The first observed complex of 9-crown-3 ether: X-ray crystallographic and solid state C NMR study of naphtho-9-crown-3 ether and its 2:1 LiClO4 complex

The X-ray crystal structure of naphtho-9-crown-3 ether, 1 is reported. The molecule crystallizes in the monoclinic P2(1)/c space group with a=8.866(2) Å, b=6.451(1) Å, c=20.110(4) Å and β=91.055(4)°, with Z=4. The 2:1 naphtho-9-crown-3 LiClO₄ complex, 2 crystallizes in the triclinic P-1 space group with a=10.5075(10) Å, b=11.7283(11) Å, c=15.9921(15) Å and β=84.289(2)°, with Z=2. There are two distinct complexes found in the crystal, one ordered and one disordered in the crown portion of the molecule. ¹³C CPMAS NMR spectra for 1 and 2 are presented.     

Participation of the alpha,alpha'-diiminopyridine ligand system in reduction of the metal center during alkylation

The reaction of [[2,6-(i-Pr)(2)PhN=C(Me)](2)(C(5)H(3)N)]MnCl(2) with alkylating agents formed a dinuclear Mn(I) derivative via ligand reductive coupling. In the case of the trivalent Cr analogue, a similar reaction afforded reduction toward Cr(II) but also alkylation at the pyridine ring para position followed by an unprecedented cycloaddition that generated a tricyclic system.     

Application and Structural Analysis of Triazole‐Bridged Disulfide Mimetics in Cyclic Peptides

Ruthenium‐catalysed azide–alkyne cycloaddition (RuAAC) provides access to 1,5‐disubstituted 1,2,3‐triazole motifs in peptide engineering applications. However, investigation of this motif as a disulfide mimetic in cyclic peptides has been limited, and the structural consequences remain to be studied. We report synthetic strategies to install various triazole linkages into cyclic peptides through backbone cyclisation and RuAAC cross‐linking reactions. These linkages were evaluated in four serine protease inhibitors based on sunflower trypsin inhibitor‐1. NMR and X‐ray crystallography revealed exceptional consensus of bridging distance and backbone conformations (RMSD<0.5 Å) of the triazole linkages compared to the parent disulfide molecules. The triazole‐bridged peptides also displayed superior half‐lives in liver S9 stability assays compared to disulfide‐bridged peptides. This work establishes a foundation for the application of 1,5‐disubstituted 1,2,3‐triazoles as disulfide mimetics.     

Tetra‐μ‐chloro‐1:2κ4Cl;1:3κ4Cl‐di­methyl‐2κC,3κC‐tetra­kis(tetra­hydro­furan)‐1κ2O,2κO,3κO‐chromium(II)dizinc(II)

The title compound, [CrZn₂(CH₃)₂Cl₄(C₄H₈O)₄], contains a central distorted octa­hedral Cr atom, located at an inversion center, bound to two tetra­hydro­furan ligands and four chloro ligands that bridge to two symmetry‐related tetra­hedral Zn atoms. The coordination around zinc is completed by methyl and tetra­hydro­furan ligands. This structure is compared with a previously reported complex of vanadium, and their differences in metric parameters are explained.     

KMgF3:Ni2+晶体的占位、局部结构、吸收光谱和顺磁g因子的统一解释

利用完全对角化方法和强场耦合方案,采用半自洽场(semi-SCF)自由Ni2+的d轨道模型和Ni2+-6X-(x=F,Cl,Br,I)络合物的μ-κ-α模型研究,建立了含有过渡族金属离子的晶体的局域结构与吸收光谱和顺磁g因子之间的定量关系,对KMgF3:Ni2+晶体的占位、局域结构、吸收光谱和顺磁g因子作出了统一解释,预测了KMgF3:Ni2+晶体的光谱精细结构.所得理论计算结果与实验值符合得很好.     

Purification of His-tagged hepatitis B core antigen from unclarified bacterial homogenate using immobilized metal affinity-expanded bed adsorption chromatography

Hepatitis B core antigen (HBcAg) is used as a diagnostic reagent for the detection of hepatitis B virus infection. In this study, immobilized metal affinity-expanded bed adsorption chromatography (IMA-EBAC) was employed to purify N-terminally His-tagged HBcAg from unclarified bacterial homogenate. Streamline Chelating was used as the adsorbent and the batch adsorption experiment showed that the optimal binding pH of His-tagged HBcAg was 8.0 with a binding capacity of 1.8 mg per ml of adsorbent. The optimal elution condition for the elution of His-tagged HBcAg from the adsorbent was at pH 7 in the presence of 500 mM imidazole and 1.5 M NaCl. The IMA-EBAC has successfully recovered 56% of His-tagged HBcAg from the unclarified E. coli homogenate with a purification factor of 3.64. Enzyme-linked immunosorbent assay (ELISA) showed that the antigenicity of the recovered His-tagged HBcAg was not affected throughout the IMA-EBAC purification process and electron microscopy revealed that the protein assembled into virus-like particles (VLP).     

Carbodicarbene: geminal-Bimetallic Coordination in Selective Manner

The reaction of Pd(OAc)₂ with free carbodicarbene (CDC) generates a Pd acetate trinuclear complex 1 via intramolecular C(sp³)−H bond activation at one of the CDC methyl side arms. The solid structure of 1 reveals the capability of CDC to facilitate a double dative bond with two palladium centers in geminal fashion. This is attributed to the chelating mode of CDC, which can frustrate π-conjugation within the CDC framework. Such effect maybe also amplified by ligand-ligand interaction. The formation of other gem-bimetallic Pd−Pd, Pd−Au, and Ni−Au provides further structural evidence for this proof-of-concept in selective installation. Structural analysis is supported by computational calculations based on state-of-the-art energy decomposition analysis (EDA) in conjunction with natural orbitals for chemical valence (NOCV) method.     

The influence of electrolyte concentration on nanofractures fabricated in a 3D-printed microfluidic device by controlled dielectric breakdown

A three-dimensional-printed microfluidic device made of a thermoplastic material was used to study the creation of molecular filters by controlled dielectric breakdown. The device was made from acrylonitrile butadiene styrene by a fused deposition modeling three-dimensional printer and consisted of two V-shaped sample compartments separated by 750 µm of extruded plastic gap. Nanofractures were formed in the thin piece of acrylonitrile butadiene styrene by controlled dielectric breakdown by application voltage of 15–20 kV with the voltage terminated when reaching a defined current threshold. Variation of the size of the nanofractures was achieved by both variation of the current threshold and by variation of the ionic strength of the electrolyte used for breakdown. Electrophoretic transport of two proteins, R-phycoerythrin (RPE; <10 nm in size) and fluorescamine-labeled BSA (f-BSA; 2–4 nm), was used to monitor the size and transport properties of the nanofractures. Using 1 mM phosphate buffer, both RPE and f-BSA passed through the nanofractures when the current threshold was set to 25 µA. However, when the threshold was lowered to 10 µA or lower, RPE was restricted from moving through the nanofractures. When we increased the electrolyte concentration during breakdown from 1 to 10 mM phosphate buffer, BSA passed but RPE was blocked when the threshold was equal to, or lower than, 25 µA. This demonstrates that nanofracture size (pore area) is directly related to the breakdown current threshold but inversely related to the concentration of the electrolyte used for the breakdown process.