Calibration by differentiation - Self-supervised calibration for X-ray microscopy using a differentiable cone-beam reconstruction operator.

High-resolution X-ray microscopy (XRM) is gaining interest for biological investigations of extremely small-scale structures. XRM imaging of bones in living mice could provide new insights into the emergence and treatment of osteoporosis by observing osteocyte lacunae, which are holes in the bone of few micrometres in size. Imaging living animals at that resolution, however, is extremely challenging and requires very sophisticated data processing converting the raw XRM detector output into reconstructed images. This paper presents an open-source, differentiable reconstruction pipeline for XRM data which analytically computes the final image from the raw measurements. In contrast to most proprietary reconstruction software, it offers the user full control over each processing step and, additionally, makes the entire pipeline deep learning compatible by ensuring differentiability. This allows fitting trainable modules both before and after the actual reconstruction step in a purely data-driven way using the gradient-based optimizers of common deep learning frameworks. The value of such differentiability is demonstrated by calibrating the parameters of a simple cupping correction module operating on the raw projection images using only a self-supervisory quality metric based on the reconstructed volume and no further calibration measurements. The retrospective calibration directly improves image quality as it avoids cupping artefacts and decreases the difference in grey values between outer and inner bone by 68-94%. Furthermore, it makes the reconstruction process entirely independent of the XRM manufacturer and paves the way to explore modern deep learning reconstruction methods for arbitrary XRM and, potentially, other flat-panel computed tomography systems. This exemplifies how differentiable reconstruction can be leveraged in the context of XRM and, hence, is an important step towards the goal of reducing the resolution limit of in vivo bone imaging to the single micrometre domain.

Towards polarization-based excitation tailoring for extended Raman spectroscopy.

Undoubtedly, Raman spectroscopy is one of the most elaborate spectroscopy tools in materials science, chemistry, medicine and optics. However, when it comes to the analysis of nanostructured specimens or individual sub-wavelength-sized systems, the access to Raman spectra resulting from different excitation schemes is usually very limited. For instance, the excitation with an electric field component oriented perpendicularly to the substrate plane is a difficult task. Conventionally, this can only be achieved by mechanically tilting the sample or by sophisticated sample preparation. Here, we propose a novel experimental method based on the utilization of polarization tailored light for Raman spectroscopy of individual nanostructures. As a proof of principle, we create three-dimensional electromagnetic field distributions at the nanoscale using tightly focused cylindrical vector beams impinging normally onto the specimen, hence keeping the traditional beam-path of commercial Raman systems. In order to demonstrate the convenience of this excitation scheme, we use a sub-wavelength diameter gallium-nitride nanostructure as a test platform and show experimentally that its Raman spectra depend sensitively on its location relative to the focal vector field. The observed Raman spectra can be attributed to the interaction with transverse and pure longitudinal electric field components. This novel technique may pave the way towards a characterization of Raman active nanosystems, granting direct access to growth-related parameters such as strain or defects in the material by using the full information of all Raman modes.

Aggregated neutrophil extracellular traps resolve inflammation by proteolysis of cytokines and chemokines and protection from antiproteases.

Papillon-Lefèvre syndrome (PLS) is characterized by nonfunctional neutrophil serine proteases (NSPs) and fulminant periodontal inflammation of unknown cause. Here we investigated neutrophil extracellular trap (NET)-associated aggregation and cytokine/chemokine-release/degradation by normal and NSP-deficient human and mouse granulocytes. Stimulated with solid or soluble NET inducers, normal neutrophils formed aggregates and both released and degraded cytokines/chemokines. With increasing cell density, proteolytic degradation outweighed release. Maximum output of cytokines/chemokines occurred mostly at densities between 2 × 107 and 4 × 107 neutrophils/cm3. Assessment of neutrophil density in vivo showed that these concentrations are surpassed during inflammation. Association with aggregated NETs conferred protection of neutrophil elastase against α1-antitrypsin. In contrast, eosinophils did not influence cytokine/chemokine concentrations. The proteolytic degradation of inflammatory mediators seen in NETs was abrogated in Papillon-Lefèvre syndrome (PLS) neutrophils. In summary, neutrophil-driven proteolysis of inflammatory mediators works as a built-in safeguard for inflammation. The absence of this negative feedback mechanism might be responsible for the nonresolving periodontitis seen in PLS.-Hahn, J., Schauer, C., Czegley, C., Kling, L., Petru, L., Schmid, B., Weidner, D., Reinwald, C., Biermann, M. H. C., Blunder, S., Ernst, J., Lesner, A., Bäuerle, T., Palmisano, R., Christiansen, S., Herrmann, M., Bozec, A., Gruber, R., Schett, G., Hoffmann, M. H. Aggregated neutrophil extracellular traps resolve inflammation by proteolysis of cytokines and chemokines and protection from antiproteases.

Chiroptical response of a single plasmonic nanohelix.

We investigate the chiroptical response of a single plasmonic nanohelix interacting with a weakly focused circularly polarized Gaussian beam. The optical scattering at the fundamental resonance is characterized experimentally and numerically. The angularly resolved scattering of the excited nanohelix is verified experimentally and it validates the numerical results. We employ a multipole decomposition analysis to study the fundamental and first higher-order resonance of the nanohelix, explaining their chiral properties in terms of the formation of chiral dipoles.

The Formation of Calcified Nanospherites during Micropetrosis Represents a Unique Mineralization Mechanism in Aged Human Bone.

Osteocytes-the central regulators of bone remodeling-are enclosed in a network of microcavities (lacunae) and nanocanals (canaliculi) pervading the mineralized bone. In a hitherto obscure process related to aging and disease, local plugs in the lacuno-canalicular network disrupt cellular communication and impede bone homeostasis. By utilizing a suite of high-resolution imaging and physics-based techniques, it is shown here that the local plugs develop by accumulation and fusion of calcified nanospherites in lacunae and canaliculi (micropetrosis). Two distinctive nanospherites phenotypes are found to originate from different osteocytic elements. A substantial deviation in the spherites' composition in comparison to mineralized bone further suggests a mineralization process unlike regular bone mineralization. Clearly, mineralization of osteocyte lacunae qualifies as a strong marker for degrading bone material quality in skeletal aging. The understanding of micropetrosis may guide future therapeutics toward preserving osteocyte viability to maintain mechanical competence and fracture resistance of bone in elderly individuals.

Mode Matching for Optical Antennas.

The emission rate of a point dipole can be strongly increased in the presence of a well-designed optical antenna. Yet, optical antenna design is largely based on radio-frequency rules, ignoring, e.g., Ohmic losses and non-negligible field penetration in metals at optical frequencies. Here, we combine reciprocity and Poynting's theorem to derive a set of optical-frequency antenna design rules for benchmarking and optimizing the performance of optical antennas driven by single quantum emitters. Based on these findings a novel plasmonic cavity antenna design is presented exhibiting a considerably improved performance compared to a reference two-wire antenna. Our work will be useful for the design of high-performance optical antennas and nanoresonators for diverse applications ranging from quantum optics to antenna-enhanced single-emitter spectroscopy and sensing.

Plasmonic gold helices for the visible range fabricated by oxygen plasma purification of electron beam induced deposits.

Electron beam induced deposition (EBID) currently provides the only direct writing technique for truly three-dimensional nanostructures with geometrical features below 50 nm. Unfortunately, the depositions from metal-organic precursors suffer from a substantial carbon content. This hinders many applications, especially in plasmonics where the metallic nature of the geometric surfaces is mandatory. To overcome this problem a post-deposition treatment with oxygen plasma at room temperature was investigated for the purification of gold containing EBID structures. Upon plasma treatment, the structures experience a shrinkage in diameter of about 18 nm but entirely keep their initial shape. The proposed purification step results in a core-shell structure with the core consisting of mainly unaffected EBID material and a gold shell of about 20 nm in thickness. These purified structures are plasmonically active in the visible wavelength range as shown by dark field optical microscopy on helical nanostructures. Most notably, electromagnetic modeling of the corresponding scattering spectra verified that the thickness and quality of the resulting gold shell ensures an optical response equal to that of pure gold nanostructures.

Low temperature solid-state wetting and formation of nanowelds in silver nanowires.

This article focuses on the microscopic mechanism of thermally induced nanoweld formation between silver nanowires (AgNWs) which is a key process for improving electrical conductivity in NW networks employed for transparent electrodes. Focused ion beam sectioning and transmission electron microscopy were applied in order to elucidate the atomic structure of a welded NW including measurement of the wetting contact angle and characterization of defect structure with atomic accuracy, which provides fundamental information on the welding mechanism. Crystal lattice strain, obtained by direct evaluation of atomic column displacements in high resolution scanning transmission electron microscopy images, was shown to be non-uniform among the five twin segments of the AgNW pentagonal structure. It was found that the pentagonal cross-sectional morphology of AgNWs has a dominant effect on the formation of nanowelds by controlling initial wetting as well as diffusion of Ag atoms between the NWs. Due to complete solid-state wetting, at an angle of ∼4.8°, the welding process starts with homoepitaxial nucleation of an initial Ag layer on (100) surface facets, considered to have an infinitely large radius of curvature. However, the strong driving force for this process due to the Gibbs-Thomson effect, requires the NW contact to occur through the corner of the pentagonal cross-section of the second NW providing a small radius of curvature. After the initial layer is formed, the welded zone continues to grow and extends out epitaxially to the neighboring twin segments.

Development of an optimal filter substrate for the identification of small microplastic particles in food by micro-Raman spectroscopy.

When analysing microplastics in food, due to toxicological reasons it is important to achieve clear identification of particles down to a size of at least 1 µm. One reliable, optical analytical technique allowing this is micro-Raman spectroscopy. After isolation of particles via filtration, analysis is typically performed directly on the filter surface. In order to obtain high qualitative Raman spectra, the material of the membrane filters should not show any interference in terms of background and Raman signals during spectrum acquisition. To facilitate the usage of automatic particle detection, membrane filters should also show specific optical properties. In this work, beside eight different, commercially available membrane filters, three newly designed metal-coated polycarbonate membrane filters were tested to fulfil these requirements. We found that aluminium-coated polycarbonate membrane filters had ideal characteristics as a substrate for micro-Raman spectroscopy. Its spectrum shows no or minimal interference with particle spectra, depending on the laser wavelength. Furthermore, automatic particle detection can be applied when analysing the filter surface under dark-field illumination. With this new membrane filter, analytics free of interference of microplastics down to a size of 1 µm becomes possible. Thus, an important size class of these contaminants can now be visualized and spectrally identified. Graphical abstract A newly developed aluminium coated polycarbonate membrane filter enables automatic particle detection and generation of high qualitative Raman spectra allowing identification of small microplastics.

Electromechanically Tunable Suspended Optical Nanoantenna.

Coupling mechanical degrees of freedom with plasmonic resonances has potential applications in optomechanics, sensing, and active plasmonics. Here we demonstrate a suspended two-wire plasmonic nanoantenna acting like a nanoelectrometer. The antenna wires are supported and electrically connected via thin leads without disturbing the antenna resonance. As a voltage is applied, equal charges are induced on both antenna wires. The resulting equilibrium between the repulsive Coulomb force and the restoring elastic bending force enables us to precisely control the gap size. As a result the resonance wavelength and the field enhancement of the suspended optical nanoantenna can be reversibly tuned. Our experiments highlight the potential to realize large bandwidth optical nanoelectromechanical systems.

Vertically Oriented Growth of GaN Nanorods on Si Using Graphene as an Atomically Thin Buffer Layer.

The monolithic integration of wurtzite GaN on Si via metal-organic vapor phase epitaxy is strongly hampered by lattice and thermal mismatch as well as meltback etching. This study presents single-layer graphene as an atomically thin buffer layer for c-axis-oriented growth of vertically aligned GaN nanorods mediated by nanometer-sized AlGaN nucleation islands. Nanostructures of similar morphology are demonstrated on graphene-covered Si(111) as well as Si(100). High crystal and optical quality of the nanorods are evidenced through scanning transmission electron microscopy, micro-Raman, and cathodoluminescence measurements supported by finite-difference time-domain simulations. Current-voltage characteristics revealed high vertical conduction of the as-grown GaN nanorods through the Si substrates. These findings are substantial to advance the integration of GaN-based devices on any substrates of choice that sustains the GaN growth temperatures, thereby permitting novel designs of GaN-based heterojunction device concepts.

Index matching at the nanoscale: light scattering by core-shell Si/SiO x nanowires.

Silicon nanowires (SiNWs) show strong resonant wavelength enhancement in terms of absorption as well as scattering of light. However, in most optoelectronic device concepts the SiNWs should be surrounded by a contact layer. Ideally, such a layer can also act as an index matching layer which could nearly halve the strong reflectance of light by silicon. Our results show that this reduction can be overcome at the nanometer scale, i.e. SiNWs embedded in a silica (SiO x ) layer can not only maintain their high scattering cross sections but also their strong polarization dependent scattering. Such effects can be useful for light harvesting or optoelectronic applications. Moreover, we show that it is possible to optically determine the diameters of the embedded nanoscale silicon (Si) cores.

Ultrasensitive silicon nanowire for real-world gas sensing: noninvasive diagnosis of cancer from breath volatolome.

We report on an ultrasensitive, molecularly modified silicon nanowire field effect transistor that brings together the lock-and-key and cross-reactive sensing worlds for the diagnosis of (gastric) cancer from exhaled volatolome. The sensor is able to selectively detect volatile organic compounds (VOCs) that are linked with gastric cancer conditions in exhaled breath and to discriminate them from environmental VOCs that exist in exhaled breath samples but do not relate to the gastric cancer per se. Using breath samples collected from actual patients with gastric cancer and from volunteers who do not have cancer, blind analysis validated the ability of the reported sensor to discriminate between gastric cancer and control conditions with >85% accuracy, irrespective of important confounding factors such as tobacco consumption and gender. The reported sensing approach paves the way to use the power of silicon nanowires for simple, inexpensive, portable, and noninvasive diagnosis of cancer and other disease conditions.

Ultrafast Dynamics of Lasing Semiconductor Nanowires.

Semiconductor nanowire lasers operate at ultrafast timescales; here we report their temporal dynamics, including laser onset time and pulse width, using a double-pump approach. Wide bandgap gallium nitride (GaN), zinc oxide (ZnO), and cadmium sulfide (CdS) nanowires reveal laser onset times of a few picoseconds, driven by carrier thermalization within the optically excited semiconductor. Strong carrier-phonon coupling in ZnO leads to the fastest laser onset time of ∼1 ps in comparison to CdS and GaN exhibiting values of ∼2.5 and ∼3.5 ps, respectively. These values are constant between nanowires of different sizes implying independence from any optical influences. However, we demonstrate that the lasing onset times vary with excitation wavelength relative to the semiconductor band gap. Meanwhile, the laser pulse widths are dependent on the optical system. While the fastest ultrashort pulses are attained using the thinnest possible nanowires, a sudden change in pulse width from ∼5 to ∼15 ps occurs at a critical nanowire diameter. We attribute this to the transition from single to multimode waveguiding, as it is accompanied by a change in laser polarization.

Role of silicon nanowire diameter for alkyl (chain lengths C1-C18) passivation efficiency through Si-C bonds.

The effect of silicon nanowire (Si NW) diameter on the functionalization efficiency as given by covalent Si-C bond formation is studied for two distinct examples of 25 ± 5 and 50 ± 5 nm diameters (Si NW25 and Si NW50, respectively). A two-step chlorination/alkylation process is used to connect alkyl chains of various lengths (C1-C18) to thinner and thicker Si NWs. The shorter the alkyl chain lengths, the larger the surface coverage of the two studied Si NWs. Increasing the alkyl chain length (C2-C9) changes the coverage on the NWs: while for Si NW25 90 ± 10% of all surface sites are covered with Si-C bonds, only 50 ± 10% of all surface sites are covered with Si-C bonds for the Si NW50 wires. Increasing the chain length further to C14-C18 decreases the alkyl coverage to 36 ± 6% in thin Si NW25 and to 20 ± 5% in thick Si NW50. These findings can be interpreted as being a result of increased steric hindrance of Si-C bond formation for longer chain lengths and higher surface energy for the thinner Si NWs. As a direct consequence of these findings, Si NW surfaces have different stabilities against oxidation: they are more stable at higher Si-C bond coverage, and the surface stability was found to be dependent on the Si-C binding energy itself. The Si-C binding energy differs according to (C1-9)-Si NW > (C14-18)-Si NW, i.e., the shorter the alkyl chain, the greater the Si-C binding energy. However, the oxidation resistance of the (C2-18)-Si NW25 is lower than for equivalent Si NW50 surfaces as explained and experimentally substantiated based on electronic (XPS and KP) and structure (TEM and HAADF) measurements.

Fabrication and characterization of plasmonic nanocone antennas for strong spontaneous emission enhancement.

Plasmonic antennas are attractive nanostructures for a large variety of studies ranging from fundamental aspects of light-matter interactions at the nanoscale to industry-relevant applications such as ultrasensitive sensing, enhanced absorption in solar cells or solar fuel generation. A particularly interesting feature of these antennas is that they can enhance the fluorescence properties of emitters. Theoretical calculations have shown that nanocone antennas provide ideal results, but a high degree of manufacturing precision and control is needed to reach optimal performance. In this study, we report on the fabrication of nanocones with base diameters and heights in the range of 100 nm with variable aspect ratios using focused ion beam milling of sputtered nano-crystalline gold layers. The controlled fabrication process allows us to obtain cones with tailored plasmon resonances. The measured plasmon spectra show very good agreement with finite-difference time-domain calculations. Theoretical investigations predict that these nanocones can enhance the spontaneous emission rate of a quantum emitter by several hundred times while keeping its quantum efficiency above 60%.

Optical nano-structuring in light-sensitive AgCl-Ag waveguide thin films: wavelength effect.

Irradiation of photosensitive thin films results in the nanostructures formation in the interaction area. Here, we investigate how the formation of nanostructures in photosensitive waveguide AgCl thin films, doped by Ag nanoparticles, can be customized by tuning the wavelength of the incident beam. We found, silver nanoparticles are pushed towards the interference pattern minima created by the interference of the incident beam with the excited TEn-modes of the AgCl-Ag waveguide. The interference pattern determines the grating constant of the resulting spontaneous periodic nanostructures. Also, our studies indicate a strong dependence of the shape and size distribution of the formed Ag nano-coalescences on the wavelength of the incident beam. It also influences on the surface coverage of the sample by the formed silver nanoparticles and on period of the self-organized nano-gratings. It is found, exposure time and intensity of the incident light are the most determinant parameters for the quality and finesse of our nanostructures. More intense incident light with shorter exposure time generates more regular nanostructures with smaller nano-coalescences and, produces gratings with higher diffraction efficiency. At constant intensity longer exposure time produces more complete nanostructures because of optical positive feedback. We observed exposure with longer wavelength produces finer gratings.

A time-resolved numerical study of the vapor-liquid-solid growth kinetics describing the initial nucleation phase as well as pulsed deposition processes.

Today, the vapor-liquid-solid (VLS) growth mechanism is a common process for the metal catalyzed bottom-up growth of semiconductor nanowires (NWs). Nevertheless, most of the literature only is concerned with the steady-state NW growth which applies when the amount of material supplied is equal to the amount consumed by the NW growth at the same time. While this description is suitable for chemical vapor deposition (CVD) or electron beam evaporation (EBE) processes after the initial nucleation time, problems arise when pulsed growth processes like pulsed laser deposition (PLD) are used since in this case the steady state growth condition cannot be applied. Moreover, the initial phase of NW growth cannot be described with steady state growth conditions, either. In this work, we present a modeling approach for VLS NW growth based on numerical simulations, which is capable of describing the nucleation phase of the VLS growth process as well as a pulsed deposition process.

Stimulus-Responsive Gas Marbles as an Amphibious Carrier for Gaseous Materials.

Gas marbles are a new family of particle-stabilized soft dispersed system with a soap bubble-like air-in-water-in-air structure. Herein, stimulus-responsive character is successfully introduced to a gas marble system for the first time using polymer particles carrying a poly(tertiary amine methacrylate) (pKa ≈7) steric stabilizer on their surfaces as a particulate stabilizer. The gas marbles exhibited long-term stability when transferred onto the planar surface of liquid water, provided that the solution pH of the subphase is basic and neutral. In contrast, the use of acidic solutions led to immediate disintegration of the gas marbles, resulting in release of the inner gas. The critical minimum solution pH required for long-term gas marble stability correlates closely with the known pKa value for the poly(tertiary amine methacrylate) stabilizer. It also demonstrates amphibious motions of the gas marbles.

Design of Laser Activated Antimicrobial Porous Tricalcium Phosphate-Hydroxyapatite Scaffolds for Orthopedic Applications.

The field of bone tissue engineering is steadily being improved by novel experimental approaches. Nevertheless, microbial adhesion after scaffold implantation remains a limitation that could lead to the impairment of the regeneration process, or scaffold rejection. The present study introduces a methodology that employs laser-based strategies for the development of antimicrobial interfaces on tricalcium phosphate-hydroxyapatite (TCP-HA) scaffolds. The outer surfaces of the ceramic scaffolds with inner porosity were structured using a femtosecond laser (λ = 800 nm; τ = 70 fs) for developing micropatterns and altering local surface roughness. The pulsed laser deposition of ZnO was used for the subsequent functionalization of both laser-structured and unmodified surfaces. The impact of the fs irradiation was investigated by Raman spectroscopy and X-ray diffraction. The effects of the ZnO-layered ceramic surfaces on initial bacterial adherence were assessed by culturing Staphylococcus aureus on both functionalized and non-functionalized scaffolds. Bacterial metabolic activity and morphology were monitored via the Resazurin assay and microscopic approaches. The presence of ZnO evidently decreased the metabolic activity of bacteria and led to impaired cell morphology. The results from this study have led to the conclusion that the combination of fs laser-structured surface topography and ZnO could yield a potential antimicrobial interface for implants in bone tissue engineering.