Templating photodimerization of trans-cinnamic acid esters with a water-soluble Pd nanocage

A water-soluble octahedral Pd nanocage acting as a reaction vessel templates the photodimerization of substituted trans-cinnamic acid methyl esters in water. Irradiation of the host-guest complexes of trans-cinnamic acid methyl esters with the Pd nanocage resulted in selective formation of a syn head-head dimer in addition to the corresponding cis isomer. These results suggest that the guest molecules are preoriented in a selective fashion with the hydrophilic ester group facing water and the hydrophobic aryl group tucked within the cavity of the host. Such an orientation occurs at the hydrophobic-hydrophilic interface between the nanocage exterior and interior. Weak intermolecular C-H-pi and pi-pi interactions between the host and the guest(s) are likely to be responsible for the lack of mobility of the reactant olefins during their short excited-state lifetime.     

Cucurbituril adamantanediazirine complexes and consequential carbene chemistry

Adamantanediazirines, precursors of adamantanylidenes, form 1:1 complexes (guest to host) with cucurbit[7]uril and cucurbit[8]uril and a 3:1 complex with a Pd nanocage in water. (1)H NMR spectra suggested that these complexes are stable in water on the NMR time scale. While photolysis of adamantanediazirines in water gave mainly adamantanone and adamantanol via adamantanylidene as intermediate, the 1:1 complexes of adamantanediazirine with cucurbiturils gave intramolecular C-H insertion products of adamantanylidene in >90% yield. The study establishes that significant control of carbene reactivity can be achieved when the precursor is encapsulated within a tight inert cavity. While the general characteristics of molecular containers can be understood on the basis of concepts such as "confinement" and "weak interactions", each one is unique and deserves careful scrutiny.     

Cavity-directed synthesis within a self-assembled coordination cage: highly selective [2 + 2] cross-photodimerization of olefins

Herein reported is the highly selective [2 + 2] cross-photodimerization of olefins within a self-assembled coordination cage that acts as a molecular flask in an aqueous medium. An M(6)L(4) coordination nanocage that self-assembles from six Pd(II) complexes and four tridentate ligands accommodates two different kinds of large olefin molecules such as acenaphthylene and 5-ethoxynaphthoquinone in a pairwise selective fashion. This prerequisite recognition mode makes possible the selective [2 + 2] cross-photodimerization of the olefins within the cavity. The reaction is extremely efficient in terms of reaction rate, stereoselectivity, and, most importantly, pairwise selectivity. Maleimide derivatives, which themselves are photochemically inactive under ordinary conditions, are also cross-dimerized with acenaphthylene or dibenzosuberenon quite efficiently. These results are in sharp contrast to those of common photodimerization in organic media, where the yields and selectivities are generally poor to moderate. The key step of the exclusive formation of the cross-dimers stems from the selective formation of ternary complexes before irradiation, which is governed by the size compatibility of the guests with the confined space of the cavity.     

Self-assembled coordination cage as a reaction vessel: triplet sensitized [2+2] photodimerization of acenaphthylene, and [4+4] photodimerization of 9-anthraldehyde

Inner cavity of Pd-nanocage has been used as a reaction vessel for performing triplet sensitized [2+2] photodimerization of acenaphthylene using water soluble xanthene dyes (Eosin Y and Rose Bengal) as sensitizers, and [4+4] photodimerization of 9-anthraldehyde. Although the [4+4] photodimerization of 9-anthraldehyde gave similar results to solution reaction, the xanthene dye sensitized [2+2] triplet state photodimerization of acenaphthylene encapsulated within Pd-nanocage yielded the syn dimer in quantitative yield. The results obtained from the triplet state [2+2] photodimerization of acenaphthylene within Pd-nanocage is remarkable given the fact that the photodimerization reaction when performed in methanol in the presence of Eosin Y and Rose Bengal gave the syn and anti dimers in the ratio 0.5 and 0.6, respectively. Preaggregation of molecules encapsulated inside Pd-nanocage in a syn fashion seems to be the governing factor for such a behavior.     

Palladium nanoparticles supported on a poly(N-vinyl-2-pyrrolidone)-modified mesoporous carbon nanocage as a novel heterogeneous catalyst for the Heck reaction in water

Palladium nanoparticles supported on poly(N-vinyl-2-pyrrolidone)/CKT-3 (a mesoporous carbon nanocage) were employed effectively as novel heterogeneous catalyst for the Heck coupling reaction. The results showed that aryl halides (-Cl, -Br, -I) underwent coupling with a variety of alkenes at 60 °C in water under aerobic conditions. The very stable nanocomposite catalyst was easily recovered, showed negligible Pd leaching, and retained good activity for at least ten successive runs without any additional activation.     

Gemini型表面活性剂疏水链中肉桂酸基团的光致二聚反应

采用紫外光谱、 红外光谱和质谱研究了Gemini型表面活性剂N,N'-二对丁氧基肉桂酰胺基胱氨酸钠(SDBCC)溶液的光化学反应过程和产物, 分析了SDBCC浓度对分子疏水链中肉桂酸基团光化学反应产物分布和光致二聚产率的影响. 结果表明, 在不同浓度下, SDBCC分子疏水链中的肉桂酸基团的光化学反应过程均以光致二聚反应为主, 且为分子内光致二聚产物. 但聚集体形成前后在光照过程中肉桂酸基团的光致二聚反应产率随SDBCC浓度的变化趋势不同, 聚集体形成前光致二聚反应产率随浓度的增加而增大, 聚集体形成后光致二聚反应产率随浓度的增大而减小. 综合光化学反应过程、 拓扑条件和聚集体结构进一步分析了胶束和囊泡的存在对SDBCC分子疏水链中肉桂酸基团光致二聚反应的影响.     

Functional monomers and polymers. CVIII. Photodimerization of pendant thymine bases in thymine containing poly-lysine derivatives

The photodimerization reaction of pendant thymine bases in thymine-containing poly-lysine derivatives was studied over a wide range in aqueous solution. It was found that the quantum yield of the photodimerization of pendant thymine bases is affected mainly by the conformation of the polymers in solution. The differences in photoreaction behavior were discussed for poly-D -, poly-L -, and poly-DL -lysine derivatives.     

9-乙烯基蒽和对-N,N-二甲氨基苯乙烯激基络合物的生成和光二聚反应

测定了9-乙烯基蒽和对-N,N-二甲氨基苯乙烯体系在不同极性的溶剂中的荧光光谱和荧光量子产率。发现随着溶剂极性的增加,激基络合物的荧光发生红移,荧光量子产率降低。同时9-乙烯基蒽和对-N,N-二甲氨基苯乙烯之间的光二聚产物的相对产率也降低。并讨论了经过激基络合物中间体的光二聚反应机理。     

Functional monomers and polymers. CXIX.. Synthesis and photochemical reaction of polymethacrylate derivative containing 6-cyanouracil

A polymethacrylate derivative containing 6-cyanouracil was prepared, and its photochemical reaction was studied. The 6-cyanouracil derivative was found to show high reactivity for the photochemiccal reaction. The photochemical-reaction product was identified as a cyclobutanetype photodimer, and the photodimer was formed in high yield even from the monomeric compound of 6-cyanouracil under UV irradiation in low concentration. The quantum yield of the photodimerization of the 6-cyanouracil derivative was greater than that of the thymine derivative. The photodimerization of the 6-cyanouracil derivative could not be quenched by usual triplet quenchers, but was found to be quenched by the polymeric derivative of adenine, suggesting a specific interaction.     

Enhancement of intramolecular excimer formation and photodimerization of anthrylmethyl α,ω-alkanedioates via hydrophobic interactions

The fluorescence spectra and photodimerization of anthrylmethyl a,w-alkanedioates (A-Mn-A) both in organic and in aqueous organic mixed solvents have been studied.In aqueous organic mixed solvents strong intramolecular excimer emission is detected and the quantum yield for the intramolecular photodimerization is significantly greater than those in organic solvents.These observations suggest that hydrophobic interactions force A-Mn-A molecule to self-coil.The ratio of the head-to-head to head-to-tail products in the intramolecular photodimers of A-Mn-A depends on the length of the linking chain.This work presents a successful example of application of hydrophobic interactions to enhancement of large-ring formation.     

Design of Green-Emitting Salts from Substituted Pyridines: Understanding the Solid-State Photodimerization of trans-1,2-bis(4-pyridyl)ethylene

Polymorphic salts of trans-1,2-bis(4-pyridyl)ethylene (bpe), 2 [bpeH₂] ⋅ (SO₄)(2HSO₄) ( 1 ) and [bpeH₂] ⋅ 2HSO₄ ( 2 ) have been synthesized and their structures determined by X-ray crystallography. The Schmidt postulate predicts that neither of the salts will give rise to photodimerization so they can both potentially be applied as green light emitters. Despite the predictions, 1 undergoes a stereospecific solid-state photodimerization reaction with 100 % yield. This is due to UV induced combination of sliding and pedal-like movement of the pyridyl ring system that influences the alignment of C=C bonds. The sliding motion is restricted in 2 . Consequently, the green emission from 1 is completely quenched after photodimerization. It is evident that counter ions play a dominant role in dis- and enabling photodimerization; their degree of protonization and lattice placement are important solvent controlled design parameters towards crystal structures that can act as future light emitters.     

一含肉桂酸的单链Bola型两亲分子在有机溶剂中的光致二聚和聚集行为

制备了一种含肉桂酸基团的Bola型两亲分子HDC(4-(10-羟基癸氧基)-10-羟基癸氧基肉桂酸酯). 第一次观察到该分子在有机溶剂中经紫外光照发生光致二聚. 分离出来的二聚HDC在20%的乙醇/水混合溶剂中能形成球形的囊泡. 同时发现溶剂的介电常数大小与光致二聚过程密切相关, 介电常数的大小不仅关系到反应发生与否, 而且直接影响到反应的速率.     

Encapsulation of chiral Fe(salan) in nanocages with different microenvironments for asymmetric sulfide oxidation

The solid catalysts for asymmetric oxidation of sulfides were prepared by encapsulating a chiral iron salan complex [Fe(salan)] in the nanocages of mesoporous silicas. The microenvironment of nanocages was finely tuned using silylation reagents with different kinds of organic groups, such as propyl (C3), 1-butyl-3-propyl-4,5-dihydroimidazolium bromide (ILBr), N-propyl-N,N,N-tri-n-butylammonium chloride (TBNCl) and N-propyl-N,N,N-tri-n-butylammonium bromide (TBNBr), and investigated by water and benzene adsorption. Fe(salan) encapsulated in the amphiphilic nanocage shows much higher enantioselectivity and activity than that in hydrophobic or hydrophilic nanocage for the asymmetric oxidation of thioanisole using H(2)O(2) as oxidant. The TOF of Fe(salan) encapsulated in the nanocage modified with TBNBr can reach as high as 220 h(-1), even higher than homogeneous Fe(salan) with a TOF of 112 h(-1). The enhanced catalytic activity is mainly due to the fast diffusion of H(2)O(2) and sulfide in the amphiphilic nanocage. The above results suggest that the microenvironment modification of the nanocage is an efficient method to synthesize highly efficient solid catalysts for asymmetric catalysis.     

Photodimerization of hydrophobic guests within a water-soluble nanocapsule

Conducting reactions in environmentally benign conditions is one of the major objectives of “green chemistry.” In this context, developing ways to conduct reactions in water seems obvious. In this report, we present our results on photodimerization of select guest molecules placed within the rigid reaction cavity of a water-soluble cavitand, octa acid. The results presented herein highlight the value of a supramolecular approach in achieving selectivity in photoreactions and opening reaction pathways that are latent in solution chemistry.     

Effects of molecular structure and environment on the photodimerization of substituted anthracenes

Photochemical and photophysical studies of a number of 9-substituted anthracene sandwich pairs in their corresponding photodimer crystal matrices have been carried out. Corresponding studies have also been made in methylcyclohexane matrices at 6 K. Photodimerization of the 9-methyl, 9-chloro and 9-cyano derivatives in the photodimer matrices occurs at 6 K with unit quantum yield. The presence of excimer fluorescence from sandwich pairs indicates the lack of a perfect topochemical orientation while activation processes, leading to photodimerization, involve molecular re-orientation from more stable ground state configurations which are achieved within the constraints imposed by the solvent or crystalline cage.     

THE MECHANISM OF PHOTOCHEMICAL ADDITION OF CYSTEINE TO URACIL AND FORMATION OF DIHYDROURACIL

Abstract— A proposed mechanism for the photochemical addition of L -cysteine to uracil with the concurrent formation of dihydrouracil is shown to proceed through the triplet excited state of uracil which can abstract hydrogen atoms from cysteine to form dihydrouracil. This triplet state is the same one as that leading to photodimerization. The thiyl radicals generated add to ground state uracil molecules. The data permit a re-evaluation of the quantum yield for intersystem crossing of uracil in water which shows dimerization in aqueous solution to have a maximum efficiency of 56 per cent. The formation of the cross-adduct and dihydrouracil may be sensitized but the efficiency of the reaction is related to the ability of the sensitizer to be photoreduced and not to its triplet energy.     

Heterogeneous Suzuki and copper-free Sonogashira cross-coupling reactions catalyzed by a reusable palladium(II) complex in water medium

A new polystyrene anchored Pd(II) azo complex has been synthesized and characterized. The present Pd(II) azo complex behaves as a very efficient heterogeneous catalyst in the Suzuki coupling and Sonogashira coupling reaction in water medium. Aryl halides, coupled with phenylboronic acids (Suzuki-Miyaura reaction) or terminal alkyne (Sonogashira reaction), smoothly afford the corresponding cross-coupling products in excellent yields (83-100% yield for Suzuki reaction and 68-96% yield for Sonogashira reaction of aryl halides) under phosphine-free reaction conditions in the presence of polystyrene anchored Pd(II) azo complex catalyst in water medium. Furthermore, the catalyst has shown good thermal stability and recyclability. This polymer-supported Pd(II) catalyst could be easily recovered by simple filtration of the reaction mixture and reused for more than six consecutive trials without a significant loss of its catalytic activity.     

Penicillamine functionalized B12N12 and B12CaN12 nanocages act as potential inhibitors of proinflammatory cytokines: A combined DFT analysis,ADMET and molecular docking study

The adsorption of penicillamine (PCA) on pure B₁₂N₁₂ and B₁₂CaN₁₂ nanocages in aqueous and chloroform solvents has been evaluated using density functional theory (DFT) calculations. The interaction of PCA on B₁₂N₁₂ nanocages is chemisorption through its four nucleophilic sites: amine, carbonyl, hydroxyl and thiol. The most stable adsorption configuration was achieved when zwitterionic PCA adsorbs via its carbonyl group in water with value of ?1.723 eV, in contrast, when neutral PCA adsorbs via its amine group in chloroform with value of ?1.68 eV. Intercalated calcium ion within B₁₂N₁₂ nanocage (B₁₂CaN₁₂) was shown to attract PCA onto nanocage surface, resulting in higher solubility and adsorption energy after their complexation in water and chloroform. The adsorption of multiple PCA molecules from their amine and carbonyl groups on pure and B₁₂CaN₁₂ nanocages were also evaluated where two and three molecules can be chemisorbed on boron atoms of the nanocage surfaces with the adsorption energy per PCA reduces slightly with the increasing the amount of drugs due to the curvature effects. Molecular docking study indicates that PCA from its NH₂ group on B₁₂CaN₁₂ nanocage has the best binding affinity and inhibition potential of tumor necrosis factor-alpha (TNF-α) and Interleukin-1 (IL-1) receptors as compared with the other adsorption systems. Molecular docking and ADMET analysis displayed that the chosen compounds pass Lipinski Rule and have appropriate pharmacokinetic features suitable as models for developing anti-inflammatory agents.     

THEORETICAL INVESTIGATION OF EXCIMER AND EXCIPLEX STATES OF URACIL AND HALOGEN DERIVATIVES: EFFECT OF NONPARALLELISM OF BASES

Theoretical modeling of initial steps of the photodimerization mechanism of uracil, 5-methyl-and 5-halogen derivatives was performed. The interaction energy of bases in stacked dimers in the ground and lowest excited states was calculated as a function of the distance between the base planes and of the rotation angles within the perturbation theory for the extended Hückel treatment. The existence of excimer and exciplex region on the potential surface of the excited state was revealed. The excimer (exciplex) geometry has the planes nonparallel with more close contact of the C5-C6 bonds as compared to the ground state of dimers. The results provide new information useful for understanding the photodimerization mechanism of bases and testifies that the singlet excimer state can be a precursor of the photodimerization reaction.     

反-4-(4-R-苯乙烯基)吡啶光二聚反应的研究

通过反-4-(4-R-苯乙烯基)吡啶[R=H(Ⅰa),Me(Ⅰb),OMe(Ⅰc),OH(Ⅰd),Me2N(Ⅰe)］在稀盐酸中的光二聚反应合成了4个r-1,c-2,t-3,t-4-1,3-双(4-R-苯基)-2,4-二(4-吡啶基)环丁烷[R=H(Ⅱa),Me(Ⅱb),OMe(Ⅱc),OH(Ⅱd)］,除Ⅱa外,其余为新化合物.光二聚反应具有高度立体选择性且几乎是定量完成的.研究发现,随着取代基供电子能力的提高,光二聚反应速率下降.反应的高度立体选择性以及该反应不受空气中氧气影响的事实表明光二聚反应是按激发单重态历程进行的.研究还发现Ⅰa～Ⅰd在有机溶剂中主要发生反-顺异构化反应,随着溶剂极性增加,反-顺异构化速度加快,表明其反-顺异构化反应亦经激发单重态历程.本文检测到了Ⅰa在稀盐酸溶液中的激基缔合物荧光.