Azidoethoxyphenylalanine as a Vibrational Reporter and Click Chemistry Partner in Proteins

An unnatural amino acid, 4‐(2‐azidoethoxy)‐L ‐phenylalanine (AePhe, 1 ), was designed and synthesized in three steps from known compounds in 54 % overall yield. The sensitivity of the IR absorption of the azide of AePhe was established by comparison of the frequency of the azide asymmetric stretch vibration in water and dimethyl sulfoxide. AePhe was successfully incorporated into superfolder green fluorescent protein (sfGFP) at the 133 and 149 sites by using the amber codon suppression method. The IR spectra of these sfGFP constructs indicated that the azide group at the 149 site was not fully solvated despite the location in sfGFP and the three‐atom linker between the azido group and the aromatic ring of AePhe. An X‐ray crystal structure of sfGFP‐149‐AePhe was solved at 1.45 Å resolution and provides an explanation for the IR data as the flexible linker adopts a conformation which partially buries the azide on the protein surface. Both sfGFP‐AePhe constructs efficiently undergo a bioorthogonal strain‐promoted click cycloaddition with a dibenzocyclooctyne derivative.     

Total Synthesis of (+)‐Rubriflordilactone A

Two enantioselective total syntheses of the nortriterpenoid natural product rubriflordilactone A are described, which use palladium‐ or cobalt‐catalyzed cyclizations to form the CDE rings, and converge on a late‐stage synthetic intermediate. These key processes are set up through the convergent coupling of a common diyne component with appropriate AB‐ring aldehydes, a strategy that sets the stage for the synthetic exploration of other members of this family of natural products.     

Fundamental experiments in plasticity and creep of aluminum—Extension of previous results

Paper presents combined stress experiments in plasticity and creep of aluminum 1100-0. The purpose of these experiments was to determine the motion of the yield surface in tension-torsion space for three complicated prestressing paths, to investigate the validity of the normality hypothesis, to investigate the development of creep strains after prestressing, and finally to investigate the validity of the constant volume hypothesis.It is shown that the law of hardening proposed by the author previously [3,5,6] is valid, except possibly when the prestress path intersects the yield surface at a small angle. It is also shown that the normality hypothesis is valid. After prestressing the creep strain vector has in the beginning the same direction as the plastic strain vector but later its direction may change. Finally it is shown that at the level of permanent strains less than 1% the plastic strains follow the constant volume hypothesis but the creep strains do so only when they begin to appear.     

Experience in making rheological measurements at high pressures

Summary We review the difficulties encountered in the design and operation of apparatus for rheological studies on liquids at pressures up to 900 MN m^–2 and temperatures from –30 to 120°C. Such rheological information is required in connection with elastohydrodynamic lubrication in which high pressures and shear rates are encountered.With 3 figures     

Dynamics of turbulent air-flow in droplet driven sprays

This paper presents a study of the fundamental mechanics of droplet and gas motion in sprays. Only vertical sprays are considered and our theoretical analysis identifies two main flow zones, corresponding to where the droplet velocity is much greater than or of the same order as the induced air velocity. Analytical asymptotic results for the induced air velocity for small and large downstream distances confirmed a full numerical calculation and also agreed with experimental results. The second half of the paper deals with some of the most important aspects of spray jets in a cross flow. We find that the ratio of the cross-wind speed to the induced air jet speedU ₀/V _j is a crucial factor for specifying the dynamical behaviour. We present results for an axi-symmetric spray in uniform cross flow for bothweak andstrong cross-winds.     

A physical decomposition of the stress tensor for complex flows

Traditionally, the components of the stress with respect to a relevant coordinate system are used for the purpose of stress visualisation and interpretation. A case for using a flow dependent measure to interpret and visualise stress is made for two dimensional flow, together with a suggestion for extending the idea to three dimensions. The method is illustrated for Newtonian and Oldroyd B fluids in both the eccentrically rotating cylinder and flow past a cylinder benchmark problems. In the context of a generalised Newtonian fluid, the relation between the flow-dependent stress measure to other field variables under certain flow conditions, is examined and is indicative of its importance in complex flow.

Fully Protected Glycosylated Zinc (II) Phthalocyanine Shows High Uptake and Photodynamic Cytotoxicity in MCF‐7 Cancer Cells

Phthalocyanine photosensitizers are effective in anticancer photodynamic therapy (PDT) but suffer from limited solubility, limited cellular uptake and limited selectivity for cancer cells. To improve these characteristics, we synthesized isopropylidene‐protected and partially deprotected tetra β‐glycosylated zinc (II) phthalocyanines and compared their uptake and accumulation kinetics, subcellular localization, in vitro photocytotoxicity and reactive oxygen species generation with those of disulfonated aluminum phthalocyanine. In MCF‐7 cancer cells, one of the compounds, zinc phthalocyanine {4}, demonstrated 10‐fold higher uptake, 5‐fold greater PDT‐induced cellular reactive oxygen species concentration and 2‐fold greater phototoxicity than equimolar (9 μm ) disulfonated aluminum phthalocyanine. Thus, isopropylidene‐protected β‐glycosylation of phthalocyanines provides a simple method of improving the efficacy of PDT.     

Carbophilic 3‐Component Cascades: Access to Complex Bioactive Cyclopropyl Diindolylmethanes

Naturally occurring indole‐3‐carbinol and 3,3‐diindolylmethane show bioactivity in a number of disparate disease areas, including cancer, prompting substantial synthetic analogue activity. We describe a new approach to highly functionalised derivatives that starts from allene gas and proceeds via the combination of a three‐component Pd⁰‐catalysed cascade with a one‐pot, three‐component carbophilic Pt^II cascade linked to a stereoselective acid‐catalysed Mannich–Michael reaction that generates complex cyclopropyl diindolylmethanes which show selective activity against prostate cancer cell lines.     

Network topology and dispersive kinks observed by high-resolution photoemission spectroscopy in cuprate high-temperature superconductors

Electron-phonon interactions appear to explain some of, but not all, the features of the dispersive kinks in recently observed by angle-resolved photoemission spectroscopy. The remaining anomalies have led to suggestions that magnon, and not phonon, interactions are involved. If one abandons the effective-medium approximation and replaces it with dopant-centred filamentary percolation, a picture emerges that is consistent not only with the photoemission experiments but also with tunnelling, infrared and neutron scattering data.