Prof. Nikolai D. Denkov, Ph.D., D.Sc.

Fellow of the Bulgarian Academy of Sciences

nd@lcpe.uni-sofia.bg
+359 2 8161 639
Interests
  • Foams, Antifoams and Detergency
  • Rheology of Foams and Emulsions
  • Food Emulsions and Emulsification
  • Colloid Crystals and Nanomaterials
  • Light Scattering and Electrokinetic Phenomena
Bio

Acting Head of Laboratory “Active formulations and materials” at the Department of Chemical & Pharmaceutical Engineering (DCPE), Faculty of Chemistry & Pharmacy, Sofia University, Bulgaria.

PhD (1993), DSc (2007) and Professor (2008) in Physical Chemistry. Vice Dean of the Faculty (2004-2008), Head of Department (2008-2015), Deputy Minister (2014-2016) and Minister (2017,2021-2022) of education and science of Bulgaria. He worked as visiting researcher in JRDC (Japan), senior researcher in Rhone-Poulenc R&D (France), lead scientist in Unilever R&D (USA), and guest professor in France (ESPCI-Paris and Univ. Lille).

His research includes experimental and theoretical studies on the formation, stability, rheology and applications of disperse systems, and on the surfactant control of their properties. He has published > 190 research articles, including 2 papers in Nature, 1 in Nature Physics, 1 in Nature Commun. and 17 invited reviews, cited > 10000 times in the literature (h-index = 51). He has presented > 45 plenary and invited lectures at international conferences and > 90 invited seminars in universities and research institutions around the world. He has led > 45 projects with multinational companies, incl. Unilever, BASF, PepsiCo, Saint Gobain, Wacker, Dow Corning and Heineken, and is a co-inventor of 14 filed and granted patents. Supervisor and co-supervisor of 12 completed PhD Theses, and 2 other Theses are under preparation. He is a member of the Physical Sciences working group in European Space Agency (ESA) and of the Council of the International Association of Colloid and Interface Scientists (IACIS).

For his research achievements, in 2019 Prof. Denkov was awarded the Solvay Prize of the European Colloid and Interface Society (ECIS) and was elected as a regular member of Academia Europaea. In 2020 he received the Lectureship Award of the Division of Colloid and Surface Chemistry in Japan. He is recipient of the highest national award for scientific achievements “Pythagoras” by the Bulgarian ministry of education and science (2010).

Detailed CV
Publications
Most recent publications
S. Tsibranska, S. Iliev, A. Ivanova, N. Aleksandrov, S. Tcholakova, N. Denkov
Colloids Surf. A 2024
697
134466

Medium- to long-chain alkanes can form upon cooling intermediate phases between isotropic liquid and solid crystalline, called rotator phases, where relative freedom of the molecules to rotate about their long axis is combined with long range translational order. Rotator phases are well documented experimentally but the mechanism of their formation at the molecular level is still not fully explained. In a previous work, we have shown that molecular dynamics simulations can produce rotator phases upon cooling of hexadecane [S. Iliev et al., J. Col. Int. Sci., 2023, 638, 743]. The aim of the current work is to develop a procedure to identify the specific ordered phase obtained in the simulations. The influence of the cooling rate on the freezing process of hexadecane (bulk and surfactant-interfaced to water) is tested as well. Several parameters are combined to quantify the degree of ordering and the type of phase in the studied systems. These are the tilt angle of the molecules with respect to the crystallite plane, the radial distribution function of the centre of mass of the molecules in the crystallite, the percentage of the gauche torsion angles in the molecules, the angle of the second principal axis of each molecule with respect to the x axis of the coordinate system, and estimates from Voronoi analysis. The results show that the systems form a rotator phase, which transitions gradually towards the thermodynamically most stable triclinic crystal, and the transformation progresses to different extent depending on the system. The influence of the cooling rate is related only to the size of the largest crystallite formed, the other parameters of the freezing process remain unaffected. The work also presents a robust procedure for obtaining and identifying different types of ordered phases in alkane-containing systems with thoroughly tested computational protocol and a comprehensive set of structural analyses. Several key characteristics are advanced, compared to previous research [Ryckaert et al., Mol. Phys., 1989, 67, 957; Wentzel et al., J. Chem. Phys. 2011, 134, 224504], namely, a new methodology is proposed to compute the unit cell deformation parameter and azimuthal angle from MD simulation trajectories of the freezing process in alkane-containing systems. The suggested structural analysis, which is independent of the coordinate system, is applicable to any linear-chain system with polycrystalline structure.

Triacylglycerols (TAGs) exhibit a monotropic polymorphism, forming three main polymorphic forms upon crystallization: α, β’ and β. The distinct physicochemical properties of these polymorphs, such as melting temperature, subcell lattice structure, mass density, etc., significantly impact the appearance, texture, and long-term stability of a wide range products in the food and cosmetics industries. Additionally, TAGs are also of special interest in the field of controlled drug delivery and sustained release in pharmaceuticals, being a key material in the preparation of solid lipid nanoparticles. The present article outlines our current understanding of TAG phase behavior in both bulk and emulsified systems. While our primary focus are investigations involving monoacid TAGs and their mixtures, we also include illustrative examples with natural TAG oils, highlighting the knowledge transfer from simple to intricate systems. Special attention is given to recent discoveries via X-ray scattering techniques. The main factors influencing TAG polymorphism are discussed, revealing that a higher occurrence of structural defects in the TAG structure always accelerates the rate of the α → β polymorphic transformation. Diverse approaches can be employed based on the specific system: incorporating foreign molecules or solid particles into bulk TAGs, reducing drop size in dispersed systems, or using surfactants that remain fluid during TAG particle crystallization, ensuring the necessary molecular mobility for the polymorphic transformation. Furthermore, we showcase the role of TAG polymorphism on a recently discovered phenomenon: the creation of nanoparticles as small as 20 nm from initial coarse emulsions without any mechanical energy input. This analysis underscores how the broader understanding of the TAG polymorphism can be effectively applied to comprehend and control previously unexplored processes of notable practical importance.

V. Georgiev, Z. Mitrinova, A. Gers-Barlag, G. Jaunky, N. Denkov, S. Tcholakova
Colloids Surf. A 2024
681
132838

The effects of antifoam and surfactant concentration on the foamability of solutions of an anionic (SLES) and nonionic (Brij 35) surfactants and a series of polyvinyl alcohols with 88% and 98% degree of hydrolysis and molecular masses between 31 and 205 kDa, were studied. Three methods which differ in the way of air incorporation were used for foaming – Bartsch test, shake test and Ultra Turrax. Mixed silicone oil-silica particles antifoam was studied. The antifoam was introduced in the foaming solution as pre-dispersed in organic solvent or as antifoam-in-water emulsion. It was shown that the antifoam is very active in the fast foaming methods (Bartsch and shake tests) for the slow adsorbing polymers PVA and has no any activity in the slow foaming method (Ultra Turrax) for the fast adsorbing surfactants with electrostatic stabilization (SLES). The efficiency of pre-dispersed in organic solvent antifoam is much higher as compared to that of emulsified antifoam, due to the faster segregation of the silica particles and silicone oil in the emulsified antifoam. The antifoam efficiency increases with antifoam concentration and with lowering the surfactant concentration. In a given foaming method, the antifoam efficiency is the highest in PVA solutions with 98% DH, intermediate for PVA with 88% DH and Brij 35, and the lowest for SLES solutions. At a certain degree of hydrolysis, the molecular mass of PVA has no significant effect on the antifoam activity. Good correlation between the antifoam efficiency and the stability of the pseudo emulsion film formed between the antifoam globule and the bubble surface is established, showing that the electrostatic repulsion is more efficient to prevent the entering of the antifoam globules on the air-water interface, as compared to the steric repulsion.

D. Cholakova, A. Biserova, S. Tcholakova, N. Denkov
Colloids Surf. A 2024
692
134037

Small emulsion drops typically exhibit spherical shape at positive interfacial tension due to the energy minimization principle. However, in a series of studies (Denkov et al., Nature, 2015, 528, 392–395; Cholakova et al., Nature Phys., 2021, 17, 1050–1055) we showed that alkane droplets stabilized by appropriate saturated long-chain surfactants may spontaneously change their shape upon cooling, morphing into various polyhedra; hexagonal, tetragonal and triangular platelets; rod-like particles and even synthetic swimmers. These deformations are governed by the formation of thin plastic rotator phases adjacent to the drop surface. Although alkanes have numerous industrial applications, they cannot be used in food and pharma related products, in which most often triglyceride molecules are employed. The possibility for self-shaping of triglyceride drops has been demonstrated, but the detailed understanding of the process is currently missing. In the present study, we performed model experiments aimed to reveal the conditions under which the triglyceride emulsion drops may change their shape upon cooling. We show that most of the various non-spherical shapes known for alkanes can be reproduced with triglyceride droplets providing that the surfactant adsorption layer freezes before the nucleation of the oily molecules inside the drops. By comparing the behavior of triglyceride and alkane droplets, we draw unified picture and provide guiding principles which can be used for selection of appropriate surfactants enabling the spontaneous shape deformations upon cooling of oily drops of different chemical compositions.

D. Cholakova, M. Pantov, S. Tcholakova, N. Denkov
Crystal Growth Des. 2024
24
362 - 377

Crystallization of alkane mixtures has been studied extensively for decades. However, the majority of the available data consider the behavior of alkanes with chain length of 21 C atoms or more. Furthermore, important information about the changes of the unit cell structure with the temperature is practically absent. In this work, the phase behavior of several pure alkanes CnH2n+2, with n ranging between 13 and 21, and their binary, ternary, or multicomponent equimolar mixtures are investigated by X-ray scattering techniques. Both bulk alkanes and oil-in-water emulsions of the same alkanes were studied. The obtained results show the formation of mixed rotator phases for all systems with chain length difference between the neighboring alkanes of Δn ≤ 3. Partial demixing is observed when Δn = 4, yet the main fraction of the alkane molecules arranges in a mixed rotator phase in these samples. This demixing is suppressed if an alkane with an intermediate chain length is added to the mixture. Interestingly, a steep temperature dependence of the interlamellar spacing in mixed rotator phases was observed upon cooling to temperatures down to 10 °C below the melting temperature of the mixture. The volumetric coefficient of thermal expansion of the rotator phases of mixed alkanes (αV ≈ 2 × 10-3 °C-1) is around 10 times bigger compared to that of the rotator phases of pure alkanes. The experiments performed with emulsion drops containing the same alkane mixture while stabilized by different surfactants showed that the surfactant template also affects the final lattice spacing which is observed at low temperatures. In contrast, no such dependence was observed for drops stabilized by the same surfactant while having different initial diameters; in this case, only the initial temperature of the crystallization onset was affected.

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