Theoretical Study of the Metal-Controlled Dehydrogenation Mechanism of MN₂H₃BH₃ (M = Li, Na, K): A New Family of Hydrogen Storage Material

Metal hydrazineboranes (MHBs), as a kind of new hydrogen storage materials, show excellent hydrogen storage performance and dehydrogenation properties. Herein, we designed multiple dehydrogenation pathways to compare the metal-controlled effect. Quantum chemistry theory is used to calculate the crystal structure for determining the molecular structure. With an increase of the metal radius, the energy difference of the isomers also increases. The dehydrogenation pathways of lithium hydrazineborane (path A) and sodium hydrazineborane (path B) appear totally similar to each other in the dehydrogenation process despite the energy barrier, as well as the comparison paths A′ (for LiHB) and B′ (for NaHB). In contrast with LiHB and NaHB, the tautomeric reaction occurs in the potassium hydrazineborane (KHB) first, and the following dehydrogenation path is similar to that of the LiHB and NaHB. It explores the hydrogen-release properties of the different metal hydrazineboranes and also indcates the affection of the metal in the metal hydrazineboranes hydrogen-storage system

Combination Multinitrogen with Good Oxygen Balance: Molecule and Synthesis Design of Polynitro-Substituted Tetrazolotriazine-Based Energetic Compounds

We investigated 5,8-dinitro-5,6,7,8-tetrahydrotetrazolo­[1,5-<i>b</i>]­[1,2,4]­triazine (short for DNTzTr (<b>1</b>)) using various ab initio quantum chemistry methods. We proposed an additional three novel polynitro-substituted tetrazolotriazine-based compounds with exceptional performance, including 5,8-dinitro-5,6-dioxotetrazolo­[1,5-<i>b</i>]­[1,2,4]­triazine, DNOTzTr (<b>2</b>), 4,5,9,10-tetranitro­[1,2,4,5]­tetrazolo­[3,4-<i>b</i>]­[1,2,4,5]­tetrazolo­[3′,4′:5,6]­triazino­[2,3-<i>e</i>]­triazine, TNTzTr (<b>3</b>), and 4,5,6,10,11,12-hexanitro-bis­[1,2,4,5]­tetrazolo­[3′,4′:5,6]­triazino­[2,3-<i>b</i>:2′,3′-<i>e</i>]­triazine, HNBTzTr (<b>4</b>). The optimized structure, electronic density, natural bond orbital (NBO) charges and HOMO–LUMO orbitals, electrostatic potential on surface of molecule, IR- and NMR-predicted spectra, as well as thermochemical parameters were calculated with the B3LYP/6-311+G­(2d) level of theory. Critical parameters such as density, enthalpy of formation (EOF), and detonation performance have also been predicted. Characters with positive EOF (1386.00 and 1625.31 kJ/mol), high density (over 2.00 g/cm³), outstanding detonation properties (<i>D</i> = 9.82 km/s, <i>P</i> = 45.45 GPa; <i>D</i> = 9.94 km/s, <i>P</i> = 47.30 GPa), the perfect oxygen balance set to zero, and acceptable impact sensitivity led novel compounds <b>3</b> and <b>4</b> to be very promising energetic materials. This work provides the theoretical molecule design and a reasonable synthesis path for further experimental synthesis and testing

Two coordination polymers with 3-hydrazino-4-amino-1,2,4-triazole as ligand: synthesis, crystal structures, and non-isothermal kinetic analysis

<div><p>Two coordination polymers, [Mn₂(HATr)₄(NO₃)₄·2H₂O]_n (<b>1</b>) and [Cd₂(HATr)₄(NO₃)₄·H₂O]_n (<b>2</b>), were obtained from the corresponding metal nitrate with 3-hydrazino-4-amino-1,2,4-triazole (HATr) and characterized through elemental analysis and IR spectroscopy. The structures were determined by single-crystal X-ray diffraction. The results show that both complexes crystallize in the triclinic <i>P-1</i> space group and have six-coordinate distorted octahedral structures, which are made up of infinite 1-D chains running along the <i>a</i> axis of metals linked by bridging-chelating HATr ligands. The coordination sites are in agreement with the computational results. Additionally, the decomposition temperatures were determined by differential scanning calorimetry and the kinetic parameters were calculated using Kissinger’s and Ozawa–Doyle’s methods; the energies of combustion for <b>1</b> and <b>2</b> were −7186.25 and −6922.53 kJ M⁻¹ and the enthalpies of formation were obtained as −1002.35 and −457.27 kJ M⁻¹, respectively.</p></div

Cadmium(II) Coordination Polymers of 4‑Pyr-poly-2-ene and Carboxylates: Construction, Structure, and Photochemical Double [2 + 2] Cycloaddition and Luminescent Sensing of Nitroaromatics and Mercury(II) Ions

Solvothermal reactions of Cd­(NO₃)₂·4H₂O with 4-pyr-poly-2-ene (ppene) in the presence of benzene-1,2-dicarboxylic acid (1,2-H₂BDC), benzene-1,3-dicarboxylic acid (1,3-H₂BDC), benzene-1,4-dicarboxylic acid (1,4-H₂BDC), benzene-1,3,5-tricarboxylic acid (1,3,5-H₃BTC), or 4,4′-oxidibenzoic acid (4,4′-H₂OBA) afforded five Cd­(II) coordination polymers [Cd­(ppene)­(1,2-BDC)]_<i>n</i> (<b>1</b>), [Cd­(ppene)­(1,3-BDC)]_<i>n</i> (<b>2</b>), [{Cd­(ppene)­(1,4-BDC)}<b>­·</b>MeCN]_<i>n</i> (<b>3</b>) (Liu et al. Inorg. Chem. Commun. 2015, 58, 1−4), [{Cd­(ppene)­(1,3,5-HBTC)}­·0.5­(ppene)]_<i>n</i> (<b>4</b>), and [Cd­(ppene)­(4,4′-OBA)]_<i>n</i> (<b>5</b>), respectively. Upon UV light irradiation, <b>1</b>, <b>3</b>, and <b>4</b> can undergo a double [2 + 2] cycloaddition reaction to yield their corresponding photoproducts including [Cd₂(4-tp-3-lad)­(1,2-BDC)₂]_<i>n</i> (<b>1a</b>, 4-tp-3-lad = 2,3,5,6-tetra­(pyridin-4-yl)­bicyclo[2.2.0]­hexane), [{Cd₂(4-tp-3-lad)­(1,4-BDC)₂}­·2MeCN]_<i>n</i> (<b>3a</b>), and [{Cd₂(4-tp-3-lad)­(1,3,5-HBTC)₂}­·(ppene)]_<i>n</i> (<b>4a</b>) in a single-crystal-to-single-crystal manner. Compounds <b>1</b>, <b>2</b>, <b>4</b>, <b>5</b>, <b>1a</b>, <b>3a</b>, and <b>4a</b> have been structurally characterized by elemental analysis, infrared spectroscopy, powder X-ray diffraction, and single-crystal X-ray diffraction. Compounds <b>1</b>, <b>1a</b>, <b>4</b> and <b>4a</b> consist of two-dimensional (2D) (4,4) networks, in which one-dimensional (1D) [Cd₂(1,2-BDC)₂]_<i>n</i> or [Cd₂(1,3,5-HBTC)₂]_<i>n</i> chains are linked by ppene or 4-tp-3-lad bridges. <b>2</b> has a three-dimensional (3D) 3-fold interpenetrated framework formed from bridging 1D [Cd₂(1,3-BDC)₂]_<i>n</i> double chains by ppene ligands. Compounds <b>3a</b> and <b>5</b> contain 3D frameworks assembled by linking 2D [Cd₂(1,4-BDC)₂]_<i>n</i> or [Cd₂(4,4′-OBA)₂]_<i>n</i> networks by 4-tp-3-lad or ppene bridges. In the three photoreactions, each ppene ligand had its two conjugated CC bonds parallel to those of the neighboring ppene. The resulting ppene pair was transformed into the only product, 4-tp-3-lad, through a unique double [2 + 2] cycloaddition. Photoluminescence properties of these compounds in water were also investigated. Compound <b>3a</b> as a representative example was proven to be an efficient probe for dual detections of nitroaromatics and Hg²⁺ in aqueous solutions

LIF and LIFRα mRNA expression levels in wild-type mouse decidua throughout gestation.

<p>Wild type (WT) mouse implantation sites were collected from n = 3 mice/time point. E6, 8 and 10 embryos were analyzed as whole implantation sites (IS) and E13, 15 and 17 were dissected to obtain the decidua only. <b>(a)</b> LIF, <b>(b)</b> LIFRα and <b>(c)</b> gp130 mRNA expression was determined by semi-quantitative PCR normalized to β2-microglobulin. Data are mean ± SEM, ANOVA, Tukey’s post-hoc test, *p<0.05, n = 3/time point.</p

LIF inhibition during placental development impairs spiral artery remodelling in mice.

<p><b>(a, b)</b> Representative photomicrographs of E13 implantation sites treated with PEG control or PEGLA from E10-13, immunostained for α-smooth muscle actin (SMA). Bars represent 1mm (<b>(a)</b> top panel), 50μm (<b>(a)</b> lower panel) and 20μm <b>(b)</b>. Inset is the negative control. Decidual <b>(a)</b> and myometrial <b>(b)</b> vessels from PEGLA treated pregnant mice have altered, narrow vessel morphology and thicker smooth muscle lining compared to PEG control. <b>(c)</b> Staining intensity was analysed in 3 mid-sagital implantation site sections per mouse (n = 4/group) and averaged using CellSens software, quantified as staining intensity (pixels) per decidual area (%). <b>(d)</b> Cross-sectional decidual vessel area (μm) was measured using CellSens software. Data are mean ± SEM, students t-test, *p<0.05, **p<0.01. <b>(e)</b> Cytokeratin positive (red) trophoblast and α-SMA positive (green) smooth muscle cells (arrows) were co-localized using immunofluorescence. Inset is the negative control.</p

LIF and LIFRα co-localization with cytokeratin to detect invasive EVTs in wild-type mouse decidua.

<p>Wild type (WT) mouse implantation sites were collected from n = 3 mice/time point and 2μm serial sections were immunostained for cytokeratin, LIF and LIFRα. Representative photomicrographs of mid-gestation (E10 and E13) implantation site sections are shown here. Both LIF and LIFRα co-localized with cytokeratin in maternal decidual vessels. Bars represent 20μm. Insets are negative controls.</p

LIF inhibition during placental development alters decidual immune cell activation transcription factors.

<p><b>Representative photomicrographs of</b> F4/80 macrophage immunostaining performed on E10 or E13 implantation sites treated with PEG control or PEGLA from E8-10 or E10-13 respectively <b>(a)</b>. Bars represent 200μm. Inset is the negative control. Arrows denote F4/80-positive immunostained marcrophages. <b>(b)</b> Staining intensity was analysed in 3 mid-sagital implantation site sections per mouse (n = 4/group) and staining area per decidual are calculated and averaged using CellSens software. Data are mean ± SEM. <b>(c)</b> MCP-1, <b>(d)</b> IL-10 and <b>(e)</b> IFN-γ mRNA expression was determined by semi-quantitative PCR normalized to β2-microglobulin in PEG or PEGLA treated mouse decidual tissue. Data are mean ± SEM, students t-test, *p<0.05.</p

Populus euphratica SSR data

Populus euphratica SSR dat

Populus pruinosa SSR data

Populus pruinosa SSR dat