Titania-mediated stabilization of fluorescent dye encapsulation in mesoporous silica nanoparticles.

Mesoporous silica nanoparticles hosting guest molecules are a versatile tool with applications in various fields such as life and environmental sciences. Current commonly applied pore blocking strategies are not universally applicable and are often not robust enough to withstand harsh ambient conditions (e.g. geothermal). In this work, a titania layer is utilized as a robust pore blocker, with a test-case where it is used for the encapsulation of fluorescent dyes. The layer is formed by a hydrolysis process of a titania precursor in an adapted microemulsion system and demonstrates effective protection of both the dye payload and the silica core from disintegration under otherwise damaging external conditions. The produced dye-MSN@TiO2 particles are characterized by means of electron microscopy, elemental mapping, ζ-potential, X-ray diffraction (XRD), nitrogen adsorption, Thermogravimetric analysis (TGA), fluorescence and absorbance spectroscopy and Fourier Transform Infrared Spectroscopy - Total Attenuated Reflectance (FT-IR ATR). Finally, the performance of the titania-encapsulated MSNs is demonstrated in long-term aqueous stability and in flow-through experiments, where owing to improved dispersion encapsulated dye results in improved flow properties compared to free dye properties. This behavior exemplifies the potential advantage of carrier-borne marker molecules over free dye molecules in applications where accessibility or targeting are a factor, thus this encapsulation method increases the variety of fields of application.

Tip-Induced Nanopatterning of Ultrathin Polymer Brushes.

Patterned, ultra-thin surface layers can serve as templates for positioning nanoparticlesor targeted self-assembly of molecular structures, for example, block-copolymers. This work investigates the high-resolution, atomic force microscopebased patterning of 2 nm thick vinyl-terminated polystyrene brush layers and evaluates the line broadening due to tip degradation. This work compares the patterning properties with those of a silane-based fluorinated self-assembled monolayer (SAM), using molecular heteropatterns generated by modified polymer blend lithography (brush/SAM-PBL). Stable line widths of 20 nm (FWHM) over lengths of over 20000 µm indicate greatly reduced tip wear, compared to expectations on uncoated SiOx surfaces. The polymer brush acts as a molecularly thin lubricating layer, thus enabling a 5000 fold increase in tip lifetime, and the brush is bonded weakly enough that it can be removed with surgical accuracy. On traditionally used SAMs, either the tip wear is very high or the molecules are not completely removed. Polymer Phase Amplified Brush Editing is presented, which uses directed self-assembly to amplify the aspect ratio of the molecular structures by a factor of 4. The structures thus amplified allow transfer into silicon/metal heterostructures, fabricating 30 nm deep, all-silicon diffraction gratings that could withstand focused high-power 405 nm laser irradiation.

Dry under water: air retaining properties of large-scale elastomer foils covered with mushroom-shaped surface microstructures.

Superhydrophobic surfaces are well known for most different functions in plants, animals, and thus for biomimetic technical applications. Beside the Lotus Effect, one of their features with great technical, economic and ecologic potential is the Salvinia Effect, the capability to keep a stable air layer when submerged under water. Such air layers are of great importance, e.g., for drag reduction (passive air lubrication), antifouling, sensor applications or oil-water separation. Some biological models, e.g., the floating fern Salvinia or the backswimmer Notonecta, show long term stable air retention even under hydrodynamic conditions. Therefore, they are ideal models for the development of technical biomimetic air retaining surfaces. Up to now, several prototypes of such surfaces have been developed, but none provides both, stable air retention and cost effective large scale production. Meanwhile, a novel biomimetic surface is commercially available and produced on a large scale: an adhesive elastomeric film with mushroom-shaped surface microstructures that mimic the adhesion system of animals. In this study, we show that these films, which have been initially developed for a different purpose, due to their specific geometry at the microscale, are capable of stable air retention under water. We present first results concerning the capabilities of mushroom-shaped surface microstructures and show that this elastomer foil is able to stabilize a permanent air layer under water for more than two weeks. Further, the stability of the air layer under pressure was investigated and these results are compared with the predicted theoretical values for air retention of microstructured surfaces. Here, we could show that they fit to the theoretical predictions and that the biomimetic elastomer foil is a promising base for the development of an economically and efficient biomimetic air retaining surface for a broad range of technical applications.

Air Retention under Water by the Floating Fern Salvinia: The Crucial Role of a Trapped Air Layer as a Pneumatic Spring.

The ability of floating ferns Salvinia to keep a permanent layer of air under water is of great interest, e.g., for drag-reducing ship coatings. The air-retaining hairs are superhydrophobic, but have hydrophilic tips at their ends, pinning the air-water interface. Here, experimental and theoretical approaches are used to examine the contribution of this pinning effect for air-layer stability under pressure changes. By applying the capillary adhesion technique, the adhesion forces of individual hairs to the water surface is determined to be about 20 µN per hair. Using confocal microscopy and fluorescence labeling, it is found that the leaves maintain a stable air layer up to an underpressure of 65 mbar. Combining both results, overall pinning forces are obtained, which account for only about 1% of the total air-retaining force. It is suggested that the restoring force of the entrapped air layer is responsible for the remaining 99%. This model of the entrapped air acting is verified as a pneumatic spring ("air-spring") by an experiment shortcircuiting the air layer, which results in immediate air loss. Thus, the plant enhances its air-layer stability against pressure fluctuations by a factor of 100 by utilizing the entrapped air volume as an elastic spring.

Development of thermo-reporting nanoparticles for accurate sensing of geothermal reservoir conditions.

The inaccessibility of geological reservoirs, both for oil and gas production or geothermal usage, makes detection of reservoir properties and conditions a key problem in the field of reservoir engineering, including for the development of geothermal power plants. Herein, an approach is presented for the development of messenger nanoparticles for the determination of reservoir conditions, with a proof of concept example of temperature detection under controlled laboratory conditions. Silica particles are synthesized with a two-layer architecture, an inner enclosed core and an outer porous shell, each doped with a different fluorescent dye to create a dual emission system. Temperature detection happens by a threshold temperature-triggered irreversible release of the outer dye, thus changing the fluorescence signal of the particles. The reported particle system consequently enables a direct, reliable and fast way to determine reservoir temperature. It also displays a sharp threshold for accurate sensing and allows detection at concentration ranges as low as few nanograms of nanoparticles per milliliter.

3D-Printed Scanning-Probe Microscopes with Integrated Optical Actuation and Read-Out.

Scanning-probe microscopy (SPM) is the method of choice for high-resolution imaging of surfaces in science and industry. However, SPM systems are still considered as rather complex and costly scientific instruments, realized by delicate combinations of microscopic cantilevers, nanoscopic tips, and macroscopic read-out units that require high-precision alignment prior to use. This study introduces a concept of ultra-compact SPM engines that combine cantilevers, tips, and a wide variety of actuator and read-out elements into one single monolithic structure. The devices are fabricated by multiphoton laser lithography as it is a particularly flexible and accurate additive nanofabrication technique. The resulting SPM engines are operated by optical actuation and read-out without manual alignment of individual components. The viability of the concept is demonstrated in a series of experiments that range from atomic-force microscopy engines offering atomic step height resolution, their operation in fluids, and to 3D printed scanning near-field optical microscopy. The presented approach is amenable to wafer-scale mass fabrication of SPM arrays and capable to unlock a wide range of novel applications that are inaccessible by current approaches to build SPMs.

[Polymicrobial liver abscesses and pleural empyema in a 40-year-old male after tooth extraction and closed periodontal treatment: A case report]. / Polymikrobielle Leberabszesse und Pleuraempyem bei einem 40-jährigen Mann nach Zahnextraktion und geschlossener Parodontitis-Behandlung: Ein Fallbericht.

We report on a 40-year-old patient who presented with fever, right upper abdominal pain, right-sided chest pain and acute dyspnea. Imaging revealed several liver abscesses, as well as extensive right pleural empyema. Sixteen weeks previously, the patient underwent tooth extraction of the third molars (18, 28, 38, 48) and a first molar (46), and systematic closed periodontitis treatment. Four different species of the physiological microbiota of the oral cavity were detected in the pleura or liver abscess punctate (Streptococcus anginosus, Streptococcus constellatus, Actinomyces odontolyticus, Prevotella denticola). An underlying immune defect was ruled out. Ultrasound-guided drainage of liver abscesses and surgical treatment of pleural empyema by video-assisted thoracoscopy (VATS) and insertion of thoracic suction drains was performed, accompanied by targeted antibiotic therapy. Over a course of 6 weeks, the patient recovered completely. The case report illustrates severe infectious side effects of major dental interventions, and it critically summarizes current dental guideline recommendations on peri-interventional antimicrobial therapy. Therefore, a good clinical follow up after major tooth extractions is imperative.

Tuning the Wettability of a Thin Polymer Film by Gradually Changing the Geometry of Nanoscale Pore Edges.

Controlling wetting of solids by liquids attracts attention because of its scientific and technological importance. In this paper, the wettability of a highly uniform porous poly(methyl methacrylate) film on a silicon substrate containing a high density of randomly distributed self-similar pores was gradually tuned by changing the shape of nanometric crownlike structures around the pores. Fine-tuning the topography of these thin films was performed by isothermal annealing. The equilibrium contact angle of a water droplet placed on the surface of the films could be varied from 72 to 102°. The contact angle changes were assumed to be a consequence of changes in surface topography in the nanoscale. A simple method of a quantitative description of the change of the topography of these films was developed. Critical dimensions of these films were determined in horizontal and vertical directions relative to the surface plane. The slope coefficient (SC) describing how sharp the structures are, is defined as the ratio between the critical dimensions: the root-mean-square roughness σ and the autocorrelation length ξ. For SC > 0.08, the contact angle increased proportionally to the value of SC, whereas for SC < 0.08, the contact angle proportionally decreased. At the highest SC values, the contact angles were 6-10% higher than those predicted for flat porous surfaces using the Cassie-Baxter equation. We suggest that this discrepancy is due to the capillary tension caused by the submicron-scale undulation of the triple line, which was found to be proportional to the height of the crownlike pore edges and the value of SC. The same effect is responsible for the linear dependence of the contact angle on the SC value.

Mechanically Induced Switching of Molecular Layers.

Within the field of switchable surfaces, azobenzenes are an extensively studied group of molecules, known for reversibly changing conformation upon illumination with light of different wavelengths. Relying on the ability of the molecules to change properties and structure as a response to external stimuli, they have been incorporated in various devices, such as molecular switches and motors. In contrast to the well-documented switching by light irradiation, we report the discovery of mechanically triggered switching of self-assembled azobenzene monolayers, resulting in changes of surface wettability, adhesion, and friction. This mechanically induced cis-trans isomerization is triggered either locally and selectively by AFM or macroscopically by particle impact. The process is optically reversible, enabling consecutive switching cycles. Collective switching behavior was also observed, propagating from the original point of impact in a domino-like manner. Finally, local force application facilitated nondestructive and erasable nanopatterning, the cis-trans nanolithography.

Quasi-Solid-State Single-Atom Transistors.

The single-atom transistor represents a quantum electronic device at room temperature, allowing the switching of an electric current by the controlled and reversible relocation of one single atom within a metallic quantum point contact. So far, the device operates by applying a small voltage to a control electrode or "gate" within the aqueous electrolyte. Here, the operation of the atomic device in the quasi-solid state is demonstrated. Gelation of pyrogenic silica transforms the electrolyte into the quasi-solid state, exhibiting the cohesive properties of a solid and the diffusive properties of a liquid, preventing the leakage problem and avoiding the handling of a liquid system. The electrolyte is characterized by cyclic voltammetry, conductivity measurements, and rotation viscometry. Thus, a first demonstration of the single-atom transistor operating in the quasi-solid-state is given. The silver single-atom and atomic-scale transistors in the quasi-solid-state allow bistable switching between zero and quantized conductance levels, which are integer multiples of the conductance quantum G0  = 2e2 /h. Source-drain currents ranging from 1 to 8 µA are applied in these experiments. Any obvious influence of the gelation of the aqueous electrolyte on the electron transport within the quantum point contact is not observed.

A robust AFM-based method for locally measuring the elasticity of samples.

Investigation of the local sample elasticity is of high importance in many scientific domains. In 2014, Herruzo et al. published a new method based on frequency-modulation atomic force microscopy to locally determine the elasticity of samples (Nat. Commun.2014, 5, 3126). This method gives evidence for the linearity of the relation between the frequency shift of the cantilever first flexural mode Δf1 and the square of the frequency shift of the second flexural mode Δf22. In the present work, we showed that a similar linear relation exists when measuring in contact mode with a certain load FN and propose a new method for determining the elastic modulus of samples from this relation. The measurements were performed in non-dry air at ambient temperature on three different polymers (polystyrene, polypropylene and linear low-density polyethylene) and a self-assembled monolayer of 1H,1H,2H,2H-perfluorodecyltrichlorosilane (FDTS) on a silicon oxide substrate perforated with circular holes prepared by polymer blend lithography. For all samples the relation was evidenced by recording Δf1, Δf2 and FN as a function of the Z-displacement curves of the piezoelectric scanner. The occurence of a plastic deformation followed by an elastic deformation is shown and explained. The necessary load FN for measuring in the elastic domain was assessed for each sample, used for mapping the frequency shifts Δf1 and Δf2 and for determining the elastic modulus from Δf22/Δf1. The method was used to give an estimate of the Young's modulus of the FDTS thin film.

Macro-mechanics controls quantum mechanics: mechanically controllable quantum conductance switching of an electrochemically fabricated atomic-scale point contact.

Here, we present a silver atomic-scale device fabricated and operated by a combined technique of electrochemical control (EC) and mechanically controllable break junction (MCBJ). With this EC-MCBJ technique, we can perform mechanically controllable bistable quantum conductance switching of a silver quantum point contact (QPC) in an electrochemical environment at room temperature. Furthermore, the silver QPC of the device can be controlled both mechanically and electrochemically, and the operating mode can be changed from 'electrochemical' to 'mechanical', which expands the operating mode for controlling QPCs. These experimental results offer the perspective that a silver QPC may be used as a contact for a nanoelectromechanical relay.

Air-water interface of submerged superhydrophobic surfaces imaged by atomic force microscopy.

Underwater air retention of superhydrophobic hierarchically structured surfaces is of increasing interest for technical applications. Persistent air layers (the Salvinia effect) are known from biological species, for example, the floating fern Salvinia or the backswimmer Notonecta. The use of this concept opens up new possibilities for biomimetic technical applications in the fields of drag reduction, antifouling, anticorrosion and under water sensing. Current knowledge regarding the shape of the air-water interface is insufficient, although it plays a crucial role with regards to stability in terms of diffusion and dynamic conditions. Optical methods for imaging the interface have been limited to the micrometer regime. In this work, we utilized a nondynamic and nondestructive atomic force microscopy (AFM) method to image the interface of submerged superhydrophobic structures with nanometer resolution. Up to now, only the interfaces of nanobubbles (acting almost like solids) have been characterized by AFM at these dimensions. In this study, we show for the first time that it is possible to image the air-water interface of submerged hierarchically structured (micro-pillars) surfaces by AFM in contact mode. By scanning with zero resulting force applied, we were able to determine the shape of the interface and thereby the depth of the water penetrating into the underlying structures. This approach is complemented by a second method: the interface was scanned with different applied force loads and the height for zero force was determined by linear regression. These methods open new possibilities for the investigation of air-retaining surfaces, specifically in terms of measuring contact area and in comparing different coatings, and thus will lead to the development of new applications.

Copper atomic-scale transistors.

We investigated copper as a working material for metallic atomic-scale transistors and confirmed that copper atomic-scale transistors can be fabricated and operated electrochemically in a copper electrolyte (CuSO4 + H2SO4) in bi-distilled water under ambient conditions with three microelectrodes (source, drain and gate). The electrochemical switching-on potential of the atomic-scale transistor is below 350 mV, and the switching-off potential is between 0 and -170 mV. The switching-on current is above 1 µA, which is compatible with semiconductor transistor devices. Both sign and amplitude of the voltage applied across the source and drain electrodes (Ubias) influence the switching rate of the transistor and the copper deposition on the electrodes, and correspondingly shift the electrochemical operation potential. The copper atomic-scale transistors can be switched using a function generator without a computer-controlled feedback switching mechanism. The copper atomic-scale transistors, with only one or two atoms at the narrowest constriction, were realized to switch between 0 and 1G0 (G0 = 2e2/h; with e being the electron charge, and h being Planck's constant) or 2G0 by the function generator. The switching rate can reach up to 10 Hz. The copper atomic-scale transistor demonstrates volatile/non-volatile dual functionalities. Such an optimal merging of the logic with memory may open a perspective for processor-in-memory and logic-in-memory architectures, using copper as an alternative working material besides silver for fully metallic atomic-scale transistors.

Template-controlled piezoactivity of ZnO thin films grown via a bioinspired approach.

Biomaterials are used as model systems for the deposition of functional inorganic materials under mild reaction conditions where organic templates direct the deposition process. In this study, this principle was adapted for the formation of piezoelectric ZnO thin films. The influence of two different organic templates (namely, a carboxylate-terminated self-assembled monolayer and a sulfonate-terminated polyelectrolyte multilayer) on the deposition and therefore on the piezoelectric performance was investigated. While the low negative charge of the COOH-SAM is not able to support oriented attachment of the particles, the strongly negatively charged sulfonated polyelectrolyte leads to texturing of the ZnO film. This texture enables a piezoelectric performance of the material which was measured by piezoresponse force microscopy. This study shows that it is possible to tune the piezoelectric properties of ZnO by applying templates with different functionalities.

Active multi-point microrheology of cytoskeletal networks.

Active microrheology is a valuable tool to determine viscoelastic properties of polymer networks. Observing the response of the beads to the excitation of a reference leads to dynamic and morphological information of the material. In this work we present an expansion of the well-known active two-point microrheology. By measuring the response of multiple particles in a viscoelastic medium in response to the excitation of a reference particle, we are able to determine the force propagation in the polymer network. For this purpose a lock-in technique is established that allows for extraction of the periodical motion of embedded beads. To exert a sinusoidal motion onto the reference bead an optical tweezers setup in combination with a microscope is used to investigate the motion of the response beads. From the lock-in data the so called transfer tensor can be calculated, which is a direct measure for the ability of the network to transmit mechanical forces. We also take a closer look at the influence of noise on lock-in measurements and state some simple rules for improving the signal-to-noise ratio.

Novel roles for well-known players: from tobacco mosaic virus pests to enzymatically active assemblies.

The rod-shaped nanoparticles of the widespread plant pathogen tobacco mosaic virus (TMV) have been a matter of intense debates and cutting-edge research for more than a hundred years. During the late 19th century, their behavior in filtration tests applied to the agent causing the 'plant mosaic disease' eventually led to the discrimination of viruses from bacteria. Thereafter, they promoted the development of biophysical cornerstone techniques such as electron microscopy and ultracentrifugation. Since the 1950s, the robust, helically arranged nucleoprotein complexes consisting of a single RNA and more than 2100 identical coat protein subunits have enabled molecular studies which have pioneered the understanding of viral replication and self-assembly, and elucidated major aspects of virus-host interplay, which can lead to agronomically relevant diseases. However, during the last decades, TMV has acquired a new reputation as a well-defined high-yield nanotemplate with multivalent protein surfaces, allowing for an ordered high-density presentation of multiple active molecules or synthetic compounds. Amino acid side chains exposed on the viral coat may be tailored genetically or biochemically to meet the demands for selective conjugation reactions, or to directly engineer novel functionality on TMV-derived nanosticks. The natural TMV size (length: 300 nm) in combination with functional ligands such as peptides, enzymes, dyes, drugs or inorganic materials is advantageous for applications ranging from biomedical imaging and therapy approaches over surface enlargement of battery electrodes to the immobilization of enzymes. TMV building blocks are also amenable to external control of in vitro assembly and re-organization into technically expedient new shapes or arrays, which bears a unique potential for the development of 'smart' functional 3D structures. Among those, materials designed for enzyme-based biodetection layouts, which are routinely applied, e.g., for monitoring blood sugar concentrations, might profit particularly from the presence of TMV rods: Their surfaces were recently shown to stabilize enzymatic activities upon repeated consecutive uses and over several weeks. This review gives the reader a ride through strikingly diverse achievements obtained with TMV-based particles, compares them to the progress with related viruses, and focuses on latest results revealing special advantages for enzyme-based biosensing formats, which might be of high interest for diagnostics employing 'systems-on-a-chip'.

Chemical bath deposition of textured and compact zinc oxide thin films on vinyl-terminated polystyrene brushes.

In this study we investigated the influence of an organic polystyrene brush on the deposition of ZnO thin films under moderate conditions. On a non-modified SiO x surface, island growth is observed, whereas the polymer brush induces homogeneous film growth. A chemical modification of the polystyrene brushes during the mineralization process occurs, which enables stronger interaction between the then polar template and polar ZnO crystallites in solution. This may lead to oriented attachment of the crystallites so that the observed (002) texture arises. Characterization of the templates and the resulting ZnO films were performed with ζ-potential and contact angle measurements as well as scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray diffraction (XRD). Infrared spectroscopy (IR) measurements were used to investigate the polystyrene brushes before and after modification.

Atomic Scale Plasmonic Switch.

The atom sets an ultimate scaling limit to Moore's law in the electronics industry. While electronics research already explores atomic scales devices, photonics research still deals with devices at the micrometer scale. Here we demonstrate that photonic scaling, similar to electronics, is only limited by the atom. More precisely, we introduce an electrically controlled plasmonic switch operating at the atomic scale. The switch allows for fast and reproducible switching by means of the relocation of an individual or, at most, a few atoms in a plasmonic cavity. Depending on the location of the atom either of two distinct plasmonic cavity resonance states are supported. Experimental results show reversible digital optical switching with an extinction ratio of 9.2 dB and operation at room temperature up to MHz with femtojoule (fJ) power consumption for a single switch operation. This demonstration of an integrated quantum device allowing to control photons at the atomic level opens intriguing perspectives for a fully integrated and highly scalable chip platform, a platform where optics, electronics, and memory may be controlled at the single-atom level.