Innovative reactions mediated by zirconocene

Radical reactions mediated by Schwartz reagent and zirconocene(alkene) complex are firstly described. Schwartz reagent is a promising alternative to tributyltin hydride and the first transition metal hydrido complex used as a radical mediator in organic synthesis. A zirconocene(alkene) complex effects single electron transfer to alkyl halide to generate the corresponding alkyl radical. Secondly, serendipitous allylic C-H bond activation of the coordinating alkene of zirconocene(alkene) complex and its application to organic synthesis are summarized. By utilizing equilibrium between zirconocene(alkene) and zirconocene 2-alkenyl hydride, reaction of acid chloride with zirconocene(alkene) provides the corresponding homoallylic alcohol by sequential attacks of the hydride and 2-alkenyl moieties. A set of hydride and 2-alkenyl attacks on 1,4-diketone yields 6-heptene-1,4-diol derivative in high yield with high stereoselectivity. Selective capture of the hydride with diisopropyl ketone gives zirconocene 2-alkenyl alkoxide, which is a useful reagent for stereoselective allylation of aldehyde and imine. alpha-Halo carbonyl compounds undergo radical allylation with the zirconocene 2-alkenyl alkoxide which serves as a substitute for allyltin.     

新显色剂4-BPA-TB测定钢铁中铋的含量

本文研究了华东师大新合成的显色剂 4- BPA- TB(俗称三溴偶氮膦 )与 Bi3+的显色反应。在 HCl O4和乙醇介质中试剂与 Bi3+生成蓝色的络合物 ,其最大吸收波长位于 6 4 4 nm。新显剂的最大吸收波长位于5 47nm,摩尔吸收系数 4.4× 1 0 4 L· mol- 1 · cm- 1 。Bi3+的含量在 5— 40 μg/2 5 m L 范围内符合比耳定律。用新显色剂测定了钢铁中的铋、结果令人满意。     

用多波长K系数校正光谱试剂空白

试剂空白校正是光谱分析中亟待解决的问题之一，提出采用一种新的以零吸收波长试剂的空白吸光度为分母的光谱多波长Ｋ系数校正空白影响的新方法，首先通过模拟实验数据并应用模拟纯光谱与校正光谱间的误差确定选择零波长，继而运用各波长Ｋ系数从实验混合光谱中通过△Ａ＝Ａ－Ｋ．Ａ校正试剂空白得到真实光谱，最后以Ｚｎ－ＰＡＲ，Ｃｕ－ＴＡＰＰ及Ｈｇ－Ｈ２Ｄｚ３个典型体系空白校正为例说明本法的初步应用。     

Carboxylic Acid Salts as Dual-Function Reagents for Carboxylation and Carbon Isotope Labeling

The potassium salts of carboxylic acids are developed as efficient carboxylating agents through CO₂ exchange. We describe these carboxylates as dual-function reagents because they function as a combined source of CO₂ and base/metalating agent. By using the salt of a commercially available carboxylic acid, this protocol overcomes difficulties when using CO₂ gas or organometallic reagents, such as pressurized containers or strictly inert conditions. The reaction proceeds under mild conditions, does not require transition metals or other additives, and shows broad substrate scope. Through the preparation of several biologically important molecules, we show how this strategy provides an opportunity for isotope labeling with low equivalents of labeled CO₂.     

A Three-Component Arene Difunctionalization: Merger of C(sp3)/(sp2)−H Bond Addition

A tandem three-component C−H bond addition involving the activation of an inert C(sp³)−H bond is reported. The process enables the direct regioselective synthesis of 1,2-difunctionalized arenes with the formation of C(sp³)− and C(sp²)−C(arene) bonds. 2-Iodobenzoic acid derivatives behave as masked bifunctional reagent (BFR) and react with 2-pyridyl-methyl sulfoximine (MPyS) protected aliphatic acids bearing α,α-disubstituted groups, and alkenes to produce β-aryl-δ-alkenyl amide derivatives in a single operation. The transformation involves Pd(II)/Pd(IV) and Pd(II)/Pd(0) catalytic systems. Detailed mechanistic studies, including density functional theory (DFT) calculations, reveal the formation of large T-shaped palladacycles and the onset of a 1,2-palladium migration via decarboxylation.     

Mechanochemistry-Amended Barbier Reaction as an Expedient Alternative to Grignard Synthesis**

Organomagnesium halides (Grignard reagents) are essential carbanionic building blocks widely used in carbon-carbon and carbon-heteroatom bond-forming reactions with various electrophiles. In the Barbier variant of the Grignard synthesis, the generation of air- and moisture-sensitive Grignard reagents occurs concurrently with their reaction with an electrophile. Although operationally simpler, the classic Barbier approach suffers from low yields due to multiple side reactions, thereby limiting the scope of its application. Here, we report a mechanochemical adaptation of the Mg-mediated Barbier reaction, which overcomes these limitations and facilitates the coupling of versatile organic halides (e.g., allylic, vinylic, aromatic, aliphatic) with a diverse range of electrophilic substrates (e.g., aromatic aldehydes, ketones, esters, amides, O-benzoyl hydroxylamine, chlorosilane, borate ester) to assemble C−C, C−N, C−Si, and C−B bonds. The mechanochemical approach has the advantage of being essentially solvent-free, operationally simple, immune to air, and surprisingly tolerant to water and some weak Brønsted acids. Notably, solid ammonium chloride was found to improve yields in the reactions of ketones. Mechanistic studies have clarified the role of mechanochemistry in the process, indicating the generation of transient organometallics facilitated by improved mass transfer and activation of the surface of magnesium metal.     

Polydimethylsiloxane composites containing 1,2-naphtoquinone 4-sulphonate as unique dispositive for estimation of casein in effluents from dairy industries

A unique dispositive to determine casein which is the most abundant protein in dairy sewages has been proposed. In this sensing technology, the derivatization reagent 1,2-naphtoquininone 4-sulphonate (NQS) is embedded into a polydimethylsiloxane-tetraethylortosilicate-SiO₂ nanoparticles composite (PDMS-TEOS-SiO₂NPs). When the composite is immersed into the samples, casein is extracted from the solution and derivatized inside the PDMS matrix after 10 min at 100 °C. The sensing support changes its color from yellow to orange depending on the casein concentration. Quantitative analysis can be carried out by measuring the absorbance with a reflection probe or by image-processing tool (GIMP). This sensor provides good sensitivity and precision (RSD% <12%). The method validation has been done by applying the biocinchoninic acid method (BCA). Moreover, semiquatitative analysis of casein can be performed by visual observation. Taking into account the advantages of small size, rapidity, simplicity, good stability and high compatibility in aqueous solution, this sensor is expected to have potential practical applications for in-situ determination of casein. Finally the method has been applied to analyze effluents from dairy industries.     

A critical review on photochemical conversions in flow analysis

Photochemical conversions are cost-effective and environmental friendly processes that require mild experimental conditions and avoid generation of highly acidic wastes. Treated samples are then compatible with most of the analytical techniques. These characteristics become more relevant when the photoconversions are accomplished to flow analysis, thus allowing exploitation of incomplete reactions, the effective use of the photogenerated unstable radicals and in-line sample treatment. Decreasing of reagent consumption and waste generation, sample processing in a closed environment, and improvement of efficiency of the photochemical processes are other inherent advantages. These aspects are critically reviewed in this article, which emphasizes applications to fractionation and speciation analysis, photo-induced luminescence, miniaturization, and in-line waste treatment. Design of flow-through photochemical cells, use of auxiliary reagents in homogeneous and heterogeneous media, and configurations of flow manifolds are also discussed.     

Field measurement of nitrate in marine and estuarine waters with a flow analysis system utilizing on-line zinc reduction

A sensitive reagent-injection flow analysis method for the spectrophotometric determination of nitrate in marine, estuarine and fresh water samples is described. The method is based on the reduction of nitrate in a micro column containing zinc granules at pH 6.5. The nitrite formed is reacted with sulfanilamide and N-(1-naphthyl)ethylene diamine (Griess reagent), and the resulting azo compound is quantified spectrophotometrically at 520 nm. Water samples in the range of 3-700 μg L⁻¹ NO₃⁻-N can be processed with a throughput of up to 40 samples per hour, a detection limit of 1.3 μg L⁻¹ and reproducibility of 1.2% RSD (50 μg L⁻¹ NO₃⁻-N, n = 10). The proposed method was successfully applied for the determination of nitrate in estuarine waters and the reliability was assessed by the analyses of certified reference materials and recovery experiments. The method is suitable for waters with a wide range of salinities, and was successfully used for more than 3200 underway nitrate measurements aboard SV Pelican1 in the “Two Bays” cruise in January 2010.     

Spatially selective reagent delivery into cancer cells using a two-layer microfluidic culture system

In this work, we demonstrate a two-layer microfluidic system capable of spatially selective delivery of drugs and other reagents under low shear stress. Loading occurs by hydrodynamically focusing a reagent stream over a particular region of the cell culture. The system consisted of a cell culture chamber and fluid flow channel, which were located in different layers to reduce shear stress on cells. Cells in the center of the culture chamber were exposed to parallel streams of laminar flow, which allowed fast changes to be made to the cellular environment. The shear force was reduced to 2.7 dyn cm⁻² in the two-layer device (vs. 6.0 dyn cm⁻² in a one-layer device). Cells in the side of the culture chamber were exposed to the side streams of buffer; the shear force was further reduced to a greater extent since the sides of the culture chamber were separated from the main fluid path. The channel shape and flow rate of the multiple streams were optimized for spatially controlled reagent delivery. The boundaries between streams were well controlled at a flow rate of 0.1 mL h⁻¹, which was optimized for all streams. We demonstrated multi-reagent delivery to different regions of the same culture well, as well as selective treatment of cancer cells with a built in control group in the same well. In the case of apoptosis induction using staurosporine, 10% of cells remained viable after 24 h of exposure. Cells in the same chamber, but not exposed to staurosporine, had a viability of 90%. This chip allows dynamic observation of cellular behavior immediately after drug delivery, as well as long-term drug treatment with the benefit of large cell numbers, device simplicity, and low shear stress.