Surface water retardation around single-chain polymeric nanoparticles: critical for catalytic function?

Stals, Patrick J. M.; Cheng, Chi‐Yuan; Beek, Lotte van; Wauters, A.C.; Palmans, Anja R. A.; Han, Songi; Meijer, E. W.

doi:10.1039/c5sc02319j

Cited by 45 publications

(48 citation statements)

References 37 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Further, the helicity of these internal domains can be tuned based on the chirality of the alkyl side chains of the BTA units . These complex internal domains have further been used to design a broad array of SCNPs, which are catalytically active in water …”

Section: Architecture Beyond Intramolecular Crosslinksmentioning

confidence: 99%

Macromolecular Superstructures: A Future Beyond Single Chain Nanoparticles

Frisch

Tuten

Barner‐Kowollik

2020

Israel Journal of Chemistry

View full text Add to dashboard Cite

Over the last 100 years polymer chemistry has flourished in all areas and enabled control over synthetic polymer architectures – including chain lengths, dispersity and monomer sequences. Compared to the architectures of biomacromolecules, these scientific achievements mainly took place on the level of primary structures. The plethora of functions carried out by proteins in nature, however, does not only result from their primary structure, but from its folding into perfectly defined 3D structures. Striving towards a similar architectural control and function in synthetic polymers, the field of single chain nanoparticles (SCNPs) emerged. In this review, we analyze the state of the art and identify what is currently standing between polymer chemistry and perfectly controlled synthetic macromolecular architectures. Based on the current challenges in the field of SCNPs, we discuss potential avenues to break today's barriers and explore future applications reaching beyond the current‐state‐of‐the‐art.

show abstract

Section: Architecture Beyond Intramolecular Crosslinksmentioning

confidence: 99%

Macromolecular Superstructures: A Future Beyond Single Chain Nanoparticles

Frisch

Tuten

Barner‐Kowollik

2020

Israel Journal of Chemistry

View full text Add to dashboard Cite

show abstract

“…Research has shown that hetero‐dimers using a Thymine‐diaminopyridine, or a Hamilton wedge‐cyanuric acid combination can be utilized for SCNP formation. In addition, self‐complementary systems can also be used, in particular 2‐Ureido‐4[1H]‐pyrimidinone (UPy) quadrupule hydrogen bonding dimerization, and Benzene‐1,3,5‐tricarboxamide (BTA) self‐assembly . BTAs show significant advantage for this purpose as they exhibit threefold hydrogen bonding and stacking that results in helical structures.…”

Section: Protein‐like Structurementioning

confidence: 99%

“…Using a suite of SCNP with varying functionality (Fig. ), the group probed BTA‐PEG‐TEMPO, hexadecyl‐PEG‐TEMPO, and unfunctionalized‐PEG‐TEMPO polymers using electron paramagnetic resonance (EPR) and Overhauser dynamic nuclear polarization (ODNP) NMR relaxometry . They discovered that using the surface water diffusivity at the surface of the SCNP is the only experimental signature that, when probed, gives any insight into the local environment around a folded and unfolded SCNP.…”

Section: Protein‐like Functionmentioning

confidence: 99%

Protein‐like structure and activity in synthetic polymers

Cole

Hanlon

Rodriguez

et al. 2016

J. Polym. Sci. Part A: Polym. Chem.

View full text Add to dashboard Cite

The structure and activity of proteins is the gold standard for functional polymeric materials. This highlight seeks to calibrate the reader with respect to recent attempts to mimic the various structural and functional traits of proteins using the techniques of modern polymer chemistry. From advances in sequence-controlled polymers (primary structure), to peptidomimetics, foldamers, single-chain nanoparticles (secondary and tertiary structure), accessing the various structural aspects of protein chemistry is a vibrant research area. Likewise, the properties and utility of proteins in applications such as catalysis and molecular recognition are being emulated in the laboratory to great effect. Rather than provide an exhaustive review on any one of these topics, this article seeks to highlight the common thread among them, encouraging discussion and collaboration that will result in the next generation of smart materials with advanced structure and function.

show abstract

“…27 Recently, Overhauser dynamic nuclear polarization NMR has been employed to investigate the local water translational diffusion dynamics at the site where catalysis would occur. 28 All these experiments have provided detailed information on the properties of SCPNs and the factors that may affect their catalytic performance. While these approaches were mostly focused on structural aspects, methods that are able to directly monitor the catalytic reaction are still lacking.…”

Section: Introductionmentioning

confidence: 99%

“…[22][23][24] A number of techniques have been employed to investigate the BTA-based SCPNs and to improve our understanding of how their 3D structures relate to their functions. [25][26][27][28] Circular dichroism (CD) spectroscopy and scattering techniques have been utilized to study their inner structure and shape; 25,26 single-molecule force spectroscopy has been introduced to provide information on the folding kinetics and pathways. 27 Recently, Overhauser dynamic nuclear polarization NMR has been employed to investigate the local water translational diffusion dynamics at the site where catalysis would occur.…”

Section: Introductionmentioning

confidence: 99%

Catalytic single-chain polymeric nanoparticles at work: from ensemble towards single-particle kinetics

Liu

Turunen

Waal

et al. 2018

Mol. Syst. Des. Eng.

Self Cite

View full text Add to dashboard Cite

a Folding a single polymer chain around catalytically active sites to construct catalytic single chain polymeric nanoparticles (SCPNs) is a novel approach to mimic the activity and selectivity of enzymes. In order to relate the efficiency of SCPNs to their three-dimensional structure, a better understanding of their catalytic activity at an individual level, rather than at an ensemble level, is highly desirable. In this work, we present the design and preparation of catalytic SCPNs and a family of fluorogenic substrates, their characterization at the ensemble level as well as our progress towards analyzing individual SCPNs with single-molecule fluorescence microscopy (SMFM). Firstly, organocopper-based SCPNs together with rhodamine-based fluorogenic substrates were designed and synthesized. The SCPNs catalyze the carbamate cleavage reaction of mono-protected rhodamines, with the dimethylpropargyloxycarbonyl protecting group being cleaved most efficiently. A systematic study focusing on the conditions during catalysis revealed that the ligand acceleration effect as well as the accumulation of substrates and catalytically active sites in SCPNs significantly promote their catalytic performance. Secondly, a streptavidin-biotin based strategy was developed to immobilize the catalytic SCPNs on the surface of glass coverslips. Fluorescence correlation spectroscopy experiments confirmed that the SCPNs remained catalytically active after surface immobilization. Finally, single-SCPN activity measurements were performed. The results qualitatively indicated that fluorescent product molecules were formed as a result of the catalytic reaction and that individual fluorescent product molecules could be detected. So far, no evidence for strongly different behaviors has been observed when comparing individual SCPNs.

show abstract

Surface water retardation around single-chain polymeric nanoparticles: critical for catalytic function?

Abstract: A library of water-soluble dynamic single-chain polymeric nanoparticles (SCPN) was prepared using a controlled radical polymerisation technique followed by the introduction of functional groups, including probes at targeted positions.

Cited by 45 publications

References 37 publications

Macromolecular Superstructures: A Future Beyond Single Chain Nanoparticles

Macromolecular Superstructures: A Future Beyond Single Chain Nanoparticles

Protein‐like structure and activity in synthetic polymers

Catalytic single-chain polymeric nanoparticles at work: from ensemble towards single-particle kinetics

Contact Info

Product

Resources

About