In 2021, the EDC focuses on „Polymers and Surfactants in Detergents and Cleaning Agents – Effects, Benefits, and Applications “. We will discuss the role of natural and synthetic ingredients in detergents and cleaners, as well as their production and modification and aspects of sustainability and environmental friendliness.

Spoken Language: English Category: Fundamental Research The self-assembly of block copolymers in solution is controlled by polarity differences of the blocks towards the selective solvent. The block volume or better yet the volume ratios control the shape of the micelle. While block copolymer micelles in the form of spheres, cylinders and vesicles have been studied in detail in the past 25 years,[1] it was discovered only recently[2] that high asymmetry in favor of the hydrophobic block leads to block copolymer microparticles with an inner morphology of highly ordered channel systems.[3] These channel systems often adopt triply periodic minimal surfaces with cubic (lm3m), double diamond (Pn3m) and gyroid lattice – termed cubosomes, or inverse hexagonal (HII) phases as the organic analogues to mesoporous silica – termed hexosomes. In this presentation, I summarize recent progress from us and others to understand the formation of these inverse morphologies and how to introduce specific functionalities through block chemistry, e.g. carbonization for energy conversion, biodegradation for drug release, and fluorescens for bioimaging.[4,5] Literature: [1]  Y. Mai, A. Eisenberg, Chem. Soc. Rev. 2012, 41, 5969–5985. [2]  Y. La, C. Park, T. J. Shin, S. H. Joo, S. Kang, K. T. Kim, Nat. Chem. 2014, 6, 534–541. [3]  C. K. Wong, X. Qiang, A. H. E. Müller, A. H. Gröschel, Prog. Polym. Sci. 2020, 102, 101211. [4]  C. K. Wong, M. Heidelmann, M. Dulle, X. Qiang, S. Förster, M. H. Stenzel, A. H. Gröschel, J. Am. Chem. Soc. 2020, 142, 10989–10995. [5]  H. Chen, Y. Fan, N. Zhang, S. Trépout, B. Ptissam, A. Brûlet, B. Z. Tang, M.-H. Li, Chem. Sci. 2021, 16, 6511–6512.

Spoken Language: English Category: Fundamental Research Polyelectrolytes are water-soluble macromolecules and when two polyelectrolytes of opposite charge are mixed together in solution, interpolyelectrolyte complexes (IPECs) are formed[1]. IPECs formed by ionic-assembly in aqueous solutions have attracted broad scientific interest. Depending on their molecular build-up, their behavior and properties in aqueous solution are affected by pH, ionic strength, and temperature. In the present work, polyanions and polycations were synthesized via Atom Transfer Radical Polymerization (ATRP) and were subsequently employed for forming IPECs. As polyanions, we synthesized hydrophobically modified polyacrylates (hm-PAA) with a length of 100 monomer units containing acrylic acid and alkyl-acrylates with a statistical distribution of the monomers along the chain. The hydrophobicity was modified by changing the length of the alkyl chain, in our case, we used butyl and dodecyl and their amount as 10 and 20-mol%. In addition to that, the double­-hydrophilic cationic copolymer poly (2-(dimethylamino)ethylmeth-acrylate)-b-polyethylene oxide (PDMAEMA-b-PEO) was synthesized as a block copolymer. For obtaining diblock copolymers monomethylated PEO (mPEO) was used as a macroinitiator, where the PEO block ensures IPEC solubility at equimolar mixing ratios, biocompatibility, and low toxicity [2]. Detailed information regarding their IPECs structures in solutions formed by complexation with PDMAEMA-b-PEO was obtained by static and dynamic light scattering (SLS, DLS) and small angle neutron scattering (SANS). References: [1] Pergushov D V., Müller AHE, Schacher FH (2012) Micellar interpolyelectrolytecomplexes. Chem Soc Rev 41:6888–6901. [2] Pioge S, Fontaine L, Gaillard C, et al (2009) Self-assembling properties of well defined poly(ethylene oxide)-b-poly (ethyl acrylate) diblock copolymers. Macromolecules 42:4262–4272.

Spoken Language: English Category: Fundamental Research The combination of polymers as thickener with microemulsions as carrier for hydrophobic substances result in an interesting colloidal system. A main interest is to control the structure and properties of those polymer-microemulsion systems by changing the different parameters, such as pH, salt, or temperature. Formerly, hydrophobically modified (HM) multiarm polymers were investigated in mixtures with oil-in-water (O/W) microemulsions in respect to network formation and the resulting rheologic properties. The hydrophobic domains interact with the hydrophobic core of the microemulsion and form interconnected networks where the microemulsion droplets acted as knots and the hydrophilic polymer chain as linkers [1,2]. Of special interest are hydrophobically modified thermo-responsive (HMTR) block-polymers in aqueous solution which can be used as thermo-active thickeners or thermo-responsive amphiphiles for solubilization of hydrophobic molecules. However, the solubilization capacity of such systems is generally low. Hence, the combination with microemulsions (MEs) as carriers for hydrophobic substances results in loaded systems, where the rheologic properties of the microemulsion solution can be tuned and switched via temperature. A biofriendly microemulsion consisting of Tween 20 (polyoxyethylene-(20)-sorbitan monolaurate) as surfactant, ethylhexylglycerol as cosurfactant, isopropylpalmitate as oil and water as solvent was used. The HMTR block-polymers have a dodecyl chain as hydrophobic modification, ~200 units of N,N‑dimethylacrylamide as permanently hydrophilic block, and 30 units of a thermo-responsive monomer with a lower critical solution temprerature such as N-isopropylacrylamide [3]. The structure of the ME-polymer aggregates in aqueous solution was investigated in the temperature range of 20‑60°C for concentrations between 0.5‑5 %wt by scattering techniques and rheology. References [1] P. Malo de Molina, C. Herfurth, A. Laschewsky, and M. Gradzielski, Langmuir 28, 15994 (2012). [2] P. Malo de Molina, M.S. Appavou, and M. Gradzielski, Soft Matter 10, 5072 (2014). [3] M. Hechenbichler, A. Laschewsky, and M. Gradzielski, Colloid Polym. Sci. 299, 205 (2021).

Spoken Language: English Category: Fundamental Research The self-assembly behaviour of oppositely charged polyelectrolyte surfactant complexes (PESCs) is very rich and quite a number of structurally different arrangements such as pearl-necklace structures,  rodlike aggregates, uni- or multilamellar vesicles has been reported.[1] Aside from fundamental scientific interest, PESCs have found application in cosmetics, detergency and enhanced oil recovery EOR.[2] Some PESCs show a remarkable increase in viscosity near charge equilibrium, while other very similar systems do not show any appreciable effect. The exact structural prerequisites to achieve a significant increase in viscosity are still unclear. Here, we study PESCs consisting of the cationic polydiallyldimethylammonium chloride (PDADMAC) and sodium dodecylsulfate (SDS) and compare the results to the previously investigated PESCs of SDS and the cationically modified hydroxyethyl cellulose (JR 400). [3] Under similar conditions, PDADMAC based PESCs do not significantly increase the viscosity of solutions, as was observed for JR 400. The observed differences in the macroscopic viscosity were linked to the differences in the mesoscopic structure, explicitly confirmed by the small angle neutron scattering (SANS). While JR 400 /SDS PESCs would form an interdigitated complex structure, the PDADMAC /SDS would favour the formation of a segregated core-shell structure. The latter one is less efficient in anchoring the PE to the complex, resulting in less pronounced increase in viscosity. [1] Gradzielski, M.; Hoffmann, I. Current opinion in colloid & interface science 2018, 35, 124–141. [2] Chiappisi, L.; Simon, M.; Gradzielski, M. ACS Appl. Mater. Interfaces 2015, 7, 6139–6145. [3] Hoffmann,  I.;  Farago,  B.;  Schweins,  R.;  Falus,  P.;  Sharp,  M.;  Prévost,  S.;  Gradzielski, M. J. Chem. Phys. 2015, 143, 074902.

Spoken Language: English Category: Fundamental Research Nature produces efficiently unlimited amounts of polysaccharides (PS) with structural diversity and functional versatility. By chemical modification of PS, a myriad of novel functional polymers with designed properties is available; PS and their derivatives will be increasingly used in commercial applications and thus contribute to a sustainable world. In the frame of our studies to design the structure and hence properties of water soluble PS derivatives, novel concepts for the PS chemistry are developed in addition to the conventional direct modification of the functional groups by etherification or esterification. A novel approach is based on reactive platform derivatives of PS containing sulfonic acid ester- and phenyl carbonate moieties (T. Heinze et. al., in Cellulose Science and Technology – Chemistry, Analysis, and Applications, Th. Rosenau, A. Potthast, J. Hell (Eds.), John Wiley & Sons, 2018, pp. 1-18). The preparation of PS phenyl carbonates could be easily carried out under homogeneous reaction conditions applying various reaction systems including Ionic Liquids, which are not only most efficient solvents but also environmentally friendly due to their inherent properties like stability and recyclability. The phenyl carbonate groups, which may possess different functions in the aromatic systems to control their reactivity, are easily accessible to nucleophilic displacement reactions using multifunctional amines that are also important naturally occurring molecules. Thus, a broad variety of novel, finally completely bio-based and water soluble PS derivatives could be obtained that were studied regarding their activity as redeposition inhibitors and soil release agents. Representative results of derivatives of different PS backbones (cellulose, xylan) of different degrees of substitution obtained by conversion with hydroxyalkyl amines, which contains oxygen atoms and secondary and tertiary amino moieties in the spacers, will be presented (WO 2019/243071; WO 2015/044061). From these studies, structure-properties relations can be concluded to optimize the structure for these applications.

Spoken Language: English Award Session: Young Scientist Award – Master thesis: Jan Nilles Young Scientist Award – Doctoral thesis: Dr. Lars Gabriel

Spoken Language: English Category: Fundamental Research Polysaccharide are the most important biopolymers and thus, a well available and sustainable source for bio-based functional polymers. While cellulose or starch are well investigated and their derivatives are commercially used to a large extent, the chemical modification of a myriad of other polysaccharides is not studied in detail. Therefore, my work was focused on the heterogeneously feasible carboxymethylation and sulfoethylation of different polysaccharides to generate water soluble products, on one hand. On the other hand, the available but underestimated hemicellulose xylan was studied regarding modular synthesis approaches to produce new soluble functional polymers. The water-soluble products obtained were characterized in detail and their effect as detergent additives was evaluated. The carboxymethylation was performed for a variety of polysaccharides to analyse their reactivity under technical relevant conditions. The reaction-influencing parameters were varied and interpreted. The sulfoethylation was also studied in detail by varying relevant reaction parameters and comparing the reaction behaviour of different polysaccharides. In case of chitosan, chemoselective conversions of hydroxyl- and amino groups could be achieved for these etherification reactions and even mixed sulfoethyl-carboxymethyl ethers became available. The interaction of these anionic polysaccharides derivatives with cellulose surface was investigated by QCM-D measurements and a significant effects as anti-greying agents in detergents could be shown. Xylan was converted into xylan phenylcarbonate as reactive intermediate for modular synthesis approaches. Using a variety of different amines, xylan phenylcarbonates were converted into functional xylan carbamates that demonstrate their versatility as activated intermediates. Xylan carbamates were studied regarding their bioactivity and their thermal- and hydrophobic properties. In addition, they are active as soil-release additive in detergents.

Spoken Language: English Category: Fundamental Research Since more than two decades renewable natural oils constantly gain importance in the manufacturing of surfactants. However the source of this natural part of surfactants is not diverse but depends largely on palm kernel oil and to a smaller extent on coconut oil. Lauric oils for many reasons became the standard in oleo chemistry. Alternative available natural oils based on plants that grow in the moderate zone of the globe would bio-diversify the one-way road to oleo based surfactants. Vegetable oils from the temperate zone are different to those from the tropical part of the earth. The carbon chain length of these triglycerides are longer (C18) and depending on the oil there is a higher degree of unsaturation, demonstrated in the individual iodine numbers. This clearly has effects in chemical reactions and in applications as well. The double bonds of C18 polyunsaturated fatty acids (C18-PUFA) with respect to melting point and viscosity show similar behaviors like branching in saturated C-chains with the advantage of very good biodegradation properties of the C18-PUFAs. Chemical modifications in principle are also possible at the double bonds. On the other hand this increased reactivity asks for a higher attention as usual when working with unsaturated substances. In this respect quality of raw materials and the use of natural anti-oxidants support good sensorial characteristics. In any case surfactants based on plant oils of the moderate zone are not drop-in solutions in home care consumer goods. Two examples oleylglucamides from sunflower oil and cationic surfactants from sunflower/rapseed oil are shown.  New developed formulations with these surfactants show at least comparable performance versus cleaning products containing current palm kernel oil/coconut oil. It can be concluded that C18-UFA based plant oils enlarge the base of oleo feedstocks for sustainable surfactants.

Spoken Language: English Category: Fundamental Research Laundry detergents consumers are adopting more sustainable washing habits, such as low temperature wash and use of concentrated liquid detergents. This creates new challenges for the performance of this type of detergents, in particular for stain removal. We show the latest lab work results where we demonstrate  the importance of water quality in laundry stain removal process and how green chelate GLDA enhances stain removal and boosts performance of concentrated liquid detergents.

Poster 31 Marta Wojcieszak, Poznan University of Technology: "Surface Properties of Morpholinium Herbicidal Ionic Liquids" Poster 32 Alessia Costantini, UNIRED SRL: "Project Design of a Mild Cleanser for Oily Acne Prone Skin" Poster 33 Maximilian Krappel, Universität Stuttgart: "Efficiency Boosting of Surfactants in Microemulsions with Novel Amphiphilic Poly(ethylene oxide)-poly(alkyl glycidyl ether) Polymers" Find further information on the page: Poster Presentations

Spoken Language: English Category: Fundamental Research Dye transfer is an unwanted severe effect in household washing processes. Loose dye from colored fabrics can stain white or light-colored clothes and lead to an unpleasant discoloration. Todays color detergents contain polymers, which are effective as dye transfer inhibitors (DTI) especially for cottons but much less effective for delicate fibers like polyamide, which is prone to take up dyes from all different fiber types. Many different ideas have been evaluated in recent years to overcome this problem and a proof of concept was found for various DTI concepts. But to further improve the dye transfer inhibition performance of a detergent, it is important to understand the molecular interactions of detergent components like anionic and nonionic surfactants and DTI polymer with dye in solution and at interfaces. We used atomic force microscopy (AFM) directly in aqueous mixtures to characterize the adsorbed layers of dye, surfactant [1] and DTI polymer on graphite as model surface, which allowed the allocation of individual components. Quantitative adsorption studies on carbon black as well as UV-Vis spectroscopy and surface tension measurements complete the picture. Two different mechanisms were found to play a decisive role in the adsorption of dye on surfaces in the presence of surfactants [2]: the competitive adsorption of individual components and the incorporation of dye into hemicylindrical surfactant aggregates on model surfaces. As known from DTI polymer in solution, a dye-polymer complex is formed on model surfaces above the CAC of the polymer. In the presence of surfactants above the CMC, the adsorption of the polymer is inhibited due to the dominant adsorption of surfactants. References [1] W. von Rybinski, M. Jabnoun, J. van Megen, F. Oesterhelt and C. Seidel, Colloid Polym Sci, 293 2015, 3107-3117. [2] Y.Zhan, “Study of Interactions between Surfactant, Polymer and Dye in Solution and at Interfaces“ Dissertation Heinrich-Heine-Universität Düsseldorf (2020)

Spoken Language: English Category: Fundamental Research We present a new disinfectant cleaner technology that imparts long lasting disinfection properties to treated surfaces. It combines specific surfactants, quat-based biocidal actives and a proprietary polymer to achieve optimal cleaning and disinfection, together with ability of the cleaned surface to withstand multiple cycles of abrasion and remain free of microbial recontamination.  The technology relies on interactions between micelles of the biocidal quaternary ammonium compounds and the polymer. Such interaction is investigated by X-ray diffraction measurements that show the appearance of long range interactions between quaternary ammonium micelles in presence of polymer. Other additives in the cleaning formula, in particular detergency surfactants, are carefully selected to provide optimal cleaning performance while preserving the specific interaction of polymer and quaternary ammonium biocides. When deposited on the surface during the cleaning process, the polymer-quaternary ammonium complexes allow trapping the quat biocidal actives on the surface in a sub-micronic invisible film that protects them from repeated abrasion.  We show that low level release of the quats by the film when contacted by bacteria or virus is sufficient to allow the surface to self-sanitize after more than 6 wet-and-dry abrasion cycles and microbial recontaminations. Besides best-in-class cleaning and disinfection performances, thorough microbiological testing of the formula demonstrates long lasting disinfection against virus and bacteria compliant with most stringent world standards, including US EPA RSS and UK BSI PAS2424.

Spoken Language: English Category: Fundamental Research The innovative easy-to-clean concept with hydrophilic protective layers, which are formed by functional collagen peptides on cleaned surfaces, enables the development of more environmentally friendly cleaning agents that work effectively even in mild pH conditions. In addition to a convincing cleaning result, extended cleaning cycles, lower water consumption and easier cleaning are already documented advantages. During the cleaning process, surfactants displace the dirt and a hydrophilic protein film forms on the cleaned surface as a natural surface protection. Depending on the nature of the cleaner used, surfactants are also absorbed on and in the protective film. When rinsed with water, these layers partially dissolve and release the surfactants, while a thin protein layer remains as surface protection. It has been shown that this mechanism can be used effectively to combat biofilms. Using real-time measurements on a quartz crystal microbalance, it was possible to show, for example, that milk could be effectively cleaned off the hydrophilic protective layer as a model system. Further studies investigated the protective effect of the hydrophilic protein layer against surface adhesion and growth of microorganisms. In addition, the transport or fixation of active substances, such as biocidal quaternary ammonium compounds and esterquats, on cleaned surfaces is also conceivable, with which surfaces can be temporarily protected against pathogenic substances.

Spoken Language: English Category: Fundamental Research Saponins are amphiphilic molecules which are found in a large variety in nature, granting them the attribute bio-surfactants. Most of these molecules have very strong biological effects e.g. haemolytic activity. This is due to the rather strong interaction with lipid membranes. In the present contribution we study the interaction of glycyrrhizin with lipid vesicles (namely DMPC [1] and DOPG based). Glycyrrhizin is of great interest due to its interesting self-assembly behavior and also due to its potential anti-viral activity. Moreoever, in contrast to other saponins, it is less haemolytic. First, the general shape of the structures formed upon mixing the saponin with lipids is analyzed by cryogenic transmission electron microscopy (cryo-TEM) in the case of pure DOPG and a sample with the highest glycyrrhizin content of 50 mol%. Moreover, results from several scattering methods are employed to characterize the  size  of the formed mixed structures. Wide-angle X-ray scattering (WAXS) resolves the glycyrrhizin content-dependent acyl-chain correlation distance. Small angle scattering with neutrons and X-rays (SANS/SAXS) is used to determine the overall size, membrane thickness and, membrane contrast profile. [1]Dargel, C.; Hannappel, Y. and Hellweg, T. Heating-Induced DMPC/Glycyrrhizin Bicelle-to-Vesicle Transition: A X-Ray Contrast Variation Study, Biophys J. , 118(10), 2411-2425.

Spoken Language: English Category: Fundamental Research, Membrane Mimetic, Dug Discovery Polymers and detergents are important membrane mimetics. To tune the properties of polymers for individual applications, design rules are crucially needed. For this purpose, a modular polymer architecture will be introduced to membrane protein research: dendritic polyglycerol. Polymers are commonly described as ‘cookie cutters’ that punch out membrane proteins and the surrounding lipidome from membranes. Surprisingly, amphiphilic polyglycerol sulphate leaves membrane structures intact and enables their purification. This leads to new purification concepts for membrane proteins and sheds light on the widespread utility of detergents for the purification of functional membrane proteins. Moreover, amphiphilic polyglycerol sulphate enables the analysis of functional drug targets, such as the outer membrane protein T (OmpT), vitamin B12 transporter (BtuCD), and G protein-coupled receptors (GPCRs). The modular construction of dendritic polymers facilitates structure-property studies and will revolutionize the discovery of custom-made polymers for future applications in structural biology and drug discovery.

Spoken Language: English Category: Fundamental Research Investigation of carbon dioxide (CO2) as sustainable resource is of fundamental interest for research and industrial applications. It can be used as a building block in chemical compounds such as polymers or surfactants.[1] Substituting ethylene oxide (EO) units in abundantly produced non-ionic EO-surfactants by CO2 can increase the sustainability and save natural and fossil resources. Similarly interesting, introducing CO2 gives a new tuning parameter for non-ionic surfactants, allowing to better match particular application requirements and thereby a more economical consumption and potentially even opening up pathways for novel formulations.[2] The solubilization potential of CO2 towards industrial relevant oils (decane, isopropylpalmitate, bis(2-ethylhexyl)carbonate) with different polarity has been characterized by small-angle neutron scattering (SANS) and compared with data from static and dynamic light scattering (SLS, DLS), interfacial tension measurements (IFT) and quantitative NMR (qNMR). At a given surfactant concentration, the use of CO2-containing surfactants can greatly increase the solubilization capacity for oils compared to that of conventional EO-surfactants, as the incorporation of CO2 into the head group renders the surfactant more effective with respect to their interfacial activity. Funding: This project is part of “DreamResourceConti” (033R222C) and funded by the German Federal Ministry of Education and Research (BMBF) within the funding priority “r+Impuls – Innovative Technologien für Ressourceneffizienz – Impulse für industrielle Ressourceneffizienz”. References: [1] J. Langanke, J. Hofmann, K. Böhm, M. Subhani, T. Müller, W. Leitner, C. Gürtler, “Carbon dioxide (CO2) as sustainable feedstock for polyurethane production”, Green Chem., 16, 1865-1870 (2014). [2] M. Tupinamba Lima, V. Spiering, S. Kurt-Zerdeli, D. Brüggemann, M. Gradzielski, R. Schomäcker, “The hydrophilic-lipophilic balance of carboxylate and carbonate modified nonionic surfactants”, Colloids and Surfaces A, 569, 156-163 (2019).