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Robust processes to fabricate densely packed high-aspect-ratio (HAR) vertical semiconductor nanostructures are important for applications in microelectronics, energy storage and conversion. One of the main challenges in manufacturing these nanostructures is pattern collapse, which is the damage induced by capillary forces from numerous solution-based processes used during their fabrication. Here, using an array of vertical silicon (Si) nanopillars as test structures, we demonstrate that pattern collapse can be greatly reduced by a solution-phase deposition method to coat the nanopillars with self-assembled monolayers (SAMs). As the main cause for pattern collapse is strong adhesion between the nanopillars, we systematically evaluated SAMs with different surface energy components and identified H-bonding between the surfaces to have the largest contribution to the adhesion. The advantage of the solution-phase deposition method is that it can be implemented before any drying step, which causes patterns to collapse. Moreover, after drying, these SAMs can be easily removed using a gentle air-plasma treatment right before the next fabrication step, leaving a clean nanopillar surface behind. Therefore, our approach provides a facile and effective method to prevent the drying-induced pattern collapse in micro- and nanofabrication processes.

Here, on ITO//Au patterned substrates SAMs of ferrocene (Fc) on the Au regions and of anthraquinone (AQ) on the ITO areas are prepared, exhibiting three stable redox states. Furthermore, by selectively oxidizing or reducing the Fc or AQ units, respectively, the surface properties are locally modified. As a proof-of-concept, such a confinement of the properties is exploited to locally form host-guest complexes with β-cyclodextrin on specific surface regions depending on the applied voltage.

We report the sequential growth of supramolecular copolymers on gold surfaces, using oppositely charged dendritic peptide amphiphiles. By including water-solubilising thermoresponsive chains in the monomer design, we observed non-linear effects in the temperature-dependent sequential growth. The step-wise copolymerisation process is characterised using temperature dependent SPR and QCM-D measurements. At higher temperatures, dehydration of peripheral oligoethylene glycol chains supports copolymer growth due to more favourable comonomer interactions. Both monomers incorporate methionine amino acids but remarkably, desorption of the copolymers via competing sulphur gold interactions with the initial monomer layer is not observed. The surface-confined supramolecular copolymers remain kinetically trapped on the metal surface at near neutral pH and form viscoelastic films with a tuneable thickness.

In this Tutorial Review, we describe the development of new ligands for functionalizing and stabilizing metallic gold in the form of planar gold surfaces and gold nanoparticles (NPs). Starting from the state-of-the-art of organosulfur ligands, we describe the gold-sulfur bond formation and the nature of the resulting interface. In addition, we explain methods to prepare ordered monolayers on planar surfaces and stable ligand shells around NPs, illustrating important pioneering studies and examples of current research. Moreover, we highlight recent advancement in functionalizing gold by N-heterocyclic carbenes (NHCs), a promising alternative ligand class regarding stability and variable design strategies. We discuss the chemistry of the carbene-gold bond and report on advantages of this new ligand. Additionally, selected examples of current research illustrate the formation of ultra-stable self-assembled monolayers of NHCs on gold surfaces as well as the preparation of NHC-stabilized gold NPs.

We report a facile strategy to grow supramolecular copolymers on Au surfaces by successively exposing a surface-anchored monomer to solutions of oppositely charged peptide comonomers. Charge regulation on the active chain end of the polymer sufficiently slows down the kinetics of the self-assembly process to produce kinetically trapped copolymers at near-neutral pH. We thereby achieve architectural control at three levels: The β-sheet sequences direct the polymerization away from the surface, the height of the supramolecular copolymer brushes is well-controlled by the stepwise nature of the alternating copolymer growth, and 2D spatial resolution is realized by using micropatterned initiating monomers. The programmable nature of the resulting architectures renders this concept attractive for the development of customized biomaterials or chiral interfaces for optoelectronics and sensor applications., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A simple and high yield synthesis of water-soluble arylazopyrazoles (AAPs) featuring superior photophysical properties is reported. The introduction of a carboxylic acid allows the diverse functionalization of AAPs. Based on structural modifications of the switching unit the photophysical properties of the AAPs could be tuned to obtain molecular switches with favorable photostationary states. Furthermore, AAPs form stable and light-responsive host-guest complexes with β-cyclodextrin (β-CD). Our most efficient AAP shows binding affinities comparable to azobenzenes, but more effective switching and higher thermal stability of the Z-isomer. As a proof-of-principle, we investigated two CD-based supramolecular systems, containing either cyclodextrin vesicles (CDVs) or cyclodextrin-functionalized gold nanoparticles (CDAuNPs), which revealed excellent reversible, light-responsive aggregation and dispersion behavior. To conclude, AAPs have great potential to be incorporated as molecular switches in highly demanding and multivalent photoresponsive systems.

Coupling of plasmon resonances in metallic gap antennas is of interest for a wide range of applications due to the highly localized strong electric fields supported by these structures, and their high sensitivity to alterations of their structure, geometry, and environment. Morphological alterations of asymmetric nanoparticle dimer antennas with (sub)-nanometer size gaps are assigned to changes of their optical response in correlative dark-field spectroscopy and high-resolution transmission electron microscopy (HR-TEM) investigations. This multimodal approach to investigate individual dimer structures clearly demonstrates that the coupling of the plasmon modes, in addition to well-known parameters such as the particle geometry and the gap size, is also affected by the relative alignment of both nanoparticles. The investigations corroborate that the alignment of the gap forming facets, and with that the gap area, is crucial for their scattering properties. The impact of a flat versus a rounded gap structure on the optical properties of equivalent dimers becomes stronger with decreasing gap size. These results hint at a higher confinement of the electric field in the gap and possibly a different onset of quantum transport effects for flat and rounded gap antennas in corresponding structures for very narrow gaps., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Gold nanoparticles (Au NPs) with tailor-made structures and properties are highly desirable for applications in catalysis and sensing. In this context, surface modifications of Au NPs are of particular relevance. Herein, we present a sequential surface modification of Au NPs with Ag(I) coordination complexes, which can be converted into Ag(0)-doped Au NPs by simple ligand-exchange reaction. The key innovative element of this surface modification is a multifunctional bioxazoline-based ligand that brings coordinated Ag(I) into close proximity to the particle surface., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The molecular recognition of carbohydrates and proteins mediates a wide range of physiological processes and the development of synthetic carbohydrate receptors ("synthetic lectins") constitutes a key advance in biomedical technology. In this article we report a synthetic lectin that selectively binds to carbohydrates immobilized in a molecular monolayer. Inspired by our previous work, we prepared a fluorescently labeled synthetic lectin consisting of a cyclic dimer of the tripeptide Cys-His-Cys, which forms spontaneously by air oxidation of the monomer. Amine-tethered derivatives of N-acetylneuraminic acid (NANA), β-D-galactose, β-D-glucose and α-D-mannose were microcontact printed on epoxide-terminated self-assembled monolayers. Successive prints resulted in simple microarrays of two carbohydrates. The selectivity of the synthetic lectin was investigated by incubation on the immobilized carbohydrates. Selective binding of the synthetic lectin to immobilized NANA and β-D-galactose was observed by fluorescence microscopy. The selectivity and affinity of the synthetic lectin was screened in competition experiments. In addition, the carbohydrate binding of the synthetic lectin was compared with the carbohydrate binding of the lectins concanavalin A and peanut agglutinin. It was found that the printed carbohydrates retain their characteristic selectivity towards the synthetic and natural lectins and that the recognition of synthetic and natural lectins is strictly orthogonal.

Patchy surfaces: An azide-terminated self-assembled monolayer was patterned with the peptide sequence (EIAALEK)(3) by using microcontact printing. This sequence forms stable coiled-coil heterodimers with the complementary peptide (KIAALKE)(3). By introducing this peptide to the surface of phospholipid liposomes and cyclodextrin vesicles, liposomes and vesicles can be immobilized at the patterned surface., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Human hands are complex biomechanical systems that allow for dexterous tasks with many degrees of freedom. Coordination of the fingers is essential for many activities of daily living and involves integrating sensory signals. During this sensory integration, the central nervous system deals with the uncertainty of sensory signals. When handling compliant objects, force and position are related. Interactions with stiff objects result in reduced position changes and increased force changes compared to compliant objects. Literature has shown sensory integration of force and position at the shoulder. Nevertheless, differences in sensory requirements between proximal and distal joints may lead to different proprioceptive representations, hence findings at proximal joints cannot be directly transferred to distal joints, such as the digits. Here, we investigate the sensory integration of force and position during pinching. A haptic manipulator rendered a virtual spring with adjustable stiffness between the index finger and the thumb. Participants had to blindly reproduce a force against the spring. In both visual reference trials and blind reproduction trials, the relation between pinch force and spring compression was constant. However, by covertly changing the spring characteristics in catch trials into an adjusted force-position relation, the participants' weighting of force and position could be revealed. In agreement with previous studies on the shoulder, participants relied more on force sense in trials with higher stiffness. This study demonstrated stiffness-dependent sensory integration of force and position feedback during pinching. [ABSTRACT FROM AUTHOR]

Due to the ability to combine the separately unique characteristics of assembled and disassembled nanoparticles (NPs), the stimuli-responsive self-assembly of NPs has attracted considerable interest in functional material applications especially biomaterials. Here we demonstrate a facile and versatile approach to regulate the self-assembly process and transition pH of Au NPs by fine-tuning the co-modified pH-responsive compounds and poly(ethylene glycol) (PEG). Importantly the transition pH (ΔpH=0.4) of the system can be predetermined in the range of 8.2-5.8 (assembled to disassembled) and 8.2-4.2 (disassembled to assembled), which ideally covers the pH of normal tissue, tumor tissue milieu and organelles. The results of fluorescence imaging, Raman spectroscopy and photothermal conversion of the stimuli-responsive Au NPs shows the potential application for tumor specificity theranostics. In a nutshell this study provides a useful toolkit to design tumor-activatable self-assembled NPs with high specificity and universality. [ABSTRACT FROM AUTHOR]

The exposure to airborne particulates and surface deposition are important pathways for many human health assessments. Our primary focus is on air quality modeling issues associated with the emission of airborne particulates from contaminated surfaces via wind erosion and the subsequent deposition onto other areas. In this context, the analysis is directed at long-term impacts associated with wind-erosion-induced movement from a contaminated area onto residential and other property. For this type of application, detailed inputs on soil moisture, armoring, and other factors are typically not known as a function of time. The defined scope and data limitations generally render more detailed and data-intensive approaches impractical compared with more simplified empirical models. We compare and contrast selected empirical models to show the central tendency as a function of the type of applications (flat-regional and flat-local) as examples. This review demonstrates the importance of applying empirical wind erosion equations in a manner that is consistent with their development and with due consideration of sites-specific features and the specific air quality analysis under evaluation. Of importance to this review are: the scale of analysis, flat vs. pile (elevated) sources, and an appropriate representation of uncertainty. Without consideration of such factors within dispersion modeling analyses of airborne paniculate concentrations or surface deposition rates, the exposure analysis can be substantially biased. [ABSTRACT FROM AUTHOR]

Bangladesh is a small poor country with a huge population. Unfortunately this poor country is probably the most disaster prone in the world. Rapid growth in population and a slow rate of growth of the economy have forced a substantial part of the ever-increasing population to settle in areas too risky for human habituation, such as in newly emerging chars. Thus a large number of new settlements in coastal areas, in char lands and old settlements situated near fluctuating rivers are all in constant threat of being removed away by the disasters such as cyclones, tidal surges and river bank erosion. Almost every year natural disasters occur in Bangladesh and have created a vulnerable situation for our community people. It is well known to all that nature is beyond the control of human beings. But the massive loss caused by disasters can be minimized by proper disaster management. For this reason, disaster management has become recognized as a discipline in the world. This paper discusses the theoretical aspects, stages, and approaches of disaster management, especially the regulatory framework and social work perspectives to disaster management in Bangladesh. [ABSTRACT FROM AUTHOR]

Paraquat, as one of the most widely used herbicides globally, is highly toxic to humans, and chronic exposure and acute ingestion leads to high morbidity and mortality rates. Here, we report user-friendly, photo-responsive paraquat-loaded supramolecular vesicles, prepared via one-pot self-assembly of amphiphilic, ternary host-guest complexes between cucurbit[8]uril, paraquat, and an azobenzene derivative. In this vesicle formulation, paraquat is only released upon UV or sunlight irradiation that converts the azobenzene derivative from its trans- to its cis- form, which in turn dissociates the ternary host-guest complexations and the vesicles. The cytotoxicity evaluation of this vesicle formulation of paraquat on in vitro cell models, in vivo zebrafish models, and mouse models demonstrates an enhanced safety profile. Additionally, the PQ-loaded vesicles’ herbicidal activity against a model of invasive weed is nearly identical to that of free paraquat under natural sunlight. This study provides a safe yet effective herbicide formulation. Paraquat is a widely used herbicide that is highly toxic to humans upon acute ingestion or chronic exposure. Here, the authors generate a photosensitive formulation that releases paraquat upon exposure to UV light or sunlight, which shows an improved safety profile in zebrafish and mouse models, while maintaining substantial herbicidal activity. [ABSTRACT FROM AUTHOR]