Spectroscopic study of chloranil charge-transfer complexes of amino acids and related compounds

The absorption maxima, molar absorptivities, infrared spectra, compositions, formation constants, and pH dependence of amino acid—chloranil complexes have been determined with purified chloranil The n-π charge-transfer interaction depends on the presence of an unprotonated amino group; pH 9 is optimal for complex formation, but once formed, the complex is stable in a highly acidic medium and may be quantitatively extracted by hexanol. The molar absorptivities of the chloranil complexes of glycine, iminodiacetic acid, NTA, EDTA, DTPA and TTHA were measured. There is a linear relationship between the logarithm of the molar absorptivities of their chloranil complexes and the number of carboxylic groups in the molecule. There is an inverse linear relationship between the molar absorptivities of chloranil—metal—EDTA complexes and the logarithm of the stability constants of the EDTA chelates. This leads to a new method of determining the stability constants of complexes involving a nitrogen-donating group.     

Coupling molecular rigidity and flexibility on fused backbones for NIR-II photothermal conversion

Great attention is being increasingly paid to photothermal conversion in the near-infrared (NIR)-II window (1000–1350 nm), where deeper tissue penetration is favored. To date, only a limited number of organic photothermal polymers and relevant theory have been exploited to direct the molecular design of polymers with highly efficient photothermal conversion, specifically in the NIR-II window. This work proposes a fused backbone structure locked via an intramolecular hydrogen bonding interaction and double bond, which favors molecular planarity and rigidity in the ground state and molecular flexibility in the excited state. Following this proposal, a particular class of NIR-II photothermal polymers are prepared. Their remarkable photothermal conversion efficiency is in good agreement with our strategy of coupling polymeric rigidity and flexibility, which accounts for the improved light absorption on going from the ground state to the excited state and nonradiative emission on going from the excited state to the ground state. It is envisioned that such a concept of coupling polymeric rigidity and flexibility will offer great inspiration for developing NIR-II photothermal polymers with the use of other chromophores.

Low bandgap and large deformation generally conflict each other. This work couples molecular rigidity and flexibility by intramolecular hydrogen bonds and double bonds to achieve NIR-II light absorption and reinforced internal conversion at the same time.     

3R,4R-dihydroxy-L-proline: a potent and specific β-D-glucuronidase inhibitor

The title compound, a naturally-occurring amino acid found in virotoxins, competitively inhibits bovine β-D-glucuronidase but does not affect other glycosidases.     

Advantages of deuterium modification of nitroxide spin labels for biological epr studies

The spin label, perdeuterio-N-(1-oxy 1-2,2,6,6-tetramenthyl-4-piperidinyl)maleimide (DMSL) was synthesized and its EPR and saturation transfer EPR spectra were compared to those of the hydrogen analogue, HMSL- The labels were studied as freely tumbling entities and also bound to bovine serum albumin (BSA). Significant gains in spectral resolution and detectability were observed for DMSL relative to HMSL.     

Electrical properties of diamond surfaces functionalized with molecular monolayers

Recent studies have shown that semiconductor surfaces such as silicon and diamond can be functionalized with organic monolayers, and that these monolayer films can be used to tether biomolecules such as DNA to the surfaces. Electrical measurements of these interfaces show a change in response to DNA hybridization and other biological binding processes, but the fundamental nature of the electrical signal transduction has remained unclear. We have explored the electrical impedance of polycrystalline and single-crystal diamond surfaces modified with an organic monolayer produced by photochemical reaction of diamond with 1-dodecene. Our results show that, by measuring the impedance as a function of frequency and potential, it is possible to dissect the complex interfacial structure into frequency ranges where the total impedance is controlled by the molecular monolayer, by the diamond space-charge region, and by the electrolyte. The results have implications for understanding the ability to use molecularly modified semiconductor surfaces for applications such as chemical and biological sensing.     

Ballistic impact to access the high-rate behaviour of individual silk fibres

A revision of a classic transverse fibre impact technique is presented, as applied to the problem of obtaining the high strain-rate constitutive behaviour of commercial Bombyx mori silk. Medium tenacity nylon was also studied. Two approaches are presented: firstly a fixed pre-stress, varied impact velocity method that derives stress–strain behaviour by inverse fit; and secondly a fixed impact velocity, varied pre-stress approach, assuming basic elastic jump conditions to obtain a locus of post-impact states. The post-impact stress–strain states obtained using the two approaches converge for silk but diverge for nylon. This we attribute to silk's fine structure being able to homogenise energy dissipation at static and dynamic deformation rates. However, the coarser microstructure of nylon results in a different loading path dependence, thus divergence in the two approaches. It was also noted that silk exhibited a comparatively stable level of impact energy absorption under varying pre-stress, when compared to nylon.     

A finite element model for ultrasonic cutting

Using a single-blade ultrasonic cutting device, a study of ultrasonic cutting of three very different materials is conducted using specimens of cheese, polyurethane foam and epoxy resin. Initial finite element models are created, based on the assumption that the ultrasonic blade causes a crack to propagate in a controlled mode 1 opening, and these are validated against experimental data from three point bend fracture tests and ultrasonic cutting experiments on the materials. Subsequently, the finite element model is developed to represent ultrasonic cutting of a multi-layered material. Materials are chosen whose properties allow a model to be developed that could represent a multi-layer food product or biological structure, to enable ultrasonic cutting systems to be designed for applications both in the field of food processing and surgical procedures. The model incorporates an estimation of the friction condition between the cutting blade and the material to be cut and allows adjustment of the frequency, cutting amplitude and cutting speed.