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1.
The association between azacryptand hosts and oxoanion guests is reviewed. Positively charged hosts are the most effective; we focus on protonated azacryptands. Assessment of quantitative data suggests an anion cryptate effect and provides clear evidence for charge-based selectivity. Crystal structures show both cavity and cleft binding sites for anions within the series of cryptands studied. These two binding modes exhibit different pH dependence offering the possibility for design of monitoring/clean-up strategies based on a variation of appropriate host(s) and pH conditions. 相似文献
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Han G Mokari T Ajo-Franklin C Cohen BE 《Journal of the American Chemical Society》2008,130(47):15811-15813
Photoactivatable organic fluorophores and fluorescent proteins have been widely adopted for cellular imaging and have been critical for increasing temporal and spatial resolution, as well as for the development of superresolution microscopy techniques. At the same time, semiconducting nanocrystal quantum dots (QDs) have shown superior brightness and photostability compared to both organic fluorophores and proteins. As part of our efforts to develop nanoparticles with novel optical properties, we have synthesized caged quantum dots, which are nonluminescent under typical microscopic illumination but can be activated with stronger pulses of UV light. We show that ortho-nitrobenzyl groups efficiently quench QDs of different compositions and emissions and can be released from the nanoparticle surface with UV light, both in solution and in live cells. This caging is dependent on the emission of the QD, but it is effective through the visible spectrum into the nIR, offering a large array of new colors for photoactivatable probes. Like organic and protein-based photoactivatable probes, caged QDs can confer increased spatial and temporal resolution, with the added brightness and photostability of QDs. 相似文献
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Cornelia Ritter Nathalie Nett Dr. Carlos G. Acevedo‐Rocha Dr. Richard Lonsdale Katja Kräling Dr. Felix Dempwolff Dr. Sabrina Hoebenreich Prof. Dr. Peter L. Graumann Prof. Dr. Manfred T. Reetz Prof. Dr. Eric Meggers 《Angewandte Chemie (International ed. in English)》2015,54(45):13440-13443
Engineered cytochrome P450 monooxygenase variants are reported as highly active and selective catalysts for the bioorthogonal uncaging of propargylic and benzylic ether protected substrates, including uncaging in living E. coli. observed selectivity is supported by induced‐fit docking and molecular dynamics simulations. This proof‐of‐principle study points towards the utility of bioorthogonal enzyme/protecting group pairs for applications in the life sciences. 相似文献
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[reaction: see text] A caged 4-hydroxy-2-nonenal (4-HNE) has been prepared and its photochemistry investigated. Upon photolysis, 1 releases 4-HNE in up to 100% yield. From these photolyses, 4-HNE could be isolated in up to 91% yield. 4-HNE is produced under either aerobic or anaerobic conditions. The caging strategy does not require prior preparation of 4-HNE and, therefore, represents a three-step synthetic route to the bioactive enal in 48% overall yield. 相似文献
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Cai-Chao Ye Feng-Qi Zhao Xue-Hai Ju 《Phosphorus, sulfur, and silicon and the related elements》2013,188(8):997-1002
Abstract Strain energies (SE) of typical caged silanes were evaluated at the B3LYP/6-31+G** and B3LYP/aug-cc-pVDZ levels, in combination with the isodesmic and homodesmotic reactions. The SE values of Si4H4 and Si8H8 are 512 kJ/mol and 336–338 kJ/mol, respectively, at the B3LYP/6-31+G** level, whereas the SE values of the caged silanes with five-number or larger rings are very small. In comparison, the SE value of Si8H8 is much smaller than 656–707 kJ/mol of cubane (C8H8), since the Si?Si bond length (2.274 Å) of Si8H8 is much larger than the corresponding C?C bond length of cubane. The large electron charge density at body-center of Si4H4 causes strong repulsion between the cage center and Si?Si bond, which leads to the Si?Si bond bending. The electron charge density at the face center of Si4H4 is more than two times of that of Si8H8, which also contributes significantly to the large SE difference between Si4H4 and Si8H8. 相似文献
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Protein phosphorylation constitutes a major type of post-translational modifications mobilizing a high number of genes. It is involved in many crucial cell processes and largely participates in the features of the proteome. For several biological and technical reasons, the characterization of protein phosphorylation requires a combination of distinct procedures. In this review, a special emphasis is given to analytical strategies connected with the determination of the presence of phosphorylation sites and their localization by mass spectrometry (MS). The feasibility of selected combinations of analytical approaches for diverse objectives of phosphoproteomic research is discussed. 相似文献
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Three new caged prenylxanthones (xanthone=9H‐xanthen‐9‐one), named neobractatin ( 1 ), 3‐O‐methylneobractatin ( 2 ), and 3‐O‐methylbractatin ( 3 ), along with eight known compounds, were isolated from the twig of Garcinia bracteata. The structures of the new compounds were elucidated on the basis of 1D‐ and 2D‐NMR experiments, including HMBC, HSQC, 1H,1H‐COSY, and ROESY, as well as HR‐MS analysis. 相似文献
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Gatterdam V Stoess T Menge C Heckel A Tampé R 《Angewandte Chemie (International ed. in English)》2012,51(16):3960-3963
Light, GSH, action! Glutathione (GSH) fulfills a universal role as redox factor, scavenger of reactive oxygen species, and as an essential substrate in the conjugation, detoxification, and reduction reactions catalyzed by glutathione S-transferase (GST). A photoactivatable glutathione allows the GSH-GST network to be triggered by light. GST fusion proteins can be assembled in situ at variable density and structures by laser-scanning activation. 相似文献
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Oraphin Chantarasriwong Ayse Batova Dr. Warinthorn Chavasiri Prof. Dr. Emmanuel A. Theodorakis Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(33):9944-9962
Natural products have been a great source of many small molecule drugs for various diseases. In spite of recent advances in biochemical engineering and fermentation technologies that allow us to explore microorganisms and the marine environment as alternative sources of drugs, more than 70 % of the current small molecule therapeutics derive their structures from plants used in traditional medicine. Natural‐product‐based drug discovery relies heavily on advances made in the sciences of biology and chemistry. Whereas biology aims to investigate the mode of action of a natural product, chemistry aims to overcome challenges related to its supply, bioactivity, and target selectivity. This review summarizes the explorations of the caged Garcinia xanthones, a family of plant metabolites that possess a unique chemical structure, potent bioactivities, and a promising pharmacology for drug design and development. 相似文献
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Dr. Rainer Müller Dr. Mevlut Citir Dr. Sebastian Hauke Prof. Dr. Carsten Schultz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(2):384-389
Phosphatidylinositol (PI) is the biosynthetic precursor for seven phosphoinositides, important signaling lipids in cells. A membrane-permeant caged PI derivative featuring a photo-removable coumarinyl group masking the negative charge of the phosphate, as well as two enzymatically removable butyrate esters for increased lipophilicity and for preventing phosphate migration, were synthesized. Rapid cell entry and cellular labeling in fixed cells was demonstrated by a photo-cross-linkable diazirine followed by attachment of a fluorophore through click chemistry. Using this technique, we found that the multifunctional caged PI derivative resided predominantly at internal membranes but rapidly changed to the plasma membrane after uncaging. Accordingly, a preliminary proteomic analysis of the lipid–protein conjugates revealed that the two major PI transport proteins PITPα and β were prime targets of the photo-cross-linked PI derivative. 相似文献
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Jae‐Sung Bae Eunkyung Jeon Su‐Young Moon Wangsuk Oh Sun‐Young Han Jeong Hun Lee Prof. Sung Yun Yang Prof. Dong‐Myung Kim Prof. Ji‐Woong Park 《Angewandte Chemie (International ed. in English)》2016,55(38):11495-11498
The preparation of bicontinuous nanoporous covalent frameworks, which are promising for caging active enzymes, is demonstrated. The frameworks have three‐ dimensionally continuous, hydrophilic pores with widths varying between 5 and 30 nm. Enzymes were infiltrated into the bicontinuous pore by applying a pressured enzyme solution. The new materials and methods allowed the amount of caged proteins to be controlled precisely. The resulting enzyme‐loaded framework films could be recycled many times with nearly no loss of catalytic activity. Entropic trapping of proteins by a bicontinuous pore with the right size distribution is an unprecedented strategy toward facile in vitro utilization of biocatalysts. 相似文献
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Hersa Milawati Dr. Yoshiyuki Manabe Takuya Matsumoto Dr. Masato Tsutsui Dr. Yoshihiro Ueda Ayane Miura Dr. Kazuya Kabayama Prof. Koichi Fukase 《Angewandte Chemie (International ed. in English)》2023,62(25):e202303750
We propose a de novo glycan display approach that combines metabolic labeling and a glycan-caging strategy as a facile editing method for cell-surface glycans. This method enables the introduction of antigen glycans onto cancer cells to induce immune responses through antibody recruiting. The caging strategy prevents the capture of α-rhamnose (an antigen glycan) by endogenous antibodies during the introduction of the glycan to the targeted cell surface, and subsequent uncaging successfully induces immune responses. Therefore, this study proposes a practical method for editing the cell-surface glycocalyx under promiscuous conditions, such as those in vivo, which paves the way for the development of glycan function analysis and regulation. 相似文献
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Three 1-(2-nitrophenyl)ethyl-caged phospho-amino acids have been synthesized for use in standard N(alpha)-fluorenylmethoxycarbonyl-based solid-phase peptide synthesis (SPPS). The most common naturally occurring phospho-amino acids, serine, threonine, and tyrosine, were prepared as protected caged building blocks by modification with a unique phosphitylating reagent. In previous work, caged phospho-peptides were made using an interassembly approach (Rothman, D. M.; Vazquez, M. E.; Vogel, E. M.; Imperiali, B. Org. Lett. 2002, 4, 2865-2868). However, this technique is limited to creating peptides without oxidation sensitive residues C-terminal to the amino acid to be modified and the methodology involves synthetic manipulations on the solid phase that may limit the utilization of the methodology. Herein we report the facile synthesis of N-alpha-Fmoc-phospho(1-nitrophenylethyl-2-cyanoethyl)-L-serine 1, N-alpha-Fmoc-phospho(1-nitrophenylethyl-2-cyanoethyl)-L-threonine 2, and N-alpha-Fmoc-phospho(1-nitrophenylethyl-2-cyanoethyl)-L-tyrosine 3. These building blocks allow the synthesis of any caged phospho-peptide sequence using standard Fmoc-based SPPS procedures. 相似文献
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Soohyun Jang Mingi Kim Prof. Dr. Sang-Hee Shim 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(29):11856-11860
In DNA points accumulation in nanoscale topography (DNA-PAINT), capable of single-molecule localization microscopy with sub-10-nm resolution, the high background stemming from the unbound fluorescent probes in solution limits the imaging speed and throughput. Herein, we reductively cage the fluorescent DNA probes conjugated with a cyanine dye to hydrocyanine, acting as a photoactivatable dark state. The additional dark state from caging lowered the fluorescent background while enabling optically selective activation by total internal reflection (TIR) illumination at 405 nm. These benefits from “reductive caging” helped to increase the localization density or the imaging speed while preserving the image quality. With the aid of high-density analysis, we could further increase the imaging speed of conventional DNA-PAINT by two orders of magnitude, making DNA-PAINT capable of high-throughput super-resolution imaging. 相似文献
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James M. Carrick Boris A. Kashemirov Charles E. McKenna 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1)
Abstract Use of a photoremovable “caging” group allows the generation of reactive molecules under mild conditions. Photo-induced phosphorylations typically have involved attachment of the photosensitive group at phosphorus.[1] We now have investigated indirect photolytic activation of an unmodified phosphonic acid group using broad band UV (Hg lamp), 308 nm XeCl excimer laser or 355 nm YAC laser irradiation of the o-nitrobenzyl C-ester of “troika acid” [(E)-12]. In alcohols or neutral buffer, irradiation of (E)-2 gave phosphorylation of the solvent plus phosphorocyanidate, the expected 2-isomer product.2All thrce UV sources gave -1:2 E:Z product distribution in MeOH. In the (E)-1 methyl C-ester, the oxime functionality absorbed strongly near 205 nm (Emax 5200), weakly at 308 nm and negligibly above 355 nm, and no photoisomerization was seen using the 355 nm source. Thus, oxime isomerization in (E)-2 at least using 355 nm irradiation. requires the o-nitrobenzyl group, and possibly involves an energy- or charge-wansfer effect. Phosphorylation of EtOH/t-BuOH mixtures by photolysis of (E)-2 showed little alkyl selectivity. consistent with photoinduced formation of an intermediate. plausibly (E)-1, which undergoes spontaneous dissociative fragmentation via a monomeric metaphosphate-like species. 相似文献
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近年来随着生物医学技术的发展,人们需要越来越细致地在分子水平上研究各种生命过程。为了能够实现实时原位地观察活细胞或组织中的生命化学过程,需要使用以物理方法来选择性激活的分子探针。以共聚焦激光技术为基础的光敏开关能很好地解决这一问题。迄今,发展和用于光敏开关的光敏剂已成为化学生物学研究的重要方向。本文重点总结了各种可应用于共聚焦激光系统的单、双光子光敏基团(单光子的光敏基团主要有:硝基苯类、香豆素类等;双光子光敏基团主要有:香豆素类、喹啉类及吲哚衍生物类)以及这几类光敏基团在化学生物学中的应用。 相似文献