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991.
LC-NMR coupling technology: recent advancements and applications in natural products analysis 总被引:4,自引:0,他引:4
Exarchou V Krucker M van Beek TA Vervoort J Gerothanassis IP Albert K 《Magnetic resonance in chemistry : MRC》2005,43(9):681-687
An overview of recent advances in nuclear magnetic resonance (NMR) coupled with separation technologies and their application in natural product analysis is given and discussed. The different modes of LC-NMR operation are described, as well as how technical improvements assist in establishing LC-NMR as an important tool in the analysis of plant-derived compounds. On-flow, stopped-flow and loop-storage procedures are mentioned, together with the new LC-SPE-NMR configuration. The implementation of mass spectrometry in LC-NMR is also useful on account of the molecular weight and fragmentation information that it provides, especially when new plant species are studied. Cryogenic technology and capillary LC-NMR are the other important recent developments. Since the plant kingdom is endless in producing potential drug candidates, development and optimization of LC-NMR techniques convert the study of natural products to a less-time-consuming task, speeding up identification. 相似文献
992.
Pittelkow M Nielsen CB Broeren MA van Dongen JL van Genderen MH Meijer EW Christensen JB 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(17):5126-5135
Host-guest interactions between the periphery of adamantylurea-functionalized dendrimers (host) and ureido acetic acid derivatives (guest) were shown to be specific, strong and spatially well-defined. The binding becomes stronger when using phosphonic or sulfonic acid derivatives. In the present work we have quantified the binding constants for the host-guest interactions between two different host motifs and six different guest molecules. The host molecules, which resemble the periphery of a poly(propylene imine) dendrimer, have been fitted with an anthracene-based fluorescent probe. The two host motifs differ in terms of the length of the spacer between a tertiary amine and two ureido functionalities. The guest molecules all contain an acidic moiety (either a carboxylic acid, a phosphonic acid, or a sulfonic acid) and three of them also contain an ureido moiety capable of forming multiple hydrogen bonds to the hosts. The binding constants for all 12 host-guest complexes have been determined by using fluorescence titrations by monitoring the increase in fluorescence of the host upon protonation by the addition of the guest. The binding constants could be tuned by changing the design of the acidic part of the guest. The formation of hydrogen bonds gives, in all cases, higher association constants, demonstrating that the host is more than a proton sensor. The host with the longer spacer (propyl) shows higher association constants than the host with the shorter spacer (ethyl). The gain in association constants are higher when the urea function is added to the guests for the host with the longer spacer, indicating a better fit. Collision-induced dissociation mass spectrometry (CID-MS) is used to study the stability of the six motifs using the corresponding third generation dendrimer. A similar trend is found when the six different guests are compared. 相似文献
993.
May JP Brown LJ van Delft I Thelwell N Harley K Brown T 《Organic & biomolecular chemistry》2005,3(14):2534-2542
A non-fluorescent quencher, based on the diaminoanthraquinone Disperse Blue 3, has been incorporated into oligonucleotides at the 5'-end, the 3'-end and internally as a thymidine derivative. Fluorimetry and fluorogenic real-time PCR experiments demonstrate that the quencher is effective with a wide range of fluorescent dyes. The anthraquinone moiety increases the melting temperature of DNA duplexes, thus allowing shorter, more discriminatory probes to be used. The quencher has been used in Scorpion primers and TaqMan probes for human DNA sequence recognition and mutation detection. 相似文献
994.
Vallée RA Marsal P Braeken E Habuchi S De Schryver FC Van der Auweraer M Beljonne D Hofkens J 《Journal of the American Chemical Society》2005,127(34):12011-12020
Experimental (Single Molecule Spectroscopy) and theoretical (quantum-chemical calculations and Monte Carlo and molecular dynamics simulations) techniques are combined to investigate the behavior and dynamics of a polymer-dye molecule system. It is shown that the dye molecule of interest (1,1'-dioctadecyl-3,3,3',3'-tetramethylindo-dicarbocyanine) adopts two classes of conformations, namely planar and nonplanar ones, when embedded in a poly(styrene) matrix. From an in-depth analysis of the fluorescence lifetime trajectories, the planar conformers can be further classified according to the way their alkyl side chains interact with the surrounding poly(styrene) chains. 相似文献
995.
Pinheiro JP Minor M van Leeuwen HP 《Langmuir : the ACS journal of surfaces and colloids》2005,21(19):8635-8642
In this work we propose a dynamic metal speciation theory for colloidal systems in which the complexing ligands are localized on the surface of the particles; i.e., there is spatial heterogeneity of binding sites within the sample volume. The differences between the complex formation and dissociation rate constants of complexes in colloidal dispersions and those in homogeneous solutions originate from the differences in kinetic and mass transport conditions. In colloidal systems, when the effective rate of dissociation of the surface complexes becomes fully diffusion controlled, its value is defined via the geometrical parameters of the particle. We assess the extent to which the conventional approach of assuming a homogeneously smeared-out ligand distribution overestimates the lability of surface complexes in colloidal ligand dispersions. The validity of the theory is illustrated by application to binding of lead and cadmium by carboxyl modified latex particles: our approach correctly predicts the formation/dissociation rate constants, which differ by several orders of magnitude from their homogeneous solution counterparts. 相似文献
996.
El Oualid F van den Elst H Leroy IM Pieterman E Cohen LH Burm BE Overkleeft HS van der Marel GA Overhand M 《Journal of combinatorial chemistry》2005,7(5):703-713
A combinatorial synthesis of oligopeptide analogues and their evaluation as protein:geranylgeranyl transferase inhibitors is presented. The combinatorial strategy is based on the random mutation, in each new generation, of one of any of the four amino acid building blocks of which the most effective compounds of the previous generation are assembled. In this way, a progressive improvement of the average inhibitory activity was observed until the fifth generation. The most active inhibitors were found to inhibit PGGT-1 in the low micromolar range (IC(50): 3.8-8.1 microM). 相似文献
997.
Time-resolved (TR) EPR was used to study the photophysics and photochemistry of 1-(3-(methoxycarbonyl)propyl)-1-phenyl[6.6]C61 (M1). The CW TREPR spectra of M1 in the photoexcited triplet state, frozen in a rigid matrix and in liquid solution at room temperature, were compared with those of 3C60. The introduction of the substituent on C60 has a striking effect on the spectra of the triplets, which is attributed to the lifting of the orbital degeneracy by the reduction in symmetry. Fourier transform (FT) EPR was used in an investigation of electron-transfer reactions in liquid solutions mediated by 3M1. Of particular interest was the system of M1/chloranil (CA)/perylene (Pe). Photoexcitation of M1 is found to lead to the formation of the chloranil anion radical and the perylene cation radical. From the chemically induced dynamic electron polarization (CIDEP) patterns in the FTEPR spectra and the dependence of the reaction kinetics on reactant concentrations, it was deduced that CA- is formed by two competing pathways following photoexcitation of M1: (1) direct electron transfer from 3M1 to CA followed by electron transfer from Pe to M1+ and (2) energy transfer from 3M1 to Pe followed by oxidative quenching of 3Pe by CA. In both pathways, M1 acts as a light-energy harvester and mediator of electron-transfer reactions from Pe to CA without itself being consumed in the process, that is, as a photocatalyst. It is found that the functionalization of C60 makes its triplet state a worse electron donor and acceptor, but it has no significant effect on the triplet energy transfer reaction. 相似文献
998.
Kasper P. van der Zwan Christoph Steinlein Dr. Klaus Kreger Prof. Dr. Hans-Werner Schmidt Prof. Dr. Jürgen Senker 《Chemphyschem》2021,22(24):2585-2593
Benzene bisamides are promising building blocks for supramolecular nano-objects. Their functionality depends on morphology and surface properties. However, a direct link between surface properties and molecular structure itself is missing for this material class. Here, we investigate this interplay for two series of 1,4-benzene bisamides with symmetric and asymmetric peripheral substitution. We elucidated the crystal structures, determined the nano-object morphologies and derived the wetting behaviour of the preferentially exposed surfaces. The crystal structures were solved by combining single-crystal and powder X-ray diffraction, solid-state NMR spectroscopy and computational modelling. Bulky side groups, here t-butyl groups, serve as a structure-directing motif into a packing pattern, which favours the formation of thin platelets. The use of slim peripheral groups on both sides, in our case linear perfluorinated, alkyl chains, self-assemble the benzene bisamides into a second packing pattern which leads to ribbon-like nano-objects. For both packing types, the preferentially exposed surfaces consist of the ends of the peripheral groups. Asymmetric substitution with bulky and slim groups leads to an ordered alternating arrangement of the groups exposed to the surface. This allows the hydrophobicity of the surfaces to be gradually altered. We thus identified two leitmotifs for molecular packings of benzene bisamides providing the missing link between the molecular structure, the anisotropic morphologies and adjustable surface properties of the supramolecular nano-objects. 相似文献
999.
Bas van Genabeek Brigitte A. G. Lamers Craig J. Hawker E. W. Meijer Will R. Gutekunst Bernhard V. K. J. Schmidt 《Journal of polymer science. Part A, Polymer chemistry》2021,59(5):373-403
Precise oligomeric materials constitute a growing area of research with implications for various applications as well as fundamental studies. Notably, this field of science which can be termed macro-organic chemistry, draws inspiration from both traditional polymer chemistry and organic synthesis, combining the molecular precision of organic chemistry with the materials properties of macromolecules. Discrete oligomers enable access to unprecedented materials properties, for example, in self-assembled structures, crystallization, or optical properties. The degree of control over oligomer structures resembles many biological systems and enables the design of materials with tailored properties and the development of fundamental structure–property relationships. This Review highlights recent developments in macro-organic chemistry from synthetic concepts to materials properties, with a focus on self-assembly and molecular recognition. Finally, an outlook for future research directions is provided. 相似文献
1000.
Pascal L. W. Welzen Sydney W. Martinez Ciriano Shoupeng Cao Alexander F. Mason Imke A. B. Welzen-Pijpers Jan C. M. van Hest 《Journal of polymer science. Part A, Polymer chemistry》2021,59(12):1241-1252
Polymersomes have gained much interest within the biomedical field as drug delivery systems due to their ability to transport and protect cargo from the harsh environment inside the body. For an improved drug efficacy, control over cargo release is however also an important factor to take into account. An often employed method is to incorporate pH sensitive groups in the vesicle membrane, which induce disassembly and content release when the particles have reached a target site in the body with the appropriate pH, such as the acidic microenvironment of tumor tissue or the endosome. In this paper, biodegradable poly(ethylene glycol)-poly(caprolactone-gradient-trimethylene carbonate)-based polymeric vesicles have been developed with disassembly features at mild acidic conditions. Modifying the polymer backbone with imidazole moieties results in vesicle disassembly upon protonation due to the lowered pH. Furthermore, upon increasing the pH efficient re-assembly into vesicles is observed due to the switchable amphiphilic nature of the polymer. When this re-assembly process is conducted in presence of cargo, enhanced encapsulation is achieved. Furthermore, the potency of the polymeric system for future biomedical applications such as adjuvant delivery is demonstrated. 相似文献