Aluminum salen and salan complexes in the ring‐opening polymerization of cyclic esters: Controlled immortal and copolymerization of rac‐β‐butyrolactone and rac‐lactide

Aluminum‐based salen and salan complexes mediate the ring‐opening polymerization (ROP) of rac‐β‐butyrolactone (β‐BL), rac‐lactide, and ε‐caprolactone. Al‐salen and Al‐salan complexes exhibit excellent control over the ROP of rac‐β‐butyrolactone, yielding atactic poly(3‐hydroxybutyrate) (PHB) with narrow PDIs of <1.15 for Al‐salen and <1.05 for Al‐salan. Kinetic studies reveal pseudo‐first‐order polymerization kinetics and a linear relationship between molecular weight and percent conversion. These complexes also mediate the immortal ROP of rac‐β‐BL and rac‐lactide, through the addition of excess benzyl alcohol of up to 50 mol eq., with excellent control observed. A novel methyl/adamantyl‐substituted Al‐salen system further improves control over the ROP of rac‐lactide and rac‐β‐BL, yielding atactic PHB and highly isotactic poly(lactic acid) (P_m = 0.88). Control over the copolymerization of rac‐lactide and rac‐β‐BL was also achieved, yielding poly(lactic acid)‐co‐poly(3‐hydroxybutyrate) with narrow PDIs of <1.10. ¹H NMR spectra of the copolymers indicate a strong bias for the insertion of rac‐lactide over rac‐β‐BL. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Controlled Radical Polymerization Mediated by Amine–Bis(phenolate) Iron(III) Complexes

Tetradentate amine–bis(phenolate) iron(III) halide complexes containing chloro substituents on the aromatic ring are extremely efficient catalysts for controlled radical polymerization. Molecular weights are in good agreement with theoretical values and polydispersity indexes (PDIs) are as low as 1.11 for styrene and methyl methacrylate polymerizations. Complexes containing alkyl substituents on the aromatic ring are less efficient. Kinetic data reveal activity for styrene polymerization among the fastest reported to date and initial studies implicate a multimechanism system. Despite the highly colored polymerization media, simple work‐up procedures yield pure white polymers.     

High-pressure vibrational study of the catalyst candidate cis-dimercaptobis(triphenylphosphine)platinum(II), cis-[(Ph3P)2Pt(SH)2

Infrared and FT-Raman spectra of cis-dimercaptobis(triphenylphosphine)platinum(II), cis-[(PPh3)2Pt(SH)2], have been measured at high external pressures up to 55 kbar with the aid of a diamond-anvil cell (DAC). The wavenumber (v) versus pressure (P) plots from the Raman data indicate the occurrence of a pressure-induced phase transition at around 15 kbar. The metal-ligand stretching mode, v(Pt-S), and the C-H stretching mode of the phenyl rings, v(C-H), are highly sensitive to the application of pressure (dv/dP approximately 1.0 cm(-1) kbar(-1)). The IR results are generally consistent with the Raman data. The pressure-induced phase transition is most probably attributable to the reorientation of the phenyl rings in the complex; similar results have been obtained for other phenyl derivatives.     

193 nm resists and lithography

A review of recent efforts to develop photoresist materials and processes for 193 nm (ArF excimer laser) photolithography is reported. Three categories of resist processes are discussed: (1) conventional single layer, (2) bilayer and (3) surface-imaged resist processes. To date, materials have been developed for each process which exhibit resolution to less than 0.25 μm with sensitivities of less than 50 mJ/cm².     

Further remark concerning spherically symmetric nonstatic separable solutions to the Einstein equations in the comoving frame

We consider nonstatic spherically symmetric fluid solutions to the Einstein equations which, in the comoving frame, have metric coefficients that are separable functions of their arguments and that have an origin. Subject to the vanishing of the heat flux, we show that all such solutions with shear and non-vanishing shear viscosity have a scalar polynomial singularity at the origin if the fluid satisfies both the weak and strong energy conditions. When combined with previous results [1] we conclude that for the metric forms under consideration, the only fluid solutions to the Einstein equations with vanishing heat flux which satisfy the energy conditions and are free of singularities at the origin are the Robertson-Walker solutions.     

The challenge of long-term stability for nucleic acid-based electrochemical sensors

Nucleic acid-based electrochemical sensors are a versatile technology enabling affinity-based detection of a great variety of molecular targets, regardless of inherent electrochemical activity or enzymatic reactivity. Additionally, their modular interface and ease of fabrication enable rapid prototyping and sensor development. However, the technology has inhibiting limitations in terms of long-term stability that have precluded translation into clinically valuable platforms like continuous molecular monitors. In this opinion, we discuss published methods to address various aspects of sensor stability, including thiol-based monolayers and anti-biofouling capabilities. We hope the highlighted works will motivate the field to develop innovative strategies for extending the long-term operational life of nucleic acid-based electrochemical sensors.     

Interband magneto-optics in single-walled carbon nanotubes

We have carried out magneto-absorption and magneto-photoluminescence experiments on micelle-suspended single-walled carbon nanotubes in magnetic fields up to 45 T. Chirality-assigned spectral peaks exhibit significant changes with increasing magnetic field, which can be quantitatively explained in terms of the theoretically predicted splittings and redshifts of the band edge due to the Aharonov–Bohm effect combined with the magnetic-field-induced alignment of the nanotubes.     

Control of thermal properties and hydrolytic degradation in poly(lactic acid) polymer stars through control of isospecificity of polymer arms

The synthesis of a family of polymer stars with arms of varied tacticities is discussed. The effect of polymer tacticity on the physical properties of these polymer stars is dramatic. Dipentaerythritol cores support six poly(lactic acid) arms. Lewis acidic tin and/or aluminum catalysts control the polymerization to afford polymer stars of variable tacticity. Analysis of these polymers by ¹H NMR spectroscopy, thermogravimetric analysis, powder X‐ray diffraction, and differential scanning calorimetry reveals the effects of tacticity control on the physical properties of the polymer stars. Hydrolytic decomposition studies suggest that the degradation profile of a polymer star may also be tuned by stereochemical control. Differences between isotactic samples derived from rac‐lactide and L ‐lactide are heightened by longer arms of 50 and 100 monomer units. Control of polymer isospecificity shows that a ～70% isotacticity bias is necessary to induce crystallinity and alter the thermal and degradation properties of the material. Above 70% isotacticity, the degradation properties and thermal transitions can be further tuned across a relatively wide range. This technique allows for significant tunability to the physical properties of aliphatic polyester polymer stars. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012