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We introduce the light-induced collapse of single glycopolymer chains in water generating fluorescent glyco single-chain nanoparticles (SCNPs) and their subsequent functionalization onto nanodiamonds. The glycopolymer precursors are prepared by polymerizing an acetylated mannose-based methacrylate monomer followed by a deprotection and postpolymerization functionalization step, introducing profluorescent photoactive tetrazole groups and furan-protected maleimide moieties. Subsequent UV irradiation in highly diluted aqueous solution triggers intramolecular tetrazole-mediated cycloadditions, yielding glyco SCNPs featuring fluorescence as well as lectin binding properties. The obtained SCNPs are coated onto nanodiamonds by adsorption, and the obtained hybrid nanoparticles are in depth characterized in terms of size, functionality, and bioactivity. Different coating densities are achieved by altering the SCNP concentration. The prepared nanoparticles are nontoxic in mouse RAW 264.7 macrophages. Furthermore, the fluorescence of the SCNPs can be exploited to image the SCNP-coated nanodiamonds in macrophage cells via confocal fluorescence microscopy.

Protein-based materials are widely used in biomedical applications. Often the proteins need to be crosslinked in order to be stable for application. Here, we explored the use of 5,5′-bisvanillin as a potentially non-toxic crosslinker that can react with lysine residues on proteins. To demonstrate the success of the crosslinking reaction, polymer–protein conjugates based on bovine serum albumin (BSA) and poly(N-isopropyl acrylamide) (PNIPAM) were employed. The BSA-PNIPAM conjugate is water soluble at room temperature, but heated above the cloud point, BSA-PNIPAM forms nanoparticles of around 70 nm that can again disassemble at lower temperatures. Reaction with 5,5′-bisvanillin prevented disassembly resulting in stable BSA nanoparticles of 50 nm in size. The formed nanoparticles were observed to be rather stable and were not easily cleaved in acidic conditions. The crosslinker 5,5′-bisvanillin was measured to have lower toxicity against A2780 lung cancer cell lines compared with the commonly applied crosslinker glutaraldehyde.

A λ-orthogonal reaction system is introduced, where visible light induced radical thiol-ene and UV light induced NITEC (Nitrile-Imine mediated Tetrazole-Ene Conjugation) ligations are consecutively employed to fabricate and functionalize PEG-based hydrogels. The fluorescent pyrazoline cycloadducts from the NITEC reaction are exploited to visualize the written structures within the hydrogels as well as to attach RGD containing functional groups to promote spatially resolved cell attachment on the hydrogel surface.

We introduce the direct light-driven homo-grafting and co-grafting of various functional polymers to graphitic nanodiamonds (grNDs) generated by thermal annealing of detonation nanodiamonds (NDs) via the light-induced photo-enol reaction in only two subsequent reaction steps. For instance, poly(pentafluorostyrene) and poly(N-isopropylacrylamide) were simultaneously co-grafted to NDs in a rapid, facile, catalyst free and modular fashion.

Looped flow processes are an efficient and versatile tool to synthesize complex macromolecular materials. Especially for light-induced ring-closure reactions, which typically require low concentrations, looped flow processes are critical for upscaling. Here, such a reactor was designed to carry out a photo-induced ring-closure reaction via a photo-enol reaction for the synthesis of cyclic polymers, leading to a reduction of required solvent in the synthesis by over a factor of 40, hence giving access to a more economical and fully scalable process.

A light-triggered strategy to functionalize nanodiamonds (NDs) with well-defined functional polymers is presented. The employed grafting approach is based on o-methylbenzaldehydes, which upon UV irradiation form o-quinodimethanes that undergo Diels–Alder reactions with dienophiles. A series of well-defined maleimide end-group functional polymers, i.e., poly(styrene) (Mn = 5800 g mol–1; Đ = 1.2), poly(N-isopropylacrylamide) (Mn = 5800 g mol–1, Đ = 1.2), and poly(2-(2′,3′,4′,6′-tetra-O-acetyl-α-d-mannosyloxy)ethyl methacrylate) (Mn = 24 300, 39 000, and 58 800 g mol–1, Đ ≤ 1.3), were prepared via reversible addition–fragmentation chain transfer (RAFT) polymerization of protected maleimide functional RAFT agents. After deprotection of the furan-protected maleimide end groups, the polymers were photografted to o-methylbenzaldehyde functional NDs and characterized in detail via infrared (IR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and thermogravimetric analysis (TGA). The grafting density decreas...

A pattern flood management method based on a streamline simulator was developed to support waterflood designs. The methodology was applied on a structurally complex oil field in the North German basin. Studies are being conducted to understand the potential for extending the current waterflood in this oil field. The objective of this study was to investigate if a conventional simulation-based waterflood design could be enhanced using streamline simulation. An alternative to using streamline simulation could be the post-processing of streamlines based on outputs of a full-field finite difference (FD) simulation model. However, there are limitations to this approach, including robustness and time considerations, especially when multiple runs with field-scale reservoir models are required. The streamline simulator contains a pattern flood management algorithm designed for optimizing the performance of waterfloods using multiple value criteria. The algorithm continuously balances patterns during forecasting runs converging to optimal injection and production rates while honoring well and field production constraints. A unique set of pattern performance diagnostics are ancillary products, for example pattern efficiencies and leakage fractions. The full-field FD dynamic model of the aforementioned oil field was adapted for the streamline simulator. Both simulation models delivered similar results at the field and well levels and matched historical observed data satisfactorily. The best pattern flood model converged on a rate schedule that led to a 4% increase in oil production, a 17% decrease in water production, and a 5% reduction in the water injection volumes over the best performance achieved using a conventional voidage replacement strategy in the FD model. These findings were validated by executing the full-field model on a FD simulator with the recommendations from the pattern flood simulation run. The streamline simulation runs executed about seven times faster. To investigate the well count optimization potential, rigorous analyses were performed on the pattern information produced by the enhanced runs. A 12.5% reduction in well count, in terms of injectors and producers, could be achieved, and the pattern flood management algorithm converged on a rate schedule that still led to an increase of 2.3% in oil production, a 22% decrease in water production, and a 10% reduction in injection volumes. The streamline-based simulation study proved useful in improving the existing waterflood design. Speedup in runtime allowed ample investigations and analysis within a given time period. Detailed analysis of allocated rate schedules and pattern information across numerous forecast runs gave deeper insight on the problem. The study highlighted that any well pattern has associated with it an optimal rate-scheduling strategy. Hence, the two components are important aspects of any successful waterflood design. The recommended rate schedules are model based and hence subject to uncertainty, requiring updates as additional information becomes available over time.

We report the facile ambient temperature generation of size tunable and well-defined (pro)fluorescent single-chain nanoparticles (SCNPs) via the photoinduced nitrile imine intramolecular cross-ligation of linear precursor polymers, constituting a platform technology as novel imaging agents. A set of three linear precursor polymers (Mn ≈ 14000 g mol–1, Đ ≈ 1.25) was synthesized via nitroxide-mediated statistical copolymerization of styrene and 4-(chloromethyl)styrene (CMS), followed by a postpolymerization modification of the resulting copolymer installing protected maleimide (PG-Mal) as well as tetrazole (Tet) moieties. The tetrazole content (% Tet) along the lateral polymer chains was varied between 12 and 24% in order to preselect not only the size of the corresponding SCNPs, but also their fluorescence and reactive properties. Finally, the applicability of the profluorescent SCNPs for fluorescence labeling was demonstrated utilizing residual surface expressed Tet moieties on the SCNPs surface in a reac...

We present a new ambient temperature synthetic approach for the preparation of single-chain polymeric nanoparticles (SCNPs) under mild conditions using a UV-light-triggered Diels–Alder (DA) reaction for the intramolecular cross-linking of single polymer chains. Well-defined random copolymers with varying contents of styrene (S) and 4-chloromethylstyrene (CMS) were synthesized employing a nitroxide-mediated radical polymerization (NMP) initiator functionalized with a terminal alkyne moiety. Postpolymerization modification with 4-hydroxy-2,5-dimethylbenzophenone (DMBP) and an N-maleimide (Mal) derivative led to the functional linear precursor copolymers. The intramolecular cross-linking was performed by activating the DMBP groups via irradiation with UV light of 320 nm for 30 min in diluted solution (cPolymer = 0.017 mg mL–1). The ensuing DA reaction between the activated DMBP and the Mal groups resulted in well-defined single-chain polymeric nanoparticles. To control the size of the SCNPs, random copolymer...

The current study introduces a tetrazole species able to perform a rapid, visible light induced nitrile imine-mediated tetrazole-ene cycloaddition (NITEC). Full conversion of the tetrazole species under mild, catalyst free conditions is reported. Importantly, the visible light ligation technology is applied as a method for the modification and ligation of polymers featuring the rapid, clean and exclusive formation of the desired cycloadduct.