A Survey of Strain-Promoted Azide–Alkyne Cycloaddition in Polymer Chemistry

Highly efficient reactions that enable the assembly of molecules into complex structures have driven extensive progress in synthetic chemistry. In particular, reactions that occur under mild conditions and in benign solvents, while producing no by-products and rapidly reach completion are attracting significant attention. Amongst these, the strain-promoted azide–alkyne cycloaddition, involving various cyclooctyne derivatives reacting with azide-bearing molecules, has gained extensive popularity in organic synthesis and bioorthogonal chemistry. This reaction has also recently gained momentum in polymer chemistry, where it has been used to decorate, link, crosslink, and even prepare polymer chains. This survey highlights key achievements in the use of this reaction to produce a variety of polymeric constructs for disparate applications.     

Modulation of the electronic states of perovskite SrCrO3 thin films through protonation via low-energy hydrogen plasma implantation approaches

Hydrogenation of transition metal oxides offers a powerful platform to tailor physical functionalities as well as for potential applications in modern electronic technologies.An ideal nondestructive and efficient hydrogen incorporation approach is important for the realistic technological applications.We demonstrate the proton injection on SrCro3 thin films via an efficient low-energy hydrogen plasma implantation experiments,without destroying the original lattice framework.Hydrogen ions accumu-late largely at the interfacial regions with amorphous character which extend about one-third of the total thickness.The Hx.SrCro3(HSCO)thin films appear like exfoliated layers which however retain the fully strained state with distorted perovskite structure.Proton doping induces the change of Cr oxidation state from Cr^4+to Cr^3+in HSCO thin films and a transition from metallic to insulat-ing phase.Our investigations suggest an attractive platform in manipulating the electronic phases in proton-based approaches and may offer a potential peeling off strategy for nanoscale devices through low-energy hydrogen plasma implantation approaches.     

Octupole vibrational states in the even-mass barium isotopes

A low-lying state of ^{132, 134, 136, 138}Ba, strongly excited in the scattering of 20 MeV α-particles at 175°, is identified as the first 3^? octupole vibrational state in each case. Angular distribution measurements for α-particle scattering to this state and the well-known first 2⁺ state in ^{132, 134, 136, 138}Ba are in agreement with harmonic-vibration coupled-channel predictions. Deformation parameters are obtained, and the deduced isoscalar transition rates are compared with measured electromagnetic transition rates. The first 3^? states of ^{132, 134, 136, 138}Ba are found to be at excitation energies of 2.070, 2.251, 2.529 and 2.879 MeV, respectively. A state in ¹³⁰Ba at an excitation energy of 1.948 MeV is tentatively identified as the first octupole-vibrational state in this nucleus.     

Mass spectra of sterically crowded trialkylsilyl derivatives of nucleosides

The electron impact mass spectra of tert-butyldimethylsilyl-, cyclo-tetramethylene-tert-butylsilyl and cyclo-tetramethylene-isopropylsilyl- ether derivatives of ribo- and 2′-deoxyribonucleosides are described in detail. The interpretation of fragmentation pathways of full and mixed derivatives was aided by metastable ion decomposition studies, precise mass and deuterium labelling measurements, and spectra of mixed derivatives containing the ‘passive’ (in these spectra) trimethylsilyl group. The sterically crowded silyl groups have a powerful fragmentation directing effect. Elimination of a bulky radical, R˙ (tert-butyl or isopropyl), from the molecular ion produces the siliconium ion [M? R]⁺, which is the precursor for most of the other prominent ions in the spectra. These arise from ‘siliconium ion rearrangements’ resulting from the interaction of the positively charged siliconium ion center with electron dense regions (i.e. oxygens) in the molecule, to form cyclic silyloxonium ions which subsequently decompose. Since the interacting oxygen and silicon must be sterically accessible, the fragment ion types and their abundances are very dependent upon structure. Consequently, [M? R]⁺ ions formed from 2′, 3′ or 5′-O-silyl groups give rise to different sets of daughter ions which, for the most part, are not found, or have very low abundances, in the mass spectra of underivatized or trimethylsilylated nucleosides. Detailed information on sugar and base moieties and isomeric substitution is readily obtained.     

Enantioselective alkylation of aldehydes with chiral organomagnesium amides (COMAs)

[reaction: see text] Dialkylmagnesiums react with chiral secondary amines to form chiral organomagnesium amides (COMAs). These reagents alkylate aldehydes to form secondary alcohols with enantioselectivities up to 91:9 er.     

Closed-loop recirculating manifold for matrix isolation in flow injection flame atomic absorption spectrometry. Analysis of silver electrolysis solutions

Two flow injection procedures have been investigated for the determination of some elements in silver electrolysis solutions, for which the problem of the formation of silver acetylide needs to be addressed. A single line manifold was found to give acceptable results for limited time periods, but for prolonged operation it was necessary to remove the silver. This was achieved with a recirculating reactor in which the silver was precipitated as the chloride and retained on a filter of nylon fibers. Good recoveries of copper, iron, nickel and zinc from solutions containing up to 100 g/l. silver were obtained with over 95% of the silver retained on the filter. The filter was regenerated rapidly by flushing with ammonia solution.     

Simultaneous determination of ergosterol, nucleosides and their bases from natural and cultured Cordyceps by pressurised liquid extraction and high-performance liquid chromatography

A simple method is described for the simultaneous determination of ergosterol, nucleosides and their bases in Cordyceps. The samples were extracted by using pressurised liquid extraction (PLE). The effects of experimental variables, such as solvent, temperature, static extraction time and cycles, on PLE efficiency have been studied. The results showed a strong influence of the solvent and temperature on extraction efficiency of PLE. The determination was achieved by high-performance liquid chromatography (HPLC) using a Zorbax NH2 analytical column (250 x 4.6 mm i.d., 5 microm) with diode-array detector (DAD). The automated preparation of the sample permits a very fast analysis which is an important goal for routine purpose.