A New Oxygen Containing Pyclen-Type Ligand as a Manganese(II) Binder for MRI and 52Mn PET Applications: Equilibrium,Kinetic, Relaxometric,Structural and Radiochemical Studies

A new pyclen-3,9-diacetate derivative ligand (H₂3,9-OPC2A) was synthesized possessing an etheric O-atom opposite to the pyridine ring, to improve the dissociation kinetics of its Mn(II) complex (pyclen = 3,6,9,15-tetraazabicyclo(9.3.1)pentadeca-1(15),11,13-triene). The new ligand is less basic than the N-containing analogue (H₂3,9-PC2A) due to the non-protonable O-atom. In spite of its lower basicity, the conditional stability of the [Mn(3,9-OPC2A)] (pMn = −log(Mn(II)), c_L = c_Mn(II) = 0.01 mM. pH = 7.4) remains unaffected (pMn = 8.69), compared to the [Mn(3,9-PC2A)] (pMn = 8.64). The [Mn(3,9-OPC2A)] possesses one water molecule, having a lower exchange rate with bulk solvents (k_ex²⁹⁸ = 5.3 ± 0.4 × 10⁷ s⁻¹) than [Mn(3,9-PC2A)] (k_ex²⁹⁸ = 1.26 × 10⁸ s⁻¹). These mild differences are rationalized by density-functional theory (DFT) calculations. The acid assisted dissociation of [Mn(3,9-OPC2A)] is considerably slower (k₁ = 2.81 ± 0.07 M⁻¹ s⁻¹) than that of the complexes of diacetates or bisamides of various 12-membered macrocycles and the parent H₂3,9-PC2A. The [Mn(3,9-OPC2A)] is inert in rat/human serum as confirmed by ⁵²Mn labeling (nM range), as well as by relaxometry (mM range). However, a 600-fold excess of EDTA (pH = 7.4) or a mixture of essential metal ions, propagated some transchelation/transmetalation in 7 days. The H₂3,9-OPC2A is labeled efficiently with ⁵²Mn at elevated temperatures, yet at 37 °C the parent H₂3,9-PC2A performs slightly better. Ultimately, the H₂3,9-OPC2A shows advantageous features for further ligand designs for bifunctional chelators.     

不锈钢1Cr18Ni9Ti中铬含量测量不确定度的评定

采用国际通用的方法研究了过硫酸铵氧化容量法测定铬含量的不确定度,分析了容量法中摩尔质量、样品质量、溶液的体积、温度等因素对测量不确定度的影响,评估了各参数的标准不确定度、合成标准不确定度和扩展不确定度。找出了影响容量法测定铬含量准确度的主要原因。     

聚晶立方氮化硼刀具切削高锰钢的磨损机制

在半精加工试验条件(切削深度ap=0．5mm，进给量f=0．3mm／r，干切)下研究了聚晶立方氮化硼刀具切削奥氏体高锰钢时的磨损机制，用WDH-Ⅱ型光电温度计测量了切削温度，用工具显微镜测量后刀面磨损量，进而考察了切削时间和切削速度对后刀面磨损量的影响，采用S-250MK型扫描电子显微镜观察刀具前、后刀面的磨损形貌和组成变化．结果表明：当切削温度为400～750℃时，聚晶立方氮化硼刀具同高锰钢中的γ相及其析出相(Fe，Mn)3C之间产生严重的机械磨损；当切削温度超过800℃时，聚晶立方氮化硼刀具同高锰钢单一γ相之间产生扩散磨损；聚晶立方氮化硼刀具适合于高速切削.     

ChemInform Abstract: Molecular Structure of Chromium Tetrafluoride in the Gas Phase

is determined by electron diffraction at 195-220 °C. The diffraction patterns are completely consistent with a molecule of tetrahedral (Td) symmetry.     

Fatigue Crack Nucleation at Σ3(1 1 2) Boundary in a Ferritic Stainless Steel

The effect of a geometrical relationship between a grain boundary (GB) plane and a tensile axis on intergranular fatigue cracking along 3(1 1 2) twin boundaries has been investigated in Fe-30%Cr alloy crystals. Fatigue experiments were carried out on the three kinds of the specimens containing the 3(1 1 2) twin boundary. It was found that the fatigue cracking behavior was sensitive to the geometry of the GB plane. In a specimen where both the GB plane and a slip vector lying in the GB plane in adjacent grains are inclined to the tensile axis at 45°, the fatigue cracks were nucleated preferentially along the twin boundary at a stress amplitude of 170 MPa. The specimen with the GB plane normal to the tensile axis showed that the fatigue crack was initiated from a slip band formed within a constituent grain at a stress amplitude of 300 MPa. When the GB plane was inclined to the tensile axis but the slip vector lying in the GB plane was normal to the tensile axis, development of additional slips formed perpendicular to the GB plane were observed at a specific site of the GB. Initiation of intergranular fatigue cracks at the site was recognized at a stress amplitude of 250 MPa. It can be suggested that the GB plane normal to the tensile axis provides the highest fatigue performance among them. The difference in the cracking property among these specimens could be understood in terms of the effective Schmid factor derived from elastically incompatible stress.     

A Novel [OSSO]-Type Chromium(III) Complex as a Versatile Catalyst for Copolymerization of Carbon Dioxide with Epoxides

A new chromium(III) complex, bearing a bis-thioether-diphenolate [OSSO]-type ligand, was found to be an efficient catalyst in the copolymerization of CO₂ and epoxides to achieve poly(propylene carbonate), poly(cyclohexene carbonate), poly(hexene carbonate) and poly(styrene carbonate), as well as poly(propylene carbonate)(cyclohexene carbonate) and poly(propylene carbonate)(hexene carbonate) terpolymers.     

Hierarchical Mn3O4 Anchored on 3D Graphene Aerogels via C−O−Mn Linkage with Superior Electrochemical Performance for Flexible Asymmetric Supercapacitor

Flexible asymmetric supercapacitors are more appealing in flexible electronics because of high power density, wide cell voltage, and higher energy density than symmetric supercapacitors in aqueous electrolyte. In virtues of excellent conductivity, rich porous structure and interconnected honeycomb structure, three dimensional graphene aerogels show great potential as electrode in asymmetric supercapacitors. However, graphene aerogels are rarely used in flexible asymmetric supercapacitors because of easily re-stacking of graphene sheets, resulting in low electrochemical activity. Herein, flower-like hierarchical Mn₃O₄ and carbon nanohorns are incorporated into three dimensional graphene aerogels to restrain the stack of graphene sheets, and are applied as the positive and negative electrode for asymmetric supercapacitors devices, respectively. Besides, a strong chemical coupling between Mn₃O₄ and graphene via the C-O-Mn linkage is constructed and can provide a good electron-transport pathway during cycles. Consequently, the asymmetric supercapacitor device shows high rate cycle stability (87.8 % after 5000 cycles) and achieves a high energy density of 17.4 μWh cm⁻² with power density of 14.1 mW cm⁻² (156.7 mW cm⁻³) at 1.4 V.     

Synthesis and electrochemical properties of copper(II), manganese(III) phthalocyanines bearing chalcone groups at peripheral or nonperipheral positions

In this study, new chalcone compound 1 , new phthalonitrile derivatives 2 and 3, new copper(II), manganese(III) phthalocyanines bearing chalcone groups at peripheral or nonperipheral positions were synthesized. Electrochemistry of tetra-(4-{(2 E )-3-[2-fluoro-4-(trifluoromethyl)phenyl]prop-2-enoyl}phenoxy) substituted Co(II)Pc and Mn(III)Pcs were studied with cyclic voltammetry (CV) to determine the redox properties of the phthalocyanines. According to the results, while the CuPcs 2a and 3a showed two Pc based reduction reactions and one Pc based oxidation reaction, MnPcs 2b and 3b gave two metal-based reduction reactions. All the redox processes are shifted toward positive potentials as a result of the increased electron-withdrawing ability of the trifluoromethyl substituents.     

Surface Acidity of H-Birnessite: Infrared Spectroscopic Study of Formic Acid Decomposition

This paper presents the adsorption and thermal decomposition mechanism of formic acid on an H-birnessite sample. Changes in the surface and structure were characterized using infrared spectroscopy, N₂ gas adsorption–desorption, and thermal analysis techniques. The acid sites of H-birnessite were investigated by infrared and thermal analysis using pyridine as a molecular probe. Decomposition of formic acid started on H-birnessite at 120°C and was complete at 400°C. Infrared spectra revealed that the molecularly adsorbed formic acid species were transformed to a formate species, and the formate species were transformed to CO. The most stable adsorption structure for formic acid was found as a molecular monodentate configuration.