Structural phase transformations induced by guest molecules in a nickel-based 2D Square lattice coordination network

Herein, we report the crystal structure and guest binding properties of a new two-dimensional (2D) square lattice (sql) topology coordination network, sql-(azpy)(pdia)-Ni, which is comprised of two linker ligands with diazene (azo) moieties, (E)-1,2-di(pyridin-4-yl)diazene(azpy) and (E)-5-(phenyldiazenyl)isophthallate(pdia). sql-(azpy)(pdia)-Ni underwent guest-induced switching between a closed (nonporous) β phase and several open (porous) α phases, but unlike the clay-like layer expansion to distinct phases previously reported in switching sql networks, a continuum of phases was formed. In effect, sql-(azpy)(pdia)-Ni exhibited elastic-like properties induced by adaptive guest binding. Single-crystal X-ray diffraction (SCXRD) studies of the α phases revealed that the structural transformations were enabled by the pendant phenyldiazenyl moiety on the pdia2– ligand. This moiety functioned as a type of hinge to enable parallel slippage of layers and interlayer expansion for the following guests: N,N-dimethylformamide, water, dichloromethane, para-xylene, and ethylbenzene. The slippage angle (interplanar distances) ranged from 54.133° (4.442 Å) in the β phase to 69.497° (5.492 Å) in the ethylbenzene-included phase. Insight into the accompanying phase transformations was also gained from variable temperature powder XRD studies. Dynamic water vapor sorption studies revealed a stepped isotherm with little hysteresis that was reversible for at least 100 cycles. The isotherm step occurred at ca. 50% relative humidity (RH), the optimal RH value for humidity control.</p

Efficient propyne/propadiene separation by microporous crystalline physiadsorbents

Selective separation of propyne/propadiene mixture to obtain pure propadiene (allene), an essential feedstock for organic synthesis, remains an unsolved challenge in the petrochemical industry, thanks mainly to their similar physicochemical properties. We herein introduce a convenient and energy-efficient physisorptive approach to achieve propyne/propadiene separation using microporous metal-organic frameworks (MOFs). Specifically, HKUST-1, one of the most widely studied high surface area MOFs that is available commercially, is found to exhibit benchmark performance (propadiene production up to 69.6 cm3/g, purity > 99.5%) as verified by dynamic breakthrough experiments. Experimental and modeling studies provide insight into the performance of HKUST-1 and indicate that it can be attributed to a synergy between thermodynamics and kinetics that arises from abundant open metal sites and cage-based molecular traps in HKUST-1

Reversible phase transformations in a double-walled diamondoid coordination network with a stepped isotherm for methane

Flexible metal−organic materials (FMOMs) with stepped isotherms can offer enhanced working capacity in storage applications such as adsorbed natural gas (ANG) storage. Unfortunately, whereas >1000 FMOMs are known, only a handful exhibit methane uptake of >150 cm3 /cm3 at 65 atm and 298 K, conditions relevant to ANG. Here, we report a double-walled 2-fold interpenetrated diamondoid (dia) network, X-dia-6-Ni, [Ni2L4(μ-H2O)]n, comprising a new azo linker ligand, L− (L− = (E)-3-(pyridin-4-yldiazenyl)- benzoate) and 8-connected dinuclear molecular building blocks. X-dia-6-Ni exhibited gas (CO2, N2, CH4) and liquid (C8 hydrocarbons)-induced reversible transformations between its activated narrow-pore β phase and γ, a large-pore phase with ca. 33% increase in unit cell volume. Single-crystal X-ray diffraction (SCXRD) studies of the as-synthesized phase α, β, and γ revealed that structural transformations were enabled by twisting of the azo moiety and/or deformation of the MBB. Further insight into these transformations was gained from variable temperature powder XRD and in situ variable pressure powder XRD. Low-temperature N2 and CO2 sorption revealed stepped Type F−II isotherms with saturation uptakes of 422 and 401 cm3 /g, respectively. X-dia-6-Ni exhibited uptake of 200 cm3 /cm3 (65 atm, 298 K) and a high CH4 working capacity of 166 cm3 /cm3 (5−65 bar, 298 K, 33 cycles), the third highest value yet reported for an FMOM and the highest value for an FMOM with a Type F−II isotherm</p

Additional file 2 of Epigenetic mechanism of Gtl2-miRNAs causes the primitive sheep characteristics found in purebred Merino sheep

Additional file 2: Table S1. The pedigree relationship between ALC and MF sheep in this study. Table S2. miRNAs in the Dlk-Gtl2 locus and their predicted target genes in the candidate pathway. Table S3. The predicted target genes of sITS-miRNA in the candidate pathway. Table S4. The separate enrichment analysis of the downregulated proteins in metabolic pathways of the ALC group. Table S5. Primers used in this study. Table S6. Guide RNA sequence information in Meg3 (IG-DMR)-KO mice

Additional file 1 of Epigenetic mechanism of Gtl2-miRNAs causes the primitive sheep characteristics found in purebred Merino sheep

Additional file 1: Figure S1. Wool characteristics of ancestral-like coarse (ALC) and modern fine (MF) wool sheep at P120 and P180. (a) The phenotypic properties of ALC wool sheep at P120 and P180. (b) The phenotypic properties of MF wool sheep at P120 and P180. (c) Proportion of medullated and unmedullated wool fibers at different developmental stages in ALC sheep. (d) Proportion of medullated and unmedullated wool fibers at different developmental stages in MF sheep. Figure S2. Wool characteristics of ancestral-like coarse (ALC) and modern fine (MF) wool sheep at P120 and P180. (a) Phylogenetic tree showing the evolutionary relationships of Gtl2-sITSs in various species. (b) Percentage of heterozygotes and homozygotes between ALC wool and MF wool varieties. (c) A small fraction of sITS in different species. Figure S3. Pathway enrichment analysis performed using the significantly downregulated metabolites in ancestral-like coarse (ALC) lambskin tissue. Figure S4. IRF2BP2 genotypes of ALC and MF wool lambs in reciprocal cross families. The primers were listed in Table S5. Figure S5. Embryonic weight of Meg3-IG-DMR-KO mice and their siblings (negative control), **P < 0.001. Figure S6. miRNAs in the Gtl2-miRNAs Locus inhibited multiple components of the PI3K-AKT Pathway. (a) The frequency of signaling pathways enriched by predicted target genes of up-regulated miRNAs in ALC group. (b) Schematic of the PI3K-mTOR pathway. (c) The up-regulated differentially expressed (DE) miRNAs at Gtl2-miRNAs locus and their predicted target genes in the PI3K-AKT pathway. Figure S7. Similar molecular mechanisms affect ALC wool traits and quality of lamb fur. a Curve graph of wool diameter distribution of Tan sheep. b Proportion of medullated and non-medullated wool of Tan sheep. c Integrated analysis of upregulated miRNAs and the functional annotation of their target genes between early developmental Tan and ALC lambs [38]. d Birth weight of ALC and MF wool lambs. e The skin ROS level of Coarse and Fine wool lambs were measured by H2-DCFDA, Coarse wool lambs: Ujimqin lambs (n = 30), Tan lambs (n = 10) and ALC wool lambs (n = 5). Fine wool lambs: Merino lambs (n = 60) and MF wool lambs (n = 5). f 8-OHdG immunostaining was perform in section of the Merino lamb skin. g The skin ROS level of adult Coarse/Fine wool sheep were measured by H2-DCFDA, Coarse wool sheep: Ujimqin sheep (n = 30), Tan sheep (n = 10) and ALC wool sheep (n = 5). Fine wool sheep: Merino sheep (n = 60) and MF wool sheep (n = 5). Figure S8. Interaction analysis of down-regulated DEPs in ALC group using online tool ( https://www.string-db.org/ ). Figure S9. Selective signal analysis of transcriptome data using different reference genomes. a The samples are obtained from half-siblings, genome version: GCA_000298735.2, Oar_V4.0. The blue dashed line: Fst = 0.6. b The samples are obtained from the reciprocal cross progeny, and the genome version is GCA_016772045.2. The blue dashed line: Fst = 0.8