Effects of pH on the Interactions and Conformation of Bovine Serum Albumin: Comparison between Chemical Force Microscopy and Small-Angle Neutron Scattering

The conformation of bovine serum albumin (BSA), as well as its interactions with negatively charged mica surfaces in saline solutions of different pH values, have been studied by small-angle neutron scattering (SANS) and chemical force microscopy (CFM), respectively. A new approach to extract the contribution of elementary interactions from the statistically averaged force-extension curves through self-consistent fitting was proposed and used to understand the effects of pH on the interactions and conformation of BSA in saline solutions. When pH increases, the SANS results reveal that the sizes of BSA molecules increase slightly, while the statistical analysis of the CFM results shows that the averaged pull-off force for the elongation monotonously decreases. The decrease of pull-off force with the increase of pH results from the decrease in the strength of hydrogen bonding and the number of interaction pairs, as well as the slight increase of the strength of van der Waals interaction. When pH approaches the isoelectric point (pI) of BSA, results from both SANS and CFM suggest a loss of long-range interactions in BSA molecules. Our results also suggest that the force-extension curve is mainly contributed by the van der Waals interaction. The combination of SANS and CFM provides new insight to understand the interactions and conformation of BSA molecules

Facile fabrication of gold nanoparticle arrays for efficient surface-enhanced Raman scattering

An effective and facile method for the fabrication of a surface-enhanced Raman scattering (SERS)-active film with closely packed gold nanoparticle (AuNP) arrays is proposed by self-assembly of different sizes ( 16, 25, 40 and 70 nm) of AuNPs at a toluene/water interface with ethanol as the inducer. The as-prepared AuNP arrays exhibit efficient Raman scattering enhancement, and the enhancement factors estimated using p-aminothiophenol as a probe molecule range from 10(5) to 10(7).

The electrochemical behavior of a system with a limited number of molecules

In this paper, based on Einstein relationship between diffusion and random walk, the electrochemical behavior of a system with a limited number of molecules was simulated and explored theoretically. The transition of the current vs time responses from discrete to continuous was clearly obtained as the number of redox molecules increased from 10 to 10(6).

Ethanol-induced formation of silver nanoparticle aggregates for highly active SERS substrates and application in DNA detection

A controllable silver nanoparticle aggregate system has been synthesized by adding different amounts of ethanol to cetyltrimethylammonium bromide (CTAB) capped silver nanoparticles (Ag-nps), which could be used as highly efficient surface-enhanced Raman scattering (SERS) active substrates. This ethanol-induced aggregation can be attributed to preferential dissolution of CTAB into ethanol, which leads a partial removal of the protective CTAB layer on Ag-nps. The optical and morphological properties of these aggregates under various volumes of ethanol were explored via UV-vis spectroscopy and atomic force microscopy.

Localization of Na+-K+ ATPases in Quasi-Native Cell Membranes

Na+-K+ ATPases have been observed and located by in situ AFM and single molecule recognition technique, topography and recognition imaging (TREC) that is a unique technique to specifically identify single protein in complex during AFM imaging. Na+-K+ ATPases were well distributed in the inner leaflet of cell membranes with about 10% aggregations in total recognized proteins. The height of Na+-K+ ATPases measured by AFM is in the range of 12-14 nm, which is very consistent with the cryoelectron microscopy result. The unbinding force between Na+-K+ ATPases in the membrane and anti-ATPases on the AFM tip is about 80 pN with the apparent loading rate at 40 nN/s.

A {Co-32} Nanosphere Supported by p-tert-Butylthiacalix[4]arene

Calixarene-capped Co-32 clusters are constructed by a sodalite Co-24(II) cage and an encapsulated Co-8(III) cube. The spherical units are arranged into three isomeric structures, two of which are stacked by the bcc lattices and the third of which is assembled by the cubic closest packing of the spherical units.

Characterization and optimization of AuNPs labeled by Raman reporters on glass based on silver enhancement

In this report, gold nanoparticles (AuNPs) labeled by Raman reporters (AuNPs-R6G) were assembled on glass and used as the seeds to in situ grow silver-coated nanostructures based on silver enhancer solution, forming the nanostructures of AuNPs-R6G@Ag, which were characterized by scanning electron microscopy (SEM) and UV-visible spectroscopy. More importantly, the obtained silver-coated nanostructures can be used as a surface enhancement Raman scattering (SERS) substrate. The different SERS activities can be controlled by the silver deposition time and assembly time of AuNPs-R6G on glass. The results indicate that the maximum SERS activity could be obtained on AuNPs-R6G when these nanostructures were assembled on glass for 2 h with silver deposition for 2 min.

From Tunneling to Hopping: A Comprehensive Investigation of Charge Transport Mechanism in Molecular Junctions Based on Oligo(p-phenylene ethynylene)s

The charge transport mechanism of oligo(p-phenylene ethynylene)s with lengths ranging from 0.98 to 5.11 nm was investigated using modified scanning tunneling microscopy break junction and conducting probe atomic force microscopy methods. The methods were based on observing the length dependence of molecular resistance at single molecule level and the current-voltage characteristics in a wide length distribution. An intrinsic transition from tunneling to hopping charge transport mechanism was observed near 2.75 nm. A new transitional zone was observed in the long length molecular wires compared to short ones. This was not a simple transition between direct tunneling and field emission, which may provide new insights into transport mechanism investigations. Theoretical calculations provided an essential explanation for these phenomena in terms of molecular electronic structures.

Surface-enhanced Raman scattering of 4-aminothiophenol self-assembled monolayers in sandwich structure with nanoparticle shape dependence: Off-surface plasmon resonance condition

A universal metal-molecule-metal sandwich architecture by the self-assembly of Ag nanoparticles (NPs) and Au NPs of various shapes interconnected with 4-aminothiophenol (4-ATP) molecules was presented. These Ag NPs/4-ATP/Au NPs sandwich structures were characterized by surface enhanced Raman scattering (SERS) using an off-surface plasmon resonance condition. Enhancement factors (EF) on the order of 10(8) for 9b(b(2)) vibration mode were observed for the 4-ATP self-assembled monolayers (SAMs) in such sandwich structures. The factors are 2 orders of magnitude larger than that on the monolayer of Au NPs of various shapes under similar condition. More importantly, remarkable increase in the intensity of b(2) vibrational modes, which is characteristic of the charge transfer (CT) behavior between metal NPs and 4-ATP molecules, was observed in these sandwich structures under 1064 nm excitation. The obtained EF on these sandwich structure for 9b(b(2)) is larger than that for 7a vibration mode by a factor of similar to 10(2), demonstrating the importance of the contribution of the CT mechanism and the CT behavior of metal contacts, which play a significant role in metal-molecule-metal nanosystems.

Surface enhanced Raman scattering of brilliant green on ag nanoparticles and applications in living cells as optical probes

In this article, surface enhanced Raman scattering (SERS) of different concentrations of brilliant green (13G) on Ag nanoparticles (AgNPs) has been investigated. The results indicate that only 10(-12) M BG can be detected on AgNPs while as low as 10(-11) M BG can be detected upon the activation of AgNPs by chloride ions. The additional improvement of the detection of BG mainly derives from the increase of the electromagnetic field around AgNPs and partially from the reorientation of BG on AgNPs induced by chloride ions, which was proved by the different spectra feature in the two systems. Adsorption of BG on AgNPs has also been demonstrated in applications of living cells as optical probes based on SERS, indicating that dye-AgNPs can probe the local environment in the living cells. The related cytotoxicity measurements demonstrated that BG-AgNPs produced little cytotoxicity to the cells, which shows great potential in biornedical applications of BG labeled-AgNPs for SERS nanosensors in cells as optical probes. Meanwhile, SERS spectra of BG on AgNPs in the presence chloride ions are expected to be used in living cells as more sensitive optical probes.

Surface enhanced Raman scattering of brilliant green on ag nanoparticles and applications in living cells as optical probes

In this article, surface enhanced Raman scattering (SERS) of different concentrations of brilliant green (13G) on Ag nanoparticles (AgNPs) has been investigated. The results indicate that only 10(-12) M BG can be detected on AgNPs while as low as 10(-11) M BG can be detected upon the activation of AgNPs by chloride ions. The additional improvement of the detection of BG mainly derives from the increase of the electromagnetic field around AgNPs and partially from the reorientation of BG on AgNPs induced by chloride ions, which was proved by the different spectra feature in the two systems. Adsorption of BG on AgNPs has also been demonstrated in applications of living cells as optical probes based on SERS, indicating that dye-AgNPs can probe the local environment in the living cells. The related cytotoxicity measurements demonstrated that BG-AgNPs produced little cytotoxicity to the cells, which shows great potential in biornedical applications of BG labeled-AgNPs for SERS nanosensors in cells as optical probes. Meanwhile, SERS spectra of BG on AgNPs in the presence chloride ions are expected to be used in living cells as more sensitive optical probes.

Syntheses, structures, and magnetic properties of two novel three-dimensional frameworks built from M4O4 cubanes and dicyanamide bridges

Two novel coordination polymers Ni-4(CH3O)(4)(CH3OH)(4)(dca)(4) (1) and Co-4(CH3O)(4)(CH3OH)(4)(dca)(4) (2) have been synthesized by solvethermal reaction. X-ray single-crystal analysis reveals that the two complexes are isostrutural and possess 3D frameworks that are built from the M4O4(M= Ni (1) and Co (2)) cubanelike building blocks linked by dicyanamide (dca) bridges. The temperature dependence of the magnetic susceptibility was measured and the DC experiment data were fitted using the Heisenberg spin Hamiltonian.

Manipulations of atoms and molecules by scanning probe microscopyk

Scanning probe microscopy (SPM), including scanning tunneling microscopy (STM) and atomic force microscopy (AFM), has become a powerful tool in building nanoscale structures required by modern industry. In this article, the use of SPM for the manipulation of atoms and molecules for patterning nanostructures for opt-electronic and biomedical applications is reviewed. The principles and procedures of manipulation using STM and AFM-based technologies are presented with an emphasis on their ability to create a wide variety of nanostructures for different applications. The interaction among the atoms/molecules, surface, and tip are discussed. The approaches for positioning the atom/molecule from and to the desired locations and for precisely controlling its movement are elaborated for each specific manipulation technique. As an AFM-based technique, the dip-pen nanolithography is also included. Finally, concluding remarks on technological improvement and future research is provided.

Downhill kinetics of biomolecular interface binding: Globally connected scenario

We study the kinetics of the biomolecular binding process at the interface using energy landscape theory. The global kinetic connectivity case is considered for a downhill funneled energy landscape. By solving the kinetic master equation, the kinetic time for binding is obtained and shown to have a U-shape curve-dependence on the temperature. The kinetic minimum of the binding time monotonically decreases when the ratio of the underlying energy gap between native state and average non-native states versus the roughness or the fluctuations of the landscape increases. At intermediate temperatures,fluctuations measured by the higher moments of the binding time lead to non-Poissonian, non-exponential kinetics. At both high and very low temperatures, the kinetics is nearly Poissonian and exponential.

The complex kinetics of protein folding in wide temperature ranges

The complex protein folding kinetics in wide temperature ranges is studied through diffusive dynamics on the underlying energy landscape. The well-known kinetic chevron rollover behavior is recovered from the mean first passage time, with the U-shape dependence on temperature. The fastest folding temperature T-0 is found to be smaller than the folding transition temperature T-f. We found that the fluctuations of the kinetics through the distribution of first passage time show rather universal behavior, from high-temperature exponential Poissonian kinetics to the relatively low-temperature highly nonexponential kinetics. The transition temperature is at T-k and T-0, T-k, T-f. In certain low-temperature regimes, a power law behavior at long time emerges. At very low temperatures ( lower than trapping transition temperature T< T-0/(4&SIM;6)), the kinetics is an exponential Poissonian process again.