Search

The population of common cuttlefish Sepia officinalis in the English Channel recently developed two life cycles: annual (spawning 1 y.o.) and biennial (spawning 2 y.o.) instead of the biennial strategy known before, associated with increasing environmental temperatures in recent decades because of climate changes. Both groups differ in the size of mature animals (110–196 mm mantle length vs. 140–262 mm) and the number of chambers in the cuttlebone (60–97 in annual vs. 93–152 in biennial). The annual group represented some 15%–20% of the population, and the proportion of early spawners increased during the reproductive period, from 3%–5% in February/March to 50%–70% in June/July. Among spawning cuttlefish males predominated as ~2:1. Such environmentally driven changes in historical ecology as exemplified by the cuttlefish might be a critical link in the adaptation of the cephalopod life cycles to changing ecosystems. [ABSTRACT FROM AUTHOR]

As our understanding and control of intra- and intermolecular interactions evolve, ever more complex molecular systems are synthesized and assembled that are capable of performing work or completing sophisticated tasks at the molecular scale. Commonly referred to as molecular machines, these dynamic systems comprise an astonishingly diverse class of motifs and are designed to respond to a plethora of actuation stimuli. In this Review, we outline the conditions that distinguish simple switches and rotors from machines and draw from a variety of fields to highlight some of the most exciting recent examples of opportunities for driven molecular mechanics. Emphasis is placed on the need for controllable and hierarchical assembly of these molecular components to display measurable effects at the micro-, meso-, and macroscales. As in Nature, this strategy will lead to dramatic amplification of the work performed via the collective action of many machines organized in linear chains, on functionalized surfaces, or in three-dimensional assemblies.

Resonant acoustic mixing (RAM) offers a simple, efficient route for mechanochemical synthesis in the absence of milling media or bulk solvents. Here, we show the use of RAM to conduct the copper-catalysed coupling of sulfonamides and carbodiimides. This coupling was previously reported to take place only by mechanochemical ball milling, while in conventional solution environments it is not efficient, or does not take place at all. The results demonstrate RAM as a suitable methodology to conduct reactions previously accessed only by ball milling and provide a detailed, systematic overview of how the amount of liquid additive, measured by the ratio of liquid volume to weight of reactants (η, in μL mg−1), can affect the course of a mechanochemical reaction and the polymorphic composition of its product. Switching from ball milling to RAM allowed for the discovery of a new polymorph of the model sulfonylguanidine obtained by catalytic coupling of di(cyclohexyl)carbodiimide (DCC) and p-toluenesulfonamide, and the ability to control reaction temperature in RAM enabled in situ control of the polymorphic behaviour of this nascent product. We show that the reaction conversion for a given reaction time does not change monotonically but, instead, achieves a maximum for a well-defined η-value. This "η-sweet-spot" of conversion is herein designated ηmax. The herein explored reactions demonstrate sensitivity to η on the order of 0.01 μL mg−1, which corresponds to an amount of liquid additive below 5 mol% compared to the reactants, and is at least one to two orders of magnitude lower than the η-value typically considered in the design of liquid-assisted ball milling mechanochemical reactions. Such sensitivity suggests that strategies to optimise liquid-assisted mechanochemical reactions should systematically evaluate η-values at increments of 0.01 μL mg−1, or even finer. At η-values other than ηmax the reaction conversion drops off, demonstrating that the same liquid additive can act either as a catalyst or an inhibitor of a mechanochemical reaction, depending on the amount. [ABSTRACT FROM AUTHOR]

Author(s): Yuriy Román-Leshkov [1]; Christopher J. Barrett [1]; Zhen Y. Liu [1]; James A. Dumesic (corresponding author) [1] Diminishing fossil fuel reserves and growing concerns about global warming indicate that [...]

Liquid alkanes with the number of carbon atoms ranging from [C.sub.7] to [C.sub.15] were selectively produced from biomass-derived carbohydrates by acid-catalyzed dehydration, which was followed by aldol condensation over solid base catalysts to form large organic compounds. These molecules were then converted into alkanes by dehydration/hydrogenation over bifunctional catalysts that contained acid and metal sites in a four-phase reactor, in which the aqueous organic reactant becomes more hydrophobic and a hexadecane alkane stream removes hydrophobic species from the catalyst before they go on further to form coke. These liquid alkanes are of the appropriate molecular weight to be used as transportation fuel components, and they contain 90% of the energy of the carbohydrate and [H.sub.2] feeds., The production of liquid fuels from renewable biomass resources is particularly attractive because gasoline- and diesel-powered hybrid electric vehicles are being developed that have overall energy efficiencies comparable to those [...]

The thermal cis-to-trans isomerization behavior of the azo groups is measured by means of flash photolysis to investigate self-assembled amphiphilic copolymers in solution. The results demonstrate the utility of isomerization spectroscopy in determining the microstructure of amphiphilic polymer solutions.

Neutron reflectometry was used to determine the distribution of salt ions and water in thin poly(acrylic acid) and poly(allylamine hydrochloride) polyelectrolyte multilayers assembled with and without salt. Increasing salt concentration reverses the exclusion of water from the substrate region, eventually leading to an asymmetric segregation of water near the substrate at high salt concentration. The counterions were found to localize near the substrate in films that were either assembled with salt or were exposed to salt solutions. In addition, the capping layer of the film was found to greatly influence the counterion distribution in the multilayer. [ABSTRACT FROM AUTHOR]

Azobenzene polymer thin films are known to spontaneously generate surface patterns in response to incident light gradients. This peculiar process is investigated in terms of the dynamics of the various azobenzene photomotions, which occur on different length scales. In particular, the formation and thermal erasure of surface relief gratings are measured as a function of film thickness and by using combinatorial samples with thickness gradients. The thermal erasure of gratings in this system provides a direct measure of the glass-transition temperature, which is found to deviate substantially from the bulk value. Thin azo films exhibit a glass transition up to 50 K higher than the bulk. These dynamical measurements allow the authors to probe the length scale of mass transport, which is found to be ∼150 nm. Furthermore, surface mass transport is completely arrested in thin films <40 nm. According to these results, mass transport involves the coordinated motion of many polymer chains in the depth of the sample, rather than surface diffusion of individual chains. [ABSTRACT FROM AUTHOR]

Azobenzene polymer thin films exhibit reversible surface mass transport when irradiated with a light intensity and/or polarization gradient, although the exact mechanism remains unknown. In order to address the role of thermal effects in the surface relief grating formation process peculiar to azo polymers, a cellular automaton simulation was developed to model heat flow in thin films undergoing laser irradiation. Typical irradiation intensities of 50 mW/cm2 resulted in film temperature rises on the order of 5 K, confirmed experimentally. The temperature gradient between the light maxima and minima was found, however, to stabilize at only 10[sup -4] K within 2 μs. These results indicate that thermal effects play a negligible role during inscription, for films of any thickness. Experiments monitoring surface relief grating formation on substrates of different thermal conductivity confirm that inscription is insensitive to film temperature. Further simulations suggest that high-intensity pulsed irradiation leads to destructive temperatures and sample ablation, not to reversible optical mass transport. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]