The meta and para OH Substitution Effect on C-Phenyl-Nitrilimine Bond-Shift Isomers

The geometric and electronic structure of 1,3-dipolar species, in particular of nitrile imines, can be surprisingly intricate. A particular example is the C-phenyl-nitrilimine, which exists as two energy minima that constitute bond-shift isomers. To examine the effect of substituents in the phenyl ring, here we investigate the meta and para OH substituted derivatives. These two nitrile imines were generated in an argon matrix by UV-irradiation of 2H-tetrazole precursors and found to photoisomerize to carbodiimides via 1H-diazirines. The different effects of the OH substitution in meta and para positions on the bond-shift isomerism are rationalized with the support of Natural Resonance Theory and Hirshfeld atomic charges. The understanding of how substitution affects the structural characteristics of C-phenyl-nitrilimines, opens a door to modulate the chemistry of those compounds (e. g. in cycloaddition reactions) by appropriate tuning of their substitution (substituent type and position).     

Cover Picture: Axis-Unfixed Biphenylphosphine-Oxazoline Ligands: Design and Applications in Asymmetric Catalytic Reactions (Chem. Rec. 10/2023)

The design and synthesis of chiral ligands plays an important role in asymmetric catalytic reactions. Over the past decades, various types of chiral phosphine-oxazolines (PHOX ligands) have been developed and have greatly advanced the field of asymmetric catalysis. Novel chiral PHOX ligand with an axis-unfixed biphenyl backbone, developed by our group, have shown interesting coordination behavior and excellent chiral inducing ability in various transition-metal-catalyzed asymmetric reactions. This personal account focuses on our developed axis-unfixed biphenylphosphine-oxazoline ligand (BiphPHOX), including an overview of its design and applications, which will provide inspiration for the exploration of novel ligands and related reactions.     

Determination of carbonate content in barite ore by headspace gas chromatography

This paper reports a method for determining the carbonate content in barite ore using headspace gas chromatography. Based on the acidification reaction, the carbonate in the barite ore was converted to CO₂ in a closed headspace vial. When the carbonate content was significant, the pressure caused changes in the CO₂ and O₂ signals and affected the measurement accuracy. It was found that carbonate content is proportional to the intensity ratio of the CO₂ to O₂ signals. Thus, the carbonate content in barite ore can be measured indirectly using a theoretical model. The results showed that the carbonate in 3 g of barite ore sample with a particle size of 74 μm could react completely with a hydrochloric acid solution (2 mol/L) at 65°C for 5 min. The method described herein had good precision (relative standard deviation < 4.14%) and accuracy (relative differences < 6.12%). Further, the limit of quantification was 0.07 mol/L. Owing to its simplicity and speed, this method can be used for the batch determination of carbonate content in barite ore.     

An Injectable Integration of Autologous Bioactive Concentrated Growth Factor and Gelatin Methacrylate Hydrogel with Efficient Growth Factor Release and 3D Spatial Structure for Accelerated Wound Healing

Growth factors are essential for wound healing owing to their multiple reparative effects. Concentrated growth factor (CGF) is a third-generation platelet extract containing various endogenous growth factors. Herein, a CGF extract solution is combined with gelatin methacrylate (GM) by physical blending to produce GM@CGF hydrogels for wound repair. The GM@CGF hydrogels show no immune rejection during autologous transplantation. Compared to CGF, GM@CGF hydrogels not only exhibit excellent plasticity and adhesivity but also prevent rapid release and degradation of growth factors. The GM@CGF hydrogels display good injectability, self-healing, swelling, and degradability along with outstanding cytocompatibility, angiogenic functions, chemotactic functions, and cell migration-promoting capabilities in vitro. The GM@CGF hydrogel can release various effective molecules to rapidly initiate wound repair, stimulate the expressions of type I collagen, transform growth factor β1, epidermal growth factor, and vascular endothelial growth factor, promote the production of granulation tissues, vascular regeneration and reconstruction, collagen deposition, and epidermal cell migration, as well as prevent excessive scar formation. In conclusion, the injectable GM@CGF hydrogel can release various growth factors and provide a 3D spatial structure to accelerate wound repair, thereby providing a foundation for the clinical application and translation of CGF.     

激光剥蚀电感耦合等离子体质谱法测定纯铝及铝丝中铁、硅、铜、锰、镁、钛、锌、铬和镍

采用激光剥蚀电感耦合等离子体质谱法测定纯铝及铝丝中铁、硅、铜、锰、镁、钛、锌、铬和镍的含量。采用低功率等离子体,以27Al为内标。样品直径为0.5~3 mm时,直径粗细与元素的信号不相关。所有元素的分馏因子在0.94~1.13之间时,可以认为没有分馏效应;纯铝和铝合金的基体效应不明显,铸铝会影响基体效应。测定了块状和丝状标准物质,测定值与认定值基本吻合,纯铝板的测定值与直读光谱法测定结果相一致。受背景干扰的影响,测定值的相对标准偏差(n=5)在2.9%~32%之间。     

钛表面钠氢氧钛纳米线的结构、生物活性和MC3T3-E1细胞响应

采用化学方法处理微弧氧化(MAO)制备的含Si、Ca元素的Ti O2涂层(SC),获得钛氢氧钠(Na0.8H1.2Ti3O7)生物活性纳米线结构。化学处理过程中,SC涂料表面出现了Ca、Na元素溶解,Si元素沉积的现象。化学处理后的SC涂层比SC涂料具有更好的吸水性和诱导磷灰石形成能力。这与处理后涂层(SHTO)特殊的纳米结构有关,在模拟体液浸泡过程中更容易形成Ti-OH。同时,钠氢氧钛纳米线的表面形貌、相组成、OH基团以及良好的湿润能力使其更加适合于MC3T3-E1细胞的粘附和增值。     

Kinetics and products of ozonation of C.I. Reactive Red 195 in a semi-batch reactor

Textile wastewater shows great threats to the environment if not well pretreated before discharge. A promising technique, ozonation, was applied to remove the color in dye solutions containing C.I. Reactive Red 195 (RR195) in a semi-batch reactor. The decolorization of RR195 by the ozone process followed pseudo-first-order kinetics. Several factors which influenced the efficiency of decolorization were studied and the reaction rate constant (k) obtained with different operational parameters was compared. Our results showed that RR195 was more easily degraded in acidic than in alkaline conditions. The dyeing auxiliaries (sodium carbonate and sodium chloride) that acted as radical scavengers could enhance the decolorization process, and the ozonation time for total color removal lengthened if the initial dye concentration was higher. The analysis of the ozonation products was performed by liquid chromatography-tandem mass spectrometer and a possible degradation pathway was predicted according to the ozonation products and structure of RR195. Our results indicated that ozonation was effective in the color removal of dyes, but further treatment might be necessary since the ozonation products are high toxic.     

Bis-triarylamine with a cyclometalated diosmium bridge: A multi-stage redox-active system

A tetra(pyrid-2-yl)-pyrazine-bridged cyclometalated diosmium complex 1(PF6)2with two distal redoxactive organic amine substituents has been synthesized and characterized. This complex displays four consecutive and separated anodic redox waves at +0.24, +0.38, +0.64, and +0.71 V vs. Ag/Ag Cl. Upon stepwise oxidation, four-step absorption spectral changes in the visible to near-infrared region have been observed. The different redox states of 1(12+through 16+) can be distinguished by the significantly different absorption spectra in the visible and near-infrared region. DFT calculations of 13+show that the spin is delocalized on both osmium–amine components.     

Solvent free synthesis of trifluoromethyl tertiary alcohols by cross Aldol reaction

Exceedingly fast preparation of trifluoromethyl tertiary alcohols has been accomplished from methyl ketones and trifluoromethyl ketones under solvent free conditions by cross Aldol reaction. The reaction was achieved in the presence of common inorganic base by grinding method at ambient temperature to give β-trifluoromethyl-β-hydroxyl ketones in high yields (up to 95%).     

二环己基-18冠-6加速锶离子在微米管支撑的水/1,2-二氯乙烷界面上的转移反应

采用玻璃微米管支撑的液/液界面通过循环伏安法(CV)研究了二环己基-18冠6(DCH18C6)加速Sr2+在水/1,2-二氯乙烷(W/DCE)界面上的转移反应,考察了DCH18C6加速Sr2+在W/DCE界面转移的影响因素,如DCH18C6和Sr2+浓度等,并求算其络合物的稳定常数。实验结果表明,Sr2+与DCH18C6发生的是一个1:1的扩散控制的界面络合转移过程,其络合常数β为5.31×1023。本研究可为理解溶剂萃取Sr2+行为提供基础理论数据。