Single Monomer Unit Research Articles

Spatially Amplified and Rigid Junction in Diblock Copolymers: Reduced Microphase Separation Size via Interface Expansion.

We introduce an approach in diblock copolymer design, where modifying the junction point with rigid bulky monomer expands the cross-sectional area of the interface and leads to a decrease in the repeat period. Using living anionic polymerization, we synthesized a series of dialkynyl midfunctionalized poly(styrene-b-methyl methacrylate) (PSM-DA) and functionalized them using the thiol-alkyne click reaction with specifically selected rigid bulky monomers: PSS-(3-mercapto)propyl-heptaisobutyl substituted (PSS) and 1-adamantanethiol (ADA). This modification, though involving only a single monomer unit within the diblock copolymer structure, brought about a significant reduction in domain size, with PSS and ADA reducing it by 18% and 15%, respectively. The results indicate a method for reducing the domain sizes of block copolymers, which could lead to advancements in lithography and various nanotechnological applications.

Step-growth polymerization by the RAFT process.

Reversible Addition-Fragmentation Chain Transfer (RAFT) step-growth polymerization is an emerging method that synergistically combines the benefits of RAFT polymerization (functional group and user-friendly nature) and step-growth polymerization (versatility of the polymer backbone). This new polymerization method is generally achieved by using bifunctional reagents of monomer and Chain Transfer Agent (CTA), that efficiently yield Single Monomer Unit Insertion (SUMI) adducts under stoichiometrically balanced conditions. This review covers a brief history of the RAFT-SUMI process and its transformation into RAFT step-growth polymerization, followed by a comprehensive discussion of various RAFT step-growth systems. Furthermore, characterizing the molecular weight evolution of step-growth polymerization is elaborated based on the Flory model. Finally, a formula is introduced to describe the efficiency of the RAFT-SUMI process, assuming rapid chain transfer equilibrium. Examples of reported RAFT step-growth and SUMI systems are then categorized based on the driving force.

Self-Assembly of Stereoblock Copolymers Driven by the Chain Folding of Discrete Poly(d-lactic acid-b-l-lactic acid) via Intramolecular Stereocomplexation

The encoding of information by defining the sequence of monomers is a highly anticipated strategy for controlling the three-dimensional structures of polymers via information-driven chain folding and self-assembly. In this paper, we report the controlled chain folding of stereoblock poly(lactic acid)s (PLAs) composed of two oligo(lactic acid) domains, [DLAn] and [LLAn], constructed by using precisely defined numbers of d- and l-lactic acids, respectively. Under the crystallization-driven self-assembly (CDSA) condition, block copolymers (BCPs) of stereoblock PLA and poly(ethylene glycol) formed planar nanostructures having unilamellar crystalline cores of stereoblock PLA. [DLAn]-[LLAn] stereoblocks were folded predominantly by intramolecular stereocomplexation (SCN) in dilute solutions in which the intermolecular interaction between BCPs was suppressed. The thickness of the planar nanostructures was precisely defined by the number of repeating units constituted of [DLAn] and [LLAn] domains. The convergent synthesis of PLA permitted the addition of a single monomer unit between the [DLAn] and [LLAn] domains, resulting in the introduction of a desired functional group at the apex of the folded chain. Our results demonstrate that information encoded in the form of a monomer sequence may shape the polymer chain and guide its self-assembly toward specific nanostructures having the desired dimensions and functions.

On‐Surface Synthesis of Porphyrin‐Complex Multi‐Block Co‐Oligomers by Defluorinative Coupling

AbstractOn‐surface chemical reaction has become a very powerful technique to synthesize nanostructures by linking small molecules in the bottom‐up approach. Given the fact that most reactants are simultaneously activated at certain temperatures, a sequential reaction in a controlled way has remained challenging. Here, we present an on‐surface synthesis of multi‐block co‐oligomers from trifluoromethyl (CF3) substituted porphyrin metal complexes. The oligomerization on Au(111) is demonstrated with a combination of bond‐resolved scanning probe microscopy and density functional theory (DFT) calculations. Even after the first oligomerization of single monomer unit, the termini of the oligomer keep the CF3 group, which can be used as a reactant for further coupling in a sequential order. Consequently, copper, cobalt, and palladium complexes of bisanthracene‐fused porphyrin oligomers were linked with each other in a designed order.

On‐Surface Synthesis of Porphyrin‐Complex Multi‐Block Co‐Oligomers by Defluorinative Coupling

AbstractOn‐surface chemical reaction has become a very powerful technique to synthesize nanostructures by linking small molecules in the bottom‐up approach. Given the fact that most reactants are simultaneously activated at certain temperatures, a sequential reaction in a controlled way has remained challenging. Here, we present an on‐surface synthesis of multi‐block co‐oligomers from trifluoromethyl (CF3) substituted porphyrin metal complexes. The oligomerization on Au(111) is demonstrated with a combination of bond‐resolved scanning probe microscopy and density functional theory (DFT) calculations. Even after the first oligomerization of single monomer unit, the termini of the oligomer keep the CF3 group, which can be used as a reactant for further coupling in a sequential order. Consequently, copper, cobalt, and palladium complexes of bisanthracene‐fused porphyrin oligomers were linked with each other in a designed order.

Multifactor Control of Vinyl Monomer Sequence, Molecular Weight, and Tacticity via Iterative Radical Additions and Olefin Metathesis Reactions.

Monomer sequence control in terms of a single monomer unit, particularly in vinyl polymers, is one of the largest challenges in polymer chemistry. Furthermore, multifactor control of monomer sequence, molecular weight, and stereoregularity is an ultimate goal. In this work, we propose a strategy to prepare C-C main-chain sequence-regulated polymers with controlled molecular weights from vinyl monomers via a combination of iterative atom transfer radical additions and olefin metathesis reactions. This strategy enabled the synthesis of sequence-regulated polymers with exact styrene-acrylate-styrene sequences in the C-C main chains, controlled molecular weights of up to 104, and stereoregularities varying with syndiotacticity, isotacticity, and heterotacticity. The utility of this strategy is further demonstrated by formation of block copolymers consisting of sequence-regulated vinyl polymer segments by combining living ROMP of norbornene derivatives.

What Came First: The Helix or the H2O?

Jiang, Tian, and colleagues observe long-range interactions between two complementary DNA strands, resulting in an ordered chain of helical water. This hidden conformation of water has been observed, but the helix is commonly associated with biomolecules. Perhaps water—necessary for biological processes—is the key driver of the predominance of helices.

Selective polymerization of a new bifunctional monomer via free radical polymerization and oxidative route

The synthesis and polymerization of a new bifunctional monomer, benzenaminium 4-styrenesulfonate, containing a vinyl and an anilinium group are reported. The vinyl group was polymerized via conventional free radical polymerization to produce poly(benzenaminium 4-styrenesulfonate), while the anilinium group was polymerized via oxidative polymerization to produce polyaniline emeraldine base salt. The characterization of functional groups by spectroscopic techniques and morphology by electron microscopy indicated clear differences between both polymers. Additionally, poly(benzenaminium 4-styrenesulfonate) was found to be water soluble, while polyaniline was only water dispersible. A copolymer using acrylic acid as the co-monomer (synthesized via free radical polymerization) and a polyaniline-poly(benzenaminium 4-styrenesulfonate) system (synthesized via oxidative polymerization) were obtained to show the advantage of having functional groups that polymerize by a selective route in a single monomer unit.

Precise Placement of Single Monomer Units in Living Ring-Opening Metathesis Polymerization

Summary Precise control of the location and sequence of monomers in a narrow-disperse polymer chain remains a significant challenge. Our strategy uses selective and quantitative single additions of cyclopropene (CPE) derivatives to precisely place functional moieties at desired locations along a polymer chain during the living ring-opening metathesis polymerization (ROMP) of norbornenes (NBEs). In order to completely reinitiate the chain end after single addition of a CPE, we lowered the reaction temperature and added a labile ligand. Under our optimized conditions, we demonstrated the exclusive placement of single moieties at pre-determined locations along a polynorbornene (PNBE) homo or block co-polymer while maintaining narrow MW distributions and controlled MWs. Some polymers were used to synthesize precisely controlled branched architectures. The ability to control the location and number of individual functional groups in a polymer chain opens exciting opportunities for the precise synthesis and manipulation of polymer structures, architectures, assemblies, and properties.

Formation of the Charge-Localized Dimer Radical Cation of 2-Ethyl-9,10-dimethoxyanthracene in Solution Phase.

Although dimer radical ions of aromatic molecules in the liquid-solution phase have been intensely studied, the understanding of charge-localized dimers, in which the extra charge is localized in a single monomer unit instead of being shared between two monomer units, is still elusive. In this study, the formation of a charge-localized dimer radical cation of 2-ethyl-9,10-dimethoxyanthracene (DMA), (DMA)2 .+ is investigated by transient absorption (TA) and time-resolved resonance Raman (TR3 ) spectroscopic methods combined with a pulse radiolysis technique. Visible- and near-IR TA signals in highly concentrated DMA solutions supported the formation of non-covalent (DMA)2 .+ by association of DMA and DMA.+ . TR3 spectra obtained from 30 ns to 300 μs time delays showed that the major bands are quite similar to those of DMA except for small transient bands, even at 30 ns time delay, suggesting that the positive charge of non-covalent (DMA)2 .+ is localized in a single monomer unit. From DFT calculations for (DMA)2 .+ , our TR3 spectra showed the best agreement with the calculated Raman spectrum of charge-localized edge-to-face T-shaped (DMA)2 .+ , termed DT.+ , although the charge-delocalized asymmetric π-stacked face-to-face (DMA)2 .+ , termed DF3.+ , is the most stable structure of (DMA)2 .+ according to the energetics from DFT calculations. The calculated potential energy curves for the association between DMA.+ and DMA showed that DT.+ is likely to be efficiently formed and contribute significantly to the TR3 spectra as a result of the permanent charge-induced Coulombic interactions and a dynamic equilibrium between charge localized and delocalized structures.

Single Molecule Nanopore Spectrometry for Peptide Detection.

Sensing and characterization of water-soluble peptides is of critical importance in a wide variety of bioapplications. Single molecule nanopore spectrometry (SMNS) is based on the idea that one can use biological protein nanopores to resolve different sized molecules down to limits set by the blockade duration and noise. Previous work has shown that this enables discrimination between polyethylene glycol (PEG) molecules that differ by a single monomer unit. This paper describes efforts to extend SMNS to a variety of biologically relevant, water-soluble peptides. We describe the use of Au25(SG)18 clusters, previously shown to improve PEG detection, to increase the on- and off-rate of peptides to the pore. In addition, we study the role that fluctuations play in the single molecule nanopore spectrometry (SMNS) methodology and show that modifying solution conditions to increase peptide flexibility (via pH or chaotropic salt) leads to a nearly 2-fold reduction in the current blockade fluctuations and a corresponding narrowing of the peaks in the blockade distributions. Finally, a model is presented that connects the current blockade depths to the mass of the peptides, which shows that our enhanced SMNS detection improves the mass resolution of the nanopore sensor more than 2-fold for the largest cationic peptides studied.

Detection of Rota Virus with the Help of Nanomaterial Based Field Effect Transistor (BIO-FET)

Biosensors are analytical devices composed of a recognition element of biological origin and a physiochemical transducer which converts the reaction into readable signals. The biosensors are providing their application in medical diagnosis and clinical analysis from last fifty years. In this work we have synthesized reduced graphene oxide, with this nano-film of RGO a FET- biosensor was developed and tested for the rapid detection of Rota-virus. It is a sensitive, specific and label free detection protocol. In the present methodology graphene; which is a single monomer unit of graphite was used and fabricated between the 3 μm apart micro-fabricated Au-electrode over hot plate at 70°C on a crystal surface by drop casting method. This thin film of graphene on FET crystal provide a better platform for attachment of antibodies through pyrene-NHS (Linker) complex. Pyrene- NHS is identified more suitable for antibody immobilization on the graphene film to be used in nano-immunosensor for the detection of specific antigens. The Rota-virus interation to its corresponding antibody were studied with respect to changes in the conductance in the graphene channel. This chemi-resistive FET transducer based 1D nanostructure have attracted much attention because of its rapid, sensitive, and cost effective point of care device for quantitative detection of Rota-virus so that gastroenteritis in infants can be detected early. The graphene nanofilm has been characterized by UV-Vis Spectroscopy, FT-IR, EDS, and SEM.

Phase coexistence and spatial correlations in reconstituting k-mer models.

In reconstituting k-mer models, extended objects that occupy several sites on a one-dimensional lattice undergo directed or undirected diffusion, and reconstitute-when in contact-by transferring a single monomer unit from one k-mer to the other; the rates depend on the size of participating k-mers. This polydispersed system has two conserved quantities, the number of k-mers and the packing fraction. We provide a matrix product method to write the steady state of this model and to calculate the spatial correlation functions analytically. We show that for a constant reconstitution rate, the spatial correlation exhibits damped oscillations in some density regions separated, from other regions with exponential decay, by a disorder surface. In a specific limit, this constant-rate reconstitution model is equivalent to a single dimer model and exhibits a phase coexistence similar to the one observed earlier in totally asymmetric simple exclusion process on a ring with a defect.

Impact of Conformational and Chemical Correlations on Microphase Segregation in Random Copolymers

Random copolymers play an important role in a range of soft materials applications and biological phenomena. An individual monomer is typically a single chemical unit whose length is comparable to or less than a Kuhn length, resulting in a monomer segment that is structurally rigid at length scales of a segregated domain. Previous work on random copolymer phase segregation addresses the impact of correlations between the chemical identities along the chains for flexible polymers. In these works, a single monomer unit is effectively a large polymer block that behaves as a random walk without conformational correlation associated with semiflexibility. In our work, we develop a model of semiflexible random copolymers using the wormlike chain model to capture conformational correlation of the polymer chains. To address the thermodynamics of microphase segregation and the structure of the segregated domains, we develop a random phase approximation up to quartic order in density fluctuations that leverages our ...

Terminal-Selective Transesterification of Chlorine-Capped Poly(Methyl Methacrylate)s: A Modular Approach to Telechelic and Pinpoint-Functionalized Polymers.

Terminal-selective transesterification of chlorine-capped poly(methyl methacrylate)s (PMMA-Cl) with alcohols was developed as a modular approach to create telechelic and pinpoint-functionalized polymers. Being sterically less hindered and electronically activated, both the α-end ethyl ester and ω-end methyl ester of PMMA-Cl were efficiently and selectively transesterified with diverse alcohols in the presence of a titanium alkoxide catalyst, while retaining the pendent esters intact, to almost quantitatively give various chlorine-capped telechelic PMMAs. In sharp contrast to conventional telechelic counterparts, the telechelic polymers obtained herein yet carry a chlorine atom at the ω-terminal to further work as a macroinitiator in living radical polymerization. The iterative process of living radical polymerization and terminal-selective transesterification successfully afforded unique pinpoint-functionalized polymers where a single functional monomer unit was introduced into the desired site of the polymer chains.

Mechanistic Insights into Temperature-Dependent Trithiocarbonate Chain-End Degradation during the RAFT Polymerization of N-Arylmethacrylamides

Mechanistic insights into trithiocarbonate degradation during the RAFT polymerization of N-arylmethacrylamides are reported. Previous work by our group showed significant RAFT agent degradation during the polymerization of N-arylmethacryloyl sulfonamides at 70 °C. Herein we report the influence of methacrylamide structure on trithiocarbonate degradation during the RAFT polymerizations of N-phenylmethacrylamide (PhMA) and N-benzylmethacrylamide (BnMA) in DMF at 70 and 30 °C. UV–vis spectroscopy revealed trithiocarbonate degradation occurs exclusively after covalent addition of monomer to the RAFT agent, with 60% trithiocarbonate degradation occurring after 12 h during the polymerization of PhMA at 70 °C compared to only 3% degradation measured during the polymerization of BnMA under identical conditions. Small molecule analogues of trithiocarbonate-functional poly(PhMA) and poly(BnMA) were synthesized by single monomer unit insertion and the kinetics and byproducts of degradation investigated by in situ 1H...

Photoexcited Energy Transfer in a Weakly Coupled Dimer.

Nonadiabatic excited-state molecular dynamics (NA-ESMD) simulations have been performed in order to study the time-dependent exciton localization during energy transfer between two chromophore units of the weakly coupled anthracene dimer dithia-anthracenophane (DTA). Simulations are done at both low temperature (10 K) and room temperature (300 K). The initial photoexcitation creates an exciton which is primarily localized on a single monomer unit. Subsequently, the exciton experiences an ultrafast energy transfer becoming localized on either one monomer unit or the other, whereas delocalization between both monomers never occurs. In half of the trajectories, the electronic transition density becomes completely localized on the same monomer as the initial excitation, while in the other half, it becomes completely localized on the opposite monomer. In this article, we present an analysis of the energy transfer dynamics and the effect of thermally induced geometry distortions on the exciton localization. Finally, simulated fluorescence anisotropy decay curves for both DTA and the monomer unit dimethyl anthracene (DMA) are compared. Our analysis reveals that changes in the transition density localization caused by energy transfer between two monomers in DTA is not the only source of depolarization and exciton relaxation within a single DTA monomer unit can also cause reorientation of the transition dipole.

The sequential dissociation of protonated polyethylene glycols

Early investigations of protonated polyethylene glycol fragmentation suggested the dissociation mechanism includes both direct and sequential processes. Experiments designed to study the proposed mechanisms of sequential dissociation are absent from the literature. In order to obtain additional experimental details about the fragmentation reactions, the dissociation of protonated polyethylene glycol was studied by energy-dependent collision-induced dissociation (CID). Key fragment ions were separated by mass differences corresponding to the loss of single monomer units. Several fragment ions were also generated by in-source fragmentation and studied by CID. These experiments indicate the primary ions undergo sequential dissociation by the loss of either one or two monomer units. The results suggest that at least two different mechanisms must be considered to explain the sequential dissociation of protonated polyethylene glycols. The reaction involving the elimination of two subunits suggests the loss of a six-membered 1,4-dioxane product, while the elimination of a single subunit involves the loss of acetaldehyde by a 1,2-hydride shift rearrangement.

The scope for synthesis of macro-RAFT agents by sequential insertion of single monomer units

The scope for synthesis of new macro-RAFT agents (Z–C(S)S–(M)–R) by sequential insertion of monomers (M) ‘one at a time’ into an initial RAFT agent (Z–C(S)S–R) has been explored. The process is illustrated with the preparation of a styrene-N-isopropylacrylamide (NIPAM) co-dimer macro-RAFT agent [(CH3)3C(CN)–CH2CH(Ph)–CH2CH(CONHiPr)–SC(S)–S-alkyl] by successive single unit monomer insertions into a cyanoisopropyl trithiocarbonate. Critical factors for success are a high transfer constant for the RAFT agent and a high rate of addition of the radical (R·) to monomer relative to further propagation. With these conditions satisfied, the rate of reaction is largely determined by the rate of R· adding to monomer. Initiator-derived by-products (Z–C(S)S–(M)–I) become an issue when R· is different from the initiator-derived radical (I·).

Utilization of 2-alkenoic acids for biosynthesis of medium-chain-length polyhydroxyalkanoates in metabolically engineered Escherichia coli to construct a novel chemical recycling system

This study describes the biosynthesis and thermal degradation of medium-chain-length polyhydroxyalkanoate (PHA), focusing on 2-alkenoic acids as a recyclable carbon source. Using metabolically engineered Escherichia coli, PHA consisting of 3-hydroxydecanoate (3HD) was synthesized from 2-decenoic acid. Solvent cast film of poly(3HD) [P(3HD)] was transparent and showed thermal property similar to that of polycaprolactone. In addition, the use of various 2-alkenoic acids (C6-C12) resulted in production of PHAs with over 95 mol% of the corresponding single monomer units. The pyrolysis product of P(3HD) was dominantly 2-decenoic acid used for the P(3HD) biosynthesis. This demonstrates the feasibility of PHA recycling via 2-alkenoic acids, which act as pyrolysis products and raw materials for PHA biosynthesis.