TEMPO/NaBr/NaClO体系氧化玉米淀粉的研究

针对以2,2,6,6-四甲基哌啶-1-氧基自由基（TEMPO）-NaClO-NaBr为代表的亚硝酰自由基选择性氧化体系,本文以玉米淀粉为原料,NaClO为氧化剂,TEMPO和NaBr为催化剂,制备了氧化玉米淀粉.在不糊化的前提下,以5 g淀粉为原料,研究了在pH为10.00,反应温度为20℃,反应时间为2.5h的条件下,不同氧化剂用量对氧化淀粉羧基质量分数的影响,通过红外光谱（IR）对氧化玉米淀粉的结构进行表征,研究结果表明,当NaClO用量为67.5 mL时,氧化淀粉的羧基质量分数可达10.60％.该研究为TEMPO/NaBr/NaClO体系氧化淀粉提供了理论参考.     

Expedient Immobilization of TEMPO by Copper‐Catalyzed Azide‐Alkyne [3+2]‐Cycloaddition onto Polystyrene Resin

TEMPO was readily grafted by copper(I)‐catalyzed azide‐alkyne cycloaddition onto polystyrene. Starting with commercially available Merrifield resin (4.3 mmol/ g) almost quantitative loading of TEMPO onto the polymer was achieved (≥ 4 mmol/ g). The so obtained PS‐CLICK‐TEMPO allowed the oxidation of alcohols to aldehydes with bleach or molecular oxygen as the terminal oxidant with high yields and selectivity in multiple cycles without loss of activity.     

Extended Lifetimes of Gold(III) Chloride Catalysts using Copper(II) Chloride and 2,2,6,6‐Tetramethylpiperidine 1‐Oxyl (TEMPO)

The turnovers of a gold(III) chloride catalyst were increased by 3,300% with the addition of several equivalents of 2,2,6,6‐tetramethylpiperidine 1‐oxyl (TEMPO) and catalytic amounts of copper(II) chloride. A three‐component coupling reaction between piperidine, phenylacetylene, and benzaldehyde yielded a propargylic amine in quantitative conversions and isolated yields when gold(III) chloride was added in catalytic amounts, but the gold catalyst decomposed and had little to no reactivity when a second set of piperidine, phenylacetylene, and benzaldehyde was added after the reaction was complete. Thus, only one cycle was possible with gold(III) chloride. The addition of TEMPO and copper(II) chloride to reactions with gold(III) chloride maintained the catalytic activity of gold for up to 33 cycles. This result demonstrates a new way to greatly increase the turnovers of a gold(III) chloride catalyst with the addition of inexpensive, commercially available reagents.     

Synthesis and catalytic performance of gold-loaded TiO2 nanofibers

Organic modification of sol–gel catalytic glassy electrodes made of a thin layer of organosilica doped with nitroxyl radical TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy) crucially enhances stability in the waste-free oxidation of alcohols to carbonyls in water. Structural comparison between analogous films made of organosilica and unmodified SiO₂ shows that the origin of the pronounced stable activity of the ORMOSIL film lies in high hydrophobic and also in the pronounced low degree of hydrophilicity. This article is dedicated to the memory of professor Angelo Patricolo, great Italian neurosurgerist and fine gentleman from Sicily     

Catalytic Synergism in a C60IL10TEMPO2 Hybrid in the Efficient Oxidation of Alcohols

A novel fullerene [5:1]hexakisadduct bearing two 2,2,6,6‐tetramethylpiperidine 1‐oxyl (TEMPO) radicals and ten 1‐propyl‐3‐methylimidazolium bromide moieties has been synthesized and characterized. Such an C₆₀IL₁₀TEMPO₂ hybrid has been successfully employed as a catalyst in the selective oxidation of a wide series of alcohols and is highly active at just 0.1 mol% loading. Moreover, it can be easily recovered by adsorption onto a multi‐layered covalently‐linked SILP phase (mlc‐SILP) through a “release and catch” approach and reused for up to 12 cycles without loss in efficiency. Interestingly, a catalytic synergistic effect of TEMPO and imidazolium bromide moieties combined in the same hybrid has been clearly shown.

     

Copper Catalysts for Selective C?C Bond Cleavage of β‐O‐4 Lignin Model Compounds

The reactivity of homogeneous copper catalysts towards the selective C C bond cleavage of both phenolic and non‐phenolic arylglycerol β‐aryl ether lignin model compounds has been explored. Several copper precursors, nitrogen ligands, and solvents were evaluated in order to optimize the catalyst system. Using the optimized catalyst system, copper(I) trifluoromethanesulfonate [Cu(OTf)]/L/TEMPO (L=2,6‐lutidine, TEMPO=2,2,6,6‐tetramethyl‐piperidin‐1‐yl‐oxyl), aerobic oxidation of the non‐phenolic β‐O‐4 lignin model compound proceeded with good selectivity for C_α C_β bond cleavage, affording 3,5‐dimethoxybenzaldehyde as the major product. Aerobic oxidation of the corresponding phenolic β‐O‐4 lignin model proceeded with different selectivity, affording 2,6‐dimethoxybenzoquinone and α,β‐unsaturated aldehyde products resulting from cleavage of the C_α C_aryl bond. At low catalyst concentrations, however, a change in selectivity was observed as oxidation of the benzylic secondary alcohol predominated with both substrates.

     

TEMPO氧化纤维素纳米纤丝对多壁碳纳米管分散性的影响

以竹粉为原料,采用2,2,6,6-四甲基哌啶-1-氧自由基（TEMPO）氧化法通过改变NaClO的添加量制备出不同羧基含量及形态的纤维素纳米纤丝（CNFs）,并将制备的CNFs作为分散剂对多壁碳纳米管（MWCNTs）进行分散处理,得到不同分散浓度的CNFs/MWCNTs悬浮液,采用Beer-Lambert定律对MWCNTs的分散量进行测定,并采用原子力显微镜（AFM）、激光粒度分析仪（LPSA）等手段评价了不同羧基含量及形态的CNFs对MWCNTs的分散效果。结果表明:随着NaClO添加量的增加,CNFs的横截面直径逐渐变小,羧基含量逐渐增加,同时,CNFs对MWCNTs的分散量逐渐增大;当CNFs的羧基含量从0.635 mmol/g增加到1.646 mmol/g时,对MWCNTs的分散量从19%增加到39%;不同CNFs/MWCNTs悬浮液中的粒度分布系数（PDI）值均小于0.3,且不同悬浮液的Zeta电位绝对值均高于30 mV,表明不同羧基含量的CNFs均能对MWCNTs有较好的分散效果;同时,随着羧基含量的增加,CNFs对MWCNTs的分散效果越好,CNFs/MWCNTs复合薄膜的抗拉应力逐渐增大,而且电阻率逐渐降低,当CNFs羧基含量为1.646 mmol/L时,CNFs/MWCNTs复合薄膜抗拉应力达到了91 MPa,薄膜电阻率低至0.1460 Ωcm。      

TEMPO体系对粘胶纤维的氧化过程研究

2,2,6,6-四甲基哌啶氧化物自由基(TEMPO)-NaClO-NaBr是一种新的选择性氧化体系,文章研究了该体系对粘胶纤维的氧化过程。CP/MAS13C-NMR反映该体系对粘胶纤维是C6位选择性氧化,并能完全氧化成纤维素糖醛酸;用CP/MAS13C-NMR、耗碱量法和酸碱中和法研究了反应过程中羧基含量的变化;粘度法对聚合度的研究显示,粘胶纤维的降聚现象在反应一开始就非常显著。