New group IIIA metal phosphate-oxalates containing dimethylammonium cations with proton conductivity.

Three new group IIIA metal phosphate-oxalate (MPO) compounds, namely [(CH3)2NH2]2[M2(HPO4)2(H2PO4)2(C2O4)] (M = Al (1), Ga (2)) and [(CH3)2NH2]2[In2(HPO4)2(H2PO4)2(C2O4)]·H2O (3), have been synthesized. Their crystal structures feature an anionic layer with the sql topology net. In particular, 1 displays a proton conductivity (σ) of 9.09 × 10-3 S cm-1 at 85 °C and under 98% relative humidity, which is the highest among MPOs. This study not only endows the main group metal-based MPO family with new members, but also contributes to further understanding of the structure-directing roles of amines and provides a feasible idea for improving the proton conductivity of MPOs.

[Ag4Br6] cluster-based 3D bromoargentate hybrid: crystal structure, optical/photoelectrical performance and theoretical study.

The self-assembly of cluster-based halide framework materials has been a matter of great interest but with great challenges. Herein, by exploiting hexamethylenetetramine (Hmta) with Td symmetry as a structural modifier, we successfully constructed and systematically characterized an unusual three-dimensional (3D) hybrid bromoargentate, namely K[NH4][Ag4Br6(Hmta)] (1), bearing a diamond-type [Ag4Br6(Hmta)]n2n- anionic skeleton built up from adamantane-like units of inorganic [Ag4Br6] clusters and organic Hmta ligands. UV-Vis diffuse reflectance analysis showed that the optical bandgap of the title compound was 2.68 eV, indicating a visible-light-responsive semiconductive behavior. More importantly, upon alternate light illumination, the so-designed compound exhibited remarkable photoelectric switching properties, with photocurrent densities (0.38 and 1.10 µA cm-2 for visible and full-spectrum light, respectively) that compete well with and even exceed those of some high-performance metal halide counterparts. Further theoretical calculations, including band structure, density of states, and wave functions, revealed that compound 1 has a unique valence band and conduction band distribution, rendering it with small effective masses (especially the electrons), which may be responsible for its good photoelectricity. Furthermore, in this work, Hirshfeld surface analysis, thermogravimetric analysis, and X-ray photoelectron spectroscopy (XPS) studies were performed.

Mixed-valence compounds based on heterometallic-oxo-clusters containing Sb(III,V): crystal structures and proton conduction.

Two isostructural Co(Cd)-antimony-oxo tartrate cluster-based compounds with a one-dimensional (1-D) belt-like structure, namely H9.2[Co(H2O)6]{M0.5(H2O)3.5{M'(H2O)4[SbVO6[Co4.2(H2O)5SbIII6(µ3-O)2(tta)6]]}}2·nH2O (M = Co, M' = Co, n = 9 (1); M = Cd0.39/Co0.61, M' = Cd0.24/Co0.76, n = 7 (2); H4tta = tartaric acid), have been synthesized by solvothermal methods. It is noteworthy that the relatively rare mixed-valence Sb(III,V) exists in the structures. The anionic clusters in both compounds appear to be in a sandwich configuration; the top and bottom layers are based on {Sb3(µ3-O)(tta)3} brackets, and the intermediate layer is occupied by {SbVO6[Co4.2(H2O)5]}. The title compounds have been characterized by single-crystal X-ray diffraction, powder X-ray diffraction, elemental analyses, thermogravimetric analyses, and UV-Vis spectroscopy. We chose compound 2 as a representative to test its proton conductivity, and the results show that the conductivity can reach 1.42 × 10-3 S cm-1 at 85 °C under 98% relative humidity.

Structural Evolution and Properties of Praseodymium Antimony Oxochlorides Based on a Chain-like Tertiary Building Unit.

Unveiling the structural evolution of single-crystalline compounds based on certain building units may help greatly in guiding the design of complex structures. Herein, a series of praseodymium antimony oxohalide crystals have been isolated under solvothermal conditions via adjusting the solvents used, that is, [HN(CH2CH3)3][FeII(2,2'-bpy)3][Pr4Sb12O18Cl15]·EtOH (1) (2,2'-bpy = 2,2'-bipyridine), [HN(CH2CH3)3][FeII(2,2'-bpy)3]2[Pr4Sb12O18Cl14)2Cl]·N(CH2CH3)3·2H2O (2), and (H3O)[Pr4Sb12O18Cl12.5(TEOA)0.5]·2.5EtOH (3) (TEOA = mono-deprotonated triethanolamine anion). Single-crystal X-ray diffraction analysis revealed that all the three structures feature an anionic zig-zag chain of [Pr4Sb12O18Cl15-x]n as the tertiary building unit (TBU), which is formed by interconnections of praseodymium antimony oxochloride clusters (denoted as {Pr4Sb12}) as secondary building units. Interestingly, different arrangements or linkages of chain-like TBUs result in one-dimensional, two-dimensional layered, and three-dimensional structures of 1, 2, and 3, respectively, thus demonstrating clearly the structural evolution of metal oxohalide crystals. The title compounds have been characterized by elemental analysis, powder X-ray diffraction, thermogravimetric analysis, and UV-Vis spectroscopy, and the photodegradation for methyl blue in an aqueous solution of compound 1 has been preliminarily studied. This work offers a way to deeply understand the assembly process of intricate lanthanide-antimony(III) oxohalide structures at the atomic level.

Single-Crystal Superstructures via Hierarchical Assemblies of Giant Rubik's Cubes as Tertiary Building Units.

Intricate superstructures possess unusual structural features and promising applications. The preparation of superstructures with single-crystalline nature are conducive to understanding the structure-property relationship, however, remains an intriguing challenge. Herein we put forward a new hierarchical assembly strategy towards rational and precise construction of intricate single-crystal superstructures. Firstly, two unprecedented superclusters in Rubik's cube's form with a size of ≈2×2×2 nm3 are constructed by aggregation of eight {Pr4 Sb12 } oxohalide clusters as secondary building units (SBUs). Then, the Rubik's cubes further act as isolable tertiary building units (TBUs) to assemble diversified single-crystal superstructures. Importantly, intermediate assembly states are captured, which helps illustrate the evolution of TBU-based superstructures and thus provides a profound understanding of the assembly process of superstructures at the atomic level.

Effect of CD40 siRNA on T helper lymphocyte-17 cells and interleukin-17, interleukin-23 in rats with experimental autoimmune myocarditis / 中华实用儿科临床杂志

Objective To investigate the effect of CD40siRNA on the pathologic changes and T helper lymphocyte (Th)-17 cells of myocardium and IL-17,IL-23 of serum in rats with experimental autoimmune myocarditis (EAM).Methods Forty 6-8 week old healthy male Lewis rats with body weight of 185-210 g were divided into EAM group,CD40siRNA group,siRNA group,and normal control group randomly,with 10 rats in each group.The rats in EAM group,CD40siRNA group and siRNA group were induced by immunization with cardiac C protein and completed Freund adjuvant in double foot pads.The rats in normal control group were injected with PBS buffer in double foot pads.On the 8th day after immunization,the rats in CD40siRNA group were injected with CD40 siRNA expression vector,and the rats in siRNA group were injected with siRNA expression vector.The rats were sacrificed on day 21 after inoculation.The histopathologic changes were observed by light microscope and the myocardial histopathology scores were calculated.The expression of RORC mRNA of myocardium was detected by real-time quantitative polymerase chain reaction (RTPCR).Enzyme linked immunoabsorption assay was used to determine the serum level of IL-17 and IL-23.Results Compared with EAM group,the myocardial histopathology score(2.34 ±0.60 vs 3.40 ±0.35,P ＜0.05),the expression ofRORC mRNA(2.13 ±0.28 vs 2.93 ±0.36,P ＜0.05) and the serum level of IL-17 (114.38 ± 8.29 vs 148.70 ± 5.04,P ＜ 0.05) and IL-23 (107.00 ± 7.69 vs 136.98 ± 23.16,P ＜ 0.05) were significantly lower in CD40 siRNA group.Conclusions It is suggested that CD40 siRNA expression vector might reduce myocardial injury by inhibiting Th-17 activation and down-regulating the expression of IL-17 and IL-23.

Construction and identification of RNA interference lentiviral vector targeting CD40 gene in rats / 中华实用儿科临床杂志

Objective To construct the RNA interference (RNAi) vector targeting the CD40 gene in rats.Methods Effective target sequences that target at CD40 gene were designed,then the oligonucleotide sequences after annealing of the complementary strands were synthetized,the DNA fragments were connected to the GV118 vectors by double digestion with HpaI and XhoI,and the lentiviral vectors which expressed short hairpin RNA were constructed.The lentiviral vectors were identified by PCR and DNA sequencing.Western blot was employed to sort the best interfering targets exogenously,and lentiviral packaging as well as assaying viral titer were also accomplished.Results CD40 siRNA was successfully inserted into the lentiviral vectors and the lentiviral vector was packaged into 293T cells.The determination of virus titer was 2.0 × 1012 TU/L.Conclusions The RNA interference lentiviral vector targeting the CD40 gene in rats was constructed successfully,which will provide the foundation for further exploring the pathogenesis of viral myocarditis and novel therapies in future.

Modulation of frequency receptive field plasticity in rat auditory cortical neurons by electrical stimulation of medial prefrontal cortex / 生理学报

Using conventional electrophysiological technique, we investigated the effects of stimulating the medial prefrontal cortex (mPFC) on plasticity of frequency receptive field (RF) in auditory cortical (AC) neurons in rats. When the mPFC was electrically stimulated, the RF plasticity of 51 (27.2%) neurons was not affected and that of 137 neurons (72.8%) was either inhibited (71 neurons, 37.7%) or facilitated (66 neurons, 35.1%). The modulation of RF plasticity by the stimulation of mPFC was dependent upon the time interval between acoustic and electrical stimuli. The best interval time that produced optimal modulation (inhibition or facilitation) ranged from 5 to 30 ms. The inhibitory modulation of mPFC prolonged RF shifting time and shortened RF recovery time. Conversely, the facilitatory modulation of mPFC shortened RF shifting time and prolonged RF recovery time. Our results suggest that the mPFC may affect the plasticity of functional activity in AC neurons, and also may participate in the process of auditory learning and memory.