RhIII-Catalyzed Direct Heteroarylation of Unactivated C(sp3)-H with N-Heteroaryl Boronates.

Disclosed herein is a rhodium(III)-catalyzed direct heteroarylation reaction between unactivated aliphatic C(sp3)-H bonds in 2-alkylpyridines and heteroaryl organoboron reagents. This catalytic protocol is compatible with various heterocyclic boronates containing ortho- and meta-pyridine, pyrazoles, furan, and quinoline with strong coordination capability. The achievement of this methodology provides an efficient route to build new C(sp3)-heteroaryl bonds.

Fluorescence Lifetime-Based Luminescent Thermometry Material with Lifetime Varying over a Factor of 50.

Recently, the growing demand for temperature detection is pushing forward the flourishing development of noncontact optical thermometry. Herein, a new red phosphor Sr2InTa1-xO6:xMn4+ (SIT:xMn4+) was first constructed and systematically investigated. Based on the fairly rapid decline of the lifetime from 0.403 to 0.008 ms by increasing the temperature from 25 to 450 K, a noncontact optical thermometer can be made from phosphor SIT:0.003Mn4+ with Sr = 1.396% K-1 at 375 K and Sa = 0.0012 K-1 at 300 K. Because the luminescence is based on the outermost 3d orbits of Mn4+, the lifetime of SIT:xMn4+ is quite sensitive to the temperature, leading to a rapid decline of the lifetime with the increase in temperature. Moreover, multiple rounds of variable-temperature studies were performed to demonstrate the stability and reversibility of SIT:0.003Mn4+. This work suggests that Mn4+-phosphors are promising candidates for application as optical thermometric material.

The synthesis of aryl-heteroaryl derivatives via the RhIII-catalyzed heteroarylation of arenes and heteroaromatic boronates.

An efficient RhIII-catalyzed strategy for constructing aryl-heteroaryl derivatives with removable ketoxime ether auxiliaries via direct C-H heteroarylation based on arenes and heteroaromatic boronates has been disclosed. This protocol could tolerate various pyridine, pyrimidine, pyrazole, thiophene, and furan heteroaromatic boronates well, providing the desired products with high reactivities and excellent regioselectivity. The easy synthetic accessibility may offer potential for application in the synthesis of heterocyclic drug molecules containing aryl-heteroaryl motifs.

Designing a Polyphosphate Polymorph of CsMg(PO3)3 as Host Lattice for Preparing Single Mn2+-Oxidation Doped Phosphor in the Open Environment.

Within Mn-activated phosphors, the oxidation state of Mn dopant strongly depends on the structural features of the host lattice. This paper reported a new polymorph of CsMg(PO3)3 (CMP) with a complicated three-dimensional (3D) framework of [Mg(PO3)3]∞ that is constructed by MgO6 octahedra and 1D infinite [PO3]∞ chains. Then we prepared a series of red phosphors CsMg1-x(PO3)3:xMn2+ (CMP:xMn2+) by high temperature solid state reactions in the open air. Powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and photoluminescence (PL) studies revealed the single Mn2+-oxidation. Under 404 nm light exciting, CMP:0.2Mn2+ can emit single-band emission at around 630 nm with full-width at half-maximum (fwhm) of 70 nm. Besides, CMP:0.2Mn2+ possesses excellent thermostability up to 450 K. These features indicate that CMP:0.2Mn2+ is suitable to be used for LED backlight display. Moreover, this work suggests that a host lattice with suitable structure feature can form single Mn2+-oxidation and is rigid enough to protect Mn2+ from being oxidized by O2 at high temperature.

RhIII-Catalyzed Direct Heteroarylation of C(sp3)-H and C(sp2)-H Bonds in Heterocycles with N-Heteroaromatic Boronates.

Herein, we disclose a RhIII-catalyzed heteroarylation of C(sp3)-H and C(sp2)-H bonds in heterocycles with organoboron reagents. This protocol displays high efficiency and excellent functional group tolerance. A range of heterocyclic boronates with strong coordinating atoms, including pyridine, pyrimidine, pyrazole, thiophene, and furan derivatives, can be extensively served as the coupling reagents. The direct heteroarylation method could supply potential application in terms of the synthesis of drug molecules with multiple heterocycles.

RhIII-Catalyzed C-H (Het)arylation/Vinylation of N-2,6-Difluoroaryl Acrylamides.

RhIII-catalyzed sp2 C-H cross-coupling of acrylamides with organoboron reactants has been accomplished using a commercially available N-2,6-difluoroaryl acrylamide auxiliary. A broad range of aryl and vinyl boronates as well as a variety of heterocyclic boronates with strong coordinating ability can serve as the coupling partners. This transformation proceeds under moderate reaction conditions with excellent functional group tolerance and high regioselectivity.

Two microporous Fe-based MOFs with multiple active sites for selective gas adsorption.

Two Fe-based porous MOFs have been constructed from dimeric Fe-clusters and rod-shaped heterobimetallic {Fe2Na3}n chains as SBUs, respectively. Both of them exhibit highly selective CO2 adsorption over CH4 and N2, owing to their abundant multiple active sites.

22-Azametallacrown-8 complex with a triazole-bridged ligand: synthesis, structure and magnetic properties.

Reaction of Mn(OAc)2·4H2O with the H2L ligand affords a new manganese 22-MC-8 azametallacrown [Mn8(µ3-O)2(µ3-OH)2(µ2-OH)2(L)6(OAc)2(OH2)4]·2DMF (H2L = 3-(2-oxyphenyl)-5-(pyrazin-2-yl)-1,2,4-triazole). The structural analysis of the complex reveals that the azaMC ring possesses -[Mn-O-Mn-N-N-Mn-N-N-Mn-N-N]- connectivity. The magnetic behavior of the complex shows the dominant antiferromagnetic interactions between the manganese ions with S = 4 and the frequency-dependent out-of-phase signal.

Targeted functionalization of porous materials for separation of alcohol/water mixtures by modular assembly.

Three isoreticular hydrogen-bonded frameworks with functionalized pore structures were constructed by a modular self-assembly process in which a series of amino acids with various substituents serve as facile exchange subassemblies to decorate the pore wall. The ordered amino acid side-chain groups in the pore channels play an important role in determining the adsorption behavior of the framework materials, and ensure exclusive adsorption of methanol/water over ethanol. Gas-chromatographic separation experiments demonstrated that alcohols can be efficiently separated from ternary water/methanol/ethanol mixtures and revealed a key influence of the adsorbate-host framework interaction on the practical separation performance of mixtures.

Borromean-entanglement-driven assembly of porous molecular architectures with anion-modified pore space.

A series of metal-organic frameworks based on a flexible, highly charged Bpybc ligand, namely 1⋅Mn⊃OH(-), 2⋅Mn⊃SO(4)(2-), 3⋅Mn⊃bdc(2-), 4⋅Eu⊃SO(4)(2-) (H(2)BpybcCl(2) = 1,1'-bis(4-carboxybenzyl)-4,4'-bipyridinium dichloride, H(2)bdc = 1,4-benzenedicarboxylic acid) have been obtained by a self-assembly process. Single-crystal X-ray-diffraction analysis revealed that all of these compounds contained the same n-fold 2D→3D Borromean-entangled topology with irregular butterfly-like pore channels that were parallel to the Borromean sheets. These structures were highly tolerant towards various metal ions (from divalent transition metals to trivalent lanthanide ions) and anion species (from small inorganic anions to bulky organic anions), which demonstrated the superstability of these Borromean linkages. This non-interpenetrated entanglement represents a new way of increasing the stability of the porous frameworks. The introduction of bipyridinium molecules into the porous frameworks led to the formation of cationic surface, which showed high affinities to methanol and water vapor. The distinct adsorption and desorption isotherms of methanol vapor in four complexes revealed that the accommodated anion species (of different size, shape, and location) provided a unique platform to tune the environment of the pore space. Measurements of the adsorption of various organic vapors onto framework 1⋅Mn⊃OH(-) further revealed that these pores have a high adsorption selectivity towards molecules with different sizes, polarities, or π-conjugated structures.

Bipyridinium array-type porous polymer displaying hydrogen storage, charge-transfer-type guest inclusion, and tunable magnetic properties.

A multifunctional pillared-layer porous coordination polymer, {[Mn(2)(Bpybc)(ox)(2)]8 H(2)O}(n), has been constructed based on a flexible viologen derivative, 1,1'-bis(4-carboxybenzyl)-4,4'-bipyridinium dichloride (H(2)BpybcCl(2)), and an oxalate (ox) coligand. Single-crystal X-ray analysis reveals that the compound possesses multichannels with dimensions of about 6.1x6.6 A along the [110] and [-110] directions and 4.2x7.6 A along [100], and a void space of about 41.4 %. Hydrogen adsorption measurements at 77 K and 1 atm indicate that the compound exhibits a hydrogen uptake of 0.71 wt %. Owing to the incorporation of bipyridinium acceptor units, the compound can selectively accommodate aromatic donors into its nanosized pores based on charge-transfer interactions in an elastic way, and afford a specific color to different guests. Furthermore, the effect of perturbation exerted by the guest molecules on its magnetic properties has been investigated. The results indicate that the donor inclusion has little effect on its antiferromagnetic behavior, whereas dehydration of the compound decreases the strength of the magnetic exchange couplings and results in a change of the antiferromagnetic transition temperature from 14.7 to 9.8 K.

Novel polythreaded coordination polymer: from an armed-polyrotaxane sheet to a 3D polypseudorotaxane array, photo- and thermochromic behaviors.

A novel coordination compound, {[Cd(BDC)(Bpybc)(1.5)].10H(2)O}(n), obtained by the reaction of CdCl(2) with 1,1'-bis(4-carboxybenzyl)-4,4'-bipyridinium dichloride (H(2)BpybcCl(2)) and 1,4-benzenedicarboxylic acid (H(2)BDC), contains 1D polymeric chains that are comprised of alternating rings and rods and dangling lateral arms. These 1D polymeric motifs are interlaced via rotaxane-like mechanical linkages to give 2D armed-polyrotaxane sheets, which are further mutually polythreaded via pseudorotaxane-like mechanical linkages to form a 3D polypseudorotaxane array. Notably, a sandwich-type donor-acceptor-donor stacking is formed within each ring as a consequence of both types of polythreading in this species, and photoinduced and thermal-induced reduction of bipyridinium occurs with a color change from light yellow to blue.

The formation of a hydrated homochiral helix from an achiral zwitterionic salt, spontaneous chiral symmetry breaking and redox chromism of crystals.

A unique supramolecular helix assisted by water tetramers is obtained by static evaporation of aqueous solution of a zwitterionic salt, 1,1'-bis(4-carboxylatebenzyl)-4,4'-bipyridinium; spontaneous chiral symmetry breaking occurs in crystallization; interestingly, redox chromism behavior of crystals upon exposure to alcohol atmosphere has been observed.

Strong electron-accepting methylviologen dication confined in magnetic hosts: synthesis, structural characterization, charge-transfer and magnetic properties of {(MV)2[Ni(SCN)5].Cl.2H2O}n and {(MV)[m(N3)2(SCN)2]}n (M=Mn, Co).

Three hybrid host-guest compounds {(MV)2[Ni(SCN)5].Cl.2H2O}n (1), {(MV)[Mn(N3)2(SCN)2]}n (2) and {(MV)[Co(N3)2(SCN)2}n (3) (where MV2+ = methylviologen dication) have been obtained by self-assembly methods and characterized by X-ray crystallography, spectral methods and magnetic measurements. Compound 1 shows a quasi-two-dimensional structure which is formed by novel single thiocyanate-bridged Ni(II) chains connected through S...S interactions. Compounds 2 and 3 are isostructural, containing single micro(1,3)-azide bridged Mn(II)/Co(II) square layers. MV2+, as a strong electron-acceptor and a template, is embedded between the anionic layers in all three compounds. The charge-transfer (CT) interactions between MV2+ and the anionic hosts have been revealed by structural analysis and UV-vis diffuse reflection spectroscopy. The magnetic studies of the compounds show antiferromagnetic interactions between adjacent metal ions (J = -34.52(7) cm(-1) for 1, J = -3.90(2) cm(-1) for 2 and J = -10.96(6) cm(-1) for 3).

[Construction of the recombinant adenovirus carrying porcine interferon gamma (poIFNgamma) and identification of its antiviral activity].

The total RNA was extracted from peripheral blood mononuclear cells (PBMC) which was isolated from Meishan porcine and induced with concanavaline A (ConA), then the porcine interferon gamma gene (PoIFNgamma, 501bp) was amplified by RT-PCR. The result of sequencing demonstrated that the amplified PoIFNgamma had 100% nucleotide homology with the other porcine IFNgamma sequence published on GenBank. The objective gene (PoIFNgamma) was inserted into adenoviral shuttle vector, pShuttle-CMV, to construct recombinant plasmid pSh-PoIFNgamma. And it was co-electrotransformated with adenoviral skeletal vector pAdEasy-1 into competent cells of BJ5183. The transforms were cultured at 37 degrees C for 24h on kanamycin resistance plate and selected for smaller colonies. Then, the extracted recombinant plasmid was named pAd-Sh-PoIFNgamma, which was confirmed by Pac I digestion, and transformed into XL10-Glod(r) for copious preparation. pAd-Sh-PoIFNgamma linearized with Pac I was co-transfected with liposome into 293 package cell-line. After 7d-10d, the typical cytopathic effect indicated that recombinant adenoviral genome (deleted with E1 and E3 genes) carrying PoIFNgamma was successfully packaged into intact virion. The recombinant virion was successively seeded to the 10th generation and the viral genome was extracted from each generation by PCR. The antiviral activity of PoIFNgamma was tested by CPE50 method. The results showed that the PoIFNgamma expressed by adenovirus had high antiviral activity, which was 1.3 x 10(6) U/mL against VSV in MDBK cells. The results demonstrated that the recombinant adenovirus carrying PoIFNgamma could be stably passaged.

[Construction of recombinant retroviral vector carrying porcine interferon-gamma and its expression in porcine kidney cells (PK-15)].

Porcine interferon-gamma (PoIFN-gamma) of Chinese local brand, Meishan porcine, was cloned and inserted into retroviral vector pLXSN (neo r) . Using Lipofectamine, this recombinant plasmid was transfected into retroviral packing cell line, PA317 cells. These transfected cells were selected by DMEM containing 400microg/mL G418 for one week. RNA was extracted from the supernatant of these selected PA317 cells and the PoIFN-gamma gene could be amplified by RT-PCR. Pocine kidney cells and PK-15 cells were infected by the supernatant and were selected by 400 microg/mL, 600 microg/mL and 800 microg/mL G418, respectively. Those PK-15 cells were detected by indirect immunofluorescence assay and it was found that PoIFN-gamma mainly anchored in cellular membrane. The supernatant of the selected PK-15 was tested for the antiviral bioactivity after 48 hours of passage. The anti-VSV (vesicular stomatitis virus) activity in MDBK (bovine kidney cell) was 1200IU/10(6) cells. In addition, the effect of rPoIFNgamma-anti-FMDV was determined using cytopathic effect inhibition. The results indicate that PoIFN-gamma has been inserted into retroviral vector and recombinant retrovirus has been successfully packaged in PA317 cells. Furthermore, this retrovirus can infect PK-15 cells and express PoIFN-gamma with natural antiviral bioactivity and can inhibit VSV and FMDV.