Potential energy surfaces for HenNe+ ions: ab initio and diatomics-in-molecule results

The potential energy surface of He2Ne+ has been reinvestigated using a combination of ab initio and diatomics-in-molecule (DIM) calculations. In contrast to the reports of two recent studies the ion is found to have an asymmetric linear He-Ne-He structure, with no barrier to formation from the separated atoms on the ground-state surface. The He-Ne+ bond lengths at the potential minimum are 1.51 and 1.81 A, and the total bonding energy is 0.717 eV. Comparing the He2Ne+ energy to that of HeNe+, the bonding energy for the second helium atom is 0.06 eV, about 10% of that of the first He atom. The saddle point between the two equivalent minima is a symmetric structure, 0.0074 eV above the potential minimum. A symmetric geometry becomes the overall potential minimum if the 2s hole on the Ne is excluded from the reference states of a multireference configuration interaction calculation. A DIM potential was created for the HenNe+ family of ions. The DIM potential is consistent with the asymmetric He2Ne+ ion serving as a core; it predicts a slightly more asymmetric geometry than the ab initio results. Additional helium atoms form five-membered rings around the bonds of the core ion to fill the first shell and then add to the ends of the cluster. The asymmetric core ion and the highly compact structure help to account for the lack of apparent shell structure in the mass spectrometry of HenNe+ clusters. Finally, we recommend that the value De=0.63+/-0.04 eV be adopted for the ground state of HeNe+.     

Heteropolynuclear Sodium(I) Lead(II) Complex: Crystal and Molecular Structure of a Novel 3‐D Polymer, [(en)Pb(μ3‐ONO)2Na(μ3‐ONO)2Na(μ‐O2ClO2)Na]n

A novel 3D polymeric heteropolynuclear sodium(I) lead(II) complex containing different ligands, [NaPb(ClO₄)(en)(NO₂)₂] was synthesized and characterized by elemental analysis and IR, and ¹H‐, ¹³C‐, and ²⁰⁷Pb‐NMR spectroscopy. The single‐crystal X‐ray data of [NaPb(ClO₄)(en)(NO₂)₂]_n established that the complex is a three‐dimensional polymer, [(en)Pb(μ₃‐ONO)₂Na(μ₃‐ONO)₂Na(μ‐O₂ClO₂)Na]_n. The Pb and Na atoms have four‐ and eight‐coordinate geometry, respectively. The lone pair of electrons at the Pb^II atom is ‘stereochemically active’.     

Fragmentation of wastewater sludge floc by planar ice front

Floc size has substantial impact on sludge dewaterability, which might be increased or reduced after freezing and thawing. It is commonly assumed that floc size would be increased by low-speed freezing, with a planar ice front rejecting most flocs ahead of it to form large aggregates. We demonstrate in this work that an advancing planar ice front can not only engulf an activated sludge floc of size 3030 mum, but also fragment it. During floc freezing, when the ice engulfed a thin layer of floc, the latter would be pulled apart vertically by the action of the former. This particular portion of floc was then axially elongated and fixed in the frozen layer, with accumulated force pushing upward. In the present test the floc's vertical length was increased by over 92% and its width decreased by 37% over freezing. The force measurement and floc morphology tracking revealed that the force gradient that pulled apart the floc was 0.0027 N/m. The floc under investigation was fragmented at the point where the normal stress acting on the interior network exceeded 8 Pa.     

Reconstruction of the water-oxidizing complex in manganese-depleted Photosystem II using synthetic manganese complexes

The efficiency of a trinuclear and two binuclear manganese complexes in reconstituting electron transport and O(2) evolution activity in Mn-depleted Photosystem II preparations is analyzed. The trinuclear Mn-complex is more efficient than two binuclear Mn-complexes in restoring oxygen evolution, but it is less effective as an electron donor than binuclear Mn-complexes. It is inferred from our results that recovery of electron transport and O(2) evolution with polynuclear Mn-complexes is affected with different factors. Moreover, the trinuclear Mn-complex is extremely sensitive to the addition of CaCl(2). It is suggested that there is an interaction between Ca(2+) and carboxyl within the trinuclear Mn-complex during photoactivation and this interaction benefits the ligation of Mn atom to the apo-WOC and form an active WOC. Binuclear Mn(III)Mn(III) complex shows slightly higher efficiency than binuclear Mn(III)Mn(IV) complex in restoration of O(2) evolution activity. The efficiency of three Mn-complexes in the reconstitution of WOC is in an order: trinuclear Mn(3)(III)>binuclear Mn(III)Mn(III)>binuclear Mn(III)Mn(IV).     

Molecular films of water-miscible ionic liquids formed on glassy carbon electrodes: characterization and electrochemical applications

This letter describes the formation and possible electrochemical applications of molecular films of water-miscible imidazolium-based ionic liquids (ILs) on glassy carbon (GC) electrodes. X-ray photoelectron spectroscopy (XPS) and electrochemical results indicate that the water-miscible ILs used in this study can interact with the GC electrode and form molecular films on the electrode surface. The formed molecular films are found to possess striking electrochemical properties such as electrocatalysis toward ascorbic acid (AA) and the capability to facilitate direct electron transfer of horseradish peroxidase (HRP). This demonstration would pave the way for new electrochemical applications of water-miscible ILs and is envisaged to be useful for the investigation of the electrochemical properties of water-miscible ILs in aqueous media provided the same counteranion is used as the supporting electrolyte.     

Concise and Efficient Synthesis of Dehydropeptide Analogues from Unsaturated 5（4H）—Oxazolone

Some dehydropeptide analogues were directly synthesized by the reaction of unsaturated oxazolones with free amino acids.     

Di­chloro­bis(1‐propyl­imidazolidine‐2‐thione‐κS)­cobalt(II)

The crystal structure of the title compound, [CoCl₂(C₆H₁₂N₂S)₂], consists of monomer units of a Co^II atom coordinated to two 1‐propyl­imidazolidine‐2‐thione ligands and to two chloride ions. The heterocyclic thione ligand is monodentate and coordinated to the metal through the thione S atom. The environment around the Co^II atom is a slightly distorted tetrahedron. The Co—S bond lengths are 2.341 (2) and 2.330 (2) Å, and the Co—Cl bond lengths are 2.234 (2) and 2.238 (2) Å. The most important point of distortion is the S—Co—S bond angle of only 97.83 (8)°. Intramolecular classical hydrogen bonds are found between the chloride ions and the N—H groups. Additionally, intra‐ and intermolecular non‐classical hydrogen bonds are found.     

化“材”为“筑”

Chemistry is a central, practical and creative discipline. The development of chemistry plays an important role in the progress of science and society, as well as the improvement of the quality of human life. This paper introduces the chemical knowledge of stone, concrete, glass and other inorganic nonmetallic building materials by the anthropomorphically story. Taking nanomaterials as an example, the prospect of building materials development in the future is put forward.     

甲烷氧化偶联Na2WO4-Mn/SiO2催化剂热效应的研究

采用固定床微型反应装置,研究了甲烷氧化偶联反应过程中Na2WO4-Mn/S iO2催化剂床层的热效应和催化性能的关系,考察了反应炉温、CH4/O2比和反应气体空速对催化剂床层热点分布的影响.研究结果表明,甲烷氧化偶联催化剂床层的热效应强烈依赖于反应条件.反应炉温越高,CH4/O2比越低,反应气体空速越大,催化剂床层的热点温度越高.结合催化性能和热效应关系的研究,为优化甲烷氧化偶联的反应操作提供了实验依据.     

An Efficient and High‐Yield One‐Pot Synthesis of Bis(oxazoline)s

An efficient and mild one‐pot synthesis of bis(oxazoline) (BOX) ligands is developed from reactions of dicarboxy dichlorides with β‐amino alcohols in the presence of 11.0 equiv. NEt₃ followed by the addition of 3.6 equiv. methanesulfonyl chloride (MsCl). Nine different BOX ligands were prepared in excellent yields of ≥ 80%. Advantages of this improved synthesis are mild reaction conditions, short total reaction time of 9 h, and high isolated yields.