Photochemically induced electron transfer from [3]ferrocenophanylbutanoate anions

The anions of 4-([3]ferrocenophanyl)butanoic acids (Id and IId), when excited by light of around 240 nm wavelength in aqueous solution in the presence of N₂O, undergo photo-oxidation to zwitterions (III and IV respectively) in a manner completely analogous to the reaction of 4-ferrocenylbutanoate anion. The differences in the kinetic parameters of the reactions are thought to be attributable in part to slight tilting of the cyclopentadienyl rings caused by the connecting trimethylene bridge.     

Self-assembling porphyrin-modified peptides

[structure: see text] We report the synthesis and characterization of a novel supramolecular assembly that features long-range electronic coupling between porphyrins covalently attached to a designed peptide scaffold. The resulting construct self-assembles to form extended organized aggregates in which the porphyrins engage in exciton coupling.     

Sound radiation around a flying fly

Many insects produce sounds during flight. These acoustic emissions result from the oscillation of the wings in air. To date, most studies have measured the frequency characteristics of flight sounds, leaving other acoustic characteristics--and their possible biological functions--unexplored. Here, using close-range acoustic recording, we describe both the directional radiation pattern and the detailed frequency composition of the sound produced by a tethered flying (Lucilia sericata). The flapping wings produce a sound wave consisting of a series of harmonics, the first harmonic occurring around 190 Hz. In the horizontal plane of the fly, the first harmonic shows a dipolelike amplitude distribution whereas the second harmonic shows a monopolelike radiation pattern. The first frequency component is dominant in front of the fly while the second harmonic is dominant at the sides. Sound with a broad frequency content, typical of that produced by wind, is also recorded at the back of the fly. This sound qualifies as pseudo-sound and results from the vortices generated during wing kinematics. Frequency and amplitude features may be used by flies in different behavioral contexts such as sexual communication, competitive communication, or navigation within the environment.     

The temporal effect in listeners with mild to moderate cochlear hearing impairment

This study examines the relationship between a temporal masking effect and cochlear hearing impairment. The threshold level of a long-duration broadband masker needed to mask a short-duration tonal signal was measured for signals presented 2 ms (short-delay) or 202 ms (long-delay condition) after masker onset. The difference between these thresholds is the temporal effect. In two previous studies with normal-hearing listeners, estimates of gain of the cochlear active process derived from such data suggested a decrease in gain during the course of the masker. This hypothesis was further examined in the present study by testing listeners with mild to moderate cochlear hearing impairment. Results are consistent with a decrease in gain in the short-delay condition with increasing hearing impairment, and also less change in gain with increasing hearing impairment.     

Activation of muscarinic acetylcholine receptors elicits pigment granule dispersion in retinal pigment epithelium isolated from bluegill

Background

In fish, melanin pigment granules in the retinal pigment epithelium disperse into apical projections as part of the suite of responses the eye makes to bright light conditions. This pigment granule dispersion serves to reduce photobleaching and occurs in response to neurochemicals secreted by the retina. Previous work has shown that acetylcholine may be involved in inducing light-adaptive pigment dispersion. Acetylcholine receptors are of two main types, nicotinic and muscarinic. Muscarinic receptors are in the G-protein coupled receptor superfamily, and five different muscarinic receptors have been molecularly cloned in human. These receptors are coupled to adenylyl cyclase, calcium mobilization and ion channel activation. To determine the receptor pathway involved in eliciting pigment granule migration, we isolated retinal pigment epithelium from bluegill and subjected it to a battery of cholinergic agents.

Results

The general cholinergic agonist carbachol induces pigment granule dispersion in isolated retinal pigment epithelium. Carbachol-induced pigment granule dispersion is blocked by the muscarinic antagonist atropine, by the M₁ antagonist pirenzepine, and by the M₃ antagonist 4-DAMP. Pigment granule dispersion was also induced by the M₁ agonist 4-[N-(4-chlorophenyl) carbamoyloxy]-4-pent-2-ammonium iodide. In contrast the M₂ antagonist AF-DX 116 and the M₄ antagonist tropicamide failed to block carbachol-induced dispersion, and the M₂ agonist arecaidine but-2-ynyl ester tosylate failed to elicit dispersion.

Conclusions

Our results suggest that carbachol-mediated pigment granule dispersion occurs through the activation of M_odd muscarinic receptors, which in other systems couple to phosphoinositide hydrolysis and elevation of intracellular calcium. This conclusion must be corroborated by molecular studies, but suggests Ca²⁺-dependent pathways may be involved in light-adaptive pigment dispersion.

     

Langmuir monolayers of bent-core molecules

A systematic study of five different, symmetric bent-core liquid crystals in Langmuir thin films at the air/water interface is presented. Both the end chains (siloxane vs hydrocarbon) and the core (more or less amphiphilic) are varied, to allow an exploration of different possible layer structures at the interface. The characterization includes systematic surface pressure isotherms, Brewster angle microscopy, and surface potential measurements. The properties of these layers are strongly dependent on the individual type of molecule: the molecules with amphiphilic end chains lie quite flat on the surface, while the molecules with hydrophobic end chains construct multilayer structures. In both cases, the three-dimensional collapse structure is reversible.     

Metal-directed self-assembly of bimetallic dithiocarbamate transition metal cryptands and their binding capabilities

A novel family of redox-active dinuclear transition metal based cryptands self-assembled from dithiocarbamate ligands has been synthesised; depending upon the nature of the spacer groups these new cryptand systems have been shown to electrochemically recognise the binding of cations or anions.     

Competitive reactions in solutions of poly-L-histidine, calf thymus DNA, and synthetic polyanions: determining the binding constants of polyelectrolytes

The physicochemical characteristics of a nonviral gene delivery system will govern its functional bioactivity; however, empiricism dominates the literature in this field, and a significant deficiency of quantitative investigation and evaluation of nonviral gene delivery vehicles remains. Herein, we derive a physical model and experimental method to quantitatively determine the binding constants between a model polycationic nonviral gene delivery vehicle poly-L-histidine (PLH) and calf thymus DNA. The approach has utility to a variety of systems and is not limited to the described polymer model. The interaction of PLH with DNA was monitored by fluorescence quenching of an ethidium bromide probe in the pH range 4 to 8. The interaction increased with pH decrease with the most pronounced change between pH 6 and 7. The obtained pH-dependence of fraction of salt bonds formed between PLH and DNA was used to estimate pK(a) of PLH in the presence of DNA, which equaled 6.24. The interaction of PLH with DNA in the presence of added synthetic polyanions was studied by the same approach and found to be controlled by pH, nature of the charge groups of the polyanion, and its degree of polymerization. In the mixture with sodium poly(styrenesulfonate) the interaction was negligible in the whole studied pH range, whereas in the mixtures with sodium poly(acrylate) (PA) or sodium poly(methacrylate), DNA was able to compete effectively for the binding with PLH. For PA samples with degree of polymerization higher than degree of polymerization of PLH, DP(PA) > DP(PLH), the fraction of polycation bound to DNA was constant regardless of DP(PA.) In contrast, at DP(PA) < DP(PLH), a pronounced increase in the bound fraction was observed. It substantiates the notion that the binding energy of two polymers is mainly controlled by the DP of the shorter component of polyelectrolyte complex. The data on PLH distribution between DNA and added polyanion with different values of DP were treated according to the developed procedure to yield the effective binding constants of PLH with DNA and polyanion-competitor, calculated both per mole of interacting units K(1) and mole of interacting chains K(n). In all cases, K(1) had similar numerical values reflecting common type of interaction stabilizing the complexes, i.e., electrostatics. Slight variation of K(1) yielded in drastic changes in K(n) and alteration of dominance of PLH interaction with DNA or synthetic polyanion. The results of the study can have a high impact in deriving the correlation between the binding constant of a polycation to DNA and its ability to serve as gene delivery vehicle.     

Fluorinated polymerizable phosphonium salts from PH3: Surface properties of photopolymerized films

An array of highly fluorinated polymerizable phosphonium salts (HFPPS) were synthesized from PH₃ and utilized in UV‐curable formulations. Inclusion of these salts at very low loading (0.1–1 wt %) into hexanediol diacrylate (HDDA) resulted in hydrophobic surfaces. The water repellency was achieved with short C₄F₉ fluorocarbon appendages in the monomer as opposed to the bioaccumulative C₈F₁₇ appended polymers. The physical properties of these new monomers were also characterized. The molecular architecture of the monomers had a pronounced effect on both their physical properties along with the degree of hydrophobicity imparted in the polymer. Salts utilizing the bis(trifluoromethylsulfonyl)imide anion displayed excellent compatibility with HDDA, while the chloride salts were insoluble. Time‐of‐flight secondary ion mass spectrometry (TOF‐SIMS) confirmed the presence of the HFPPS at the surface of the polymer coating. For the first time this demonstrates how these salts may be used to functionalize the surface of a UV‐cured film with ionic species. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2782–2792