Highly Proton-Conductive Zinc Metal-Organic Framework Based On Nickel(II) Porphyrinylphosphonate

The design of new solid-state proton-conducting materials is a great challenge for chemistry and materials science. Herein, a new anionic porphyrinylphosphonate-based MOF ( IPCE-1Ni ), which involves dimethylammonium (DMA) cations for charge compensation, is reported. As a result of its unique structure, IPCE-1Ni exhibits one of the highest value of the proton conductivity among reported proton-conducting MOF materials based on porphyrins (1.55×10⁻³ S cm⁻¹ at 75 °C and 80 % relative humidity).     

Extraction-chromatographic behavior of Zr(IV) and Hf(IV) on TRU and LN resins in mixtures of HNO3 and HF

The behavior of group-4 homologs Zr and Hf on extraction-chromatographic sorbents LN resin and TRU resin in mixtures of HF and HNO₃ is considered. Distribution coefficients of the elements in the mixtures of 5·10⁻⁴ M–1 M HF and 0.01 M–5 M HNO₃ are determined. Strong retention of both elements was found on LN resin in the range of concentrations c(HF) ≤ 0.01 M for all concentrations of HNO₃. Retention tends to gradually disappear while increasing c(HF) to 0.5 M. On TRU resin retention is observed only in solutions with c(HNO₃) ≥ 2 M and c(HF) ≤ 0.01 M. The possibility of separating Zr(IV) and Hf(IV) on LN resin is illustrated in two different acid mixtures, whereas their separation on TRU resin under the conditions studied in this work is difficult. The results obtained can be used to isolate analytes from multicomponent mixtures during analytical tasks, as well as to separate them from each other.

     

Diastereoselective Cyclobutenol Synthesis: A Heterogeneous Palladium-Catalyzed Oxidative Carbocyclization-Borylation of Enallenols

A highly selective and efficient oxidative carbocyclization/borylation of enallenols catalyzed by palladium immobilized on amino-functionalized siliceous mesocellular foam (Pd-AmP-MCF) was developed for diastereoselective cyclobutenol synthesis. The heterogeneous palladium catalyst can be recovered and recycled without any observed loss of activity or selectivity. The high diastereoselectivity of the reaction is proposed to originate from a directing effect of the enallenol hydroxyl group. Optically pure cyclobutenol synthesis was achieved by the heterogeneous strategy by using chiral enallenol obtained from kinetic resolution.     

Unsupervised constrained radar imaging of low resolution targets

A linear spectral estimation technique, the PDFT algorithm, is used as part of a nonlinear iterative reconstruction scheme to obtain improved radar images. The iterative PDFT algorithm is used to address the limited resolution problem inherent to imaging objects buried in soil and hidden under foliage. This is achieved by subsequent application of two properties of the PDFT algorithm: the energy parameter of the PDFT algorithm is used to determine the target shape, while the shape information in turn is used to obtain super-resolved images. We describe algorithms able to exploit both properties automatically and without manual intervention. Two methods are investigated in particular, one iteratively optimizing the constraints by monitoring the energy parameter, the other method computing energy values for all points, from which a weighted prior function is determined. In addition, we discuss variants of both algorithm which provide an optimized trade-off between computation time and performance. Additional attention is given to situations, where a known target is embedded in an unknown background. Imaging results are presented for both synthetic and measured data.     

Tetraphenylantimony carboxylates in the cascade Pd-catalyzed C-phenylation reaction of methyl acrylate in the presence of peroxide

Tetraphenylantimony(V) carboxylates have been used in the palladium-catalyzed C-phenylation reaction of methyl acrylate in the presence of (PhCO₂)₂ or t-BuOOH under mild conditions (50 °C). The peroxides promote a cascade participation of the organoantimony compound and result in the transfer of three phenyl groups. Organoantimony intermediates have been isolated from the reaction.     

Application of Horner–Emmons Olefination to the Crown-Ether Derivatives

An effective synthetic approach to the preparation of a new crown-ether vinylogs involving the Horner–Emmons olefination of carbonyl precursors with the use of C₂- and C₅-phosphonates was proposed. The effects of the conjugation chain length and the nature of the terminal polar functions in the phosphonate reagent on the yield and process stereoselectivity were discussed.     

Nitroxides with two pK values--useful spin probes for pH monitoring within a broad range

A series of 4-dialkylamino-2,5-dihydroimidazole nitroxides with pyridine-4-yl, 4-dimethylaminophenyl or 4-hydroxyphenyl groups in position 2 of the imidazole ring were prepared using the reaction of RMgBr with corresponding 5-dialkylamino-4,4-dimethyl-4H-imidazole 3-oxides. The EPR spectra of the nitroxides were shown to be pH-sensitive due to consecutive protonation of the amidino moiety and the basic group(s) at position 2 of the imidazole ring. The 5,5-dimethyl-4-(dimethylamino)-2-ethyl-2-pyridine-4-yl-2,5-dihydro-1H-imidazol-1-oxyl showed a monotonic increase in the isotropic nitrogen hyperfine (hfi) coupling constant alpha(N) of 1 .4 G over a pH range from 2 to 6.5. Such a broad range of pH-sensitivity could be useful for many biophysical and biomedical applications, including pH-monitoring in the stomach.