Using the Assembly Time as a Tool to Control the Surface Morphology and Separation Performance of Membranes with a Tannic Acid-Fe3+ Selective Layer.

Thin-film composite (TFC) membranes containing a metal-polyphenol network (MPN)-based selective layer were fabricated on a porous polyacrylonitrile support. The MPN layer was formed through coordination-based self-assembly between plant-based tannic acid (TA) and an Fe3+ ion. For the first time, we demonstrate that TFC membranes containing TA-Fe3+ selective layers can separate small organic solutes in aqueous media from equimolar mixtures of solutes. The effect of the assembly time on the characteristics and performance of the fabricated selective layer was investigated. An increase in the assembly time led to the formation of selective layers with smaller effective pore sizes. The tannic acid-Fe3+ selective layer exhibited a low rejection towards neutral solutes riboflavin and poly(ethylene glycol) while high rejections were observed for anionic dyes of orange II and naphthol green B. Permeation selectivities in the range of 2-27 were achieved between neutral and charged dyes in both single- and mixed-solute experiments, indicating the significant role of Donnan exclusion and the charge-selective nature of the membranes. The rejection efficiency improved with an increasing assembly time. Overall, this study demonstrates that the assembly time is a vital casting parameter for controlling the permeance, rejection and selectivity of thin-film composite membranes with a tannic acid-Fe3+ selective layer.

An enzymatic continuous-flow reactor based on a pore-size matching nano- and isoporous block copolymer membrane.

Continuous-flow biocatalysis utilizing immobilized enzymes emerged as a sustainable route for chemical synthesis. However, inadequate biocatalytic efficiency from current flow reactors, caused by non-productive enzyme immobilization or enzyme-carrier mismatches in size, hampers its widespread application. Here, we demonstrate a general-applicable and robust approach for the fabrication of a high-performance enzymatic continuous-flow reactor via integrating well-designed scalable isoporous block copolymer (BCP) membranes as carriers with an oriented and productive immobilization employing material binding peptides (MBP). Densely packed uniform enzyme-matched nanochannels of well-designed BCP membranes endow the desired nanoconfined environments towards a productive immobilized phytase. Tuning nanochannel properties can further regulate the complex reaction process and fortify the catalytic performance. The synergistic design of enzyme-matched carriers and efficient enzyme immobilization empowers an excellent catalytic performance with >1 month operational stability, superior productivity, and a high space-time yield (1.05 × 105 g L-1 d-1) via a single-pass continuous-flow process. The obtained performance makes the designed nano- and isoporous block copolymer membrane reactor highly attractive for industrial applications.

Modification of Polyacrylonitrile Ultrafiltration Membranes to Enhance the Adsorption of Cations and Anions.

Ion adsorbing ultrafiltration membranes provide an interesting possibility to remove toxic ions from water. Furthermore, it is also possible to recover valuable elements. In this work, we demonstrate two easy strategies to modify polyacrylonitrile membranes with anion and cation adsorbing groups. The membranes were modified to have positively charged amine groups or negatively charged carboxyl groups. The success of the reactions was confirmed using IR spectroscopy and zeta-potential measurements. The membranes carrying negatively charged groups provided a negative zeta-potential and had an isoelectric point at pH 3.6, while the membranes carrying positively charged groups had a positive zeta-potential in the analyzed pH range. Since only the surface of the polymer was modified, the pore size and permeance of the membranes were not drastically affected. The membranes prepared by both modification strategies had a pure water permeance higher than 1000 L/(m2 h bar) and a water contact angle of 44.3 and 57.2°, respectively. Therefore, the membranes can be operated at low pressures with reasonable flux. Additionally, SEM images showed that the membranes were still open-pored. Adsorption tests using a positively and a negatively charged dye as well as a toxic cation and an anion were performed to analyze the adsorption behavior. Both membranes were able to adsorb the oppositely charged dyes as well as the copper and chromate ions. Therefore, these membranes are good candidates to purify water streams containing hazardous ions.

Hybrid Organic-Inorganic-Organic Isoporous Membranes with Tunable Pore Sizes and Functionalities for Molecular Separation.

Accomplishing on-demand molecular separation with a high selectivity and good permeability is very desirable for pollutant removal and chemical and pharmaceutical processing. The major challenge for sub-10 nm filtration of particles and molecules is the fabrication of high-performance membranes with tunable pore size and designed functionality. Here, a versatile top-down approach is demonstrated to produce such a membrane using isoporous block copolymer membranes with well-defined pore sizes combined with growth of metal oxide using sequential infiltration synthesis and atomic layer deposition (SIS and ALD). The pore size of the membranes is tuned by controlled metal oxide growth within and onto the polymer channels, enabling up to twofold pore diameter reduction. Following the growth, the distinct functionalities are readily incorporated along the membrane nanochannels with either hydrophobic, cationic, or anionic groups via straightforward and scalable gas/liquid-solid interface reactions. The hydrophilicity/hydrophobicity of the membrane nanochannel is significantly changed by the introduction of hydrophilic metal oxide and hydrophobic fluorinated groups. The functionalized membranes exhibit a superior selectivity and permeability in separating 1-2 nm organic molecules and fractionating similar-sized proteins based on size, charge, and hydrophobicity. This demonstrates the great potential of organic-inorganic-organic isoporous membranes for high-performance molecular separation in numerous applications.

Ultrastructure and electrophysiology of thermosensitive sensilla coeloconica in a tropical katydid of the genus Mecopoda (Orthoptera, Tettigoniidae).

In many acoustic insects, mate finding and mate choice are primarily based on acoustic signals. In several species with high-intensity calling songs, such as the studied katydid Mecopoda sp., males exhibit an increase in their thoracic temperature during singing, which is linearly correlated with the amount of energy invested in song production. If this increased body temperature is used by females as an additional cue to assess the male's quality during mate choice, as has been recently hypothesized ("hot-male" hypothesis), thermosensory structures would be required to evaluate this cue. In the present study, therefore, we investigated the ultrastructure and physiology of thermosensitive sensilla coeloconica on the antennal flagella of Mecopoda sp. using a combination of electron microscopy and electrophysiological recording techniques. We could identify three distinct types of sensilla coeloconica based on differences in the number and branching pattern of their dendrites. Physiological recordings revealed the innervation by antagonistically responding thermoreceptors (cold and warm) and bimodal hygro-/thermoreceptors (moist or dry) in various combinations. Our findings indicate that Mecopoda sp. females are capable of detecting a singing male from distances of at least several centimetres solely by assessing thermal cues.

Hearing with exceptionally thin tympana: Ear morphology and tympanal membrane vibrations in eneopterine crickets.

The receiver sensory system plays a crucial role in the evolution of new communication signals in insects. Among acoustic communicating crickets, the tribe Lebinthini (Eneopterinae) has evolved a unique communication system in that males produce exceptionally high-frequency calls and females respond with vibratory signals to guide males towards them. In this study, we describe nine species of Eneopterinae in which the sound receiving structures have undergone considerable morphological changes. We revealed that the anterior tympanal membrane (ATM) of the ear was extremely thin, as little as 0.35 µm thick, and to the best of our knowledge, this is the thinnest tympanal membrane found in crickets thus far. Measurements of tympanum vibrations obtained from Lebinthus bitaeniatus demonstrated a strong sensitivity towards higher frequencies. The finding also coincides with the neuronal tuning of ascending neurons and the behavioural response of the Lebinthini. The morphologically specialized ATM and its mechanical sensitivity for high frequencies, therefore, may have driven the sensory exploitation of an anti-predator behaviour that led to the evolution of a new communication system known for this group of crickets. The hypothetical phylogenetic origin of the investigated tympanal ears is discussed.

"Sensory structures on the antennal flagella of two katydid species of the genus Mecopoda (Orthoptera, Tettigonidae)".

The typology, number and distribution pattern of antennal sensilla in two species of the genus Mecopoda were studied using scanning electron microscopy. The antennae of both sexes of both species attain a length of 10cm. The antenna is made up of three basic segments: the scape, pedicel and flagellum, which is composed of more than 200 flagellomeres. We distinguished two types of sensilla chaetica, one type of sensilla trichodea, five types of sensilla basiconica and one type of sensilla coeloconica. The possible function of the sensilla was discussed. Six types of sensilla were considered as olfactory, one of which could also have a thermo- and hygrosensitive function. The remaining types of sensilla identified had a purely mechanosensory function, a dual gustatory- and mechanosensory function and a thermo- and/or hygrosensory function, respectively. Consistent sex specific differences in the types, numbers and distribution of antennal sensilla were not found. Interspecific differences were identified especially in terms of the numbers of sensilla chaetica.

Concept of an Active Amplification Mechanism in the Infrared Organ of Pyrophilous Melanophila Beetles.

Jewel beetles of the genus Melanophila possess a pair of metathoracic infrared (IR) organs. These organs are used for forest fire detection because Melanophila larvae can only develop in fire killed trees. Several reports in the literature and a modeling of a historic oil tank fire suggest that beetles may be able to detect large fires by means of their IR organs from distances of more than 100 km. In contrast, the highest sensitivity of the IR organs, so far determined by behavioral and physiological experiments, allows a detection of large fires from distances up to 12 km only. Sensitivity thresholds, however, have always been determined in non-flying beetles. Therefore, the complete micromechanical environment of the IR organs in flying beetles has not been taken into consideration. Because the so-called photomechanic sensilla housed in the IR organs respond bimodally to mechanical as well as to IR stimuli, it is proposed that flying beetles make use of muscular energy coupled out of the flight motor to considerably increase the sensitivity of their IR sensilla during intermittent search flight sequences. In a search flight the beetle performs signal scanning with wing beat frequency while the inputs of the IR organs on both body sides are compared. By this procedure the detection of weak IR signals could be possible even if the signals are hidden in the thermal noise. If this proposed mechanism really exists in Melanophila beetles, their IR organs could even compete with cooled IR quantum detectors. The theoretical concept of an active amplification mechanism in a photon receptor innervated by highly sensitive mechanoreceptors is presented in this article.

Thermomechanical properties of the stimulus transducing cuticle in the infrared organ of Merimna atrata (Coleoptera, Buprestidae).

The pyrophilous Australian "fire-beetle" Merimna atrata strongly depends on the occurrence and localization of forest fires for its reproduction. As a special adaptation to its unusual biology, elaborate infrared (IR) organs have evolved in this species. The IR-organs consist of a specialized cuticular portion, the absorbing area, innervated by a sensory complex. The sensory complex contains a thermosensitive multipolar neuron with a specialized dendritic region, the terminal dendritic mass, and a mechanosensitive unit represented by a chordotonal organ (CO). Evidence for the IR-receptive function so far has only been provided for the multipolar neuron. Based on morphological data, it has been hypothesized that the CO could also be involved in IR-reception by measuring minute thermal deformations of the absorbing area. To test this hypothesis, we investigated structural features like cuticle thickness, reduced Young's modulus and hardness of the absorbing area. The results were used in finite element simulations to analyze the thermomechanical behavior and performance of the IR-organ. Our findings indicate that considerable thermal deformation of the absorbing area occurs, supporting the hypothesis that the CO could function as photomechanical IR-receptor. Interestingly, at the innervation site of the CO the lowest relative displacements of the absorbing area were found. This may indicate that the CO as putative photomechanic IR-receptor has not been adapted according to the requirements of highest sensitivity. Probable benefits of the bimodal innervation by a thermosensory and a mechanosensory unit and their possible interaction for an improved performance of the IR-organ are discussed.

Bimodal innervation of the infrared organ of Merimna atrata (Coleoptera, Buprestidae) by thermo- and mechanosensory units.

The pyrophilous Australian "fire-beetle"Merimna atrata approaches forest fires and possesses abdominal infrared (IR) organs. Each round IR organ is centrally innervated by a sensory complex showing two different units: one thermoreceptive multipolar neuron and one mechanosensitive chordotonal organ (CO) consisting of two scolopidia. We investigated the CO and found that the scolopidia are mononematic (the scolopale cap remains below the cuticle) and monodynal (one sensory cell per scolopidium). The dendrites of the scolopidia extend anteriorly and are attached by their caps to the cuticle about in the middle of the absorbing area. Structural features at the site of innervation suggest that the CO measures minute thermal deformations caused by IR absorption. Therefore, an additional photomechanic component which has been described for the IR receptors of pyrophilous jewel beetles of the genus Melanophila can be proposed for the IR organ of Merimna. Because scolopidia can measure displacements in the subnanometer range, the CO may enhance the sensitivity of the IR organ. The sensory complex of the Merimna IR organ shows the same units and similar cuticular modifications as the tympanal organs of some noctuid moths. Therefore, a parallel evolution of insect ears and the Merimna IR organ is discussed.

Superhydrophobic surfaces of the water bug Notonecta glauca: a model for friction reduction and air retention.

Superhydrophobic surfaces of plants and animals are of great interest for biomimetic applications. Whereas the self-cleaning properties of superhydrophobic surfaces have been extensively investigated, their ability to retain an air film while submerged under water has not, in the past, received much attention. Nevertheless, air retaining surfaces are of great economic and ecological interest because an air film can reduce friction of solid bodies sliding through the water. This opens perspectives for biomimetic applications such as low friction fluid transport or friction reduction on ship hulls. For such applications the durability of the air film is most important. While the air film on most superhydrophobic surfaces usually lasts no longer than a few days, a few semi-aquatic plants and insects are able to hold an air film over a longer time period. Currently, we found high air film persistence under hydrostatic conditions for the elytra of the backswimmer Notonecta glauca which we therefore have chosen for further investigations. In this study, we compare the micro- and nanostructure of selected body parts (sternites, upper side of elytra, underside of elytra) in reference to their air retaining properties. Our investigations demonstrate outstanding air film persistence of the upper side of the elytra of Notonecta glauca under hydrostatic and hydrodynamic conditions. This hierarchically structured surface was able to hold a complete air film under hydrostatic conditions for longer than 130 days while on other body parts with simple structures the air film showed gaps (underside of elytra) or even vanished completely after a few days (sternites). Moreover, the upper side of the elytra was able to keep an air film up to flow velocities of 5 m/s. Obviously the complex surface structure with tiny dense microtrichia and two types of larger specially shaped setae is relevant for this outstanding ability. Besides high air film persistence, the observation of a considerable fluid velocity directly at the air-water interface indicates the ability to reduce friction significantly. The combination of these two abilities makes these hierarchically structured surfaces extremely interesting as a biomimetic model for low friction fluid transport or drag reduction on ship hulls.