2023-07-25, Cölfen, Helmut

Analytical ultracentrifugation (AUC) is a classical polymer and colloid analysis technique invented by Theodor Svedberg 100 years ago. Modern hard- and software and powerful computers make it now possible to develop the methodology beyond what was possible with this technique before. This perspective aims to describe new possibilities, which extend the possibilities of AUC beyond the classical repertoire of the determination of distributions of sedimentation coefficient, particle size, and molar mass as well as stoichiometries and interaction constants of interacting systems. High-resolution simultaneous characterization of particle size and optical property distributions, investigation of nucleation by reaction in the AUC cell, characterization of particle interactions at a very high concentration, and characterization of complex fluids or osmotic pressures over large concentration ranges even crossing phase boundaries are among the discussed topics. They show that even after 100 years of successful application, AUC still has much yet unexplored potential in colloid and polymer science. Graphical Abstract This perspective paper spans from the days of invention of analytical ultracentrifugation to now including nonmainstream methodology and instrumentation, which has a huge potential for the future. This includes multiwavelength detectors, high-resolution particle size distributions, chemical reactions in the ultracentrifuge, high-concentration work, osmotic pressure distributions, and characterization of complex fluids.

2023-03-30, Chen, Zongkun, Schmid, Ralf, Wang, Xingkun, Fu, Mengqi, Han, Zhongkang, Fan, Qiqi, Scheer, Elke, Huang, Minghua, Nielaba, Peter, Cölfen, Helmut

Two-dimensional (2D) materials prepared by a solution-phase growth route exhibit many unique properties and are promising for use in various fields. However, simple, rational and green fabrication of target materials remains challenging due to the lack of guiding principles. Here we propose a universal qualitative model for 2D materials grown for layered and non-layered crystal structures by a solution-phase growth route; both theoretical simulation and experimental results confirm the model’s validity. This model demonstrates that 2D growth can be controlled by only tuning the reaction concentration and temperature, and has been applied to fabricate more than 30 different 2D nanomaterials in water at room temperature and in the absence of additives. Furthermore, the model shows promise for optimizing the experimental design of numerous other 2D nanomaterials.

2023, Feng, Yanhuizhi, Cölfen, Helmut, Xiong, Rui

Cellulose is the most abundant naturally-occurring polymer, and possesses a one-dimensional (1D) anisotropic crystalline nanostructure with outstanding mechanical robustness, biocompatibility, renewability and rich surface chemistry in the form of nanocellulose in nature. Such features make cellulose an ideal bio-template for directing the bio-inspired mineralization of inorganic components into hierarchical nanostructures that are promising in biomedical applications. In this review, we will summarize the chemistry and nanostructure characteristics of cellulose and discuss how these favorable characteristics regulate the bio-inspired mineralization process for manufacturing the desired nanostructured bio-composites. We will focus on uncovering the design and manipulation principles of local chemical compositions/constituents and structural arrangement, distribution, dimensions, nanoconfinement and alignment of bio-inspired mineralization over multiple length-scales. In the end, we will underline how these cellulose biomineralized composites benefit biomedical applications. It is expected that this deep understanding of design and fabrication principles will enable construction of outstanding structural and functional cellulose/inorganic composites for more challenging biomedical applications.

2023, Gruber, Dominik, Ruiz Agudo, Cristina, Cölfen, Helmut

Cationic complex coacervates are contemplated for various medical applications controlling carrier or release processes. Here, lower Mw poly(allylamine hydrochloride) (15 kg/mol) and (hydrogen)phosphate as cross-linking units were chosen to facilitate a sufficient coacervation and subsequently a controllable phosphate release, essential for consecutive mineralization reactions. In addition, the rheological characteristics of the obtained coacervates were assessed, exhibiting a pronounced liquid character, which enables beneficial properties toward remineralization applications such as high wettability and moldability. In light of our results, macroscopic hydrogels are considered for the first time as an ion source for the mineralization of crystalline calcium phosphate phases, representing an entirely new class of preceding mineralization species for potential applications in dentistry and osteology.

2023-07-24, Meldrum, Fiona C., Cölfen, Helmut

2023-02, Madeja, Benjamin, Avaro, Jonathan Thomas, Van Driessche, Alexander E.S., Rückel, Markus, Wagner, Elisabeth, Cölfen, Helmut, Kellermeier, Matthias

True control over the morphology of gypsum crystals formed via homogeneous precipitation from solution has rarely been reported in the literature. In this work, we have tested a large number of dissolved additives (polymers as well as small molecules) with respect to their ability to alter the typical microscopic appearance of precipitated gypsum powders, which is usually characterized by a mixture of single-crystalline needles and twinned plates. Among the many additives studied, a copolymer of vinylpyrrolidone and acrylic acid (PVP-co-PAA) was identified as powerful growth modifier for gypsum already at low concentrations. In both slow titration and rapid mixing experiments, unconventional blocky crystals with tilted stacking edges as well as pseudo-hexagonal plates could be synthesized reproducibly with the help of the copolymer. Systematic characterization revealed the dynamic mode of action of the newly identified growth modifier, which seems to stabilize a highly reactive face of gypsum and promote the formation of macrosteps. The degree of morphological control achieved in this way is unprecedented in the case of calcium sulfate and may devise entirely new concepts for additive design in the areas of plasters and cementitious materials, gypsum wallboard production and/or scale prevention.

2023, Konsek, Julian, Knaus, Jennifer, Avaro, Jonathan Thomas, Sturm, Elena V., Cölfen, Helmut

A novel approach for the production of a bioinspired dentine replacement material is introduced. An apatite–gelatin nanocomposite material was cross-linked with various cross-linkers. These nanocomposites have a high resemblance to mammalian dentine regarding its composition and properties. A precipitation reaction was used to produce apatite–gelatin nanocomposites as starting materials. Cross-linking of the gelatin has to be performed to produce dentine-like and thus tough and robust apatite–gelatin nanocomposites. Therefore, the efficacy of various protein cross-linkers was tested, and the resulting materials were characterized by scanning electron microscopy, transmission electron microscopy, powder X-ray diffraction, and EXAFS as well as CHNS analysis and tested for their mechanical performance using Vickers hardness measurements as well as for their dissolution stability in EDTA. Especially glutaraldehyde, proanthocyanidins, and transglutaminase gave promising results with hardness values of up to 63 HV0.2. To further improve the material properties, we combined the effective cross-linker transglutaminase with casein, which led to an improved interconnection between the single nanocomposite platelets. By doing so, a cross-linked composite was obtained, which shows even higher hardness values than does human dentine, at 76 HV_0.2. The combination of apatite–gelatin nanocomposites with an effective cross-linker resulted in a bioinspired material with composition and properties close to those of human dentine.

2023-07-19, Avasthi, Ilesha, Lerner, Harry, Grings, Jonas, Gräber, Carla, Schleheck, David, Cölfen, Helmut

Mineral plastics are a promising class of bio-inspired materials that offer exceptional properties, like self-heal ability, stretchability in the hydrogel state, and high hardness, toughness, transparency, and non-flammability in the dry state along with reversible transformation into the hydrogel by addition of water. This enables easy reshape-ability and recycling like the solubility in mild acids to subsequently form mineral plastics again by base addition. However, current mineral plastics rely on petrochemistry, are hardly biodegradable, and thus persistent in nature. This work presents the next generation of mineral plastics, which are bio-based and biodegradable, making them a promising, new class of polymers for the development of environmentally friendly materials. Physically cross-linked (poly)glutamic-acid (PGlu)-based mineral plastics are synthesized using various alcohol-water mixtures, metal ion ratios and molecular weights. The rheological properties are easily adjusted using these parameters. The general procedure involves addition of equimolar solution of CaCl₂ to PGlu in equal volumes followed by addition of iPrOH (iPrOH:H₂O = 1:1) under vigorous stirring conditions. The ready biodegradability of PGlu/CaFe mineral plastic is confirmed in this study where the elements N, Ca, and Fe present in it tend to act as additional nutrients, supporting the growth of microorganisms and consequently, promoting the biodegradation process.

2023, Chen, Zongkun, Fan, Qiqi, Huang, Minghua, Cölfen, Helmut

Since the intercalation of anions into layered hydroxides (LHs) has a great impact not only on their nucleation and growth but also on their structure, composition, and size, the intercalation chemistry of LHs has aroused the strong interest of researchers. However, the progress in the fundamental understanding of LHs intercalated with guest anions have not been paralleled by a concomitant development of the preparation and performance improvement of such materials. Considering the guidance of a timely in-depth review for scientists in this area, a systematic introduction about the development that is made on the above-mentioned issues is highly needed but yet missing so far. Herein, recent advances in understanding the chemical composition and structure of LHs intercalated with guest anions are systematically summarized. Meanwhile, typical and emerging bottom-up synthesis methods of LHs intercalated with anions are reviewed, and the potential impact of external reaction parameters on the intercalation of anions into LHs are discussed . Besides, different analytical characterization techniques employed in the examination of guest anion-intercalated LHs are deliberated upon. Finally, although progress is slow in exploring the intercalation mechanism, as many examples as possible are included in this review and inferred the possible intercalation mechanism.

2023, Burgos‐Ruiz, Miguel, Elert, Kerstin, Ruiz‐Agudo, Encarnacion, Cölfen, Helmut, Rodriguez‐Navarro, Carlos

The relatively recent development of nanolimes (i.e., alcoholic dispersions of Ca(OH)2 nanoparticles) has paved the way for new approaches to the conservation of important art works. Despite their many benefits, nanolimes have shown limited reactivity, back-migration, poor penetration, and lack of proper bonding to silicate substrates. In this work a novel solvothermal synthesis process is presented by which extremely reactive nanostructured Ca(OH)2 particles are obtained using calcium ethoxide as the main precursor species. Moreover, it is demonstrated that this material can be easily functionalized with silica-gel derivatives under mild synthesis conditions, thereby preventing particle growth, increasing total specific surface area, enhancing reactivity, modifying colloidal behavior, and functioning as self-integrated coupling agents. Additionally, the formation of calcium silicate hydrate (CSH) nanocement is promoted by the presence of water, resulting in optimal bonding when applied to silicate substrates, as evidenced by the higher reinforcement effect produced on treated Prague sandstone specimens as compared to those consolidated with nonfunctionalized commercial nanolime. The functionalization of nanolimes is not only a promising strategy for the design of optimized consolidation treatments for the cultural heritage, but may also have important implications for the development of advanced nanomaterials for building, environmental, or biomedical applications.