Optimal Sensing Protocol for Statistically Polarized Nano-NMR with NV Centers.

Diffusion noise represents a major constraint to successful liquid state nano-NMR spectroscopy. Using the Fisher information as a faithful measure, we theoretically calculate and experimentally show that phase sensitive protocols are superior in most experimental scenarios, as they maximize information extraction from correlations in the sample. We derive the optimal experimental parameters for quantum heterodyne detection (Qdyne) and present the most accurate statistically polarized nano-NMR Qdyne detection experiments to date, leading the way to resolve chemical shifts and J couplings at the nanoscale.

Highly efficient sequestration of aqueous lead on nanostructured calcite substrates.

Following defocused ion beam sputtering, large area highly corrugated and faceted nanoripples are formed on calcite (10.4) faces in a self-organized fashion. High resolution atomic force microscopy (AFM) imaging reveals that calcite ripples are defined by facets with highly kinked (11.0) and (21¯.12) terminations.In situAFM imaging during the exposure of such modified calcite surfaces to PbCl2aqueous solution reveals that the nanostructured calcite surface promotes the uptake of Pb. In addition, we observed the progressive smoothing of the highly reactive calcite facet terminations and the formation of Pb-bearing precipitates elongated in registry with the underlying nanopattern. By SEM-EDS analysis we quantified a remarkable 500% increase of the Pb uptake rate, up to 0.5 atomic weight % per hour, on the nanorippled calcite in comparison to its freshly cleaved (10.4) surfaces. These results suggest that nanostructurated calcite surfaces can be used for developing future systems for lead sequestration from polluted waters.

Atomic force microscopy for the evaluation of corneal surface roughness after femtosecond laser flap creation and excimer ablation.

INTRODUCTION: It is well known that the femtosecond laser lamellar cut induces some degree of surface roughness. Nevertheless, as in femtosecond laser-assisted LASIK (FS-LASIK), an excimer LASIK ablation is performed, and the post-ablation stromal bed should show some degree of smoothening. We decided to compare, using atomic force microscopy (AFM), the roughness of the corneal stromal bed, after a femtosecond lasers device flap was created with or without an excimer myopic ablation. METHODS: Using 6 freshly enucleated porcine eyes, we created in every eye a flap using a femtosecond laser. Additionally, in 3 eyes, an excimer laser ablation to correct-3 diopters (D) was made. AFM imaging of the remaining corneal stroma was performed. Ten different square areas of 20 µm x 20 µm at the central area of the stroma of each corneal sample were studied. The roughness parameters used were the root-mean-square deviation from a perfectly flat surface. RESULTS: The RMS deviation was 360 ± 120 nm in femtosecond laser only, and 110 ± 20 nm in those cases where excimer is also involved (p < 0.0001). CONCLUSIONS: Our results show that the roughness of the surface treated with excimer is clearly lower than in the group with no excimer ablation; thus, the application of laser excimer after a flap created by femtosecond laser seems to soften the nano-irregularities created by this technique.

Atomic force microscopy comparative analysis of the surface roughness of two posterior chamber phakic intraocular lens models: ICL versus IPCL.

BACKGROUND: To compare the anterior surface roughness of two commercially available posterior chamber phakic intraocular lenses (IOLs) using atomic force microscopy (AFM). METHODS: Four phakic IOLs were used for this prospective, experimental study: two Visian ICL EVO+ V5 lenses and two iPCL 2.0 lenses. All of them were brand new, were not previously implanted in humans, were monofocal and had a dioptric power of - 12 diopters (D). The anterior surface roughness was assessed using a JPK NanoWizard II® atomic force microscope in contact mode immersed in liquid. Olympus OMCL-RC800PSA commercial silicon nitride cantilever tips were used. Anterior surface roughness measurements were made in 7 areas of 10 × 10 µm at 512 × 512 point resolution. The roughness was measured using the root-mean-square (RMS) value within the given regions. RESULTS: The mean of all anterior surface roughness measurements was 6.09 ± 1.33 nm (nm) in the Visian ICL EVO+ V5 and 3.49 ± 0.41 nm in the iPCL 2.0 (p = 0.001). CONCLUSION: In the current study, we found a statistically significant smoother anterior surface in the iPCL 2.0 phakic intraocular lenses compared with the VISIAN ICL EVO+ V5 lenses when studied with atomic force microscopy.

Magnetic pulses enable multidimensional optical spectroscopy of dark states.

The study and manipulation of low dipole moment quantum states have been challenging due to their inaccessibility by conventional spectroscopic techniques. Controlling the spin in such states requires unfeasible strong magnetic fields to overcome typical decoherence rates. However, the advent of terahertz technology and its application in magnetic pulses opens up a new scenario. In this article, we focus on an electron-hole pair model to demonstrate that it is possible to control the precession of the spins and to modify the transition rates to different spin states. Enhancing transitions from a bright state to a dark state with different spins means that the latter can be revealed by ordinary spectroscopy. We propose a modification of the standard two-dimensional spectroscopic scheme in which a three pulse sequence is encased in a magnetic pulse. Its role is to drive transitions between a bright and a dark spin state, making the latter susceptible to spectroscopic investigation.

Nanostructured Micelle Nanotubes Self-Assembled from Dinucleobase Monomers in Water.

Despite the central importance of aqueous amphiphile assemblies in science and industry, the size and shape of these nano-objects is often difficult to control with accuracy owing to the non-directional nature of the hydrophobic interactions that sustain them. Here, using a bioinspired strategy that consists of programming an amphiphile with shielded directional Watson-Crick hydrogen-bonding functions, its self-assembly in water was guided toward a novel family of chiral micelle nanotubes with partially filled lipophilic pores of about 2 nm in diameter. Moreover, these tailored nanotubes are successfully demonstrated to extract and host molecules that are complementary in size and chemical affinity.

Limits on Spectral Resolution Measurements by Quantum Probes.

The limits of frequency resolution in nano-NMR experiments have been discussed extensively in recent years. It is believed that there is a crucial difference between the ability to resolve a few frequencies and the precision of estimating a single one. Whereas the efficiency of single frequency estimation gradually increases with the square root of the number of measurements, the ability to resolve two frequencies is limited by the specific timescale of the signal and cannot be compensated for by extra measurements. Here we show theoretically and demonstrate experimentally that the relationship between these quantities is more subtle and both are only limited by the Cramér-Rao bound of a single frequency estimation.

Analysis of corneal stromal roughness after iFS 150 kHz and LenSx femtosecond LASIK flap creation in porcine eyes.

PURPOSE: To describe and compare the stromal bed roughness obtained after laser in situ keratomileusis (LASIK) flap creation using a corneal femtosecond laser platform (iFS 150) and a "dual" femtosecond (FS) laser platform (LenSx). METHODS: This ex vivo experimental study was conducted in an animal model using 12 freshly enucleated porcine eyes, six with each femtosecond laser. The standard laser treatment parameters were used for the experiment. After LASIK flap creation, the corneal stromal roughness was assessed using atomic force microscopy (AFM) in contact mode immersed in liquid. In each sample, surface measurements were obtained in 60 regions of six eyes per FS laser in 10 20 × 20-micron areas of the central corneal stroma at 512 × 512-point resolution. The surface roughness was measured and the root-mean-square (RMS) values of the roughness were obtained. RESULTS: The mean RMS ± standard deviation values were 430 ± 150 nm for the corneal femtosecond laser platform and 370 ± 100 nm for the dual FS laser platform (P < 0.011). CONCLUSIONS: In this experimental study with AFM, we found smoother stromal beds after LASIK flap creation with LenSx compared to iFS 150 kHz. Further studies are needed to understand visual implications of the differences found.

Hybrid Nanoscopy of Hybrid Nanomaterials.

The combination of complementary techniques to characterize materials at the nanoscale is crucial to gain a more complete picture of their structure, a key step to design and fabricate new materials with improved properties and diverse functions. Here it is shown that correlative atomic force microscopy (AFM) and localization-based super-resolution microscopy is a useful tool that provides insight into the structure and emissive properties of fluorescent ß-lactoglobulin (ßLG) amyloid-like fibrils. These hybrid materials are made by functionalization of ßLG with organic fluorophores and quantum dots, the latter being relevant for the production of 1D inorganic nanostructures templated by self-assembling peptides. Simultaneous functionalization of ßLG fibers by QD655 and QD525 allows for correlative AFM and two-color super-resolution fluorescence imaging of these hybrid materials. These experiments allow the combination of information about the topography and number of filaments that compose a fibril, as well as the emissive properties and nanoscale spatial distribution of the attached fluorophores. This study represents an important step forward in the characterization of multifunctionalized hybrid materials, a key challenge in nanoscience.

Location and Effects of an Antitumoral Catechin on the Structural Properties of Phosphatidylethanolamine Membranes.

Green tea catechins exhibit high diversity of biological effects including antioncogenic properties, and there is enormous interest in their potential use in the treatment of a number of pathologies. It is recognized that the mechanism underlying the activity of catechins relay in part in processes related to the membrane, and many studies revealed that the ability of catechins to interact with lipids plays a probably necessary role in their mechanism of action. We present in this work the characterization of the interaction between an antitumoral synthetically modified catechin (3-O-(3,4,5-trimethoxybenzoyl)-(-)-catechin, TMCG) and dimiristoylphosphatidyl-ethanolamine (DMPE) membranes using an array of biophysical techniques which include differential scanning calorimetry, X-ray diffraction, infrared spectroscopy, atomic force microscopy, and molecular dynamics simulations. We found that TMCG incorporate into DMPE bilayers perturbing the thermotropic transition from the gel to the fluid state forming enriched domains which separated into different gel phases. TMCG does not influence the overall bilayer assembly of phosphatidylethanolamine systems but it manages to influence the interfacial region of the membrane and slightly decrease the interlamellar repeat distance of the bilayer. TMCG seems to be located in the interior of the phosphatidylethanolamine bilayer with the methoxy groups being in the deepest position and some portion of the molecule interacting with the water interface. We believe that the reported interactions are significant not only from the point of view of the known antitumoral effect of TMCG, but also might contribute to understanding the basic molecular mechanism of the biological effects of the catechins found at the membrane level.

Highly ordered n/p-co-assembled materials with remarkable charge mobilities.

Controlling self-organization and morphology of chemical architectures is an essential challenge in the search for higher energy-conversion efficiencies in a variety of optoelectronic devices. Here, we report a highly ordered donor/acceptor functional material, which has been obtained using the principle of ionic self-assembly. Initially, an electron donor π-extended tetrathiafulvalene and an electron-acceptor perylene-bisimide were self-organized separately obtaining n- and p-nanofibers at the same scale. These complementary n- and p-nanofibers are endowed with ionic groups with opposite charges on their surfaces. The synergic interactions establish periodic alignments between both nanofibers resulting in a material with alternately segregated donor/acceptor nanodomains. Photoconductivity measurements show values for these n/p-co-assembled materials up to 0.8 cm(2) V(-1) s(-1), confirming the effectiveness in the design of these heterojunction structures. This easy methodology offers great possibilities to achieve highly ordered n/p-materials for potential applications in different areas such as optoelectonics and photovoltaics.

Correlative atomic force microscopy and localization-based super-resolution microscopy: revealing labelling and image reconstruction artefacts.

Hybrid microscopy: A correlative microscopy tool that combines in situ super-resolution fluorescence microscopy based on single-molecule localization and atomic force microscopy is presented. Direct comparison with high- resolution topography allows the authors to improve fluorescence labeling and image analysis in super-resolution imaging.

Channeling motion of gold nanospheres on a rippled glassed surface.

Gold nanospheres have been manipulated by atomic force microscopy on a rippled glass surface produced by ion beam sputtering and coated with an ultrathin (10 nm thick) graphitic layer. This substrate is characterized by irregular wavy grooves running parallel to a preferential direction. Measurements in ambient conditions show that the motion of the nanoparticles is confined to single grooves ('channels'), along which the particles move till they are trapped by local bottlenecks. At this point, the particles cross the ripple pattern in a series of consecutive jumps and continue their longitudinal motion along a different channel. Moreover, due to the asymmetric shape of the ripple profiles, the jumps occur in the direction of minimum slope, resembling a ratchet mechanism. Our results are discussed, extending a collisional model, which was recently developed for the manipulation of nanospheres on flat surfaces, to the specific geometry of this problem.

Computer vision distance measurement from endoscopic sequences: prospective evaluation in laparoscopic ventral hernia repair.

BACKGROUND: Research in computer vision and mobile robotics has developed a family of popular algorithms known as Visual Simultaneous Localization And Mapping (Visual SLAM). These algorithms can provide 3D models of body cavities using the images obtained from standard monocular endoscopes. The 3D models can be used to estimate hernia defect measurements during laparoscopic ventral hernia repair (LVHR). METHODS: We conducted a descriptive and comparative prospective study to analyze results from 15 patients who underwent LVHR. Three methods of measurement were used in each patient: two classical methods (needle and tape) and a new visual SLAM measurement (VSM) method. The major and minor axes of the ellipse-shaped hernia defect were measured. RESULTS: Both axes could be measured using the VSM method in all patients except one (93%). The tape method measured 63% of the axes, but was difficult to perform because of patient comorbidities and because of limited range of motion of the laparoscopic tools. The needle method obtained 73% of measurements, because of patient comorbidities. The tape method was the most accurate (accuracy up to 0.5 cm because of tape resolution). The needle method was relatively inaccurate, with a mean error of >3 cm. The VSM method was as accurate as the tape method. The mean time taken to perform measurements was 40 s for the VSM method (range 29-60 s), 169 s for the needle method (range 66-300 s), and 186 s for the tape method (range 110-322 s). CONCLUSIONS: The needle method is relatively inaccurate and invasive. The tape method is accurate, but is not easy to perform and is relatively time consuming. The VSM method is noninvasive and fast and is as accurate as the tape method.

Mechanically interlocked single-wall carbon nanotubes.

Extensive research has been devoted to the chemical manipulation of carbon nanotubes. The attachment of molecular fragments through covalent-bond formation produces kinetically stable products, but implies the saturation of some of the C-C double bonds of the nanotubes. Supramolecular modification maintains the structure of the SWNTs but yields labile species. Herein, we present a strategy for the synthesis of mechanically interlocked derivatives of SWNTs (MINTs). In the key rotaxane-forming step, we employed macrocycle precursors equipped with two π-extended tetrathiafulvalene SWNT recognition units and terminated with bisalkenes that were closed around the nanotubes through ring-closing metathesis (RCM). The mechanically interlocked nature of the derivatives was probed by analytical, spectroscopic, and microscopic techniques, as well as by appropriate control experiments. Individual macrocycles were observed by HR STEM to circumscribe the nanotubes.

Low frequency signal detection via correlated Ramsey measurements.

The low frequency region of the spectrum is a challenging regime for quantum probes. We support the idea that, in this regime, performing Ramsey measurements carefully controlling the time at which each measurement is initiated is an excellent signal detection strategy. We use the Fisher information to demonstrate a high quality performance in the low frequency regime, compared to more elaborated measurement sequences, and to optimize the correlated Ramsey sequence according to any given experimental parameters, showing that correlated Ramsey rivals with state-of-the-art protocols, and can even outperform commonly employed sequences such as dynamical decoupling in the detection of low frequency signals. Contrary to typical quantum detection protocols for oscillating signals, which require adjusting the time separation between pulses to match the half period of the target signal, and consequently see their scope limited to signals whose period is shorter than the characteristic decoherence time of the probe, or to those protocols whose target is primarily static signals, the time-tagged correlated Ramsey sequence simultaneously tracks the amplitude and the phase information of the target signal, regardless of its frequency, which crucially permits correlating measurements in post-processing, leading to efficient spectral reconstruction.

Physicochemical characterization of Acidiphilium sp. biofilms.

The biofilm formation of a strain of the extremophile bacterium Acidiphilium sp., capable of donating electrons directly to electrodes, was studied by different surface characterization techniques. We develop a method that allows the simultaneous study of bacterial biofilms by means of fluorescence microscopy and atomic force microscopy (AFM), in which transparent graphitic flakes deposited on a glass substrate are used as a support for the biofilm. The majority of the cells present on the surface were viable, and the growth of the biofilms over time showed a critical increase of the extracellular polymeric substances (EPS) as well as the formation of nanosized particles inside the biofilm. Also, the presence of Fe in Acidiphilium biofilms was determined by X-ray photoelectron spectroscopy (XPS), whereas surface-enhanced infrared absorption spectroscopy indicated the presence of redox-active proteins.

Spinning and translational motion of Sb nanoislands manipulated on MoS2.

Antimony nanoislands grown on a MoS2 surface in ultra-high vacuum have been manipulated by atomic force microscopy (AFM) in ambient conditions. The island profiles have been digitized and provided as an input to a collisional algorithm based on classical mechanics. Assuming that the islands are rigid and static friction is high enough to prevent further motion after the passage of the probing tip, the direction of motion and the angle of rotation of the islands have been reproduced numerically. For a given spacing between the scan lines, the angle of deflection with respect to the fast scan direction and the angular speed of the islands are expected to vary with the friction between islands and substrate. From a comparison between model and experiment a shear strength in the order of 0.2 MPa is estimated.

Degradation of PET Bottles by an Engineered Ideonella sakaiensis PETase.

Extensive plastic production has become a serious environmental and health problem due to the lack of efficient treatment of plastic waste. Polyethylene terephthalate (PET) is one of the most used polymers and is accumulating in landfills or elsewhere in nature at alarming rates. In recent years, enzymatic degradation of PET by Ideonella sakaiensis PETase (IsPETase), a cutinase-like enzyme, has emerged as a promising strategy to completely depolymerize this polymer into its building blocks. Here, inspired by the architecture of cutinases and lipases homologous to IsPETase and using 3D structure information of the enzyme, we rationally designed three mutations in IsPETase active site for enhancing its PET-degrading activity. In particular, the S238Y mutant, located nearby the catalytic triad, showed a degradation activity increased by 3.3-fold in comparison to the wild-type enzyme. Importantly, this structural modification favoured the function of the enzyme in breaking down highly crystallized (~31%) PET, which is found in commercial soft drink bottles. In addition, microscopical analysis of enzyme-treated PET samples showed that IsPETase acts better when the smooth surface of highly crystalline PET is altered by mechanical stress. These results represent important progress in the accomplishment of a sustainable and complete degradation of PET pollution.

Electropolymerized network of polyamidoamine dendron-coated gold nanoparticles as novel nanostructured electrode surface for biosensor construction.

Polyfuntionalized gold nanoparticles were prepared by using 2-mercaptoethanesulfonic acid, p-aminothiophenol and cysteamine core polyamidoamine G-4 dendron as capping ligands. The nanoparticles were electropolymerized on a Au electrode surface through the formation of a bisaniline-cross-linked network. The enzyme tyrosinase was further crosslinked on this nanostructured matrix. The enzyme electrode, poised at -100 mV, was used for the amperometric quantification of cathecol. The biosensor showed a linear response from 50 nM to 10 µM cathecol, with a low detection limit of 20 nM and a sensitivity of 1.94 A M(-1) cm(2). The electrode retained 96% and 67% of its initial activity after 16 and 30 days of storage at 4 °C under dry conditions.