Unmodified "GNP-oligonucleotide" nanobiohybrids: a simple route for emission enhancement of DNA intercalators

We present herein a simple method for enhancing the emission of DNA intercalators in homogeneous nanobiohybrids of unlabeled oligonucleotides and unmodified gold nanoparticles (GNPs). Pristine single‐stranded DNA (ss‐DNA) has been wrapped around unmodified GNPs to induce metal‐enhanced fluorescence (MEF) of DNA intercalators, such as ethidium bromide and propidium iodide. The thickness of the ss‐DNA layer on the gold nanosurface determines the extent of MEF, since this depends on the position of the intercalator in relation to the metal surface. Presumably, at a suitable thickness of this DNA layer, more of the intercalator is localized at the optimum distance from the nanoparticle to give rise to MEF. Importantly, no external spacer or coating agent was needed to induce the MEF effect of the GNPs. The concentration ratios of Au to DNA in the nanohybrids, as well as the capping agents applied to the GNPs, play key roles in enhancing the emission of the intercalators. The dimensions of both components of the nanobiohybrids, that is, the size of the GNPs and the length of the oligonucleotide, have considerable influences on the emission enhancement of the intercalators. Emission intensity increased with increasing size of the GNPs and length of the oligonucleotide only when the DNA efficiently wrapped the nanoparticles. An almost 100 % increment in the quantum yield of ethidium bromide was achieved with the GNP–DNA nanobiohybrid compared with that with DNA alone (in the absence of GNP), and the fluorescence emission was enhanced by 50 % even at an oligonucleotide concentration of 2 nM . The plasmonic effect of the GNPs in the emission enhancement was also established by the use of similar nanobioconjugates of ss‐DNA with nonmetallic carbon nanoparticles and TiO₂ nanoparticles, with which no increase in the fluorescence emission of ethidium bromide was observed.     

Single crystal-to-single crystal irreversible transformation from a discrete vanadium(V)-alcoholate to an aldehydic-vanadium(IV) oligomer

An unprecedented single crystal-to-single crystal transformation occurs when a binuclear oxovanadium(V) compound [V(V)(2)O(2)(L)(2)] 1 involving 2,6-bis(hydroxymethyl)-p-cresol (H(3)L) as a bridging ligand is exposed simultaneously to white light and aerial oxygen to generate an oligomeric compound [V(IV)(2)O(2)(L*)(2)] 2 (H(2)L* is 3-hydroxymethyl-5-methylsalicylaldehyde). Each vanadium(V) center in 1 is reduced to vanadium(IV) in 2 at the expense of a two-electron alcohol-to-aldehyde oxidation in the coordinated ligand. The additional electron being released is possibly consumed by molecular oxygen to generate hydrogen peroxide.     

Physical realization and possible identification of topological excitations in quantum Heisenberg anti-ferromagnet on a two dimensional lattice

Physical spin configurations corresponding to topological excitations, expected to be present in the XY limit of a quantum spin 1/2 Heisenberg anti-ferromagnet, are probed on a two dimensional square lattice. Quantum vortices (anti-vortices) are constructed in terms of coherent staggered spin field components, as limiting case of meronic (anti-meronic) configurations. The crucial role of the associated Wess-Zumino-like (WZ-like) term is highlighted in our procedure. The time evolution equation of coherent spin fields used in this analysis is obtained by applying variational principle on the quantum Euclidean action corresponding to the Heisenberg anti-ferromagnet on lattice. It is shown that the WZ-like term can distinguish between vortices and anti-vortices only in a charge sector with odd topological charges. Our formalism is distinctly different from the conventional approach for the construction of quantum vortices (anti-vortices).     

Probing internal environment of sol–gel bulk and thin films using multiple fluorescent probes

The selection of sol compositions, conditions of preparation and storage of gels are an important aspects for encapsulating biomolecules in gel matrix for applications in biosensor. In the present investigation, fluorescence spectroscopic measurements (emission and fluorescence lifetimes) were carried out in bulk gel and thin films prepared from sols with water and tetraethyl-orthosilicate (TEOS) containing different fluorescent probes viz Hoechst 33258 (H258), Pyranine (Py), and 7-Azaindole (7-AI) in different sols. Sols were prepared with addition of water, HCl and surfactant Triton X-100, and stored at room temperature (RT) and low temperature (4 °C). The spectral characteristics have been compared for two different storage conditions as a function of aging. The results of the present study clearly suggested that the internal environment of gels specifically the content of water inside the pores of the sol–gel matrix can be controlled by storage at 4 °C as compared to RT.     

Simulation Study of the Conformational Properties of Diblock Polyelectrolytes in Salt Solutions

Coarse-grained molecular dynamics simulations are performed to understand the behavior of diblock polyelectrolytes in solutions of divalent salt by studying the conformations of chains over a wide range of salt concentrations. The polymer molecules are modeled as bead spring chains with different charged fractions and the counterions and salt ions are incorporated explicitly. Upon addition of a divalent salt, the salt cations replace the monovalent counterions, and the condensation of divalent salt cations onto the polyelectrolyte increases, and the chains favor to collapse. The condensation of ions changes with the salt concentration and depends on the charged fraction. Also, the degree of collapse at a given salt concentration changes with the increasing valency of the counterion due to the bridging effect. As a quantitative measure of the distribution of counterions around the polyelectrolyte chain, we study the radial distribution function between monomers on different polyelectrolytes and the counterions inside the counterion worm surrounding a polymer chain at different concentrations of the divalent salt. Our simulation results show a strong dependence of salt concentration on the conformational properties of diblock copolymers and indicate that it can tune the self-assembly behaviors of such charged polyelectrolyte block copolymers.     

Influence of Gold Nanoparticles of Varying Size in Improving the Lipase Activity within Cationic Reverse Micelles

Herein, we report the effect of gold nanoparticles (GNPs) in enhancing lipase activity in reverse micelles of cetyltrimethylammonium bromide (CTAB)/water/isooctane/n‐hexanol. The size and concentration of the nanoparticles were varied and their specific roles were assessed in detail. An overall enhancement of activity was observed in the GNP‐doped CTAB reverse micelles. The improvement in activity becomes more prominent with increasing concentration and size of the GNPs (0–52 μM and ca. 3–30 nm, respectively). The observed highest lipase activity (k₂=1070±12 cm³ g^?1 s^?1) in GNP‐doped CTAB reverse micelles ([GNP]: 52 μm, ca. 20 nm) is 2.5‐fold higher than in CTAB reverse micelles without GNPs. Improvement in the lipase activity is only specific to the GNP‐doped reverse micellar media, whereas GNP deactivates and structurally deforms the enzyme in aqueous media. The reason for this activation is probably due to the formation of larger‐sized reverse micelles in which the GNP acts as a polar core and the surfactants aggregate around the nanoparticle (‘GNP pool’) instead of only water. Lipase at the augmented interface of the GNP‐doped reverse micelle showed improved activity because of enhancement in both the substrate and enzyme concentrations and increased flexibility in the lipase conformation. The extent of the activation is greater in the case of the larger‐sized GNPs. A correlation has been established between the activity of lipase and its secondary structure by using circular dichroism and FTIR spectroscopic analysis. The generalized influence of GNP is verified in the reverse micelles of another surfactant, namely, cetyltripropylammonium bromide (CTPAB). TEM, dynamic light scattering (DLS), and UV/Vis spectroscopic analysis were utilized to characterize the GNPs and the organized aggregates. For the first time, CTAB‐based reverse micelles have been found to be an excellent host for lipase simply by doping with appropriately sized GNPs.     

Vibration-actuated drop motion on surfaces for batch microfluidic processes

When a liquid drop is subjected to an asymmetric lateral vibration on a nonwettable surface, a net inertial force acting on the drop causes it to move. The direction and velocity of the drop motion are related to the shape, frequency, and amplitude of vibration, as well as the natural harmonics of the drop oscillation. Aqueous drops can be propelled through fluidic networks connecting various unit operations in order to carry out batch processing at the miniature scale. We illustrate the integration of several unit operations on a chip: drop transport, mixing, and thermal cycling, which are precursor steps to carrying out advanced biological processes at microscale, including cell sorting, polymerase chain reaction, and DNA hybridization.