Self-assembled monolayers (SAMs) on gold prepared from amine-terminated alkanethiols have long been employed as model positively charged surfaces. Yet in previous studies significant amounts of unexpected oxygen containing species are always detected in amine terminated SAMs. Thus, the goal of this investigation was to determine the source of these oxygen species and minimize their presence in the SAM. The surface composition, structure, and order of amine-terminated SAMs on Au were characterized by X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectroscopy (ToF-SIMS), sum frequency generation (SFG) and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. XPS determined compositions of amine-terminated SAMs in the current study exhibited oxygen concentrations of 2.4 ± 0.4 atomic %, a substantially lower amount of oxygen than reported in previously published studies. High-resolution XPS results from the S2p, C1s and N1s regions did not detect any oxidized species. Angle-resolved XPS indicated that the small amount of oxygen detected was located at or near the amine head group. Small amounts of oxidized nitrogen, carbon and sulfur secondary ions, as well as ions attributed to water, were detected in the ToF-SIMS data due to the higher sensitivity of ToF-SIMS. The lack of N-O, S-O, and C-O stretches in the SFG spectra are consistent with the XPS and ToF-SIMS results and together show that oxidation of the amine-terminated thiols alone can only account for, at most, a small fraction of the oxygen detected by XPS. Both the SFG and angle-dependent NEXAFS indicated the presence of gauche defects in the amine SAMs. However, the SFG spectral features near 2865 cm−1, assigned to the stretch of the methylene group next to the terminal amine unit, demonstrate the SAM is reasonably ordered. The SFG results also show another broad feature near 3200 cm−1 related to hydrogen-bonded water. From this multi-technique investigation it is clear that the majority of the oxygen detected within these amine-terminated SAMs arises from the presence of oxygen containing adsorbates such as tightly bound water.
SUMMARY Mantis shrimp (Stomatopoda) generate extremely rapid and forceful predatory strikes through a suite of structural modifications of their raptorial appendages. Here we examine the key morphological and kinematic components of the raptorial strike that amplify the power output of the underlying muscle contractions. Morphological analyses of joint mechanics are integrated with CT scans of mineralization patterns and kinematic analyses toward the goal of understanding the mechanical basis of linkage dynamics and strike performance. We test whether a four-bar linkage mechanism amplifies rotation in this system and find that the rotational amplification is approximately two times the input rotation, thereby amplifying the velocity and acceleration of the strike. The four-bar model is generally supported, although the observed kinematic transmission is lower than predicted by the four-bar model. The results of the morphological, kinematic and mechanical analyses suggest a multi-faceted mechanical system that integrates latches, linkages and lever arms and is powered by multiple sites of cuticular energy storage. Through reorganization of joint architecture and asymmetric distribution of mineralized cuticle, the mantis shrimp's raptorial appendage offers a remarkable example of how structural and mechanical modifications can yield power amplification sufficient to produce speeds and forces at the outer known limits of biological systems.
Extreme animal movements are usually associated with a single, high-performance behavior. However, the remarkably rapid mandible strikes of the trap-jaw ant, Odontomachus bauri, can yield multiple functional outcomes. Here we investigate the biomechanics of mandible strikes in O. bauri and find that the extreme mandible movements serve two distinct functions: predation and propulsion. During predatory strikes, O. bauri mandibles close at speeds ranging from 35 to 64 m⅐s ؊1 within an average duration of 0.13 ms, far surpassing the speeds of other documented ballistic predatory appendages in the animal kingdom. The high speeds of the mandibles assist in capturing prey, while the extreme accelerations result in instantaneous mandible strike forces that can exceed 300 times the ant's body weight. Consequently, an O. bauri mandible strike directed against the substrate produces sufficient propulsive power to launch the ant into the air. Changing head orientation and strike surfaces allow O. bauri to use the trap-jaw mechanism to capture prey, eject intruders, or jump to safety. This use of a single, simple mechanical system to generate a suite of profoundly different behavioral functions offers insights into the morphological origins of novelties in feeding and locomotion. biomechanics ͉ evolutionary origins ͉ feeding ͉ locomotion M ultifunctional morphology is an ubiquitous theme in biology. Evolutionary tradeoffs, evolutionary origins, and higher rates of lineage diversification all have been attributed to this fundamental feature (1-6). Evolutionary novelty is widely thought to arise when existing structures are co-opted for shared or novel functions (3,7,8). Examples range from feathers, which aid in both thermoregulation and flight, to bird beaks, which facilitate both feeding and sound production. One relatively unexplored and surprising example of multifunctionality is found in the extremely rapid mandible strikes of trap-jaw ants (Fig. 1).Trap-jaw ants are best known for phenomenally fast predatory strikes during which they fire their mandibles over very short timescales (9, 11). Yet some biologists also have observed trap-jaw ants using their mandibles for propulsion, specifically to jump or physically expel small intruders (12). Although the use of the mandible strike for prey-capture is widely accepted, natural history observations of mandible propulsion have stimulated discussions as to whether the jumps are the results of accidental mandible firing or intentional behaviors used for body propulsion (12, 13). In one of the few experimental studies of this phenomenon, Carlin and Gladstein (13) documented Odontomachus ruginodis using mandible strikes in a defensive behavior, specifically to eject ant intruders away from the nest entrance. However, no subsequent studies, to our knowledge, have visualized and analyzed the mechanics of these propulsive movements, particularly the use of the mandibles for selfpropulsion. Furthermore, the mandibles close over such short timescales that previous studies were unabl...
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