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Native chemical ligation (NCL) allows the chemical synthesis of proteins and peptides with excellent efficiency, starting from a mixture of unprotected short peptide fragments. The chemo and regioselectivity of NCL provide access to functional biomacromolecules such as peptides without protection-deprotection strategies under mild conditions. In contrast, less progress has been made in non-natural polymer conjugation. Metal contamination, synthetic difficulties, laborious purifications or lack of functional group tolerance limit complex functional polymer design. Here, we have studied the potential of NCL for non-natural polymer conjugation. Diblock and ABA triblock copolymers were synthesized via NCL with high efficiency within one hour at room temperature. An A-alt-B block copolymer was also synthesized with a re- markable degree of polymerization from bifunctional thioester and cysteine end functional polymers. The SEC and NMR spectroscopy analyses of the synthesized polymers confirmed the block structure of the polymers and the excellent efficiency of NCL for non-natural polymer conju- gation.

The capability of ring-opening metathesis polymerization (ROMP) to efficiently incorporate bulky monomers and conserve olefin bonds during polymerization was exploited to design water-soluble fluor...

The ultrasound-induced cleavage of macromolecules has become a routine experiment in the emerging field of polymer mechanochemistry. To date, it has not been conclusively proven whether the molecular weight of a polymer or its contour length is the determining factor for chain scission upon ultrasonication. Here we report comparative experiments that confirm unequivocally that the contour length is the decisive parameter. We utilized postpolymerization modifications of specifically designed precursor polymers to create polymers with identical chain length but different molecular mass. To demonstrate the universality of the findings, two different polymer backbones were utilized—poly(styrene) and poly(norbornene imide alkyne)—whose molecular weights were altered by bromination and removal of pendant triisopropylsilyl protecting groups, respectively. Solutions of the respective polymer pairs were subjected to pulsed ultrasound at 20 kHz and 10.4 W/cm² in order to investigate the chain scission trends. The effects of cleavage and sonochemical treatments were monitored by size exclusion chromatography. In both series, experimental data and calculations show that the molecular weight reduction upon sonication is the same for polymers with the same contour length.

The synthesis of perfectly planar, bis-substituted aromatic polyamides is reported herein. With highly flexible triethylene glycol chains attached and conformational restriction through intramolecular, bifurcated hydrogen bonds these are among the most shape-persistent yet organo-soluble polymers to date. Starting from 4-nitrosalicylic acid, our group developed a route to phenyl-2,5-bis-TEGylated aminobenzoate, which could be polymerized by addition of lithium bis(trimethylsilyl)amide (LiHMDS). Since this technique has not been applied to step-growth polycondensations of polyaramides so far, the influence of two different solvents and an N-protective group was investigated. Therefore, substituted phenyl aminobenzoate derivatives carrying a free amine or an N-protective group have been polymerized. Additionally, the tendency for self-assembly of the readily soluble bis-TEGylated poly(p-benzamide) was observed by transmission electron microscopy (TEM) in the dried state. Dynamic light scattering (DLS) measurements of chloroform solutions did not indicate the formation of aggregates. Thus, intermolecular interactions, which other aromatic polyamides typically exhibit, are prevented. The access to bis-substituted, entirely rigid poly(p-benzamide)s via this new polycondensation method paves the way for exciting new structures in materials science and supramolecular chemistry.

We have synthesized monodisperse “hairy rod oligomers” based on oligo(p-benzamide)s carrying alkyl side chains and conjugated them with polydisperse poly(ethylene glycol) (PEG) chains. The well-defined oligomers were synthesized from 4-amino-2-hexyloxybenzoic acid using a commercial peptide synthesizer. The PEG conjugated hairy rod−coil block copolymers self-assemble in polar and nonpolar organic solvents. The self-organization in solution was investigated by dynamic light scattering (DSL) and transmission electron microscopy (TEM) as a function of solvent, equilibration time, and polarity of the substrate. Individual fibers and fiberlike bundles of aggregates could be observed. As all hydrogen bond donors are intramolecularly saturated in these aramide oligomers, we propose π-stacking as the aggregation mechanism for this novel class of substituted oligoaramides. NMR studies on a model compound support this assumption.

Rod−coil copolymers with an oligomeric rod aggregate on a nanometer length scale, which is important for many applications like e.g. organic photovoltaics. However, this aggregation behavior and the driving forces such as hydrogen bonding and π−π interactions, as well as the role of side groups, are not yet fully understood. Here, we investigated these noncovalent interactions in oligo(p-benzamide)−poly(ethylene glycol) (OPBA−PEG) copolymers using solid-state NMR supported by wide-angle X-ray scattering (WAXS), differential scanning calorimetry (DSC), and polarization optical microscopy (POM). It was found that longer OPBAs form layered β-sheet-like aggregates and that these are stabilized by amide hydrogen bonds in both unsubstituted OPBAs and OPBA−PEG rod−coil copolymers. The binding of the PEG also introduces a liquid crystalline phase. As a consequence, the local structural order is improved in the copolymer. Thus, by combining different methods of structural investigation, we were able to develop a m...

By combining sacrificial synthesis with the vinyl lactone termination technique, heterotelechelic polymers were synthesized. The nonterminating nature of sacrificial synthesis was utilized to introduce a hydroxyl group at the start of the polymer chain. Lactone termination was used to functionalize the chain ends with aldehydes or carboxylic acids. The synthesis of well-defined heterotelechelic polymers was thus accomplished employing the Grubbs’ first generation catalyst as the initiator. The living nature of this polymerization allowed for precise control over the molecular weight and guaranteed full functionalization of both polymer chain ends. The presence of the functional groups is shown by MALDI-ToF and NMR measurements. Also, labeling experiments with chromophores were conducted to demonstrate the utility of such heterotelechelic polymer chains.

Organo-soluble, shape-persistent oligo- and poly(p-benzamide)s were synthesized and characterized. A triethylene glycol (TEG) substituent was introduced to the p-aminobenzoic acid monomer structure as a solubilizing side chain giving 4-amino-2-triethylene glycol benzoic acid. This new monomer was polymerized by the facile polycondensation of the corresponding acid halide derivative of the amine hydrochloric salt. Additionally, a well-defined heptamer was prepared from this monomer on a peptide synthesizer as a model compound. The TEG-substituted oligomers and polymers exhibited good solubility yet high aggregation tendency in common polar and nonpolar organic solvents. The solution self-organization of the poly(2-TEG-p-benzamide) was examined by GPC, NMR, and UV/vis spectroscopy. Transmission electron microscopy (TEM) allowed the visualization of the supramolecular assemblies, showing the formation of micrometer-sized rigid superstructures.

The synthesis of well-defined and highly functionalized thiol-functionalized polymers has been accomplished via the ring-opening metathesis polymerization (ROMP). A sacrificial synthesis-based approach was chosen for this interesting functional group since it has proven to give precise control over molecular weight and selective placement of end-groups on a different functionality before. Thiol-functionalized ROMP-polymers were successfully synthesized employing thioacetal monomers, which can be cleaved by hydrogenation leaving the desired thiol group behind. The placement of this highly reactive functional group at one chain end of a poly(norborneneimide) is demonstrated by analytical methods such as MALDI−ToF mass spectroscopy and 1H NMR of derivatized polymers. By kinetic measurements, the functionalization efficiency and the polymerization characteristics of the used dithiepine monomer were determined. In a first demonstration, the coating of gold nanoparticles is shown as one interesting application ...

The synthesis of well-defined telechelic ring-opening metathesis polymers has been achieved by Sacrificial Synthesis. With the formation of cleavable triblock-copolymers, precise control over the molecular weight and the degree of functionalization was achieved. Introducing cleavable monomers that can be addressed separately, sequential deprotection was accomplished which opened the path to more sophisticated polymeric materials bearing different substituents at their respective chain ends. Sacrificial penta- and heptablock-copolymers are also presented which allow the synthesis of well-defined telechelic polymers in good yields and significantly improved initiator efficiency.

A photosensitizer core has been covalently incorporated into a hyperbranched polyether polyol structure, using a one-step protocol. Partially deprotonated 2,2‘,4,4‘-tetrahydroxybenzophenone was used as initiator in the anionic polymerization of glycidol, yielding hyperbranched polyglycerols with benzophenone core in every macromolecule formed. Molecular weights in the range of 1500 to 5800 g/mol and moderate polydispersity (1.3 < Mw/Mn < 2) were obtained. Incorporation of the functional core was unequivocally evidenced by MALDI−TOF mass spectroscopy. Further modification via acetylation of the polyglycerol hydroxyl groups afforded polymers of lowered polarity. The photochemical and photophysical behavior of the obtained benzophenone core-containing hyperbranched polyglycerols has been investigated in a variety of solvents and compared with that of the model compound 2,2‘,4,4‘-tetramethoxybenzophenone. The hyperbranched polymer periphery induced molecular weight-dependent properties in the photoactive core...

A fully automated large-scale synthesis procedure has been developed that allows the preparation of supramolecular rod−coil copolymers on a 100 g scale. The new reaction cycle allows the stepwise growth of oligo(p-benzamide)s onto the chain end of amine-terminated polymers. Amine-terminated poly(ethylene glycol) (PEG, Mn = 5000 g mol-1) and poly(styrene) (PS, Mn = 2950 g mol-1) were prepared, and an octa(p-benzamide) oligomer block was grown from the chain end in an automated computer-controlled reaction cycle. Plotting the apparent molecular weight of the PEG copolymer against the number of reaction cycles revealed a linear relationship, which emphasized the high level of control this method offers. The block copolymers show strong aggregation in nonpolar solvents such as chloroform. Remarkably, transmission electron microscopy images of drop-cast chloroform solutions show perfectly uniform rodlike micelles for the PEG and the PS copolymer.

With the increase in complexity of functional polymers in recent years, MALDI-ToF has become an important tool for gaining precise information on polymer functionality, end groups, and, in special cases, molecular weights. Here we describe how pencil lead, deposited by simply drawing with a regular pencil onto conventional MALDI-ToF targets, can be used as a very attractive matrix for MALDI-ToF mass spectrometry of synthetic polymers. Highly sensitive polymers such as silyl hydride functional poly(styrene), poly(butadiene), and poly(isoprene) have been investigated using conventional MALDI-ToF matrices as well as pencil lead. In all cases, the use of pencil lead prevented oxidation of the highly sensitive silyl hydride end groups. It is shown that pencil lead represents an interesting alternative to the commonly used matrices in the range between 400 and 6000 g/mol due to the convenient way of deposition, its low cost, nontoxicity, and chemical inertness under sample preparation conditions.