monolayers of long-chain NBD derivatives on silver island films: Well-organized probe layer for the metal-enhanced fluorescence studies.

The metal-enhanced fluorescence (MEF) from the well-organized monolayers of two newly prepared long-chain alkylamine derivatives of nitrobenzoxadiazole (NBD-C16 and NBD-C18) deposited on silver island films (SIFs) has been investigated. The NBD derivatives were conveniently prepared by using a single step procedure in quantitative yields. The monolayers of the probes on SIFs as well as on bare-glass slides were obtained by using the Langmuir-Blodgett (LB) technique. Orientation of the NBD probe molecule in LB monolayer film was measured with polarized absorption spectroscopy. The observed tilt angle of the probe transition dipole moment with respect to the surface normal of approximately 67-68 degrees was evaluated. We observed that the NBD monolayers deposited in close proximity to silver islands show about a 16-fold increase in fluorescence intensity and shortened fluorescence lifetime compared to those on bare-glass, which are due to metal enhanced fluorescence. On the other hand, the corresponding MEF from randomly oriented film obtained by using spin coating of the probes on SIFs was only 2.5-fold. Further, we deposited mixed monolayers of NBD-C16 or NBD-C18 with various molar ratios of stearic acid to understand the polarity effect on MEF. Interestingly, we found a consistent increase in MEF efficiency with increasing molar ratio of stearic acid. Along with MEF, we also found a continuous blue-shift in emission band maxima of the probes with an increasing molar ratio of stearic acid. The observed increase in MEF efficiency is justified based on cooperative effects of (1) the modulations in electronic density of the surface plasmon absorption band of SIFs and (2) defined probe orientation that might lead to preferential excitation.

Fluorescence↗
PubMed2005

Enhanced fluorescence cyanide detection at physiologically lethal levels: reduced ICT-based signal transduction.

Three water-soluble fluorescent probes have been specifically designed to determine free cyanide concentrations up to physiologically lethal levels, >20 microM. The probes have been designed in such a way as to afford many notable sensing features, which render them unique with regard to signal transduction, photophysical characteristics, and their application to physiological cyanide determination and safeguard. The probes are readily able to reversibly bind free aqueous cyanide with dissociation constants around 4 microM3. Subsequent cyanide binding modulates the intramolecular charge transfer within the probes, a change in the electronic properties within the probes, resulting in enhanced fluorescence optical signals as a function of increased solution cyanide concentration. The ground-state chelation with cyanide produces wavelength shifts, which also enable the probes to sense cyanide in both an excitation and emission ratiometric manner, in addition to enhanced fluorescence signaling. This has enabled a generic cyanide sensing platform to be realized that is not dependent on fluorescent probe concentration, probe photodegradation, or fluctuations in the intensity of any employed excitation sources, ideal for remote cyanide sensing applications. Further, the >600 nm fluorescence emission of the probes potentially allows for enhanced fluorescence ratiometric cyanide sensing in the optical window of tissues and blood, facilitating their use for the transdermal monitoring of cyanide for mammalian safeguard or postmortem in fire victims, both areas of active research.

Cyanides↗
PubMed2005

Boronic acid fluorescent sensors for monosaccharide signaling based on the 6-methoxyquinolinium heterocyclic nucleus: progress toward noninvasive and continuous glucose monitoring.

The synthesis, characterization, and spectral properties of strategically designed boronic acid containing fluorescent sensors, o-, m-, p-BMOQBA, for the potential detection of tear glucose concentrations when immobilized in plastic disposable contact lenses is described. The new probes, BMOQBAs, consist of the 6-methoxyquinolinium nucleus as a fluorescent indicator, and the boronic acid moiety as a glucose chelating group. A control compound BMOQ, which has no boronic acid group and therefore does not bind monosaccharides has also been prepared. In this paper, we show that structural design considerations of the new probes have afforded for their compatibility within the lenses, with reduced probe sugar-bound pK(a) favorable with the mildly acidic lens environment. In addition, the new probes are readily water soluble, have high quantum yields, and can be prepared by a simple one-step synthetic procedure.

Boronic Acids↗
PubMed2005

Fluorescence sensor design for transition metal ions: the role of the PIET interaction efficiency.

Multicomponent systems 1, 2, and 3 having fluorophore-spacer-receptor architecture have been prepared with a view to understand the role of the photoinduced intramolecular electron transfer (PIET) interactions in transition metal ion sensing efficiency of these systems. Structurally similar compounds 4-amino-1,8-naphthalimide (4), 4-aminophthalimide (5), and 4-methoxy-1,8-naphthalimide (6) were used as the fluorophore moieties. Dimethylamino group (as in the case of 1a, 2a, and 3a, series A) and an aniline moiety (like in 1b, 2b, and 3b, series B) have been employed as the receptor components. A two-carbon ethylene chain serves as a spacer unit. The absorption and fluorescence spectral features of the systems have been studied in the absence and presence of various transition metal ions. All the multicomponent systems (except 1a) show weak fluorescence intensities compared to that of their constituent fluorophores (4, 5, and 6) in any given solvent. The reason for this low fluorescence quantum yield could be ascribed to the efficient PIET interaction between receptor moiety and the electron deficient fluorophore component of the systems. This has been corroborated with the estimated thermodynamic driving force (delta G*) for the PIET process in the multicomponent systems, calculated using electrochemical and spectral properties of individual components, is more negative for 2 and 3 than for 1 having electron deficient fluorophores 5, and 6, respectively. Especially, as evidenced by their low fluorescence quantum yield values, the PIET interaction is found to be more significant in the systems of series B (1b, 2b, and 3b) than the respective system of series A (1a, 2a, and 3a, respectively). The sensing capability of the systems is directly related to the efficiency of the PIET interaction in the unbound state. Accordingly, all these systems (except 1a) show significant fluorescence enhancement in the presence of transition metal ions, well known for their high fluorescence quenching behavior. The present paper describes, the feasibility of optimizing the PIET interaction in the multicomponent sensor system in unbound state, and thus transition metal ion signaling capability of the system.

Journal Article↗
PubMed2005

Metal-enhanced fluorescence from plastic substrates.

We report the first findings of Metal-Enhanced Fluorescence (MEF) from modified plastic substrates. In the past several years our laboratories have reported the favorable effects of fluorophores in close proximity to silver nanoparticles. These effects include, enhanced fluorescence intensities, (increased detectability), and reduced lifetimes, (enhanced fluorophore photostability). All of these reports have featured silver nanostructures and fluorophores which have been immobilized onto clean glass or quartz surfaces. In this report we show how plastic surfaces can be modified to obtain surface functionality, which in turn allows for silver deposition and therefore metal-enhanced fluorescence of fluorophores positioned above the silver using a protein spacer. Our findings show that plastic substrates are ideal surfaces for metal-enhanced phenomena, producing similar enhancements as compared to clean glass surfaces. Subsequently, we speculate that plastic substrates for MEF will find common place, as compared to the more expensive and less versatile traditional silica based supports.

Fluorescence↗
PubMed2005

A glucose-sensing contact lens: from bench top to patient.

In the past few years we have seen the development of several new technologies for the continuous and non-invasive monitoring of physiological glucose, such as the GlucoWatch, glucose-sensing skin patches and approaches based on a glucose-sensing tattoo. One approach that differs from current thinking is based on the determination and monitoring of tear glucose, which is well known to track blood glucose with an approximate 30 min lag time, using disposable and colorless contact lenses. These contact lenses can be worn by diabetics who can colorimetrically see changes in their contact lens color or other fluorescence-based properties, giving an indication of tear and blood glucose levels.

Biosensing Techniques↗
PubMed2004

Ophthalmic glucose sensing: a novel monosaccharide sensing disposable and colorless contact lens.

We have developed a technology for continuous tear glucose monitoring, and therefore potentially blood glucose monitoring, using a daily use, disposable contact lens embedded with sugar-sensing boronic acid containing fluorophores. The novelty of our approach is two fold. Firstly, the notion of sensing extremely low glucose concentrations in tears by our approach, and secondly, the unique compatibility of our new probes with the internal environment of the disposable, off-the-shelf, contact lenses, chosen because the physiological compatibility of disposable plastic contact lenses has already been assessed and optimized with regard to vision correction, size and oxygen/analyte permeability. Our findings show that our approach is indeed suitable for the continuous monitoring of tear glucose levels in the concentration range (50-500 microM), which track blood glucose levels which are approximately 5-10 fold higher. We believe our approach offers unique opportunities for non-invasive continuous glucose monitoring for diabetics, especially since many have eye disorders and require vision correction by either contact lenses or glasses, which is thought to be due to glycation of protein in blood vessels.

Boronic Acids↗
PubMed2004

Excitation and emission wavelength ratiometric cyanide-sensitive probes for physiological sensing.

We characterize three new fluorescent probes that show both spectral shifts and intensity changes in the presence of aqueous cyanide, allowing for both excitation and fluorescence emission wavelength ratiometric and colorimetric sensing. The relatively high binding constants of the probes for cyanide enables a distinct colorimetric change to be visually observed with as little as 10 microM cyanide. The response of the new probes is based on the ability of the boronic acid group to interact with the CN(-) anion, changing from the neutral form of the boronic acid group R-B(OH)(2) to the anionic R-B(-)(OH)3 form, which is an electron-donating group. The presence of an electron-deficient quaternary heterocyclic nitrogen center and a strong electron-donating amino group in the 6 position on the quinolinium backbone provides for the spectral changes observed upon CN(-) complexation. We have determined the binding constants for the ortho-, meta-, and para-boronic acid probes to be 0.12, 0.17, and 0.14 microM(-3). In addition we have synthesized a control compound that does not contain the boronic acid moiety, allowing for structural comparisons and a rationale for the sensing mechanism to be made. Finally we show that the affinity for monosaccharides, such as glucose or fructose, is relatively low as compared to that for cyanide, enabling the potential detection of cyanide in physiologies up to lethal levels.

Biosensing Techniques↗
PubMed2004

Noninvasive continuous monitoring of physiological glucose using a monosaccharide-sensing contact lens.

We have tested the feasibility of tear glucose sensing using a daily, disposable contact lens embedded with boronic acid-containing fluorophores as a potential alternative to current invasive glucose-monitoring techniques. Our findings show that our approach may, indeed, be suitable for the continuous monitoring of tear glucose levels in the range 50-500 microM, which track blood glucose levels that are approximately 5-10-fold higher. We compare the response of the boronic acid probes in the contact lens to solution-based measurements and can conclude that both the pH and polarity within the contact lens need to be considered with respect to choosing/designing and optimizing glucose-sensing probes for contact lenses.

Biosensing Techniques↗
PubMed2004

Advances in surface-enhanced fluorescence.

We report recent achievements in metal-enhanced fluorescence from our laboratory. Several fluorophore systems have been studied on metal particle-coated surfaces and in colloid suspensions. In particular, we describe a distance dependent enhancement on silver island films (SIFs), release of self-quenching of fluorescence near silver particles, and the applications of fluorescence enhancement near metalized surfaces to bioassays. We discuss a number of methods for various shaped silver particle deposition on surfaces.

Algorithms↗
PubMed2004

Ophthalmic glucose monitoring using disposable contact lenses--a review.

We have developed a range of disposable and colorless tear glucose sensing contact lenses, using off-the-shelf lenses embedded with new water soluble, highly fluorescent and glucose sensitive boronic acid containing fluorophores. The new lenses are readily able to track tear glucose levels and therefore blood glucose levels, which are ideally suited for potential use by diabetics. The fluorescence responses from the lenses can be monitored using simple excitation and emission detection devices. The novelty of our approach is two fold. Firstly, the notion of sensing extremely low glucose concentrations in tears, which track blood levels, by our contact lens approach, and secondly, the unique compatibility of our new glucose signaling probes with the internal mildly acidic contact lens environment. The new lenses are therefore ideal for the non-invasive and continuous monitoring of tear glucose, with about 15-min response time, and a measured shelf life in excess of 3 months. In this review article, we show that fluorescence based signaling using plastic disposable lenses, which have already been industrially optimized with regard to vision correction and oxygen/analyte permeability etc, may a notable alternative to invasive and random finger pricking, the most widely used glucose monitoring technology by diabetics.

Algorithms↗
PubMed2004

Wavelength-ratiometric probes for the selective detection of fluoride based on the 6-aminoquinolinium nucleus and boronic acid moiety.

Herein we report a set of new water-soluble fluorescent probes (N-boronobenzyl-6-aminoquinolinium bromides, BAQBAs) sensitive to aqueous fluoride. These probes shows spectral shifts and intensity changes in the presence of fluoride, in a wavelength ratiometric and colorimetric manner, enabling the detection of fluoride concentrations at visible wavelengths, in the concentration range approximately 1-300 mM. Although the sensing mechanism is different for fluoride as compared to the other halides, we have tested the utility of these probes towards the other halides, and the results reveal that the BAQBAs are in fact potential candidates towards the sensing of the all the halides, but in different concentration ranges. As the probes are based on the boronic acid moiety, which is a well-known fluoride and sugar chelator group, we have investigated the response of sugars (such as glucose and fructose, which are present in biological fluids and foodstuffs) as interferences in fluoride detection using these probes. Interestingly, the BAQBAs show a suppressed sugar response potentially allowing for the predominant fluoride sensitivity. In addition to physiological sugars, we also have assessed the response of aqueous halides as potential interferents, or indeed analytes to be sensed, and show that the new boronic acid containing probes respond well to aqueous fluoride in the presence of a high background of other species, such as in a biological cocktail of 50 mM Glucose, 50 mM aqueous Chloride and 5 mM Fructose.

Aminoquinolines↗