Merging Macromolecular and Supramolecular Chemistry Into Bioinspired Synthesis of Complex Systems

Total Page:16

File Type:pdf, Size:1020Kb

Merging Macromolecular and Supramolecular Chemistry Into Bioinspired Synthesis of Complex Systems Review DOI: 10.1002/ijch.202000004 Merging Macromolecular and Supramolecular Chemistry into Bioinspired Synthesis of Complex Systems Virgil Percec*[a] Abstract: A brief and personalized historical review that after and influenced these developments as well as the describes the merger of macromolecular and supramolecular experience of the author during his stays at the Hermann chemistry to generate the new field of bioinspired synthesis Staudinger House that hosts the Institute of Macromolecular of complex systems is presented. Historical scientific events Chemistry from the University of Freiburg are also part of that took place during the days of Hermann Staudinger and this review. Keywords: macromolecular and supramolecular chemistry · self-assembly · supramolecular dendrimers · helical chirality · polyphenylacetylene 1. Introduction last graduate student of Staudinger, they provided me mentor- ship both for my new life in Germany and in US. 1.1 The Hermann Staudinger House at the University of At that time HSH was the leading educational Institution Freiburg was for Many Years my First Home! in the world of Macromolecular Science. The next few generations of German academics were either graduate In 1981 I defected the country I was born and educated. The students, doing habilitation or being postdocs in the HSH. At Hermann Staudinger House (HSH) that hosts the Institute of that time almost every top scientist in the field would pass by Macromolecular Chemistry at the University of Freiburg was Freiburg for a seminar. Special connections with industry, the first Institution to provide me a new home. Professors H.-J. BASF, BAYER and HOECHST, to mention just few leading Cantow and G. Wegner were its two directors at that time. German companies that ultimately, I ended consulting for, Together with Professor Helmut Ringsdorf (Figure 1),[1a] the made HSH the ideal place where the young generation of future scientists would learn everything about macromolecular chemistry and the real scientific life in a very accelerated way. One month later, a letter from Professor J. P. Kennedy invited me to join his laboratory at the University of Akron. This was an old invitation that dated back to the days of my PhD when I was not allowed to travel even to Eastern countries. Professor Cantow advised me to stay in Germany. When I asked what do you think I would I do in Germany, he stated that most probably I would become a Professor by next year. However, when I decided to go to US the German community continued to provide me with advice and help. The most memorable event in Akron was soon after my arrival when Herman Mark came to give a plenary lecture for the anniversary of the Institute of Polymer Science. I reintroduced myself to him reminding him that I was an undergraduate student in Iasi when he visited to receive a Doctor Honoris Causa. I also mentioned that I defected the country. He shook my hand and said: “Of course I remember you Virgil. Welcome to this country! Now you are one of ours.” I will never forget his cordial welcoming sentence. How could he remember one of [a] V. Percec Roy & Diana Vagelos Laboratories, Department of Chemistry and Figure 1. Virgil Percec (far left) next to Helmut Ringsdorf, the last Laboratory for Research on the Structure of Matter, University of PhD student of Hermann Staudinger, H.-J. Cantow and Martin Pennsylvania, Philadelphia, Pennsylvania 19104-6323, United Moeller (in the middle) during the IUPAC Symposium in Amherst, States [1a] USA, in 1982. E-mail: [email protected] Isr. J. Chem. 2020, 60, 1–20 © 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 1 These are not the final page numbers! �� Review the many underdraduate students when he passed though the Research published more papers in JACS per year than lab I was in? This was Herman Mark, the gentleman who Harvard together with Caltech. Not only that they pioneered could build with no money the first school of Polymer Science the field of polymers but also organometallic, metathesis, in US. I felt very bad when few years later he called my office fluorine, supramolecular chemistry to name just a few. I could and invited me to become an Editor of the Journal of Polymer not turn down when several years ago the German community Science. I turned him down saying that I think I am too young asked me to edit a book[1] dedicated to the 60th anniversary of to invest my time in editorial work. When several year later he the Nobel Prize of Hermann Staudinger (Figure 3). called again, I accepted. On March 1, 1982 I joined the I searched through his life and all places he has been Department of Macromolecular Science of Case Western educated or was a faculty, Halle, Strasbourg, Karlsruhe, Reserve University in Cleveland as a faculty. During late Zurich, Freiburg, and to my surprise nobody turned down my 1982, early 1983 when Professor Wegner decided to build the invitation to contribute to this book. As a consequence, the Max Planck Institute for Polymer Research in Mainz and be one volume book became two volumes. In addition, with this its first Director HSH asked me to consider replacing him. occasion I learned about Staudinger more than he would have This was the equivalent of following in the footsteps of liked anybody to know about him except for himself. This book Hermann Staudinger. It was a very hard call for me to turn contains as much as needed to learn everything about down and therefore, I did it as polite as I could: “I had six Staudinger. For these and many other reasons Hermann months during which time I changed between four different Staudinger House was, is and will remain a very special place Departments and Universities located in three different for me. Early polymer studies done before or in parallel by countries located on two different continents. Therefore, I Berzelius, Svedberg, Carothers, Ranby, Flory, Mark, Mora- would prefer to spend some time in one place in order to wetz, Pedersen and many other who contributed to the restart my research activities.” HSH was very friendly at my development of the field of polymer or macromolecular reply and offered me a visiting professor with support for me science were discussed in historical articles and books.[2] I find and my graduate students from US. In the summer of 1984 particularly interesting that even the Nobel Lecture of when I needed more laboratory space at CWRU I was back in Pedersen on supramolecular chemistry discusses polymer Freiburg with three of my graduate students: Brian C. Auman chemistry work done at DuPont Experimental Station.[2j] In (Figure 2), Jose M. Rodriguez-Parada, both now at the Central order to follow in more details the history events discussed Research, Experimental Station of DuPont, known for many here I recommend at least references 1a,b, 2a,f,h and 24d to be years as one of the three Industrial American Universities, the consulted. other two were Bell Labs and IBM, and Timothy D. Shaffer, now at Central Research of Exxon. Soon after I became a faculty, I was invited to consult for DuPont Central Research. 2. How Would Polymer Science be Today if Karl I did it for about 30 years. However, I never visited them for Ziegler Would Have Decided to Pursue in the the consulting fee but for the intellectual challenge of discussing with its top scientists. 1920th–1930th Living Anionic Polymerization I never let my colleagues from Case Western Reserve Rather than Ziegler-Natta Polymerization of University know that in fact I was going to DuPont to take Ethylene? classes at the DuPont Industrial University while I was being paid as a consultant. There were days that DuPont Central In the 1920th to 1930th Karl Ziegler demonstrated that alkyl Professor Virgil Percec was born and educated in Romania. In 1981 he defected his native country and after short postdoctoral stays at the Hermann Staudinger House of the University of Freiburg and University of Akron he joined Case Western Reserve University on March 1, 1982 as an Assistant Professor. He was promoted to Associate Professor in 1984, to Professor in 1986 and to Leonard Case Jr Chair Professor in 1993. In 1999 he joined University of Pennsylvania as P. Roy Vagelos Chair and Professor of Chemistry. He serves as Editor and on the Editorial Boards of 24 journals, co-authored 775 peer reviewed publications, 60 patents, edited 20 books and gave over 1250 invited, plenary and endowed lectures. He has 3 Doctor Honoris Causa and received numerous awards. Of interest for the readers of this publication are the ACS Award in Polymer Chemistry (2004), Staudinger Medal from ETH (2005), H. F. Mark Medal and Award from the Austrian Institute for Science and Technology (2008), Honorary Member of the Israel Chemical Society (2009), Inaugural ACS Lecture and Award Kavli Foundation Innovations in Chemistry (2011), foreign member of the Royal Swedish Academy of Engineering Sciences IVA (2013), “Petru Poni” Medal of the Romanian Chemical Society (2014), Humboldt Award for Senior US Scientists (1997, 2011), NSF Award for creativity in Research (1990, 1995, 2000, 2015) and the C. Simionescu ACS Award and Medal in collaboration with the Romanian International Chapter for Excellence in Macromolecular Chemistry (2015). He is most known for his work on the elaboration of the stereoisomers of polyarylacetylenes, molecular, macromolecular and supramolecular liquid crystals with complex architecture, discovery and development of Ni-catalyzed Suzuki cross-coupling, borylation and mixed-ligand concepts, discovery of self- assembling dendrimers, elaboration of bioinspired synthesis of complex systems and synthetic cell biology, living polymerization methods for arylacetylenes, for radical and for condensation polymerizations.
Recommended publications
  • DNA-Functionalized Supramolecular Polymers
    DNA-functionalized supramolecular polymers Citation for published version (APA): Wijnands, S. P. W., Meijer, E. W., & Merkx, M. (2019). DNA-functionalized supramolecular polymers: dynamic multicomponent assemblies with emergent properties. Bioconjugate Chemistry, 30(7), 1905-1914. https://doi.org/10.1021/acs.bioconjchem.9b00095 Document license: CC BY-NC-ND DOI: 10.1021/acs.bioconjchem.9b00095 Document status and date: Published: 17/07/2019 Document Version: Publisher’s PDF, also known as Version of Record (includes final page, issue and volume numbers) Please check the document version of this publication: • A submitted manuscript is the version of the article upon submission and before peer-review. There can be important differences between the submitted version and the official published version of record. People interested in the research are advised to contact the author for the final version of the publication, or visit the DOI to the publisher's website. • The final author version and the galley proof are versions of the publication after peer review. • The final published version features the final layout of the paper including the volume, issue and page numbers. Link to publication General rights Copyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights. • Users may download and print one copy of any publication from the public portal for the purpose of private study or research. • You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal.
    [Show full text]
  • 2007 PMSE Fellow Ceremony
    DIVISION OF POLYMERIC MATERIALS: SCIENCE & ENGINEERING 2007 PMSE Fellow Ceremony The American Chemical Society Division of Polymeric Materials: Science and Engineering (PMSE) has just completed its process to select a new class of Fellows for 2007, and the following people have been chosen: • James Crivello • Mohamed El-Aasser • James Stoffer • Wen-Li Wu They will be inducted as the eighth class of PMSE Fellows during the PMSE/POLY Awards Reception at the Chicago ACS National Meeting on Monday, March 26, 2007. PMSE is pleased to welcome this distinguished group of polymer scientists and engineers to the ranks of fellows. A short description of their work up to the point of the induction as a PMSE Fellow is on the following pages. http://www.pmsedivision.org DIVISION OF POLYMERIC MATERIALS: SCIENCE & ENGINEERING 2007 PMSE Fellow Induction Biographies 2007 PMSE Fellow James Crivello Rensselaer Polytechnic Institute Prof. James Crivello received his B.S. in chemistry from Aquinas College in Grand Rapids, Michigan in 1962 and his Ph.D. in organic chemistry from the University of Notre Dame in 1966. He joined the General Electric Corporate Research and Development Center in 1966 and was for several years a research project manger. His fields of activity include: organic nitrations, oxidations, and arylations, polyimides, silicones, and new photo- and thermal initiators for cationic and free radical polymerizations. In 1980, he was elected a Coolidge Fellow by the staff at GE Corporate Research and Development and spent the 1986-87 year as a visiting scientist at the University of Mainz with Prof. Helmut Ringsdorf in the Federal Republic of Germany.
    [Show full text]
  • Company Update Company
    October 30, 2017 OUTPERFORM Indorama Ventures (IVL TB) Share Price: Bt45.75 Target Price: Bt55.0 (+20.2%) Company Update Company Ready to take it all . 65% of newly acquired BOPET is HVA, underscoring healthy EBITDA margins in FY18F onward . M&G’s bankruptcy is an opportunity for IVL to gain more market share in North America . OUTPERFORM, raised TP to Bt55/sh; share price weakness upon weak 3Q17 results is an opportunity to buy IVL could become a major player of BOPET Early this month, IVL signed a share purchase agreement with DuPont Teijin Films (DTF) to acquire 100% stake in their PET film business. This marks an important step for IVL to diversify into PET film used in packaging, industrial, electrical, imaging, and magnetic media. 65% of Naphat CHANTARASEREKUL DTF’s products is ‘thick’ film, which commands the same EBITDA 662 - 659 7000 ext 5000 margin as IVL’s HVA portfolio of automotive and hygiene products. DTF [email protected] COMPANY RESEARCH | RESEARCH COMPANY is a leading producer of biaxially oriented Polyethylene Terephthalate (BOPET) and Polyethylene Naphthalate (PEN). Their business Key Data comprises of eight production assets in the US, Europe, and China with 12-mth High/Low (Bt) 46.5 / 28.25 global innovation center in UK with annual capacity of 277k tons. PET Market capital (Btm/US$m) 239,957/ 7,205 film uses the same feedstock as PET but the market is small at 4.1m ton 3m avg Turnover (Btm/US$m) 747.8 / 22.5 consumption p.a. We are optimistic IVL could become a major player in Free Float (%) 29.5 this market.
    [Show full text]
  • Liste Des Lauréats Français Du Prix Gay-Lussac Humboldt
    Liste des lauréats français du prix Gay-Lussac Humboldt >Pierre AGOSTINI (2003), Physique atomique et moléculaire, CEA* Saclay > Ohio State University Josef DEUTSCHER (2005), Microbiologie, Institut National de la Recherche Agronomique - Jacques F. ARVIEUX (1994), Physique nucléaire, Université Paris 11 CNRS, Grignon Alain ASPECT (1999), Physique, Institut d’optique, Université Paris 11 – CNRS Georges DIDI-HUBERMAN (2006), Histoire de l’art, Ecole des Hautes Etudes en Sciences Didier ASTRUC (1988), Chimie, Université Bordeaux 1 Sociales Monique AUMAILLEY (1991), Biochimie cellulaire, Université Claude Bernard - Lyon 1 > Université Pierre-Henri DIXNEUF (1989), Chimie, Université Rennes 1 de Cologne Abdelhak DJOUADI (2007), Physique des particules, Université Paris 11 Claude BARDOS (1993), Mathématiques, Université Denis Diderot - Paris 7 Jean-François DUBREMETZ (1996), Biologie, Institut national de la santé et de la recherche Jean-Marie BASSET (1987), Chimie inorganique, CNRS**, Laboratoire de chimie médicale, Villeneuve d’Ascq CNRS - Université Montpellier 2 organométallique de surface, Lyon Magda ERICSON (1992), Physique nucléaire, Université Claude Bernard - Lyon I Henri C. BENOIT (1986), Chimie macromoléculaire, Université Louis Pasteur - Strasbourg 1 Gérard FEREY (2004), Chimie, Université de Versailles - Saint-Quentin Alain BENSOUSSAN (1983), Informatique, Institut national de recherche en informatique Jean-Marie FLAUD (1998), Chimie physique, Université Paris 11 et en automatique > Centre national d’études spatiales Christos FLYTZANIS
    [Show full text]
  • Curriculum Vitae Professor Dr. Martin Jansen
    Curriculum Vitae Professor Dr. Martin Jansen Name: Martin Jansen Born: 5 November 1944 Main areas of research: preparative solid-state chemistry, crystal chemistry, materials research, structure-property relationship of solids Since 1998, he has been a member of the scientific council of the Max Planck Society and a director at the Max Planck Institute for solid-state research in StuttgartHe has developed a concept for plan- ning solid state syntheses, combining computational and experimental tools, that is pointing the way to rational and efficient discovery of new materials. Academic and Professional Career since 1998 Director at the Max Planck Institute for Solid State Research, Stuttgart and Honorary Professor at the University of Stuttgart, Germany 1987 - 1998 Professor (C4) and Director of the Institute at the University of Bonn, Germany 1981 - 1987 Professor (C4), Chair B for Inorganic Chemistry of the University of Hannover, Germany 1978 Habilitation at the University of Gießen, Germany 1973 Promotion (Ph.D.) at the University of Gießen, Germany 1966 - 1970 Study of Chemistry at the University of Gießen, Germany Honours and Awarded Memberships (Selection) 2019 Otto-Hahn-Prize 2009 Centenary Prize, Royal Society of Chemistry, UK 2009 Georg Wittig - Victor Grignard Prize, Société Chimique de France 2008 Member of acatech (National Academy of Science and Engineering) Nationale Akademie der Wissenschaften Leopoldina www.leopoldina.org 1 2007 Karl Ziegler Award, Germany 2004 Honorary Doctorate of the Ludwig Maximilians-University of
    [Show full text]
  • 1 DANIELA R. RADU, Ph.D
    DANIELA R. RADU, Ph.D. Associate Professor, Mechanical and Materials Engineering, College of Engineering and Computing Florida International University, 10555 West Flagler Street, Miami, FL 33174 Tel. (O): (305) 348-4506 | Email: [email protected] EDUCATION Ph.D. in Chemistry (2004) Iowa State University, Ames, IA, USA Advisor: Professor Victor S.-Y. Lin M.S. in Chemistry (1996) “Babes-Bolyai” University, Cluj-Napoca, Romania Advisor: Professor Paul S. Agachi B.S. in Chemical Engineering (1994) “Babes-Bolyai” University, Cluj-Napoca, Romania Thesis Advisor: Professor Paul S. Agachi PROFESSIONAL EXPERIENCE Associate Professor with Tenure Department of Mechanical and Materials Engineering Florida International University, Miami, FL 33174 August 2018 – Present Associate Dean College of Mathematics, Natural Sciences and Technology January 2018 – July 2018 Delaware State University, Dover, DE Associate Professor with Tenure Department of Chemistry, Delaware State University, Dover, DE August 2017 – July 2018 Affiliated Professor Department of Materials Science and Engineering, University of Delaware October 2015 – Present Newark, DE Assistant Professor, Tenure-Track Department of Chemistry, Delaware State University, Dover, DE January 2013 – July2017 Senior Research Scientist DuPont CR&D, Experimental Station, Wilmington, DE August 2010 – December 2012 Research Scientist DuPont Central Research and Development, Experimental Station October 2007 – July 2010 Wilmington, DE Postdoctoral Research Fellow The Scripps Research Institute, La Jolla, CA
    [Show full text]
  • Ivan Julian Dmochowski, Ph.D
    Ivan Julian Dmochowski, Ph.D. Department of Chemistry, University of Pennsylvania 231 South 34 th Street, Philadelphia, PA 19104-6323 P: 215-898-6459; Email: [email protected] URL: http://dmochowskigroup.chem.upenn.edu/index.html Academic Appointments Professor of Chemistry, University of Pennsylvania, July, 2015 – Present Undergraduate Chair of Chemistry, University of Pennsylvania, Jan, 2015 – Present Associate Professor of Chemistry, University of Pennsylvania, 2010 – 2015 Assistant Professor of Chemistry, University of Pennsylvania, 2003 – 2010 Education California Institute of Technology, Pasadena, CA Helen Hay Whitney Postdoctoral Scholar in Biophysics, Sept. 2000 – Dec. 2002 California Institute of Technology, Pasadena, CA Ph.D. in Chemistry, May 2000, 1995-00 Johannes Gutenberg Universität, Mainz, Germany Research Fellow in Chemistry, 1994-95 Harvard College, Cambridge, MA A.B. in Chemistry, Magna cum Laude, 1990-94 Selected Honors 2016 Crano Award, Akron Section, American Chemical Society 2012 Awardee, McKnight Technological Innovations in Neuroscience 2011 Awardee, McGroddy Frontiers in Science, St. Joseph’s Univ. 2010 Invitee, National Academies Keck Futures Initiative Imaging Meeting 2007 Camille and Henry Dreyfus Teacher-Scholar Award 2005 NSF CAREER Award 2003 Camille and Henry Dreyfus New Faculty Award 2000 Herbert Newby McCoy Award, Caltech Chemistry Department 1990 United States Presidential Scholar Fellowships 2001-02 Helen Hay Whitney Postdoctoral Fellow 1999-00 N.I.H. Bioorganic/Bioinorganic Training Grant 1996-99 N.I.H. Biotechnology Training Grant Peer-Reviewed Publications 1 1. J.A. Rego, S. Kumar, I.J. Dmochowski, H. Ringsdorf, Synthesis of novel mixed tail triphenylene discotic liquid crystals - The search for higher order . Chem. Comm. (9) 1031- 1032, 1996.
    [Show full text]
  • Dendronized Poly(2-Oxazoline) Displays Within Only Five Monomer Repeat Units Liquid Quasicrystal, A15 and Σ Frank−Kasper Phases † † ⊥ † † ‡ § Marian N
    Communication Cite This: J. Am. Chem. Soc. 2018, 140, 16941−16947 pubs.acs.org/JACS Dendronized Poly(2-oxazoline) Displays within only Five Monomer Repeat Units Liquid Quasicrystal, A15 and σ Frank−Kasper Phases † † ⊥ † † ‡ § Marian N. Holerca, Dipankar Sahoo, , Benjamin E. Partridge, Mihai Peterca, , Xiangbing Zeng, § ∥ † Goran Ungar, , and Virgil Percec*, † Roy & Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323, United States ‡ Department of Physics and Astronomy, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6396, United States § Department of Materials Science and Engineering, University of Sheffield, Sheffield S1 3JD, United Kingdom ∥ State Key Laboratory for Mechanical Behavior of Materials, Xi’an Jiaotong University, Xi’an 710049, China *S Supporting Information discovered for self-assembling dendrons a few years later.2f ABSTRACT: Liquid quasicrystals (LQC) have been Subsequently, these three periodic and quasiperiodic arrays,10 discovered in self-assembling benzyl ether, biphenylmeth- and additional Frank−Kasper phases including the C14 and C15 yl ether, phenylpropyl ether, biphenylpropyl ether and Laves phases,11 have been transplanted to other types of soft some of their hybrid dendrons and subsequently in block matter12,13 including block copolymers,11b,14 lyotropic surfac- copolymers, surfactants and other assemblies. These tants,15 lipids and glycolipids,16 colloidal nanocrystals,17 and quasiperiodic arrays, which lack long-range translational molecules based on silsesquioxane cages.18 Frank−Kasper periodicity, are approximated by two Frank−Kasper phases and quasicrystals generated from soft matter have been periodic arrays, Pm3̅n cubic (Frank−Kasper A15) and subjected to various theoretical investigations that have − σ P42/mnm tetragonal (Frank Kasper ), which have been examined the energetic and entropic basis for their forma- discovered in complex soft matter in the same order and tion.9c,10,19 compounds.
    [Show full text]
  • Molecular Geometry and Molecular Graphics: Natta's Polypropylene And
    Molecular geometry and molecular graphics: Natta's polypropylene and beyond Guido Raos Dip. di Chimica, Materiali e Ing. Chimica \G. Natta", Politecnico di Milano Via L. Mancinelli 7, 20131 Milano, Italy [email protected] Abstract. In this introductory lecture I will try to summarize Natta's contribution to chemistry and materials science. The research by his group, which earned him the Noble prize in 1963, provided unprece- dented control over the synthesis of macromolecules with well-defined three-dimensional structures. I will emphasize how this structure is the key for the properties of these materials, or for that matter for any molec- ular object. More generally, I will put Natta's research in a historical context, by discussing the pervasive importance of molecular geometry in chemistry, from the 19th century up to the present day. Advances in molecular graphics, alongside those in experimental and computational methods, are allowing chemists, materials scientists and biologists to ap- preciate the structure and properties of ever more complex materials. Keywords: molecular geometry, stereochemistry, chirality, polymers, self-assembly, Giulio Natta To be presented at the 18th International Conference on Geometry and Graphics, Politecnico di Milano, August 2018: http://www.icgg2018.polimi.it/ 1 Introduction: the birth of stereochemistry Modern chemistry was born in the years spanning the transition from the 18th to the 19th century. Two key figures were Antoine Lavoisier (1943-1794), whose em- phasis on quantitative measurements helped to transform alchemy into a science on an equal footing with physics, and John Dalton (1766-1844), whose atomic theory provided a simple rationalization for the way chemical elements combine with each other to form compounds.
    [Show full text]
  • Spatiotemporal Control and Superselectivity in Supramolecular Polymers Using Multivalency
    Spatiotemporal control and superselectivity in supramolecular polymers using multivalency Lorenzo Albertazzia, Francisco J. Martinez-Veracoecheab, Christianus M. A. Leendersa, Ilja K. Voetsa, Daan Frenkelb, and E. W. Meijera,1 aInstitute for Complex Molecular Systems and Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology, 5600 MB Eindhoven, The Netherlands; and bDepartment of Chemistry, University of Cambridge, Cambridge CB2 1EW, United Kingdom Edited by Michael L. Klein, Temple University, Philadelphia, PA, and approved May 28, 2013 (received for review February 22, 2013) Multivalency has an important but poorly understood role in pegylated BTAs self-assemble in water through a combination of molecular self-organization. We present the noncovalent synthesis hydrogen bonding and hydrophobic effects to create long su- of a multicomponent supramolecular polymer in which chemically pramolecular polymers of ∼0.1–10 μminlength(9). distinct monomers spontaneously coassemble into a dynamic, In the biology and chemistry communities, there is intense functional structure. We show that a multivalent recruiter is able interest in the role of multivalency as a tool to encode structure to bind selectively to one subset of monomers (receptors) and and function into soft materials. Several fascinating papers trigger their clustering along the self-assembled polymer, be- reported how nature exploits multivalency to exert control over havior that mimics raft formation in cell membranes. This phe- spatial segregation and phase separation inside living cells (10). nomenon is reversible and affords spatiotemporal control over Segregation of proteins and sphingolipids in lipid raft domains the monomer distribution inside the supramolecular polymer by superselective binding of single-strand DNA to positively charged (11) is a remarkable example of this phenomenon.
    [Show full text]
  • "But She's an Avowed Communist!" L'affaire Curie at the American Chemical Society, 1953-1955
    ll. t. Ch. 20 ( 33 "BUT SHE'S AN AVOWED COMMUNIST!" L'AFFAIRE CURIE AT THE AMERICAN CHEMICAL SOCIETY, 1953-1955 Mrrt W. tr, Crnll Unvrt Intrdtn On ht hv xptd tht th Arn Chl St (ACS, n rnztn tht ld t b r n fr th dvnnt f htr nd nt n p ltl tt fr t brhp, ld rdl pt n ppltn fr bl lrt n htr. Yt th nt th th Irèn ltCr n . Aftr ntrntn ACS ffl rjtd hr brhp ppltn b f hr pltl rpttn (trnl lnd t th prCnt blf nd tvt f hr hbnd, rdr ltCr, nfrd hr f th dn bt v n rn, nd d nth n f thr tn pbll. Whn nth ltr hr frnd tnd nd pblzd hr rjtn, th b lèbr. h xtnv ntr nd rrpndn rrndn th pd t p bl t ntprr rtn t th d, hndln, nd nfn f th dn. Whn prd t n f th thr ntnt "th hnt" n th Untd Stt n th 40 nd 0, th pbl hrnt f ldn br f th Ar n Atn fr th Advnnt f Sn (AAAS, n n th dffrnt rtn. Whr th AAAS brd f drtr rpndd ttl t th ntnt rd b ltn E. U. Cndn nd Figure. 1 Irene Joliot-Curie (1897-1956). Shown here Krtl Mthr prdnt (, th ldr f th ACS late in life, Joliot-Curie shared the Nobel Prize in rfd t lt Md ltCr vn t br Chemistry with her husband Frederic in 1935. hp. "Affr Cr," t t b lld, l Intensely apolitical in her early life, she became more rvld trtrl tnn thn th ACS btn involved in French women's, socialist, and pro- th prttv ntnt f th br f th rd f Communist movements starting in the late 1930s.
    [Show full text]
  • Formation of Functionalized Supramolecular Metallo-Organic Oligomers with Cucurbituril a Thesis Presented to the Faculty Of
    Formation of Functionalized Supramolecular Metallo-organic Oligomers with Cucurbituril A thesis presented to the faculty of the College of Arts and Sciences of Ohio University In partial fulfillment of the requirements for the degree Master of Science Ian M. Del Valle December 2015 © 2015 Ian M. Del Valle. All Rights Reserved. 2 This thesis titled Formation of Functionalized Supramolecular Metallo-organic Oligomers with Cucurbituril by IAN M. DEL VALLE has been approved for the Department of Chemistry and Biochemistry and the College of Arts and Sciences by Eric Masson Associate Professor of Chemistry and Biochemistry Robert Frank Dean, College of Arts and Sciences 3 Abstract DEL VALLE, IAN M., M.S., December 2015, Chemistry Formation of Functionalized Supramolecular Metallo-organic Oligomers with Cucurbituril Director of Thesis: Eric Masson The goal of this project is to functionalize supramolecular oligomer chains with amino acids and nucleic acids in order to observe interactions with proteins and DNA. Chiral substituents are also desirable to induce helicality in the oligomer much like DNA. We explored different pathways to afford these oligomers. The first project involves forming metallo-organic oligomers using non-covalent bonds and then functionalizing them. We synthesize ligands and use alkyne-azide cycloadditions to functionalize them. These ligands can then be coordinated to various transition metals. The aromatic regions of these oligomers can then self-assemble into tube-like chains with the participation of cucurbit[8]uril. Second, we explore an alternate pathway to form functionalized chains. This second set of chains coupled amines with carboxylic acid groups attached to the ligands. This project hopes to avoid solubility problems experienced with the first project.
    [Show full text]