Scanning tunneling microscopy and Raman evidence of silicene nanosheets intercalated into graphite surfaces at room temperature.

Highly oriented pyrolytic graphite (HOPG) is an inert substrate with a structural honeycomb lattice, well suited for the growth of a two-dimensional (2D) silicene layer. It was reported that when Si atoms are deposited on the HOPG surface at room temperature, they arrange into two configurations: silicene nanosheets and three-dimensional clusters. In this work we demonstrate, by using scanning tunneling microscopy (STM) and Raman spectroscopy, that a third configuration stabilizes in the form of Si 2D nanosheets intercalated below the first top layer of carbon atoms. The Raman spectra reveal a structure located at 538 cm-1 which we ascribe to the presence of sp2 Si hybridization. Moreover, the silicon deposition induces several modifications in the graphite D and G Raman modes, which we interpret as experimental evidence of the intercalation of the silicene nanosheets. The Si atom intercalation at room temperature takes place at the HOPG step edges and it detaches only the outermost graphite layer inducing a strong tensile strain mainly concentrated on the edges of the silicene nanosheets. Theoretical calculations of the structure and energetic viability of the silicene nanosheets and of the strain distribution on the outermost graphite layer and its influence on the Raman resonances support the STM and Raman observations.

Carbon nanotube sponges as tunable materials for electromagnetic applications.

The microwave conductivity and permittivity of both single-walled and multi-walled carbon nanotube (SWCNT and MWCNT) sponges were measured while compressing the samples. Compression leads to a huge variation of the absorptance, reflectance, and transmittance of the samples. The dependence of the microwave conductivity on the sponge density follows a power-law relation with exponents 1.7 ± 0.1 and 2.0 ± 0.2 for MWCNT and SWCNT sponges, respectively. These exponents can be decreased slightly by the addition of a non-conducting component which partly electrically separates adjacent tubes within the samples. The conductivity of MWCNT sponge was measured in the terahertz range while heating in air from 300 to 513 K and it increased due to an increase of a number of conducting channels in MWCNTs.

Ultrafast dynamics in unaligned MWCNTs decorated with metal nanoparticles.

The relaxation dynamics of unaligned multi-walled carbon nanotubes decorated with metallic nanoparticles have been studied by using transient optical measurements. The fast dynamics due to the short-lived free-charge carriers excited by the pump are not affected by the presence of nanoparticles. Conversely, a second long dynamics, absent in bare carbon nanotubes, appears only in the decorated samples. A combination of experiment and theory allows us to ascribe this long dynamics to relaxation channels involving electronic states localized at the tube-nanoparticle interface.

Challenges in quantitative single molecule localization microscopy.

Single molecule localization microscopy (SMLM), which can provide up to an order of magnitude improvement in spatial resolution over conventional fluorescence microscopy, has the potential to be a highly useful tool for quantitative biological experiments. It has already been used for this purpose in varied fields in biology, ranging from molecular biology to neuroscience. In this review article, we briefly review the applications of SMLM in quantitative biology, and also the challenges involved and some of the solutions that have been proposed. Due to its advantages in labeling specificity and the relatively low overcounting caused by photoblinking when photo-activable fluorescent proteins (PA-FPs) are used as labels, we focus specifically on Photo-Activated Localization Microscopy (PALM), even though the ideas presented might be applicable to SMLM in general. Also, we focus on the following three quantitative measurements: single molecule counting, analysis of protein spatial distribution heterogeneity and co-localization analysis.

Progress in quantitative single-molecule localization microscopy.

With the advent of single-molecule localization microscopy (SMLM) techniques, intracellular proteins can be imaged at unprecedented resolution with high specificity and contrast. These techniques can lead to a better understanding of cell functioning, as they allow, among other applications, counting the number of molecules of a protein specie in a single cell, studying the heterogeneity in protein spatial organization, and probing the spatial interactions between different protein species. However, the use of these techniques for accurate quantitative measurements requires corrections for multiple inherent sources of error, including: overcounting due to multiple localizations of a single fluorophore (i.e., photoblinking), undercounting caused by incomplete photoconversion, uncertainty in the localization of single molecules, sample drift during the long imaging time, and inaccurate image registration in the case of dual-color imaging. In this paper, we review recent efforts that address some of these sources of error in quantitative SMLM and give examples in the context of photoactivated localization microscopy (PALM).

A three-dimensional carbon nanotube network for water treatment.

The bulk synthesis of freestanding carbon nanotube (CNT) frameworks is developed through a sulfur-addition strategy during an ambient-pressure chemical vapour deposition process, with ferrocene used as the catalyst precursor. This approach enhances the CNTs' length and contorted morphology, which are the key features leading to the formation of the synthesized porous networks. We demonstrate that such a three-dimensional structure selectively uptakes from water a mass of toxic organic solvent (i.e. o-dichlorobenzene) about 3.5 times higher than that absorbed by individual CNTs. In addition, owing to the presence of highly defective nanostructures constituting them, our samples exhibit an oil-absorption capacity higher than that reported in the literature for similar CNT sponges.

Electronic and optoelectronic nano-devices based on carbon nanotubes.

The discovery and understanding of nanoscale phenomena and the assembly of nanostructures into different devices are among the most promising fields of material science research. In this scenario, carbon nanostructures have a special role since, in having only one chemical element, they allow physical properties to be calculated with high precision for comparison with experiment. Carbon nanostructures, and carbon nanotubes (CNTs) in particular, have such remarkable electronic and structural properties that they are used as active building blocks for a large variety of nanoscale devices. We review here the latest advances in research involving carbon nanotubes as active components in electronic and optoelectronic nano-devices. Opportunities for future research are also identified.

Ferromagnetic Mn-doped Si0.3Ge0.7 nanodots self-assembled on Si(100).

Densely packed epitaxial Mn-doped Si(0.3)Ge(0.7) nanodots self-assembled on Si(100) have been obtained. Their structural properties were studied using reflection high-energy electron diffraction, energy dispersive x-ray diffraction, atomic force microscopy, extended x-ray absorption fine structure measurements and high-resolution transmission electron microscopy. Mn(5)Ge(1)Si(2) crystallites embedded in Si(0.3)Ge(0.7) were found. They exhibit a ferromagnetic behaviour with a Curie temperature of about 225 K.

Playing with peptides: how to build a supramolecular peptide nanostructure by exploiting helix···helix macrodipole interactions.

A novel method to build bicomponent peptide self-assembled monolayers (SAMs) has been developed, by exploiting helix···helix macrodipole interactions. In this work, a peptide-based self-assembled monolayer composed of two helical peptides was immobilized on a gold surface. Specifically, a pyrene-containing octapeptide, devoid of any sulfur atom (A8Pyr), and a hexapeptide, functionalized at the N-terminus with (S,R) lipoic acid, for binding to gold substrates (SSA4WA) via a Au-S linkage, have been employed. Both peptides investigated attain a helical structure, because they are almost exclusively formed by strongly folding inducer C(α)-tetrasubstituted α-amino acids. We demonstrate that the two peptides generate a stable supramolecular nanostructure (a densely packed bicomponent peptide monolayer), where A8Pyr is incorporated into the SSA4WA palisade by exploiting helix···helix macrodipole interactions. The presence of both peptides on the gold surface was investigated by spectroscopic and electrochemical techniques, while the morphology of the monolayer was analyzed by ultra high-vacuum scanning tunnelling microscopy. The composition of the bicomponent SAM on the surface was studied by a combination of electrochemical and spectroscopic techniques. In particular, the amount of Au-S linkages from the sulfur-containing peptides was quantified from reductive desorption of the peptide-based SAM, while the amount of A8Pyr was estimated by fluorescence spectroscopy. The antiparallel orientation of the A8Pyr and SSA4WA peptide chains minimizes the interaction energy between the helix dipoles, suggesting that this kind of electrostatic phenomenon is the driving force that stabilizes the bicomponent SAM.

Photovoltaic response of carbon nanotube-silicon heterojunctions: effect of nanotube film thickness and number of walls.

We report on the multiwall carbon nanotube application as energy conversion material to fabricate thin film solar cells, with nanotubes acting as photogeneration sites as well as charge separators, collectors and carrier transporters. The device consists of a semitransparent thin film of nanotubes coating a n-type crystalline silicon substrate. Under illumination electron-hole (e-h) pairs, generated in the nanotubes and in the silicon substrate underneath, are split and charges are transported through the nanotubes (electrons) and the n-Si (holes). We found that a suitable thickness of the nanotube thin film, high density of Schottky junctions between nanotubes and n-Si and lowest number of nanotube walls are all fundamental parameters to improve the device incident photon to electron conversion efficiency. Multiwall carbon nanotubes have been synthesized by chemical vapour deposition in an ultra high vacuum chamber by evaporating a given amount of iron at room temperature and then exposing the substrate kept at 800 degrees C at acetylene gas. The amount of deposited iron is found to directly affect the nanotube size distribution (inner and outer diameter) and therefore the number of walls of the nanotubes.

Tuning photoresponse through size control of Cu nanoparticles deposited on multi wall carbon nanotubes.

In this paper we illustrate a simple method for the production of multiwall carbon nanotubes thin films decorated with copper metal nanoparticles. The structural information obtained from the transmission electron microscopy study performed on samples differing in the quantity of deposited Copper was linked to the opto-electronic properties evaluated with photo-electrochemical measurements. The photo-response evaluated in terms of incident photon-to-charge carrier generation efficiency varied for different sized-Cu-multiwall carbon nanotubes samples across all the visible and near-ultraviolet photon energy range with respect to the response of bare carbon tubes. The photo-response from the sample covered with of 0.5 nm Cu nominal thickness, reached 10.2%, a value 2 times higher than that measured for bare carbon tubes of 5.9%. While this value decreased to 2.8% when the Cu nominal coverage thickened up to 3 nm. The increase in the photo-response found was interpreted as being the result of a remarkable charge transfer between the Cu metal nanoparticles and the carbon atoms in the tube due to the formation of a strong ionic bond at their interface. The results obtained prove that the metal nanoparticle-carbon nanotube composites have optical, electrical and structural properties that can be applied in a variety of nanoscale architectures for novel photo-electrochemical devices.

Influence of Cu nanoparticle size on the photo-electrochemical response from Cu-multiwall carbon nanotube composites.

We show that Cu metal nanoparticle-multiwall carbon nanotube (MWCNT) assemblies can act as a new hybrid photoactive layer in photo-electrochemical devices. The carbon nanotube (CNT) composites were formed by a controlled thermal deposition of copper which produced crystalline metal nanoparticles localized on the carbon tube outer walls. The photoresponse evaluated in terms of IPCE (incident photon-to-charge carrier generation efficiency) varied for different sized-Cu-MWCNT samples across all the visible and near ultraviolet photon energy range with respect to the response of bare MWCNTs. In the case of 0.2 nm Cu nominal thickness, the IPCE increased, reaching 15%, a value 2.5 times higher than that measured for bare MWCNTs. As the Cu nominal coverage thickened, the IPCE started to decrease and become totally ineffective after 1 nm deposited Cu. The IPCE increase found was interpreted as being the result of a remarkable charge transfer between the Cu metal nanoparticles and the CNTs due to the formation of a strong ionic bond at their interface. The results obtained prove that the metal nanoparticle-CNT composites have optical, electrical and structural properties that can be applied in a variety of nanoscale architectures for novel photo-electrochemical devices.

Pharmacological treatment of mechanical edema: a randomized controlled trial about the effects of mesoglycan.

AIM: Mechanical edema (MO) is frequently found in a lot of the lower extremities' orthopedic diseases. In absence of deep vein thrombosis, MO is caused by the change in the dynamics of calf muscle pump with venous hypertension and by the change in capillary permeability which offsets the extra-vascular fluid balance resulting in edema formation. The correct treatment includes specific training for musculo-skeletal and gait recovery, together with medical treatment focused on venous endothelium. Little information is available about pharmacological treatment of this condition. Some studies suggest the efficacy of mesoglycan in venous pathology. Aim of this study was to evaluate the clinical efficacy of the pharmacological treatment (mesoglycan 50 mg p.o., twice a day) in patients affected by MO. METHODS: Forty-four patients with MO, aged 20-89 years, were randomized in two treatment groups: specific physiotherapy (Fkt) alone or physiotherapy plus mesoglycan 50 mg twice a day, per os. The patients were evaluated before treatment (t0), and after 1 month of treatment (t1), measuring ankle joint range of motion (degrees), calf circumference and malleolar circumference (cm), pain Borg CR10 Scale and adapted lymphedema Weiss Scale. Statistical analysis was performed by the Pearson's c2 test and the Mann-Whitney-Wilcoxon test. RESULTS: At the final evaluation of the objective and subjective parameters, the mesoglycan effect combined to the Fkt provided statistical differences on nearly all the parameters in comparison with the patients randomised to Fkt alone. CONCLUSIONS: The present study suggest that mesoglycan treatment (50 mg p.o., twice a day) can improve the recovery of MO, and it is well tolerated by the patients. Specific physiotherapy remains the first treatment for the recovery of both muscular pump and correct walking, but the optimal treatment of MO seems to be a synergic approach, including both pharmacological and mobilization programs.

NMR studies of protein surface accessibility.

Characterization of protein surface accessibility represents a new frontier of structural biology. A surface accessibility investigation for two structurally well-defined proteins, tendamistat and bovine pancreatic trypsin inhibitor, is performed here by a combined analysis of water-protein Overhauser effects and paramagnetic perturbation profiles induced by the soluble spin-label 4-hydroxy-2,2,6,6-tetramethyl-piperidine-1-oxyl on NMR spectra. This approach seems to be reliable not only for distinguishing between buried and exposed residues but also for finding molecular locations where a network of more ordered waters covers the protein surface. From the presented set of data, an overall picture of the surface accessibility of the two proteins can be inferred. Detailed knowledge of protein accessibility can form the basis for successful design of mutants with increased activity and/or greater specificity.

Probing the surface of a sweet protein: NMR study of MNEI with a paramagnetic probe.

The design of safe sweeteners is very important for people who are affected by diabetes, hyperlipemia, and caries and other diseases that are linked to the consumption of sugars. Sweet proteins, which are found in several tropical plants, are many times sweeter than sucrose on a molar basis. A good understanding of their structure-function relationship can complement traditional SAR studies on small molecular weight sweeteners and thus help in the design of safe sweeteners. However, there is virtually no sequence homology and very little structural similarity among known sweet proteins. Studies on mutants of monellin, the best characterized of sweet proteins, proved not decisive in the localization of the main interaction points of monellin with its receptor. Accordingly, we resorted to an unbiased approach to restrict the search of likely areas of interaction on the surface of a typical sweet protein. It has been recently shown that an accurate survey of the surface of proteins by appropriate paramagnetic probes may locate interaction points on protein surface. Here we report the survey of the surface of MNEI, a single chain monellin, by means of a paramagnetic probe, and a direct assessment of bound water based on an application of ePHOGSY, an NMR experiment that is ideally suited to detect interactions of small ligands to a protein. Detailed surface mapping reveals the presence, on the surface of MNEI, of interaction points that include residues previously predicted by ELISA tests and by mutagenesis.

D2/D3 dopamine receptor heterodimers exhibit unique functional properties.

Evidence for heterodimerization has recently been provided for dopamine D(1) and adenosine A(1) receptors as well as for dopamine D(2) and somatostatin SSTR(5) receptors. In this paper, we have studied the possibility that D(2) and D(3) receptors interact functionally by forming receptor heterodimers. Initially, we split the two receptors at the level of the third cytoplasmic loop into two fragments. The first, containing transmembrane domains (TM) I to V and the N-terminal part of the third cytoplasmic loop, was named D(2trunk) or D(3trunk), and the second, containing the C-terminal part of the third cytoplasmic loop, TMVI and TMVII, and the C-terminal tail, was named D(2tail) or D(3tail). Then we defined the pharmacological profiles of the homologous (D(2trunk)/D(2tail) and D(3trunk)/D(3tail)) as well as of the heterologous (D(2trunk)/D(3tail) and D(3trunk)/D(2tail)) cotransfected receptor fragments. The pharmacological profile of the cross-cotransfected fragments was different from that of the native D(2) or D(3) receptors. In most cases, the D(3trunk)/D(2tail) was the one with the highest affinity for most agonists and antagonists. Moreover, we observed that all of these receptor fragments reduced the expression of the wild type dopamine D(2) and D(3) receptors, suggesting that D(2) and D(3) receptors can form complexes with these fragments and that these complexes bind [(3)H]nemonapride less efficiently or are not correctly targeted to the membrane. In a second set of experiments, we tested the ability of the split and the wild type receptors to inhibit adenylyl cyclase (AC) types V and VI. All of the native and split receptors inhibited AC-V and AC-VI, with the exception of D(3), which was unable to inhibit AC-VI. We therefore studied the ability of D(2) and D(3) to interact functionally with one another to inhibit AC-VI. We found that with D(2) alone, R-(+)-7-hydroxydypropylaminotetralin hydrobromide inhibited AC-VI with an IC(50) of 2.05 +/- 0.15 nm, while in the presence of D(2) and D(3) it inhibited AC-VI with an IC(50) of 0.083 +/- 0.011 nm. Similar results were obtained with a chimeric cyclase made from AC-V and AC-VI. Coimmunoprecipitation experiments indicate that D(2) and D(3) receptors are capable of physical interaction.

Apomorphine, dopamine and phenylethylamine reduce the proportion of phosphorylated insulin receptor substrate 1.

We tested the ability of dopamine, apomorphine, phenylethylamine and pergolide to inhibit the proliferation of fetal calf serum-stimulated human breast cancer (MCF)-7 cells. While the first three compounds were able to block the proliferation of MCF-7 cells, pergolide failed to do so (up to 100 microM). The inhibitory effect of dopamine, apomorphine and phenylethylamine was also evident in serum-starved insulin-stimulated MCF-7 cells. Apomorphine also inhibited the proliferation of the human oestrogen receptor-negative breast cancer (MDA-MB231) and prostate carcinoma (LNCaP) cell lines. In a second set of experiments, we measured the ability of dopamine, apomorphine, phenylethylamine and pergolide to inhibit the phosphorylation (or increase the dephosphorylation) of the insulin receptor substrate (IRS)-1, a major intracellular substrate of the insulin-like growth factor (IGF)-1 receptor. Dopamine, apomorphine and phenylethylamine all reduced to zero the level of phosphorylated IRS-1 with potencies ranging between 0.01 and 1 microM. Finally, we found that fibroblasts from IRS-1 null (-/-) mice were less sensitive to the anti-proliferative effect of apomorphine compared to fibroblasts from wild type-mice, suggesting that the inhibition of IRS-1 phosphorylation by apomorphine is an important aspect of the activity of this compound.

Reconstitution of functional dopamine D(2s) receptor by co-expression of amino- and carboxyl-terminal receptor fragments.

An N-terminal dopamine D(2s) receptor clone was constructed and coexpressed in COS-7 cells together with a separate gene fragment coding for the C-terminal sequence of the dopamine D(2s) receptor. The truncated receptor (referred to as D(2trunc)) contained transmembrane domains I-V and the N-terminal portion of the third cytoplasmic loop, whereas the C-terminal receptor fragment (referred to as D(2tail)) contained transmembrane domains VI and VII and the adjacent intra- and extracellular sequences of the dopamine D(2s) receptor. Expression in COS-7 cells of either of these two polypeptides alone did not result in any detectable [3H]methylspiperone binding activity. However, specific [3H]methylspiperone binding could be observed after coexpression of the D(2trunc) and D(2tail) gene constructs; the number of receptors present on the plasma membrane was about 10% with respect to that of the wild type. The binding properties of the coexpressed fragments were similar to those of the wild-type dopamine D(2s) receptor for agonists and antagonists. Functional stimulation of the cotransfected D(2trunc) and D(2tail) fragments with quinpirole resulted in the inhibition of adenylate cyclase activity. Maximal inhibition corresponds to a 28% decrease in forskolin-stimulated adenylate cyclase. The apparent IC(50) of quinpirole was 5.1+/-0.3 mcM. These findings confirm and extend analogous data for other G protein-coupled receptors and indicate that this phenomenon is of general importance for the entire family of these proteins.