共查询到20条相似文献,搜索用时 15 毫秒
1.
Kai Bernitzki Dr. Michael Maue Prof. Thomas Schrader 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(42):13412-13417
The complete, entirely artificial, signal‐transduction process was realized with a pair of tailored transmembrane units that were equipped with receptor‐ and reactive sites at both amphiphilic ends. Thus, docking of the primary messenger, transmission of the signal, and release of the secondary messenger could all be imitated in a single experimental setup. The system imitates the signaling principle of receptor tyrosine kinases and employs bisphosphonate head‐groups for oligoamine‐recognition and a pair of thiol nucleophiles and pyridine disulfide tail‐groups for intravesicle SN2 displacement. This system operates in a unidirectional fashion, does not suffer from intervesicle competition, and is highly sensitive towards the lipid composition of the membrane and the nature of the primary messenger. 相似文献
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Communication between and inside cells as well as their response to external stimuli relies on elaborated systems of signal transduction. They all require a directional transmission across membranes, often realized by primary messenger docking onto external receptor units and subsequent internalization of the signal in form of a released second messenger. This in turn starts a cascade of events which ultimately control all functions of the living cell. Although signal transduction is a fundamental biological process realized by supramolecular recognition and multiplication events with small molecules, chemists have just begun to invent artificial models which allow to study the underlying rules, and one day perhaps to rescue damaged transduction systems in nature. This review summarizes the exciting pioneering efforts of chemists to create simple models for the basic principles of signal transduction across a membrane. It starts with first attempts to establish molecular recognition events on liposomes with embedded receptor amphiphiles and moves on to simple transmembrane signaling across lipid bilayers. More elaborated systems step by step incorporate more elements of cell signaling, such as primary and secondary messenger or a useful cellular response such as cargo release. 相似文献
4.
Dr. Jianming Dong Zhiqing Xun Dr. Yi Zeng Dr. Tianjun Yu Dr. Yongbin Han Dr. Jinping Chen Dr. Ying‐Ying Li Prof. Dr. Guoqiang Yang Prof. Dr. Yi Li 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(24):7931-7936
A small amphiphile that contains a coumarin unit and alkynyl groups, as a two‐photon‐cleavable segment and polymerizable groups, respectively, was designed and synthesized. The amphiphile showed a critical aggregation concentration of about 4.6×10?5 M and formed a vesicle‐type assembly. The formed vesicles were stabilized by in situ “click” polymerization without altering their morphology. Hydrophobic and hydrophilic guests can be encapsulated within the vesicle membrane and inside the aqueous core of the vesicle, respectively. The loaded guests can be released from the vesicle by using UV or near‐IR stimuli, through splitting up the amphiphilic structure of the amphiphile. Distinguished dose‐controlled photorelease of the polymeric vesicle is achieved with the maintenance of vesicular integrity, which makes the guest release dependent on the amount of cleavage of the amphiphilic structure during irradiation. This study provides a potential strategy for the development of versatile and stable drug‐delivery systems that offer sustained and photo‐triggered release. 相似文献
5.
Dr. Pengpeng Cao Dr. Oleg Khorev Dr. André Devaux Lucie Sägesser Dr. Andreas Kunzmann Prof. Achim Ecker Prof. Robert Häner Dr. Dominik Brühwiler Prof. Gion Calzaferri Prof. Peter Belser 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(12):4046-4060
Sequential insertion of different dyes into the 1D channels of zeolite L (ZL) leads to supramolecular sandwich structures and allows the formation of sophisticated antenna composites for light harvesting, transport, and trapping. The synthesis and properties of dye molecules, host materials, composites, and composites embedded in polymer matrices, including two‐ and three‐color antenna systems, are described. Perylene diimide (PDI) dyes are an important class of chromophores and are of great interest for the synthesis of artificial antenna systems. They are especially well suited to advancing our understanding of the structure–transport relationship in ZL because their core fits tightly through the 12‐ring channel opening. The substituents at both ends of the PDIs can be varied to a large extent without influencing their electronic absorption and fluorescence spectra. The intercalation/insertion of 17 PDIs, 2 terrylenes, and 1 quaterrylene into ZL are compared and their interactions with the inner surface of the ZL nanochannels discussed. ZL crystals of about 500 nm in size have been used because they meet the criteria that must be respected for the preparation of antenna composites for light harvesting, transport, and trapping. The photostability of dyes is considerably improved by inserting them into the ZL channels because the guests are protected by being confined. Plugging the channel entrances, so that the guests cannot escape into the environment is a prerequisite for achieving long‐term stability of composites embedded in an organic matrix. Successful methods to achieve this goal are described. Finally, the embedding of dye–ZL composites in polymer matrices, while maintaining optical transparency, is reported. These results facilitate the rational design of advanced dye–zeolite composite materials and provide powerful tools for further developing and understanding artificial antenna systems, which are among the most fascinating subjects of current photochemistry and photophysics. 相似文献
6.
Young‐Hwan Jeong Minjung Son Hongsik Yoon Pyosang Kim Do‐Hyung Lee Prof. Dongho Kim Prof. Woo‐Dong Jang 《Angewandte Chemie (International ed. in English)》2014,53(27):6925-6928
An artificial light‐harvesting multiporphyrin dendrimer ( 8PZnPFB ) composed of a focal freebase porphyrin ( PFB ) with eight zinc(II) porphyrin ( PZn ) wings exhibited unique photophysical property switching in response to specific guest molecule binding. UV/Vis titration studies indicated stable 1:2 host–guest complex formation between 8PZnPFB and meso‐tetrakis(4‐pyridyl)‐porphyrin ( TPyP ) for which the first and second association constants were estimated to be >108 M ?1 and 3.0×107 M ?1, respectively. 8PZnPFB originally shows 94 % energy transfer efficiency from PZn to the focal PFB . By the formation of the host–guest complex ( 8PZnPFB? 2 TPyP ) the emission intensity of 8PZnPFB is significantly decreased, and an ultrafast charge separation state is generated. The energy transfer process from PZn wings to the PFB core in 8PZnPFB is almost entirely switched to an electron transfer process by the formation of 8PZnPFB? 2 TPyP . 相似文献
7.
Ujjal Haldar Biswajit Saha Venkanna Azmeera Priyadarsi De 《Journal of polymer science. Part A, Polymer chemistry》2016,54(22):3643-3651
In this report, we have synthesized organic/inorganic hybrid peptide–poly(?‐caprolactone) (PCL) conjugates via ring opening polymerization (ROP) of ?‐caprolactone (CL) in the presence of two sequence defined peptide initiators, namely POSS‐Leu‐Aib‐Leu‐NH2 (POSS: polyhedral oligomeric silsesquioxane; Leu: Leucine; Aib: α‐aminoisobutyric acid) and OMe‐Leu‐Aib‐Leu‐NH2. Covalent attachment of peptide segments with the PCLs were examined by 1H and 29Si NMR spectroscopy, matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry (MALDI‐TOF‐MS) and FTIR spectroscopy. Supramolecular inclusion complexations of synthesized peptide‐PCL conjugates with α‐cyclodextrin (α‐CyD) were studied to understand the effect of POSS/OMe‐peptide moieties at the PCL chain ends. Inclusion complexation of peptide‐PCL conjugates with α‐CyD produced linear polypseudorotaxane, confirmed by 1H NMR, FTIR, powder X‐ray diffraction (PXRD), polarized optical microscopy (POM) and differential scanning calorimetry (DSC). Extent of α‐CyD threading onto the hybrid peptide‐PCL conjugated polymers is less than that of α‐CyD threaded onto the linear PCL. Thus, PCL chains were not fully covered by the host α‐CyD molecules due to the bulky POSS/OMe‐peptide moieties connected with the one edge of the PCL chains. PXRD experiment reveals channel like structures by the synthesized inclusion complexes (ICs). Spherulitic morphologies of POSS/OMe‐peptide‐PCL conjugates were fully destroyed after inclusion complexation with α‐CyD and tiny nanoobjects were produced. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3643–3651. 相似文献
8.
Controlled Dynamic Helicity of a Folded Macrocycle Based on a Bisterephthalamide with a Twofold Z‐Shaped Structure 下载免费PDF全文
Dr. Ryo Katoono Keiichi Kusaka Prof. Dr. Kenshu Fujiwara Prof. Dr. Takanori Suzuki 《化学:亚洲杂志》2014,9(11):3182-3187
Dynamic helicity in a folded macrocycle and control of the helical preference are described. We designed macrocycle 1 with a dual mode of folding through the integration of two flexible units that are arranged twice to form a cyclic structure. As a folding unit, we used a terephthalamide skeleton and a Z‐shaped hydrocarbon: the former acted as a control unit to induce a preference of a particular sense of dynamic helicity and the latter was just a spacer. A terephthalamide unit provided a binding site for capturing a ditopic hydrogen‐bonding guest when it adopted helically folded syn forms (M/P). Thus, only the terephthalamide unit controlled the helical sense of dynamic helicity in a folded macrocycle through the supramolecular transmission of chirality upon complexation with a chiral ditopic guest. In addition, chirality on a host could also contribute to the control of the helical preference in a folded macrocycle, which led to exceptionally enhanced chiroptical signals. 相似文献
9.
Leigh F. Jones Dr. Colin A. Kilner Malcolm A. Halcrow Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(18):4667-4675
Two bowl‐shaped cavities , each having three OH? hydrogen‐bond donors at its base, are present in double‐cone‐shaped metallacrown anion host [Co6(μ‐OH)6(μ‐L)6]m+ ( 1 m + ; HL=3{5}‐(pyrid‐2‐yl)‐5{3}‐(tert‐butyl)pyrazole). Depending on its affinity for the anions present, it can be isolated in its CoIII3CoII3 (m=3; e.g., 1 (ClO4)3) and CoIII2CoII4 (m=2; e.g., 1 (BF4)2 ? n H2O) oxidation states. See picture for photographs of isolated salts.
10.
Rotaxanes Capped with Host Molecules: Supramolecular Behavior of Adamantylated Bisimidazolium Salts Containing a Biphenyl Centerpiece 下载免费PDF全文
Petra Branná Dr. Michal Rouchal Dr. Zdeňka Prucková Dr. Lenka Dastychová Dr. René Lenobel Dr. Tomáš Pospíšil Dr. Kamil Maláč Dr. Robert Vícha 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(33):11712-11718
Bisimidazolium salts with one central biphenyl binding site and two terminal adamantyl binding sites form water‐soluble binary or ternary aggregates with cucurbit[7]uril (CB7) and β‐cyclodextrin (β‐CD) with rotaxane and pseudorotaxane architectures. The observed arrangements result from cooperation of the supramolecular stopper binding strength and steric barriers against free slippage of the CB7 and β‐CD host molecules over the bisimidazolium guest axle. 相似文献
11.
Dr. Marek Komisarski Dr. Yazmin M. Osornio Prof. Jay S. Siegel Prof. Ehud M. Landau 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(4):1262-1267
A classical conundrum in origin‐of‐life studies relates to the nature of the first chemical system: was it a carrier of genetic information or a facilitator of cellular compartmentalization? Here we present a system composed of tailor‐made nucleolipids and hydrated monoolein, which assemble at ambient temperatures to form host–guest lipidic cubic phase (LCP) materials that are stable in bulk water and can perform both functions. As such, they may represent a molecular model for a protocell in origin‐of‐life studies. Nucleolipids within the lipidic material sequester and bind selectively complementary oligonucleotide sequences from solution by virtue of base‐pairing; noncomplementary sequences diffuse freely between the LCP material and the bulk aqueous environment. Sequence specific enrichment of nucleic acids within the LCP material demonstrates an effective mechanism for selection of genetic material in these cell‐mimetic systems. 相似文献
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Zaizai Tong Junyi Zhou Runsheng Huang Jie Zhou Runke Zhang Wangqian Zhuo Guohua Jiang 《Journal of polymer science. Part A, Polymer chemistry》2017,55(15):2477-2482
Dual photo‐ and pH‐responsive polymeric vesicles are constructed from a host–guest complex between a water‐soluble pillar[6]arene and an azobenzene ended functionalized poly(ε‐caprolactone). Reversible morphological transitions between vesicles and solid aggregates are achieved upon repeated UV stimulus and pH stimulus. Moreover, the polymeric vesicles present excellent cytocompatibility toward HepG2 cells and can be further applied for controlled release of a hydrophilic model drug, DOX?HCl. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 2477–2482 相似文献
13.
Vitor Francisco Dr. Angel Piñeiro Prof. Dr. Werner M. Nau Prof. Dr. Luis García‐Río 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(52):17809-17820
A microcalorimetric study on the inclusion of monovalent and divalent metal cations by p‐sulfonatocalix[4]arene was performed. The thermodynamic parameters for the complexation of alkali metal cations and Ag+ were obtained for the first time at neutral pH. The Na+ cation is routinely present as counterion of the calixarene in neutral aqueous solution, and this must be taken into account in the determination of the thermodynamic parameters for the complexation of Na+ and the other cations by considering a sequential or a competitive binding scheme. The ΔH° and ΔS° values show that the inclusion process is entropically driven, although an influence of the temperature on the complexation reaction indicates that the enthalpic term is also an important contributor. The results also reveal that enthalpy/entropy compensation balances the gain in one contribution against a corresponding loss in the other. The obtained thermodynamic data are in contrast to the results from previous microcalorimetric studies, which showed binding constants that were orders of magnitude smaller and complexations, which were in part enthalpically driven but which neglected the influence of the alkali metal counterions. 相似文献
14.
Francesca Tancini Dr. Thomas Gottschalk Dr. W. Bernd Schweizer Dr. François Diederich Prof. Dr. Enrico Dalcanale Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(26):7813-7819
The capability of resorcinarenes to bind anions within the alkyl feet at the lower rim has been exploited as the starting point for developing a new cavitand able to engulf contact ion pairs of primary ammonium salts in chlorinated solvents with association constants (Kass) in the range of 103–104 M ?1. Methylene bridges were introduced into the upper rim to freeze the resorcinarene in the cone conformation with the four Hdown protons converging in the lower pocket, thereby maximizing the CH–anion interactions responsible for the anion binding. Four additional phosphate moieties were introduced into the lower rim in close proximity to the anionic site to provide hydrogen‐bonding‐acceptor P?O groups and promote cation complexation at the bottom of the cavitand. The binding ability of the synthesized ligands was analyzed by 1H NMR spectroscopy and, when possible, by isothermal titration calorimetry (ITC); the data were in agreement when complementary techniques were used. 相似文献
15.
Sebastian Köhling Georg Künze Katharina Lemmnitzer Dr. Marcel Bermudez Prof. Dr. Gerhard Wolber Dr. Jürgen Schiller Prof. Dr. Daniel Huster Prof. Dr. Jörg Rademann 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(16):5563-5574
Implants and artificial biomaterials containing sulfated hyaluronans have been shown to improve the healing of injured skin and bones. It is hypothesized that these effects are mediated by the binding of sulfated glycosaminoglycans (GAGs) to growth factors and cytokines, resulting in the sequestering of proteins to the wound healing site and in modulated protein activity. Given that no direct synthetic access to sulfated oligohyaluronans has been available, little is known about their protein binding and the structure of the resulting protein complexes. Here, the chemoenzymatic preparation of oligohyaluronans on the gram scale is described. Oligohyaluronans are converted into anomeric azides at the reducing end, enabling the attachment of analytical labels through an anomeric ligation reaction. A nonasulfated tetrahyaluronan–ethylenediaminetetraacetic acid derivative has been produced and used as a paramagnetic tag for the elucidation of the complex of this ligand with interleukin‐10 using paramagnetic relaxation enhancement NMR analysis. The metal ion position is resolved with 1.0 Å, enabling a refined structural model of the complex. 相似文献
16.
Frontispiece: Rotaxanes Capped with Host Molecules: Supramolecular Behavior of Adamantylated Bisimidazolium Salts Containing a Biphenyl Centerpiece 下载免费PDF全文
Petra Branná Dr. Michal Rouchal Dr. Zdeňka Prucková Dr. Lenka Dastychová Dr. René Lenobel Dr. Tomáš Pospíšil Dr. Kamil Maláč Dr. Robert Vícha 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(33)
17.
Léna Sambe Victor R. de La Rosa Khaled Belal Dr. François Stoffelbach Dr. Joel Lyskawa Dr. François Delattre Marc Bria Prof. Graeme Cooke Prof. Richard Hoogenboom Prof. Patrice Woisel 《Angewandte Chemie (International ed. in English)》2014,53(20):5044-5048
A new class of polymeric thermometers with a memory function is reported that is based on the supramolecular host–guest interactions of poly(N‐isopropylacrylamide) (PNIPAM) with side‐chain naphthalene guest moieties and the tetracationic macrocycle cyclobis(paraquat‐p‐phenylene) (CBPQT4+) as the host. This supramolecular thermometer exhibits a memory function for the thermal history of the solution, which arises from the large hysteresis of the thermoresponsive LCST phase transition (LCST=lower critical solution temperature). This hysteresis is based on the formation of a metastable soluble state that consists of the PNIPAM–CBPQT4+ host–guest complex. When heated above the transition temperature, the polymer collapses, and the host–guest interactions are disrupted, making the polymer more hydrophobic and less soluble in water. Aside from providing fundamental insights into the kinetic control of supramolecular assemblies, the developed thermometer with a memory function might find use in applications spanning the physical and biological sciences. 相似文献
18.
Dr. Nicolas Menard Prof. Dr. Olivia Reinaud Dr. Benoit Colasson 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(2):642-653
A biomimetic strategy for the monofunctionalization of a calix[6]arene core is described. It is based on host–guest chemistry (mimicking the Michaelis–Menten adduct in enzymes) and allows the finely tuned pre‐organization of the substrate (an alkyne) with respect to the reactant (three azido groups introduced at the calixarene large rim). It is shown that the thermal Huisgen reaction implemented in this work proceeds under very mild conditions with total regioselectivity of the cycloaddition process. The scope of the reaction was explored and the results suggest that such a supramolecular strategy is quite versatile and could be applied to the selective functionalization of other cavitands bearing different recognition patterns. A detailed structural, thermodynamic, and kinetic study is also reported, highlighting interesting biomimetic features: The importance of the host–guest adduct strength, the high sensitivity of the reaction to the pre‐organization of the reactive partners (alkyne vs. azide), and a significant impact of the embedment on the transition state. The self‐coordination of the monofunctionalized products was also studied and an “endo/exo” switch of the internal side‐chain could be triggered by adding competitive ligands. 相似文献
19.
Host–Guest Chemistry of a Bis‐Calix[4]pyrrole Derivative Containing a trans/cis‐Switchable Azobenzene Unit with Several Aliphatic Bis‐Carboxylates 下载免费PDF全文
Grazia Cafeo Franz H. Kohnke Giovanni Mezzatesta Aldo Profumo Camillo Rosano Antonino Villari Andrew J. P. White 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(14):5323-5327
The azobenzene unit used as a photochemically and thermally switchable linker in the assembly of a bis‐calix[4]pyrrole receptor provides a means to modulate the binding of bis‐carboxylates of significant biological importance in cancer research. Conversely, the complexation of different bis‐anionic guests has significant kinetic effects on both the photochemical and thermal trans/cis isomerization of the azobenzene unit. 相似文献
20.
Pd Uptake and H2S Sensing by an Amphoteric Metal–Organic Framework with a Soft Core and Rigid Side Arms 下载免费PDF全文
Jieshun Cui Yan‐Lung Wong Dr. Matthias Zeller Dr. Allen D. Hunter Dr. Zhengtao Xu 《Angewandte Chemie (International ed. in English)》2014,53(52):14438-14442
Molecular components of opposite character are often incorporated within a single system, with a rigid core and flexible side arms being a common design choice. Herein, molecule L has been designed and prepared featuring the reverse design, with rigid side arms (arylalkynyl) serving to calibrate the mobility of the flexible polyether links in the core. Crystallization of this molecule with PbII ions led to a dynamic metal–organic framework (MOF) system that not only exhibits dramatic, reversible single‐crystal‐to‐single‐crystal transformations, but combines distinct donor and acceptor characteristics, allowing for substantial uptake of PdCl2 and colorimetric sensing of H2S in water. 相似文献