First-Principles Prediction of Liquid/Liquid Interfacial Tension

Andersson, Martin; Bennetzen, Martin V.; Klamt, Andreas; Stipp, S. L. S.

doi:10.1021/ct500266z

Cited by 62 publications

(72 citation statements)

References 48 publications

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“…To gain insight as to the key attributes associated with the design of HandaPhos that impart the observed catalytic activity to its in situ‐derived palladium complex, density functional theory (DFT) calculations have been performed using the COSMO‐RS implicit solvent model . This allows for analysis of thermodynamic properties such as solubility, partitioning, interfacial tension, and reaction free energies in a two‐phase system such as exists with Nok‐derived nanomicelles in an aqueous medium. Surprisingly, the extent of partitioning of four mono‐ligated Pd catalysts containing XPhos, SPhos, IPr, or HandaPhos in this medium is predicted to be virtually identical.…”

Section: Methodssupporting

confidence: 90%

HandaPhos: A General Ligand Enabling Sustainable ppm Levels of Palladium‐Catalyzed Cross‐Couplings in Water at Room Temperature

et al. 2016

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A new monophosphine ligand, HandaPhos, has been identified that when complexed in a 1:1 ratio with Pd(OAc) 2 , forms a catalyst that is generally useful, enabling Pd-catalyzed cross-couplings to be run using ≤1000 ppm of this catalyst. Applications to heavily utilized Suzuki-Miyaura reactions involving highly funtionalized reaction partners are demonstrated, all run in the absence of organic solvents using environmentally benign nanoparticle reactors in water at ambient temperatures. Comparisons with existing state-of-the-art ligands and catalysts are discussed herein. Graphical abstract KeywordsLigand; Micellar Catalysis; Green Chemistry; E Factor; Suzuki-Miyaura couplings Ligated palladium remains among the most enthusiastically utilized catalysts in synthetic and materials chemistry. [1] The Nobel Prize awarded to Heck, Negishi, and Suzuki in 2010 serves to encourage further use and applications of these transition metal-mediated reactions. [2] Unfortunately, the world's supply of economically accessible palladium is Correspondence to: Bruce H. Lipshutz, lipshutz@chem.ucsb.edu. HHS Public Access Author Manuscript Author ManuscriptAuthor Manuscript Author Manuscript limited; i.e., it is an endangered element. [3] Hence, aside from its status as a precious and, therefore, costly metal, there is considerable incentive to address this issue from the perspective of sustainability. Perhaps of equal impact, especially for the pharmaceutical industry, is the amount of residual palladium found in the products, which typically requires special processing to reduce to FDA-approved levels. Two options include a move away from palladium entirely, or use of palladium at especially low levels, and preferably, with recycling. While alternative transition metals, such as nickel [4] and copper, [5] may be attractive for certain applications, palladium remains the metal of choice. Traditional uses of palladium catalysts under homogeneous conditions in organic solvents tend to employ catalyst loadings in range of 1-5 mol %. While there are isolated examples in the literature where ppm, [6] and even ppb, [6c-e] levels have been reported, none is of any generality and in virtually all cases, forcing conditions are required. Moreover, regardless of the extent of Pd invested per reaction, neither catalyst nor solvent is typically fully recycled, creating considerable organic waste especially at scale.In this report, we disclose a truly general, mild, efficient, and environmentally sustainable technology based on the new ligand, racemic "HandaPhos." When combined in a 1:1 ratio with Pd(OAc) 2 , [7] a pre-catalyst results that, via in situ reduction, enables Pd-catalyzed reactions, most notably Suzuki-Miyaura cross-couplings, to be run in water at room temperature using ppm levels of palladium ( Figure 1A). In essence, the level of ligated palladium that need be invested can be reduced by 1-2 orders of magnitude. To No other technology of this generality and environmental attractiveness is currently known.Traditional P...

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Section: Methodssupporting

confidence: 90%

HandaPhos: A General Ligand Enabling Sustainable ppm Levels of Palladium‐Catalyzed Cross‐Couplings in Water at Room Temperature

et al. 2016

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“…COSMO and COSMO-RS models are widely presented nowadays in different program complexes for molecular modeling. It shows good results in calculating of the range of parameters (for example, adsorption constants, 15 pK a values, 16 and interfacial tension 17 ). In this procedure the solvent is represented by an ideal conductor for which the total electrostatic potential due to solute and solvent wipes out on the solute boundary.…”

Section: Methodsmentioning

confidence: 99%

Quantum Chemical Approach in the Description of the Amphiphile Clusterization at the Air/Liquid and Liquid/Liquid Interfaces with Phase Nature Accounting. I. Aliphatic Normal Alcohols at the Air/Water Interface

et al. 2015

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A new model based on the quantum chemical approach is proposed to describe structural and thermodynamic parameters of clusterization for substituted alkanes at the air/liquid and liquid/liquid interfaces. The new model by the authors, unlike the previous one, proposes an explicit account of the liquid phase (phases) influence on the parameters of monomers, clusters and monolayers of substituted alkanes at the regarded interface. The calculations were carried out in the frameworks of the quantum chemical semiempirical PM3 method (Mopac 2012), using the COSMO procedure. The new model was tested in the calculations of the clusterization parameters of fatty alcohols under the standard conditions at the air/water interface. The enthalpy, Gibbs' energy and absolute entropy of formation for alcohol monomers alongside with clusterization parameters for the cluster series including the monolayer at air/water interface were calculated. In our calculations the sinkage of monomers, molecules in clusters and monolayers was varied from 1 up to 5 methylene groups. Thermodynamic parameters calculated using the proposed model for the alcohol monolayers are in a good agreement with the corresponding experimental data. However, the proposed model cannot define the most energetically preferable immersion of the monolayer molecules in the water phase.

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“…[17] Predictions of interfacial tension,u sing the slightly updated version of the method with geometrica veraging of coverages during the IFT iterations [18] are based on the BP-TZVP-C1601 parameterization [19] in the COSMOtherm [20] program and the interfacial tension (IFT) model by Andersson et. al [21] For determining the internal structures in large nanoparticles, we used the weight factor functionality in COSMOtherm to model the PEG region and the core region of the surfactant as different molecules. Three different conformers were used for the TPGS-750-M surfactant with 16 ethylene oxide units to take into account surfactant flexibility.F or the interfacial tension modelt ob er eliable, neutral molecules are needed; hence, we modeled the deprotonated form of vitamin Es uccinate with bound Na, Ka nd Rb counterions to neutralize the charge.…”

Section: Computational Detailsmentioning

confidence: 99%

Structure of Nanoparticles Derived from Designer Surfactant TPGS‐750‐M in Water, As Used in Organic Synthesis

Andersson

Gallou

Klumphu

et al. 2018

Chemistry A European J

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Using density functional theory and the COSMO-RS implicit solvent model, we predict the structure and physical chemical properties of nanomicelles derived from the designer surfactant TPGS-750-M used in organic synthesis. We predict that the influence of chain length of the PEG region is low, while the termination of the PEG chain (-OH vs.-OCH ) plays a very large role. The interfacial tension is considerably lower between the micellar and water phases for the -OH than the -OCH terminated surfactant, and our calculations reproduce the large difference observed in average particle size as a function of PEG chain termination. We propose a structure for the nanoparticles formed by TPGS-750-M in water that is consistent with a ≈50 nm average diameter, which is significantly larger than a single micelle. According to the calculations, each nanoparticle would consist of 30-40 aggregated TPGS-750-M micelles forming a compartmentalized nanoparticle, with considerable amounts of water in the PEG region. The whole particle is stabilized by vitamin E succinate at the nanoparticle-water interface. In the presence of Zn dust or powder, the surfactant collides with the Zn surface, and by interactions with the hydrophobic inner cores, form organozinc species that are protected from the surrounding water. This explains why highly moisture-sensitive Negishi-like couplings take place in surfactant-water systems.

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First-Principles Prediction of Liquid/Liquid Interfacial Tension

Cited by 62 publications

References 48 publications

HandaPhos: A General Ligand Enabling Sustainable ppm Levels of Palladium‐Catalyzed Cross‐Couplings in Water at Room Temperature

HandaPhos: A General Ligand Enabling Sustainable ppm Levels of Palladium‐Catalyzed Cross‐Couplings in Water at Room Temperature

Quantum Chemical Approach in the Description of the Amphiphile Clusterization at the Air/Liquid and Liquid/Liquid Interfaces with Phase Nature Accounting. I. Aliphatic Normal Alcohols at the Air/Water Interface

Structure of Nanoparticles Derived from Designer Surfactant TPGS‐750‐M in Water, As Used in Organic Synthesis

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