Sulfobetaine‐containing diblock and triblock copolymers via reversible addition‐fragmentation chain transfer polymerization in aqueous media

A novel bifunctional acrylamido‐based reversible addition–fragmentation chain transfer (RAFT) chain‐transfer agent (CTA), N,N′‐ethylenebis[2‐(thiobenzoylthio)propionamide] (CTA2), has been synthesized and used for the controlled free‐radical polymerization of N,N‐dimethylacrylamide (DMA). A comparative study of CTA2 and the monofunctional CTA N,N‐dimethyl‐s‐thiobenzoylthiopropionamide (CTA1) has been conducted. Polymerizations mediated by CTA1 result in poly(N,N‐dimethylacrylamide) (PDMA) homopolymers with unimodal molecular weight distributions, whereas CTA2 yields unimodal, bimodal, and trimodal distributions according to the extent of conversion. The multimodal nature of the PDMAs has been attributed to termination events and/or chains initiated by primary radicals. The RAFT polymerization of DMA with CTA2 also results in a prolonged induction period that may be attributed to the higher local concentration of dithioester functionalities early in the polymerization. A series of ω‐ and α,ω‐dithioester‐capped PDMAs have been prepared in organic media and subsequently employed as macro‐CTAs for the synthesis of diblock and triblock copolymers in aqueous media with the zwitterionic monomer 3‐[2‐(N‐methylacrylamido)‐ethyldimethylammonio] propane sulfonate (MAEDAPS). Additionally, an ω‐dithioester‐capped MAEDAPS homopolymer has been used as a macro‐CTA for the block polymerization of DMA. To our knowledge, this is the first example of a near‐monodisperse, sulfobetaine‐containing block copolymer prepared entirely in aqueous media. The diblock and triblock copolymers form aggregates in pure water that can be dissociated by the addition of salt, as determined by ¹H NMR spectroscopy and dynamic light scattering. In pure water, highly uniform, micellelike aggregates with hydrodynamic diameters of 71–93 nm are formed. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1262–1281, 2003     

Radiotracer studies of the antitumor metallocene molybdocene dichloride with biomolecules

Neutron irradiation of Cp₂MoCl₂ for 24 h afforded the radiotracer Cp₂⁹⁹MoCl₂ which was characterised by UV–Vis spectroscopy and thin layer chromatography. Binding experiments with the thiol containing protein human serum albumin (HSA) or calf thymus DNA, were monitored for ⁹⁹Mo using a gamma counter. Under the conditions investigated, molar ratios of binding of 0.2:1 (Cp₂MoCl₂:DNA) and 9.4:1 (Cp₂MoCl₂:HSA) were calculated. The results are consistent with in vitro coordination studies that have shown strong preferential interaction of Cp₂MoCl₂ with thiols versus other donor sites in biomolecules including DNA.     

A stable dual-wavelength fiber laser with tunable wavelength spacing using a polarization-maintaining linear cavity

We propose and experimentally demonstrate a stable dual-wavelength erbium-doped polarization-maintaining (PM) fiber laser with tunable wavelength spacing using an all-PM linear cavity that makes use of two reflection peaks from the PM fiber Bragg grating (PM-FBG). Experimental results show stable dual lasing lines with a wavelength separation of ∼0.22 nm and a large optical signal-to-noise ratio (OSNR) of over 40 dB under room temperature. By applying axial strain to the PM-FBG, the center wavelengths of the two lasing lines can be tuned over several nanometers and the wavelength separation between the lasing lines can also be tuned to as small as 0.05 nm, which, to our knowledge, is the smallest wavelength spacing ever obtained from a stable room-temperature dual-wavelength fiber laser. The proposed laser configuration has the advantages of simple structure, low loss, stable dual-wavelength operation and a very small lasing linewidth of ∼5 kHz . PACS 42.55.Wd; 42.81.-i; 42.81.Gs     

Improvements in Depth Selective Electron Mössbauer Spectroscopy

The conditions for achievement of high resolving power of depth selective conversion electron Mössbauer spectroscopy method at a combined installation ‘electron spectrometer–nuclear gamma-resonance spectrometer’ have been obtained. There has been made a considerable step in development of the method at its realization at a magnetic sector electron spectrometer with double focusing, equipped with electron source (a sample under investigation) of large-area and position-sensitive detector. The paper presents a prospective symmetrical version of a magnetic sector electron spectrometer that allows realizing more completely possibilities of the method. It is noted that the proposed method is particularly valuable for investigations of nanosystems, nanostrutures that contain Mössbauer nuclei.     

Hydrogen generation in nitric acid solutions of plutonium

Summary Literature data on the radiolytic generation of hydrogen in nitric acid solutions of plutonium are used to construct a model that predicts G(H₂) as a function of the nitric acid and plutonium concentrations. The model indicates that G(H₂) decreases with increasing concentration of nitric acid, in agreement with most experimental observations. The effect of the plutonium concentration on G(H₂) is secondary to the effect of the acid concentration. An equation for interpolating Gvalues for total gas is included.     

Investigation into the ROMP copolymerization of peptide‐ and PEG‐functionalized norbornene derivatives

The ring‐opening metathesis polymerizations (ROMP), using RuCl₂ (PCy₃)₂CHPh, of a series of peptide‐functionalized norbornene derivatives have been investigated. Incorporation of a PEG‐monomer was found to prevent premature precipitation of polymer strands during the course of polymerization reactions and yield water compatible polymers in high conversions. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3178–3190, 2007     

Spectral manifestations of distorted forms of Pd-porphin at helium temperatures: The effect of the matrix

The occurrence of two noninteracting forms of Pd-porphin in the ground electronic state in a wide number of Shpolskii matrices maintained at liquid helium temperature was observed with the help of the finestructure phosphorescence spectra of these systems. The ratio between these forms can be varied in wide limits by choosing a particular matrix, which indicates that the matrix plays a significant role in the conformation formation of the tetrapyrrole macrocycle. Based on comparison both with the resonance Raman spectra and with the results of investigations of metal complexes of porphin by the selective spectroscopy methods, the shortwavelength spectral form has been shown to correspond to the planar molecular structure, whereas the longwavelength form has been attributed to a nonplanar molecular structure with the distortion of the porphin macrocycle of the saddle type. The results obtained indicate that the methods of fine structure spectroscopy make it possible to efficiently study distorted molecular structures stabilized in solid matrices at low temperatures.     

What Oxidation State of Iron Determines the Amethyst Colour?

A colourless quartz crystal doped with ⁵⁷Fe³⁺ was obtained by hydrothermal synthesis in an NH₄F solution. The crystal was transformed into violet amethyst by gamma-irradiation. The change in colour was accompanied by changes in the Mössbauer spectrum that can be interpreted as the conversion of trivalent iron into the tetravalent state: Fe³⁺→Fe⁴⁺.

     

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