Cofactor-dependent enzyme catalysis in functionalized ionic solvents

Functionalized, hydrogen-bonding ionic liquids have been successfully evaluated as media for the performance of cofactor-dependent enzyme catalysed oxidations; the effects of incorporating hydroxyl groups into both the cation and anion have been studied and the dependence of activity upon water content has been evaluated.     

脯氨酸的双功能催化作用对制备光学活性环型羟酮的机理 研究

2-甲基-2-乙酰乙基-1,3-环戊二酮(1),在双功能催化剂L-(-)-脯氨酸的作用下,生成(+)-cis-9S-羟基-8S-甲基氢茚-1,5-二酮[(+)-2],化学产率100%,光学纯度93.4%e.e.;而在L-(+)-高脯氨酸的作用下,得到的是(-)-2,产率73%,光学纯度65%e.e..加一方面,3R-(醛丙硫基)-4-硫杂环已酮可差向异构的衍生物(7)分别在D-或L-脯氨酸催化下,所得到的都是呈右旋光性的非对映立体异构的产物(+)-cis-1,8-二硫杂-4R-羟基-9R,10R-十氢萘-5-酮[(+)-8],但从D-脯氨酸得出的光学纯度高得多,这些实验事实和反应机理均可以通过构象分析结合立体结构式得到合理的表达和解释。     

Proximally functionalized cavitands and synthesis of a flexible hemicarcerand

A general study on the synthesis of partly bridged octols3a-d and4c-d is described. Tri-bridged diol3c can be prepared in 54% yield in DMSO at 70°C with excess CH₂BrCl or in 52% yield in DMF at 70°C with only 4 equiv. of CH₂BrCl. 1,3-Di-bridged tetrol4a, one of the two possible di-bridged isomers formed in preference to the other, was obtained in 30% yield. Tri-bridged diols3c andd can be selectively debrominated in one step by treatment with 5 equiv. ofn-BuLi in THF to afford the corresponding dibromo derivatives8a andb in 77% and 76% yields, respectively. After incorporation of the fourth bridge, the remaining two bromines can be replaced by C(O)OMe to give9c (60%), by OH to give9d (62%) or by CN to give9f (>95%). When the lithiated derivatives of3c andd are quenched with electrophiles other thanH ⁺, a selectively functionalized tri-bridged diol with hydroxyl (8c, 47%) and selectively functionalized cavitands with thiomethyl (9g, 25%) or iodo (9h, 20%) groups can be synthesized. Two molecules of9d were coupled with CH₂BrCl in DMSO/THF under high dilution conditions to give the flexible hemicarcerand10 in 71% yield. Supplementary Data. A list of observed and calculated structure factors have been deposited with the British Document Supply Centre as Supplementary Publication No. SUP 82170 (50 pages)This paper is dedicated to the commemorative issue on the 50th anniversary of calixarenes.     

Structural relation properties of hydrothermally stable functionalized mesoporous organosilicas and catalysis

The surfactant assistant syntheses of sulfonic acid functionalized periodic mesoporous organosilicas with large pores are reported. A one-step condensation of tetramethoxysilane (TMOS) with 1,2-bis(trimethoxysilyl)ethane (BTME) and 3-mercaptopropyltrimethoxysilane (MPTMS) in highly acidic medium was performed in the presence of triblock copolymer Pluronic P123 and inorganic salt as additive. During the condensation process, thiol (-SH) group was in situ oxidized to sulfonic acid (-SO(3)H) by hydrogen peroxide (30 wt % H(2)O(2)). X-ray diffraction studies along with nitrogen and water sorption analyses reveal the formation of stable, highly hydrophobic, and well-ordered hexagonal mesoscopic structures in a wide range of -CH(2)CH(2)- concentrations in the mesoporous framework. The resultant materials were also investigated by (29)Si MAS and (13)C CP MAS NMR, thermogravimetric analyses, UV-Raman spectroscopy, and FT-IR spectroscopy. The role of the bridged organic group on the hydrothermal stability of the mesoporous materials was established, which revealed an enhancement in hydrothermal stability of the materials with incorporation of the bridged organic groups in the network. The catalytic performance of -SO(3)H functionalized mesoporous materials was investigated in the esterification of ethanol with acetic acid, and the results demonstrate that the ethane groups incorporated in the mesoporous framework have a positive influence on the catalytic behavior of the materials.     

Syntheses and characterization of functionalized polynorbornene dicarboximides for flexible substrates

In this study, we synthesized polynorbornene (PNB) dicarboximides substituted by monochlorophenyl group (PMCPhNDI) and dichlorophenyl group (PDCPhNDI) via ring‐opening polymerization using a ruthenium catalyst and investigated their thermal, mechanical, and optical properties. We also discussed the performance and application of the functionalized PNB dicarboximide films as flexible substrates for organic light‐emitting devices (OLEDs). The polymer films exhibited good optical transparency with an average transmittance of around 97% in the visible light region and good thermal stability with a 5% degradation temperature of >440°C. The polymers were applied for flexible displays, which were coated on indium tin oxide (ITO) thin films using a radio‐frequency planar magnetron sputtering system with changing the deposition substrate temperatures. A flexible OLED that was fabricated on the ITO‐grown polymer substrates exhibited a performance as comparable to the corresponding ITO‐grown glass substrates. Copyright © 2012 John Wiley & Sons, Ltd.     

Terminally functionalized polyisobutylene oligomers as soluble supports in catalysis

A new phase selective hydrocarbon soluble polymer support is described.     

SmI(2)-mediated cyclizations of derivatized beta-lactams for the highly diastereoselective construction of functionalized prolines

A series of C4-keto-functionalized 1-[(benzoyloxy)(ethoxycarbonyl)methyl]-2-azetidinones were prepared and studied for their tendency to undergo a Reformatsky-type cyclization to fused bicyclic or tricyclic beta-lactams with the single-electron reducing agent samarium diiodide. Whereas the azetidinone 21a underwent reductive cyclization, affording the potent antibiotic sanfetrinem's tricyclic [4.5.6] core structure as the major component, all other examples tested resulted in cyclization followed by an N to O acyl migration involving cleavage of the beta-lactam ring as the favored pathway. Highly functionalized proline derivatives were therefore accessed as single diastereomers through the reductive cyclization of benzoates 21b, 22, 23a,b, 24b, and 25-28. Pertinent for the success of these cyclizations was the addition of 1 equiv of tert-butyl alcohol, allowing for the protonation of the basic amide derivative obtained after the acyl migration step. The diastereoselectivities of these reactions deviate from those of similar cyclizations involving the corresponding lithium enolate. This divergence could be rationalized by the coordination of the metal ion of the samarium(III) enolate intermediate to the beta-lactam amide functionality in the cyclization step, which may not be possible for lithium enolates.     

Tandem catalysis and self-assembly: a one-pot approach to functionalized polymers

[reaction: see text] Side-chain functionalized polymers possessing terminal palladated SCS pincer complexes at each repeat unit were synthesized via ring-opening metathesis polymerization. These palladium centers function as both well-defined Heck catalysts and recognition units capable of quantitative self-assembly of pyridine-containing molecules. Exploitation of both the catalytic and self-assembly properties has led to the development of a controlled, one-pot tandem catalysis/self-assembly sequence for the synthesis of functionalized polymers.     

Synthesis of amine functionalized oxazolines with applications in asymmetric catalysis

This paper describes the synthesis of three classes of amine functionalized oxazolines that have been successfully used in asymmetric catalysis in our laboratory. Failed synthetic routes and significantly improved procedures are discussed including the synthesis of ligands for Nozaki-Hiyama-Kishi (NHK) carbonyl allylation reactions that do not require chromatography for purification.     

Biotechnological production of spider-silk proteins enables new applications

The outstanding mechanical properties of spider silks have motivated many researchers to establish biotechnological production techniques which are necessary to provide sufficient amounts of silk proteins for industrial applications. Based on recent developments in genetic engineering, two strategies for the recombinant production of spider-silk proteins have been established which are discussed in detail. Further, protein-design strategies are described, enabling the combination of silk properties with additional biological, chemical, or technical features. We highlight the potential of engineered and recombinantly-produced spider-silk proteins to provide the basis for a new generation of biomaterials.     

Cooperative catalysis of Co single atoms and nanoparticles enables selective CAr-OCH3 cleavage for sustainable production of lignin-based cyclohexanols

In this work, a dual-size MOF-derived Co catalyst(0.2Co_1-NPs@NC) composed of single atoms(Co₁) and highly dispersed nanoparticles(Co NPs) was prepared by in-situ Zn evaporation for the highperformance conversion of lignin-derived o-methoxyphenols(lignin oil) to cyclohexanols(up to 97%yield) via cascade demethoxylation and dearomatization. Theoretical calculations elaborated that the dual-size Co catalyst exhibited a cooperative effect in the selective demethoxylation proces...     

Heterogeneous photoredox catalysis using fluorescein polymer brush functionalized glass beads

Photocatalysis is a valuable and versatile method to perform a variety of chemical transformations under ambient temperatures and pressures using mild visible light. This work showcases an example of fluorescein-functionalized polymers grafted to micro-scale glass beads as heterogeneous photoredox catalysts. X-ray photoelectron spectroscopy and thermogravimetric analysis were used to analyze the resulting functional glass beads. Model reactions that are demonstrated include a cyclic condensation and a radical dehalogenation that can both be performed to high yields. Successful recyclability of the fluorescein polymer brush beads is demonstrated with detailed characterization confirming that photocatalytic polymer brushes remain tethered to the surface. As such, this allows for purification and reuse of the heterogeneous photocatalyst beads after simple filtration.     

Conformally anchoring nanocatalyst onto quartz fibers enables versatile microreactor platforms for continuous-flow catalysis

Continuous-flow microreactors offer increased reactivity and reusability via unique reaction pathways to address a wide range of practical nanocatalysis problems. However, only limited platforms exist to employ these microreactors for versatile nanocatalytic reactions. In this work, we conformally anchored nickel oxide(Ni O) nanosheets onto quartz fibers(QFs), which exhibited a high catalytic activity using the hydrogenation of 4-nitrophenol(4-NP) as a model reaction in a batch reaction study. More importantly, we demonstrated that fiber-based QF@Ni O composites(e.g., cotton, fabric, belt, felt) can be integrated as versatile platforms to develop microreactors for continuous-flow catalytic applications including hydrogenation reactions and dyecatalyzed degradation. This fiber-based three-dimensional(3 D) nanocatalyst architecture effectively drives continuous-flow catalytic reactions with unprecedented efficiency due to the easy diffusion of reactant molecules into the fibrous structure,allowing contact with catalytic active sites. Our approach to continuous-flow microreactor design uses surface hybridization as a guideline to immobilize nanocatalysts onto the QFs. These QF-based platforms, coupled with rational design, are expected to be applied to a wide range of nanocatalytic reactions.     

负载无定型钌纳米簇的原子级钴掺杂一维碳纳米笼增强析氢催化性能

析氢反应是电解水产制氢的关键反应之一.在碱性条件下,由于催化剂表面与反应过程中产生的氧物种、氢物种与催化剂的吸附未处于最佳状态,析氢反应动力学往往比较缓慢,比在酸性条件下慢2-3个数量级.目前,铂基纳米催化剂被认为是最优的析氢催化剂,但因价格昂贵、稳定性较差,限制了其在电解水器件上的大规模应用.因此,设计一种价格较为低...     

Accurate NOE-distance determination enables the stereochemical assignment of a flexible molecule - arugosin C

The application of accurate quantitative NOE-distance determination allows the relative stereochemical elucidation of conformationally flexible arugosin C some 39 years after its original report in the literature.     

Switchable catalysis: modular synthesis of functionalized Pyrimidinones via selective sulfide and halide cross-coupling chemistry

[reaction: see text] A general demonstration of orthogonal selectivity of the Liebeskind-Srogl cross-coupling protocol compared to the Suzuki-Miyaura and Stille variants is reported.     

Synthetic pathways enables the design of functionalized poly(lactic acid) with pendant mercapto groups

Functionalized poly(lactic acid) having sulfur‐protected groups along the chain have been synthesized with the ultimate aim to obtain materials for reversible and degradable self‐assembly systems. The first step in the synthesis was the preparation of hydroxy‐(4‐methyl‐phenylsulfanyl)‐propionic acid and hydroxy‐(tritylsulfanyl)‐propionic acid. These sulfur‐functionalized hydroxy acids were subsequently used as comonomers in the condensation polymerization of lactic acid producing functionalized polyesters with thio‐protected groups along the chain. The ratio of functionalized hydroxyl‐acid in the copolymer was determined by the feed ratio. The polyesters obtained were amorphous and size exclusion chromatography analysis showed a monomodal distribution. When treated with iodine, the polyesters chains bearing the tritylsulfanyl side groups assembled with the formation of S? S bridges and the molecular weight increased accordingly. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012