Fabrication of biomolecular nanostructures by scanning near-field photolithography of oligo(ethylene glycol)-terminated self-assembled monolayers

The UV photo-oxidation of oligo(ethylene glycol) (OEG)-terminated self-assembled monolayers (SAMs) has been studied using static secondary ion mass spectrometry, X-ray photoelectron spectroscopy, contact angle measurement, and friction force microscopy. OEG-terminated SAMs are oxidized to yield sulfonates, but photodegradation of the OEG chain also occurs on a more rapid time scale, yielding degradation products that remain bound to the surface via gold-sulfur bonds. The oxidation of these degradation products is the rate-limiting step in the process. Photopatterning of OEG-terminated SAMs may be accomplished by using a mask and suitable light source or by using scanning near-field photolithography (SNP) in which the mask is replaced by a scanning near-field optical microscope coupled to a UV laser. Using SNP, it is possible to fabricate patterns in SAMs with a full width at half-maximum height (fwhm) as small as 9 nm, which is approximately 15 times smaller than the conventional diffraction limit. SNP-patterned OEG-terminated SAMs may be used to fabricate protein nanopatterns. By adsorbing carboxylic acid-terminated thiols into oxidized regions and converting these to active ester intermediates, it has been possible to fabricate lines of protein molecules with widths of only a few tens of nanometers.     

Bi−P Bond Homolysis as a Route to Reduced Bismuth Compounds and Reversible Activation of P4

Bismuth diphenylphosphanides Bi(NON^R)(PPh₂) (NON^R=[O(SiMe₂NR)₂], R=tBu, 2,6‐iPr₂C₆H₃, Aryl) undergo facile decomposition via single‐electron processes to form reduced Bi and P species. The corresponding derivatives Bi(NON^R)(PCy₂) are stable. Reaction of the isolated Bi^II radical ^.Bi(NON^Ar) with white phosphorus (P₄) proceeds with the reversible and selective activation of a single P?P bond to afford the bimetallic μ,η^1:1‐bicyclo[1.1.0]tetraphosphabutane compound.     

Soft or hard ionization of molecules in helium nanodroplets? An electron impact investigation of alcohols and ethers

Electron impact (70 eV) mass spectra of a series of C1-C6 alcohols encased in large superfluid liquid helium nanodroplets (approximately 60,000 helium atoms) have been recorded. The presence of helium alters the fragmentation patterns when compared with the gas phase, with some ion product channels being more strongly affected than others, most notably cleavage of the C(alpha)-H bond in the parent ion to form the corresponding oxonium ion. Parent ion intensities are also enhanced by the helium, but only for the two cyclic alcohols studied, cyclopentanol and cyclohexanol, is this effect large enough to transform the parent ion from a minor product (in the gas phase) into the most abundant ion in the helium droplet experiments. To demonstrate that these findings are not unique to alcohols, we have also investigated several ethers. The results obtained for both alcohols and ethers are difficult to explain solely by rapid cooling of the excited parent ions by the surrounding superfluid helium, although this undoubtedly takes place. A second factor also seems to be involved, a cage effect which favors hydrogen atom loss over other fragmentation channels. The set of molecules explored in this work suggest that electron impact ionization of doped helium nanodroplets does not provide a sufficiently large softening effect to be useful in analytical mass spectrometry.     

Synthesis of dithiafulvene–quinone donor–acceptor systems: isolation of a Michael adduct

π‐Conjugated donor–acceptor systems based on dithiafulvene (DTF) donor units and various acceptor units have attracted attention for their linear and nonlinear optical properties. The reaction between p‐benzoquinone and a 1,3‐dithiole phosphonium salt, deprotonated by lithium hexamethyldisilazide (LiHMDS), gave a product mixture from which the Michael adduct [systematic name: dimethyl 2‐(3‐hydroxy‐6‐oxocyclohexa‐2,4‐dien‐1‐ylidene)‐2H‐1,3‐dithiole‐4,5‐dicarboxylate], C₁₃H₁₀O₆S₂, was isolated. It is likely that one of the unidentified products obtained previously by others from related reactions could be a similar Michael adduct.     

The effect of P-cyclohexyl groups on the coordination chemistry of phosphaguanidinates

The anion of P-dicyclohexylphosphaguanidine, Cy2PC{NiPr}{NHiPr}, forms a P,N-chelate at lithium and cobalt(II); bridging through the Nimine atom forms cyclic hexamers in the former complex.     

Room Temperature Synthesis of Phosphine-Capped Lead Bromide Perovskite Nanocrystals without Coordinating Solvents

The room temperature synthesis of perovskite nanocrystals (NCs) is typically achieved by employing a ligand-assisted reprecipitation (LARP) method, which can be handled in air, and its products are comparable to what is obtained using the traditional hot-injection method. However, the LARP method typically requires the use of coordinating polar solvents such as dimethylformamide, which are not appropriate for large-scale production due to toxicity concerns and can also degrade or form defective perovskite NCs. Herein, an amine and oleic-acid-free room temperature synthesis of lead bromide perovskite NCs is reported that uses a combination of trioctylphosphine oxide and diisooctylphosphinic acid ligands. This combination of ligands provides a stable platform for the polar-solvent-free synthesis in air of fully inorganic CsPbBr₃ (fwhm ≈ 14 nm, emission = 519 nm) and hybrid organic-inorganic FAPbBr₃ (fwhm ≈ 19 nm) NCs with photoluminescence emission between 530 and 535 nm, which is in line with the Rec. 2020 color standards. In addition, it is shown that compared to a traditionally used ligand combination, phosphine ligands can be easily removed from the surface of the NCs, which is important for the future development of this technology in optoelectronic devices.     

Chemical aspects of muon spin rotation

High energy muons induce radiation damage when they interact with molecules or ions. The chemical reactions expected to occur are summarised, and attention is then given to events likely to give rise to radicals exhibiting muon-electron hyperfine coupling. Addition of muonium atoms to double or treble bonds, which is one example of the way this can occur is considered, and, in particular, the resulting proton-muon hyperfine isotope effect is discussed. Finally, possible chemical models for paramagnetic muon centres in carbon and silicon are outlined.I thank Dr. S. Cox and Dr. A. Hill for helpful discussions.     

Modelling of layered resonators for ultrasonic separation

The potential of ultrasonic techniques for the separation and concentration of particles within a fluid has been investigated in some detail in recent years. Devices for effecting such separation typically consist of a piezoceramic transducer driving into a matching layer, fluid layer and reflector layer. This paper uses an equivalent-circuit transducer model, coupled with acoustic impedance transfer relationships to model such cells with regards to both their electrical characteristics and the strength of the resonance produced under different conditions. The model is compared with experimental results from two different cells and is shown to match experimental values well in terms of electrical characteristics and separator performance. The effects of matching layer thickness are also examined using the model. The importance of the adhesive bonding layer is demonstrated, and it is shown that the model can predict the effects of such a layer. The model is also used to demonstrate the effects of coincident resonances in cell layers and to examine the pressure distribution across cells at key frequencies.     

PRIMARY TEACHER TRAINEES’ MATHEMATICS SUBJECT KNOWLEDGE AND CLASSROOM PERFORMANCE

UK government agencies have recently set in train requirements to ‘crack down’ on primary [elementary] school teacher trainees whose own knowledge of mathematics is weak. The responsibility to identify and support (or fail) them currently rests with training providers (mainly university schools of education). We describe one approach to this process, presenting some findings concerning what trainees find difficult and how their knowledge is related to their teaching competence. We flesh out these findings with a case study of a mathematically-strong trainee whose path to qualification was less than smooth.