DOCSLIB.ORG

Separation of Enantiomers with Chiral Dendrimer

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Separation of Enantiomers with Chiral Dendrimer Western Michigan University ScholarWorks at WMU Master's Theses Graduate College 4-2002 Separation of Enantiomers with Chiral Dendrimer Jie Zhuang Follow this and additional works at: https://scholarworks.wmich.edu/masters_theses Part of the Chemistry Commons Recommended Citation Zhuang, Jie, "Separation of Enantiomers with Chiral Dendrimer" (2002). Master's Theses. 4336. https://scholarworks.wmich.edu/masters_theses/4336 This Masters Thesis-Open Access is brought to you for free and open access by the Graduate College at ScholarWorks at WMU. It has been accepted for inclusion in Master's Theses by an authorized administrator of ScholarWorks at WMU. For more information, please contact [email protected]. SEPARATION OF ENANTIOMERS WITH CHIRAL DENDRIMER by Jie Zhuang A Thesis Submitted to the Faculty of The Graduate College in partial fulfillment of the requirements for the Degree of Master of Science Department of Chemistry Western Michigan University Kalamazoo, Michigan April 2002 Copyright by Jie Zhuang 2002 ACKNOWLEDGMENTS First of all, I would like to thank my research advisor Dr. Subra Muralidharan for his precious and consistent encouragement, - assistance, guidance and support throughout the whole project. Secondly, I would like to thank my research committee, Dr. Marc W. Perkovic and Dr. Elke Schoffers. They have offered me great help during my research project and for accomplishment of my program. Thirdly, I would like to thank the PG Foundation for supporting the project. I am also very grateful to everybody who has helped me in various ways to complete research project. Finally, I would like to thank my family for their understanding, support and love. Jie Zhuang 11 SEPARATION OF ENATIOMERS WITH CHIRAL DENDRIMER Jie Zhuang, M.S. Western Michigan University, 2002 Chiral dendrimers with .unique ordered structures are especially attractive for the recognition of chiral molecules based on the three point contact model. We have successfully synthesized first generation chiral dendrimers containing L- and D­ tryptophan methyl ester moieties and characterized them by NMR, IR, UV-Visible, MS, and optical activity. L-tryptophan methyl ester dendrimer was converted to its acid form in order to attach it to aminopropyl silica for the HPLC separation of enantiomers. The aminopropyl silica containing l.52mrnols/g of NH2 groups binds about 0.3mrnols of dendrimer per gram and has about 0.4mrnols of free NH2 groups per gram. Significant differences were observed in the retention times of the enantiomers of propranolol, 1-phenyl-1-propanol, 2-phenyl-1-propanol under a variety of _mobile phase compositions. Mixtures of enantiomers could not be separated with the current column due to nonspecific interactions with free NH2 groups which resulted in poor efficiencies. However the stereoisomers 1-phenyl-1-propanol and 2- phenyl-1-propanol could be separated with much higher selectivities than with an ODS column. The present study has provided valuable fundamental information on the chiral recognition efficacy and mechanism of L-tryptophan dendrimer. TABLE OF CONTENTS ACKNOWLEDGMENTS...................................................................................... 11 LIST OF TABLES ·················································--··············································· V LIST OF FIGURES .................................................................···················............ VI INTRODUCTION.................................................................................................. 1 Stereochemistry.......................................................................................... ,.. 3 Chiral Sep!iration.............................. ..................................... ........................ 6 High Performance Liquid Chromatography (HPLC)........... ....... .. .... ............ 9 Chiral Dendrimer........................................................................................... 14 CHIRAL SEPARATION MECHANISM.............................................................. 18 OBJECTIVES ..... ,.................................................................................................. 22 EXPERIMENTS AND RESULTS ................................................................ ........ 25 Reagents .. ....... .. .. ..... .................................................. ..... ....... ......... .... ... ... ..... 25 Characterization of Compounds and Instrumentation................................... 25 Synthesis of First Generation L-Tryptphan Methyl Ester Dendrimer ........... 26 Synthesis of L-Tryptophan Dendrimer.......................................................... 33 Synthesis of Silica Immobilized L-Trytophan Dendrimer ............................ 37 Titrations ....................................................................................................... 40 Titration of NH2-Silica......................................................................... 40 Titration of L-Tryptophan Dendrimer Silica........................................ 45 Column Packing............................................................................................ 49 l1l Table of Contents-continued Choice of Enantiomer for Chiral Separation by L-Tryptophan Dendrimer Column ........................................................................................................ 51 Evaluation of the L-Tryptophan Dendrimer Stationary Phase...................... 53 Characterization as a Reverse Phase ...... :............................................. 53 Characterization as a Normal Phase..................................................... 59 Investigation of Other Enantiomeric Pairs.................................................... 66 DISCUSSION ...... ..... ..... ............................. ................................................. .......... 69 Synthesis of L-Tryptophan Dendrimer Methyl Ester, L-Tryptophan Dendrimer and Silica Immobilized With L-Tryptophan Dendrimer............. 69 UV-Visible Studies....................................................................................... 70 Separation With Polar Mobile Phase............................................................ 71 Separation With Nonpolar Mobile Phase...................................................... 73 Separation of R-l-Phenyl-1-Propanol and R-2-Phenyl-1-Propanol.............. 75 CONCLUSIONS AND SUGGESTIONS...... ............................. ................ .. ......... 77 REFERENCES....................................................................................................... 79 IV LIST OF TA BLES 1. Specific Rotations of Tryptophans and Their Dendrimers............................ 34 2. 1H NMR Chemical Shifts for L-Tryptophan Methyl Ester, L­ Tryptophan Mehtyl Ester Dendrimer and L-Tryptophan Dendrimer From Figure 12, 13, 18.................................................................................. 36 3. ElementalAnalysis of Aminopropyl and L-Tryptophan Silica..................... 39 4. IR Spectral Data for L-TryptophanMethyl Ester, L-TryptophanMehtyl Ester Dendrimer and L-Tryptophan Dendrimer Silica.................................. 43 5. Retention Times for R- and S-Propranolol at Different ACN- H20 Mixtures........................................................................................................ 54 6. Separation of R- and S-Propranolol With 95%ACN+5% Acetate Buffer at Different pH Values.................................................................................. 56 7. Separation of R- and S-Propranolol With 95%ACN+5% Succinate Buffer at Different pH Values - First Run.................................................... 57 8. Separation of R- and S-Propranolol With 95%ACN+5% Succinate Bufferof Different Ionic Strengths (0.01, 0.005 , 0.033) at pH 3.5 ............... 57 9. Separation of R- and S-Propranolol With 95%ACN+5% Succinate Bufferat Different pH Values - Second Run................................................ 58 10. Retention Times of R- and S-Propranolol Separation With 90% Hexane+10%2-Propanol Mobile Phase With Different Concentrations of Triethylamine................................................................... 63 11. Separation of R- and S-Propranolol With Hexane+ 2-Propanol Mixtures Containing 0.05M Triethylamine.................................................................. 65 12. Separation of R-1 -Phenyl-l-Propanol and R-2 -Phenyl-1 -Propanol With C1 s Column Under Reverse Phase System.................................................... 67 V LIST OF FIGURES 1. Enantiomers of Thalidomide......................................................................... 2 2. The Basic Polarimeter ..................................... :............................................. 5 3. Configurationof a-Amino Acids.................................................................. 6 4. Diagrammatic Representation of a Stationary Phase Containing an Immobilized Enantio-enriched Selector Molecule........................................ 9 5. Block Diagram Showing the Components of HPLC..................................... 10 6. Schematic Chromatogram for Zone Separation ............................................ 13 7. Two Commercially Available Dendrimer Families...................................... 15 8. A Chiral Recognition Model......................................................................... 19 9. Structure of First Generation of Tryptophan Methyl Ester Dendrimer ......... 23 10. Interaction Sites in Tryptophan Methyl Ester
Load more

Recommended publications
  • Organization of Hybrid Dendrimer-Inorganic Nanoparticles on Amphiphilic Surfaces
    4852 Macromolecules 2002, 35, 4852-4854 Organization of Hybrid Dendrimer-Inorganic Nanoparticles on Amphiphilic Surfaces Franziska Gro1hn,‡ Xiaohong Gu,† Holger Gru1 ll,§ J. Carson Meredith,⊥ Giovanni Nisato,§ Barry J. Bauer, Alamgir Karim,* and Eric J. Amis* Polymers Division and Building Materials Division, National Institute of Standards and Technology, Gaithersburg, Maryland 20899 Received October 16, 2001 Figure 1. Dendrimer-nanocluster building block: the G8 Introduction. Multiple length scale structuring of PAMAM dendrimers of 11 nm diameter include gold colloids organic-inorganic composites is a powerful technique of 3.2 nm diameter. Shown is a TEM micrograph in which the for the creation of materials and devices. Because of (stained) dendrimer appears gray and the gold appears black as well as a cartoon of the structure derived from TEM, SAXS, quantum size effects, nanoscale inorganic structures can and SANS. For details see ref 16. show special electronic, optical, optoelectronic, and magnetic behavior.1,2 To take advantage of these unique crometer length scale features. In addition to the properties, one has to be able to design such nanostruc- potential for building mesoscale materials, we also tures in a controlled manner and to organize the address the application of these stable nanoparticle nanoparticles on larger length scales. The design of components as markers for chemical and physical materials structured on multiple length scales from the labeling of other mesostructures. molecular to the macroscopic level has recently come Self-Assembly on Self-Assembled Monolayer Sub- into focus as modular chemistry. As with the develop- strates. We study the deposition of gold-containing ment of any new materials, a parallel requirement is dendrimers on stripe-patterned self-assembled mono- the need for appropriate measurement methods to layer (SAM) substrates.
    [Show full text]
  • Multiscale Modeling for Host-Guest Chemistry of Dendrimers in Solution
    Polymers 2012, 4, 463-485; doi:10.3390/polym4010463 OPEN ACCESS polymers ISSN 2073-4360 www.mdpi.com/journal/polymers Review Multiscale Modeling for Host-Guest Chemistry of Dendrimers in Solution Seung Ha Kim and Monica H. Lamm ? Department of Chemical and Biological Engineering, Iowa State University, Ames, IA 50011, USA ? Author to whom correspondence should be addressed; E-Mail: [email protected]; Tel.: 515-294-6533; Fax: 515-294-2689. Received: 15 December 2011; in revised form: 31 January 2012 / Accepted: 6 February 2012 / Published: 10 February 2012 Abstract: Dendrimers have been widely used as nanostructured carriers for guest species in a variety of applications in medicine, catalysis, and environmental remediation. Theory and simulation methods are an important complement to experimental approaches that are designed to develop a fundamental understanding about how dendrimers interact with guest molecules. This review focuses on computational studies aimed at providing a better understanding of the relevant physicochemical parameters at play in the binding and release mechanisms between polyamidoamine (PAMAM) dendrimers and guest species. We highlight recent contributions that model supramolecular dendrimer-guest complexes over the temporal and spatial scales spanned by simulation methods ranging from all-atom molecular dynamics to statistical field theory. The role of solvent effects on dendrimer-guest interactions and the importance of relating model parameters across multiple scales is discussed. Keywords: multiscale modeling; dendrimer simulations; host-guest chemistry 1. Introduction Dendrimers have received increasing attention over the past several decades as attractive candidate materials for a variety of applications such as therapeutic delivery systems [1–5], imaging agents [4,6,7], templates for catalytic metal nanoparticles [8–10], and extraction agents for the removal of organic pollutants and toxic metals from water and soil [11–14].
    [Show full text]
  • Characterization of Poly(Amidoamine) Dendrimers and Their Complexes with Cu2+ by Matrix-Assisted Laser Desorption Ionization Mass Spectrometry
    Macromolecules 2001, 34, 3567-3573 3567 Characterization of Poly(amidoamine) Dendrimers and Their Complexes with Cu2+ by Matrix-Assisted Laser Desorption Ionization Mass Spectrometry Li Zhou, David H. Russell,* Mingqi Zhao, and Richard M. Crooks* Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station, Texas 77842-3012 Received October 16, 2000; Revised Manuscript Received February 20, 2001 ABSTRACT: Hydroxyl-terminated poly(amidoamine) (PAMAM) dendrimers of generation 2-4(Gn-OH, 2+ n ) 2, 3, and 4; Mr ∼ 3.7, 6.9, and 14.3 kDa, respectively) and dendrimers encapsulating Cu ions have been investigated by matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry. Umbelliferone (7-hydroxycoumarin) and 2′,4′,6′-trihydroxyacetophenone (THAP) were used as the matrices for dendrimers with and without Cu2+ in the interior. The MALDI-TOF results provide accurate molecular weight determinations of all dendrimers and some multiple copper complexes of G2- OH and G3-OH (accuracy <0.01%). More importantly, this approach provides direct characterization of multiple-cation adducts and quantitative evaluation of the complexing capacity of dendrimers hosting transition-metal ions. The results are used to determine dendrimer structure and evaluate polydispersity. Introduction the relative concentrations of the dendrimer and metal ions, the size of the dendrimer, and the type of metal Here, we report a detailed analysis of hydroxyl- ion. Dendrimer encapsulation of metal ions is generally terminated poly(amidoamine) (PAMAM) dendrimers driven by a strong association between the ion and (Gn-OH) and their complexes with Cu2+ using matrix- intradendrimer tertiary amine groups. Chemical reduc- assisted laser desorption ionization time-of-flight (MAL- tion of dendrimer-encapsulated metal ions yields soluble DI-TOF) mass spectrometry (MS) and UV-vis spectros- dendrimer-encapsulated metal nanoparticles that usu- copy.
    [Show full text]
  • Dendpoint: a Web Resource for Dendrimer Pharmacokinetics Investigation and Prediction Lisa M
    www.nature.com/scientificreports OPEN dendPoint: a web resource for dendrimer pharmacokinetics investigation and prediction Lisa M. Kaminskas1,6*, Douglas E. V. Pires2,3,4,6 & David B. Ascher 3,4,5* Nanomedicine development currently sufers from a lack of efcient tools to predict pharmacokinetic behavior without relying upon testing in large numbers of animals, impacting success rates and development costs. This work presents dendPoint, the frst in silico model to predict the intravenous pharmacokinetics of dendrimers, a commonly explored drug vector, based on physicochemical properties. We have manually curated the largest relational database of dendrimer pharmacokinetic parameters and their structural/physicochemical properties. This was used to develop a machine learning-based model capable of accurately predicting pharmacokinetic parameters, including half- life, clearance, volume of distribution and dose recovered in the liver and urine. dendPoint successfully predicts dendrimer pharmacokinetic properties, achieving correlations of up to r = 0.83 and Q2 up to 0.68. dendPoint is freely available as a user-friendly web-service and database at http://biosig.unimelb. edu.au/dendpoint. This platform is ultimately expected to be used to guide dendrimer construct design and refnement prior to embarking on more time consuming and expensive in vivo testing. A lack of appropriate pharmacokinetic behavior has historically been one of the leading causes of drug failure in clinical trials1. Advances in controlled release technologies and nanomedicine, however, are increasingly pro- viding new opportunities to circumvent this shortcoming in rational drug development initiatives and are pro- viding renewed hope for old drug candidates. Importantly, a wide range of nanosized materials with a variety of chemico-biological traits that can be used to alter and drive the pharmaceutical behavior of loaded drugs (including colloids, nanoparticles and polymers) have been developed and explored for their potential as relatively biologically inert drug carriers.
    [Show full text]
  • Exploration of Biomedical Dendrimer Space Based on In-Vivo
    REVIEWS Drug Discovery Today Volume 24, Number 5 May 2019 Exploration of biomedical dendrimer Reviews space based on in-vivo POST SCREEN physicochemical parameters: Key factor analysis (Part 2) 1,2,3,4 2,5 3 6 Serge Mignani , João Rodrigues , René Roy , Xiangyang Shi , 7,8 9 4,10,11 Valentin Ceña , Saïd El Kazzouli and Jean-Pierre Majoral 1 Université Paris Descartes, PRES Sorbonne Paris Cité, CNRS UMR 860, Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologique, 45, rue des Saints Peres, 75006 Paris, France 2 CQM – Centro de Química da Madeira, MMRG, Universidade da Madeira, Campus da Penteada, 9020-105 Funchal, Portugal 3 Glycovax Pharma, 424 Guy Street, Suite 202, Montreal, Quebec H3J 1S6, Canada 4 Department of Pharmacy, Zhengzhou Railway Vocational & Technical College, Zhengzhou 450018, China 5 School of Materials Science and Engineering/Center for Nano Energy Materials, Northwestern Polytechnical University, Xi’an 710072, China 6 State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Chemistry, Chemical Engineering and Biotechnology, Donghua University, Shanghai 201620, PR China 7 Unidad Asociada Neurodeath, Universidad de Castilla-La Mancha, 02006 Albacete, Spain 8 Centro de Investigación Biomédica en Red para Enfermedades Neurodegenerativas, ISCIII, 28031 Madrid, Spain 9 Euromed Research Center, Euromed Faculty of Engineering, Euromed University of Fes (UEMF), Route de Meknès, 30000 Fès, Morocco 10 Laboratoire de Chimie de Coordination du CNRS, 205 route de Narbonne, 31077 Toulouse Cedex 4, France 11 Université Toulouse 118 route de Narbonne, 31077 Toulouse Cedex 4, France In nanomedicine, the widespread concern of nanoparticles in general, and dendrimers, in particular, is the analysis of key in-vivo physicochemical parameters to ensure the preclinical and clinical development of ‘safe’ bioactive nanomaterials.
    [Show full text]
  • Macromolecular Semi-Rigid Nanocavities for Cooperative Recognition of Specific Large Molecular Shapes
    ARTICLE Received 27 May 2013 | Accepted 10 Sep 2013 | Published 8 Oct 2013 DOI: 10.1038/ncomms3581 Macromolecular semi-rigid nanocavities for cooperative recognition of specific large molecular shapes Takane Imaoka1, Yuki Kawana1, Takuto Kurokawa1 & Kimihisa Yamamoto1 Molecular shape recognition for larger guest molecules (typically over 1 nm) is a difficult task because it requires cooperativity within a wide three-dimensional nanospace coincidentally probing every molecular aspect (size, outline shape, flexibility and specific groups). Although the intelligent functions of proteins have fascinated many researchers, the reproduction by artificial molecules remains a significant challenge. Here we report the construction of large, well-defined cavities in macromolecular hosts. Through the use of semi-rigid dendritic phe- nylazomethine backbones, even subtle differences in the shapes of large guest molecules (up to B2 nm) may be discriminated by the cooperative mechanism. A conformationally fixed complex with the best-fitting guest is supported by a three-dimensional model based on a molecular simulation. Interestingly, the simulated cavity structure also predicts catalytic selectivity by a ruthenium porphyrin centre, demonstrating the high shape persistence and wide applicability of the cavity. 1 Chemical Resources Laboratory, Tokyo Institute of Technology, Yokohama 226-8503, Japan. Correspondence and requests for materials should be addressed to K.Y. (email: [email protected]). NATURE COMMUNICATIONS | 4:2581 | DOI: 10.1038/ncomms3581 | www.nature.com/naturecommunications 1 & 2013 Macmillan Publishers Limited. All rights reserved. ARTICLE NATURE COMMUNICATIONS | DOI: 10.1038/ncomms3581 he ultimate challenge in host–guest chemistry is the design D H D D of synthetic hosts that can universally recognize guest Ph molecules with various structural characteristics including B B O T N size, shape and details such as the positions of functional groups.
    [Show full text]
  • Recent Advances in Click Chemistry Applied to Dendrimer Synthesis
    Molecules 2015, 20, 9263-9294; doi:10.3390/molecules20059263 OPEN ACCESS molecules ISSN 1420-3049 www.mdpi.com/journal/molecules Review Recent Advances in Click Chemistry Applied to Dendrimer Synthesis Mathieu Arseneault †, Caroline Wafer † and Jean-François Morin * Département de Chimie, Université Laval, 1045 avenue de la Médecine, Pavillon Alexandre-Vachon, QC G1V 0A6, Canada; E-Mails: [email protected] (M.A.); [email protected] (C.W.) † These authors contributed equally to this work. * Author to whom correspondence should be addressed; E-Mail: [email protected]; Tel.: +1-418-656-2812. Academic Editor: Arnaud Gautier Received: 16 April 2015 / Accepted: 12 May 2015 / Published: 20 May 2015 Abstract: Dendrimers are monodisperse polymers grown in a fractal manner from a central point. They are poised to become the cornerstone of nanoscale devices in several fields, ranging from biomedicine to light-harvesting. Technical difficulties in obtaining these molecules has slowed their transfer from academia to industry. In 2001, the arrival of the “click chemistry” concept gave the field a major boost. The flagship reaction, a modified Hüisgen cycloaddition, allowed researchers greater freedom in designing and building dendrimers. In the last five years, advances in click chemistry saw a wider use of other click reactions and a notable increase in the complexity of the reported structures. This review covers key developments in the click chemistry field applied to dendrimer synthesis from 2010 to 2015. Even though this is an expert review, basic notions and references have been included to help newcomers to the field. Keywords: dendrimer; dendron; click; Hüisgen cycloaddition; thiol-ene; thiol-yne; Diels-Alder Molecules 2015, 20 9264 1.
    [Show full text]
  • Supporting Information Nanoparticle
    Electronic Supplementary Material (ESI) for Nanoscale. This journal is © The Royal Society of Chemistry 2017 Supporting Information Nanoparticle Cellular Uptake by Dendritic Wedge Peptides: Achieving Single Peptide Facilitated Delivery Joyce C. Breger1,4, Markus Muttenthaler3,5, James B. Delehanty1, Darren Thompson3, Eunkeu Oh2,6, Kimihiro Susumu2,6, Jeffrey R. Deschamps1, George P. Anderson1, Lauren D. Field1,7, Scott A. Walper1, Philip E. Dawson3, and Igor L. Medintz1* S-1 Peptide Dendrimer Synthesis. Abbreviations. AO Amino-oxy Boc t-Butyloxycarbonyl CHO Formyl DCM Dichloromethane DIEA N,N-Diisopropylethylamine DMF N,N-Dimethylformamide Fmoc 9-Fluorenylmethyloxycarbonyl HCTU O-(1H-6- chlorobenzotriazole-1-yl)-1,1,3,3-tetramethyluronium hexafluorophosphate RP-HPLC Reversed-phase high-performance liquid chromatography MBHA 4-Methylbenzhydrylamine MS Mass spectrometry MW Molecular weight r.t. Room temperature SPPS Solid phase peptide synthesis TFA Trifluoroacetic acid Materials. N,N-Dimethylformamide (DMF), dichloromethane (DCM), acetonitrile (CH3CN) and N,N- diisopropylethylamine (DIEA) were peptide synthesis grade and purchased from Fisher Scientific (Pittsburgh, PA, USA). 4-Methylbenzhydrylamine (MBHA) resin and O-(1H-6- chlorobenzotriazole-1-yl)-1,1,3,3-tetramethyluronium hexafluorophosphate (HCTU) was purchased from Peptides International (Louisville, K, USA) and trifluoroacetic acid (TFA) from NuGen Tec (Emerville, CA, USA). Boc-amino-hexanoic acid (Boc-6-Ahx-OH / Boc-hex) was obtained from Sigma Aldrich (St. Louis, MO, USA). Standard
    [Show full text]
  • Templating of Inorganic Nanoparticles by PAMAM/PEG Dendrimer-Star
    Polymer 43 (2002) 5473–5481 www.elsevier.com/locate/polymer Templating of inorganic nanoparticles by PAMAM/PEG dendrimer–star polymers Ronald C. Hedden*, Barry J. Bauer, A. Paul Smith, Franziska Gro¨hn, Eric Amis National Institute of Standards and Technology, Gaithersburg, MD 20899, USA Received 15 April 2002; received in revised form 25 June 2002; accepted 26 June 2002 Abstract Poly(amidoamine) (PAMAM) dendrimers with amine endgroups (PAMAM–NH2) are converted to starlike copolymers by grafting of monofunctional poly(ethylene glycol) (PEG) ‘arms’ onto the dendrimer endgroups. Generation 4, 7, and 10 dendrimers are converted to 60- arm, 235-arm, and 750-arm PAMAM/PEG stars, respectively. The dendrimer–stars are studied as polymer templates for stabilization of gold and cadmium sulfide nanoparticles of 1–6 nm diameter. PAMAM/PEG star templating reactions are studied by aqueous gel permeation chromatography, ultraviolet–visible absorption spectroscopy, fluorescence spectroscopy, and transmission electron microscopy. PAMAM/PEG stars effectively control nanoparticle size in the same way as PAMAM–NH2 dendrimers. However, PAMAM/PEG stars are miscible with a wider range of solvents and with selected polymers (e.g. polymethyl methacrylate). Potential applications of dendrimer– inorganic hybrid materials (solution-phase catalysis, additives for polymer blends) could benefit from the versatile solubility of PAMAM/PEG stars. q 2002 Published by Elsevier Science Ltd. Keywords: Star polymer; Dendrimer; Nanoparticle 1. Introduction the nanoparticle size distribution. ‘Stabilizing’ refers in general to any mechanism by which a stable polymer– Poly(amidoamine) (PAMAM) dendrimers are highly inorganic nanocomposite is formed.) Dendrimers are chosen branched macromolecules prepared by alternating the as a model templating system because they are mono- addition of methyl acrylate and ethylene diamine monomers disperse and structurally well-defined.
    [Show full text]
  • Acetonitrile Shortage: Use of Isopropanol As an Alternative Elution
    Supplementary Material (ESI) for Analytical Methods This journal is © The Royal Society of Chemistry 2010 Acetonitrile Shortage: Use of (2) Ultra Performance Liquid Chromatography using Isopropanol as an organic modifier. Isopropanol as an alternative For experiments using isopropanol as a part of the eluent system, elution system for Ultra/High 60 the analysis was carried out using the same gradient as mentioned above, except that the organic modifier, acetonitrile, was replaced Performance Liquid with isopropanol. Briefly, the gradient elution began with 99:1 Chromatography (v/v) water/isopropanol reaching 20:80 water/isopropanol in 5 13.40 minutes. Trifluoroacetic acid (TFA) at 0.14 wt % a a, 65 concentration was added in water as well as in ACN as a counter Ankur M Desai, Mark Andreae, Douglas G ion to make the dendrimer surfaces hydrophobic. The gradient a,b a,c Mullen , Mark M Banaszak Holl and James R was then reequilibrated back to starting conditions in the next 1.0 Baker Jr.,*a minute. Flow rate was maintained at 0.208 mL/min. The software is equipped with three different injection options. A 3 μL of 70 sample was injected using using one of these options (“partial a loop with needle overfill”), The column temperature was 10 Michigan Nanotechnology Institute for Medicine and Biological maintained at 35 C. Sciences, University of Michigan, 9220 MSRB III, 1150 W. Medical Center Dr., Ann Arbor, MI 48109-5648. (3) (Semi-preparative) High Pressure Liquid 75 Chromatography using Isopropanol as an organic b Program in Macromolecular Science and Engineering, modifier.1 cDepartment of Chemistry, University of Michigan, Ann 15 Arbor, Michigan 48109.
    [Show full text]
  • Supported Dendrimer-Encapsulated Metal Clusters: Toward Heterogenizing Homogeneous Catalysts † ‡ § † † § † § Rong Ye, , , Aleksandr V
    This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. Article pubs.acs.org/accounts Supported Dendrimer-Encapsulated Metal Clusters: Toward Heterogenizing Homogeneous Catalysts † ‡ § † † § † § Rong Ye, , , Aleksandr V. Zhukhovitskiy, Christophe V. Deraedt, , F. Dean Toste,*, , † ‡ § and Gabor A. Somorjai*, , , † ‡ Department of Chemistry, Kavli Energy NanoScience Institute, University of California, Berkeley, Berkeley, California 94720, United States § Chemical Science Division, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, California 94720, United States CONSPECTUS: Recyclable catalysts, especially those that display selective reactivity, are vital for the development of sustainable chemical processes. Among available catalyst platforms, heterogeneous catalysts are particularly well-disposed toward separation from the reaction mixture via filtration methods, which renders them readily recyclable. Furthermore, heterogeneous catalysts offer numer- ous handlessome without homogeneous analoguesfor performance and selectivity optimization. These handles include nano- particle size, pore profile of porous supports, surface ligands and interface with oxide supports, and flow rate through a solid catalyst bed. Despite these available handles, however, conventional heterogeneous catalysts are themselves often structurally heterogeneous compared to homogeneous catalysts, which complicates efforts to optimize and expand the scope of their reactivity and selectivity. Ongoing efforts in our laboratories are aimed to address the above challenge by heterogenizing homogeneous catalysts, which can be defined as the modification of homogeneous catalysts to render them in a separable (solid) phase from the starting materials and products. Specifically, we grow the small nanoclusters in dendrimers, a class of uniform polymers with the connectivity of fractal trees and generally radial symmetry.
    [Show full text]
  • Functional Dendritic Materials Using Click Chemistry: Synthesis, Characterizations and Applications
    FUNCTIONAL DENDRITIC MATERIALS USING CLICK CHEMISTRY: SYNTHESIS, CHARACTERIZATIONS AND APPLICATIONS Per Antoni AKADEMISK AVHANDLING Som med tillstånd av Kungliga Tekniska Högskolan i Stockholm framlägges till offentlig granskning för avläggande av teknisk doktorsexamen fredagen den 13 juni 2008, kl 14.00 i sal F3, Lindstedtsvägen 26, KTH, Stockholm. Avhandlingen försvaras på engelska. Opponent: Prof. Stefan Hecht från Humboldt University, Tyskland. Copyright © 2008 Per Antoni All rights reserved Paper I © 2007 The Royal Society of Chemistry Paper II © 2008 The Royal Society of Chemistry TRITA-CHE-Report 2008:47 ISSN 1654-1081 ISBN 978-91-7415-017-9 ABSTRACT The need for new improved materials in cutting edge applications is constantly inspiring researchers to developing novel advanced macromolecular structures. A research area within advanced and complex macromolecular structures is dendrimers and their synthesis. Dendrimers consist of highly dense and branched structures that have promising properties suitable for biomedical and electrical applications and as templating materials. Dendrimers provide full control over the structure and property relationship since they are synthesized with unprecedented control over each reaction step. In this doctoral thesis, new methodologies for dendrimer synthesis are based on the concept of click chemistry in combination with traditional chemical reactions for dendrimer synthesis. This thesis discusses an accelerated growth approach, dendrimers with internal functionality, concurrent reactions and their applications. An accelerated growth approach for dendrimers was developed based on AB2‐ and CD2‐monomers. These allow dendritic growth without the use of activation or deprotection of the peripheral end‐groups. This was achieved by combining the chemoselective nature of click chemistry and traditional acid chloride reactions.
    [Show full text]