Multifold Enhancement Research Articles

Förster resonance energy transfer between acridinediones and selected fluorophores—Medium dependence

We report highly efficient Förster resonance energy transfer process between acridinedione dyes and basic fluorophores. FRET between free and β-cyclodextrin modified acridinediones as donors and fluorophoric dyes like safranine as acceptor were investigated in an alcoholic medium, polymer solution and a polymeric film. Efficiency of the processes were experimentally found by steady-state and time-resolved experiments for different donor and acceptor combinations. The associated spectral parameters viz., R0, J(λ) were calculated, the Stern–Volmer relations based on fluorescence intensity and lifetime were constructed and the rates of energy transfer were calculated. The results indicated that the dominant mechanism responsible for the excitation energy transfer is that of resonance transfer due to long range dipole–dipole interaction and the process was found to be highly efficient when the medium was a constrained one as in the case of a polymeric film. A multifold enhancement in efficiency of energy transfer was also observed when the donor was a modified acridinedione when compared to a free acridinedione. The reason is attributed to the effective binding of the acceptor into the cavity of β-cyclodextrin.

A first principles study of oxygen reduction reaction on a Pt(111) surface modified by a subsurface transition metal M (M = Ni, Co, or Fe)

We have performed first-principle density functional theory calculations to investigate how a subsurface transition metal M (M = Ni, Co, or Fe) affects the energetics and mechanisms of oxygen reduction reaction (ORR) on the outermost Pt mono-surface layer of Pt/M(111) surfaces. In this work, we found that the subsurface Ni, Co, and Fe could down-shift the d-band center of the Pt surface layer and thus weaken the binding of chemical species to the Pt/M(111) surface. Moreover, the subsurface Ni, Co, and Fe could modify the heat of reaction and activation energy of various elementary reactions of ORR on these Pt/M(111) surfaces. Our DFT results revealed that, due to the influence of the subsurface Ni, Co, and Fe, ORR would adopt a hydrogen peroxide dissociation mechanism with an activation energy of 0.15 eV on Pt/Ni(111), 0.17 eV on Pt/Co(111), and 0.16 eV on Pt/Fe(111) surface, respectively, for their rate-determining O2 protonation reaction. In contrast, ORR would follow a peroxyl dissociation mechanism on a pure Pt(111) surface with an activation energy of 0.79 eV for its rate-determining O protonation reaction. Thus, our theoretical study explained why the subsurface Ni, Co, and Fe could lead to multi-fold enhancement in catalytic activity for ORR on the Pt mono-surface layer of Pt/M(111) surfaces.

Targeting enteral endocrinal L-cells with dietary carbohydrates, by increasing the availability of miglitol in the intestinal lumen, leads to multi-fold enhancement of plasma glucagon-like peptide-1 levels in non-diabetic canines

The principle aim of this study was to design a controlled release (CR), bioadhesive formulation of miglitol (in form of pellets) which would regulate the post-prandial glucose levels via reversible inhibition of α-glucosidase enzyme as well as by modulating the glucagon-like peptide-1 (GLP-1) pathway in non-diabetic canines. A multilayered pellet formulation which was both bioadhesive (because of hydroxy propyl methyl cellulose polymer) and CR (because of the ethyl cellulose layer) was formulated. We report a novel finding that the CR formulation of miglitol (S3) induced a 2.2-fold elevation in the Cmax as well as the overall AUC0–24 of GLP-1 values in comparison to the non-CR (immediate release (IR) formulation). The S3 formulation also resulted in better, steady, and prolonged control of glucose levels over a time period of 7 h in comparison to the IR formulation possibly due to combination of both, prolonged inhibition of the α-glucosidase enzyme and enhanced plasma GLP-1 levels. The S3 formulation was stable with no changes in the dissolution profiles at both of the stability conditions tested, 25°C/60% RH and 40°C/75% RH. Aqueous polymeric coating of the pellets (in contrast to coating using organic solvents) resulted morphologically in a uniform polymeric film and also releases profiles with lower burst effect. Curing played a significant role in determining release profile of the pellets, prepared by aqueous polymeric coating method.

Multifold Enhancement of Quantum Dot Luminescence in Plasmonic Metamaterials

We report that hybridizing semiconductor quantum dots with plasmonic metamaterial leads to a multifold intensity increase and narrowing of their photoluminescence spectrum. The luminescence enhancement is a clear manifestation of the cavity quantum electrodynamics Purcell effect and can be controlled by the metamaterial's design. This observation is an essential step towards understanding loss compensation in plasmonic metamaterials with gain media and for developing metamaterial-enhanced gain media.

Enhanced fluorescence emission of Me-ADOTA+ by self-assembled silver nanoparticles on a gold film

We report a multi-fold enhancement of the fluorescence of methyl-azadioxatriangulenium chloride (Me-ADOTA·Cl) in PVA deposited on a 50nm thick gold mirror carrying an evaporation induced self-assembly of colloidal silver nanoparticles (Ag-SACs). The average measured increase in fluorescence emission of about 50-fold is accompanied by hot spots with a local enhancement in brightness close to 200. The long lifetime of the dye allows for the first direct determination of the correlation between the enhancement of emission intensity and the decrease in fluorescence lifetime. The Ag-SACs surface preparation and observed enhancements are highly reproducible. We believe that these robust plasmonic surfaces will find use in sensing platforms for ultrasensitive detection.

New insights into the membrane-binding and activation mechanism of pyruvate oxidase from Escherichia coli

Pyruvate oxidase from Escherichia coli ( EcPOX) is a thiamin diphosphate- (ThDP) and FAD-dependent peripheral membrane protein that carries out the irreversible oxidative decarboxylation of pyruvate to acetate and carbon dioxide. Concomitant two-electron reduction of the flavin cofactor was suggested to induce a structural rearrangement of the C-terminus triggering recruitment of the protein from the cytosol to the cell membrane, where the electrons are eventually transferred to final electron acceptor ubiquinone 8. Binding to the membrane, or alternatively, mild proteolytic digestion leads to a multifold enhancement of both the catalytic activity and substrate affinity. Recent X-ray crystallographic studies on EcPOX in the resting state and on a C-terminal truncation variant mimicking the membrane-bound activated form have fueled our understanding of the membrane-binding mechanism and concomitant catalytic activation. In the resting state, the auto-inhibitory C-terminal membrane anchor adopts a half-barrel/helix fold that occludes the active site. Upon activation, the C-terminus is expelled and becomes structurally flexible thereby freeing the active site. Circular dichroism spectroscopic analysis revealed the isolated C-terminus to be disordered, however, formation of a helical structure was observed in the presence of micelles. Limited proteolysis experiments indicate that activation of EcPOX involves at least two sequential structural transitions: the first occurring after binding of pyruvate to ThDP and the second after two-electron reduction of the flavin.

Spontaneous organisation of ZnS nanoparticles into monocrystalline nanorods with highly enhanced dopant-related emission

A natural self-assembly process of semiconductor nanoparticles leading to the formation of doped, monocrystalline nanorods with highly enhanced dopant-related luminescence properties is reported. ∼4 nm sized, polycrystalline ZnS nanoparticles of zinc-blende (cubic) structure, doped with Cu +-Al 3+ or Mn 2+ have been aggregated in the aqueous solution and grown into nanorods of length ∼400 nm and aspect ratio ∼12. Transmission electron microscopic (TEM) images indicate crystal growth mechanisms involving both Ostwald-ripening and particle-to-particle oriented-attachment. Sulphur–sulphur catenation is proposed for the covalent-linkage between the attached particles. The nanorods exhibit self-assembly mediated quenching of the lattice defect-related emission accompanied by multifold enhancement in the dopant-related emission. This study demonstrates that the collective behavior of an ensemble of bare nanoparticles, under natural conditions, can lead to the formation of functionalized (doped) nanorods with enhanced luminescence properties.

Influence of electron injection on performance of GaN photodetectors

It is demonstrated that short-time (up to 1200 s) electron injection into the p-region of GaN p–n junction, as a result of forward bias application, leads to a long-term multifold enhancement of the device peak responsivity as well as to a spectral broadening of the photoresponse. The effect is found to persist for several days and is related to an increased minority carrier diffusion length in the p region, due to an injected electron trapping on deep levels associated with Mg acceptors.

Multifold enhancement of the thermoelectric figure of merit in p-type BaBiTe3 by pressure tuning

As in the combinatorial approach to materials discovery, pressure tuning allows the phase space of interaction parameters that determine materials’ properties to be explored more rapidly than by traditional means. Both the thermoelectric power and electrical conductivity of BaBiTe3 are found to increase upon compression. As a result there is a dramatic increase in the dimensionless thermoelectric figure of merit ZT from ∼0.1 to ∼0.8. We suggest a mechanism for the enhancement involving an electronic topological transition. Such transitions can be induced both by means of pressure tuning and alloying, offering a potential route to reproducing the pressure induced improved behavior reported here by chemical means.

Effects of long-term treatment with acetylene on nitrogen-fixing microorganisms

Long periods of experimental incubation with acetylene led to a multifold enhancement of acetylene-reducing activity in Anabaena cylindrica, Anabaenopsis circularis, Rhodospirillum rubrum, and Azotobacter vinelandii. Rates of acetylene reduction showed a gradual increase and reached a peak after 2 to 6 h of continuous incubation under acetylene. Thereafter, enzyme activity rapidly declined. A similar enhancement of ethylene production was observed when pretreatment with acetylene was interrupted periodically by a brief exposure to ambient (or oxygen-free) atmosphere without acetylene although the decline of acetylene-reducing activity was less rapid. Pretreatment with acetylene depressed photosynthetic 14CO2 fixation and 15N2 incorporation in Anabaena cylindrica. It is concluded that assessments based on long-term experimental incubation with acetylene may grossly overestimate the actual quantities of fixed nitrogen in the field.