The properties of polymers—long chain molecules from which plastics are made—depend on the type of individual building blocks in them, as well as the order they are in and how they are arranged in space.
Although the order of the components can easily be controlled, control of their spatial arrangement, called stereochemistry, remains one of the biggest challenges in polymer chemistry. Kyoko Nozaki and a team from the University of Tokyo report in the journal Angewandte Chemie that they have made the first poly(propylene carbonate) with polymer chains built up in the form of a gradient of two stereochemically different propylene building blocks.
Poly(propylene carbonate) is used as a binding agent and as a component of biodegradable plastics. It is made from propylene oxide and carbon dioxide in a catalytic process. Propylene oxide contains three carbon atoms, two of which form a ring together with an oxygen atom. This ring opens during polymerization. Propylene oxide exists in two forms that are mirror images of each other; these are designated as the S and R stereoisomers.
Poly(propylene carbonate)s that are made primarily of one of the two forms or have both forms in an alternating pattern have been made before. Nozaki’s group has now been the first to synthesize both a stereoblock and a stereogradient. A stereoblock copolymer is a chain, half of which is made of the S form and the other half of the R form. In a stereogradient copolymer, the composition changes gradually from the S form to the R form.
Making a block copolymer is theoretically relatively easy because use of an asymmetric catalyst causes one of the two forms of building block to be used preferentially, so it is built into the polymer chains first; the less favorable form is incorporated afterward. In the case of poly(propylene carbonate), however, this process isn’t so trivial because once the favored form of the propylene oxide is converted to a polymer, the other form decomposes instead of polymerizing. The Japanese scientists found a special asymmetrical cobalt complex that allows nearly complete conversion to the polymer. Although the catalyst prefers the S form, it also ensures that it is more favorable for the R form to polymerize than to decompose.
The researchers experimented further with variations on the cobalt complex. A special ammonium side branch on a ligand brought success: It balances the degree of preference of the catalyst for the S form over the R form so that the R form begins to be incorporated into the polymer chain as the amount of the S form decreases. This allows the formation of the stereogradient copolymer. Interestingly, both of the new types of poly(propylene carbonate), stereoblock and stereogradient, are significantly more heat-tolerant than pure S or R polymers or mixtures of the two.
Author: Kyoko Nozaki, University of Tokyo (Japan), http://park.itc.u-tokyo.ac.jp/nozakilab/indexE.html
Title: Synthesis of Stereogradient Poly(propylene carbonate) by Stereo- and Enantioselective Copolymerization of Propylene Oxide with Carbon Dioxide
Angewandte Chemie International Edition, Permalink to the article: http://dx.doi.org/10.1002/anie.201007958
Kyoko Nozaki | Angewandte Chemie
Water forms 'spine of hydration' around DNA, group finds
26.05.2017 | Cornell University
How herpesviruses win the footrace against the immune system
26.05.2017 | Helmholtz-Zentrum für Infektionsforschung
Staphylococcus aureus is a feared pathogen (MRSA, multi-resistant S. aureus) due to frequent resistances against many antibiotics, especially in hospital infections. Researchers at the Paul-Ehrlich-Institut have identified immunological processes that prevent a successful immune response directed against the pathogenic agent. The delivery of bacterial proteins with RNA adjuvant or messenger RNA (mRNA) into immune cells allows the re-direction of the immune response towards an active defense against S. aureus. This could be of significant importance for the development of an effective vaccine. PLOS Pathogens has published these research results online on 25 May 2017.
Staphylococcus aureus (S. aureus) is a bacterium that colonizes by far more than half of the skin and the mucosa of adults, usually without causing infections....
Physicists from the University of Würzburg are capable of generating identical looking single light particles at the push of a button. Two new studies now demonstrate the potential this method holds.
The quantum computer has fuelled the imagination of scientists for decades: It is based on fundamentally different phenomena than a conventional computer....
An international team of physicists has monitored the scattering behaviour of electrons in a non-conducting material in real-time. Their insights could be beneficial for radiotherapy.
We can refer to electrons in non-conducting materials as ‘sluggish’. Typically, they remain fixed in a location, deep inside an atomic composite. It is hence...
Two-dimensional magnetic structures are regarded as a promising material for new types of data storage, since the magnetic properties of individual molecular building blocks can be investigated and modified. For the first time, researchers have now produced a wafer-thin ferrimagnet, in which molecules with different magnetic centers arrange themselves on a gold surface to form a checkerboard pattern. Scientists at the Swiss Nanoscience Institute at the University of Basel and the Paul Scherrer Institute published their findings in the journal Nature Communications.
Ferrimagnets are composed of two centers which are magnetized at different strengths and point in opposing directions. Two-dimensional, quasi-flat ferrimagnets...
An Australian-Chinese research team has created the world's thinnest hologram, paving the way towards the integration of 3D holography into everyday...
24.05.2017 | Event News
23.05.2017 | Event News
22.05.2017 | Event News
26.05.2017 | Life Sciences
26.05.2017 | Life Sciences
26.05.2017 | Physics and Astronomy