Control of Crystalline-Amorphous Structures of Polyhedral Oligomeric Silsesquioxanes Containing Two Types of Ammonium Side-Chain Groups and Their Properties as Protic Ionic Liquids

Polyhedral oligomeric silsesquioxanes (POSSs), Am-POSS(x,y), prepared by hydrolytic condensation, contains two types of ammonium side-chain groups, where the numbering of x and y represents the type of ammonium ions in the POSS structure, corresponding to primary (1), secondary (2), tertiary (3), and quaternary (4) ammonium ions. Mixtures of the two starting materials selected from organotrialkoxysilanes containing primary, secondary, and tertiary amines and a quaternary ammonium salt [(RO)3Si(CH2)3R′, R = CH3 or CH2CH3, R′ = NH2, NHCH3, N(CH3)2, and N(CH3)3Cl] were dissolved in dimethyl sulfoxide (DMSO). The hydrolytic condensation was performed in the presence of bis(trifluoromethansulfonyl)imide (HNTf2) and water. All Am-POSS(x,y) structures consisted of a cage-type octamer (T8-POSS), as confirmed by 29Si NMR spectrometry and matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS). Differential scanning calorimetry (DSC) and X-ray diffraction (XRD) analyses indicated that Am-POSS(1,3), Am-POSS(1,4), and Am-POSS(2,4) had amorphous structures. These POSSs have two or three differences in the number of methyl groups between the two types of ammonium side-chains. Conversely, Am-POSS(1,2), Am-POSS(2,3), and Am-POSS(3,4) had crystalline structures. The difference in the number of methyl groups between the two types of ammonium side-chains in these POSSs is only one. Therefore, the crystalline-amorphous structure of Am-POSS(x,y) is controlled by the side-chain group combinations. Furthermore, Am-POSS(1,3), Am-POSS(1,4), and Am-POSS(2,4) are protic ionic liquids with relatively low flow temperatures.

Download Full-text

Percolation Phase Transition from Ionic Liquids to Ionic Liquid Crystals

Scientific Reports ◽

10.1038/s41598-019-49493-3 ◽

2019 ◽

Vol 9 (1) ◽

Author(s):

Shen Li ◽

Yanting Wang

Keyword(s):

Phase Transition ◽

Ionic Liquid ◽

Ionic Liquids ◽

Chain Length ◽

Complex Fluids ◽

Dynamics Simulation ◽

Coarse Grained ◽

Side Chain ◽

Side Chains ◽

Side Chain Length

Abstract Due to their complex molecular structures and interactions, phase behaviors of complex fluids are quite often difficult to be identified by common phase transition analysis methods. Percolation phase transition, on the other hand, only monitors the degree of connection among particles without strict geometric requirements such as translational or orientational order, and thus suitable for pinpointing phase transitions of complex fluids. As typical complex fluids, ionic liquids (ILs) exhibit phases beyond the description of simple liquid theories. In particular, with an intermediate cationic side-chain length, ILs can form the nanoscale segregated liquid (NSL) state, which will eventually transform into the ionic liquid crystal (ILC) structure when the side chains are adequately long. However, the microscopic mechanism of this transformation is still unclear. In this work, by means of coarse-grained molecular dynamics simulation, we show that, with increasing cationic side-chain length, some local pieces of non-polar domains are gradually formed by side chains aligned in parallel inside the NSL phase, before an abrupt percolation phase transition happens when the system transforms into the ILC phase. This work not only identifies that the NSL to ILC phase transition is a critical phenomenon, but also demonstrates the importance of percolation theory to complex fluids.

Download Full-text

Biomimetic design of protic lipidic ionic liquids with enhanced fluidity

New Journal of Chemistry ◽

10.1039/c6nj00657d ◽

2016 ◽

Vol 40 (9) ◽

pp. 7795-7803 ◽

Cited By ~ 4

Author(s):

Richard A. O'Brien ◽

Manuel Sanchez Zayas ◽

Stephen T. Nestor ◽

Jamie C. Gaitor ◽

Lauran M. Paul ◽

...

Keyword(s):

Ionic Liquids ◽

Side Chains ◽

Protic Ionic Liquids ◽

Biomimetic Design

Synthesis of low-melting protic ionic liquids with C16–C20 side chains via the S-alkylation of the methimazole ring.

Download Full-text

New Functionalized Ionic Liquids Based on POSS for the Detection of Fe3+ Ion

Polymers ◽

10.3390/polym13020196 ◽

2021 ◽

Vol 13 (2) ◽

pp. 196

Author(s):

Wensi Li ◽

Shengyu Feng

Keyword(s):

Ionic Liquids ◽

Metal Ions ◽

Self Assembly ◽

Mass Spectra ◽

Click Reaction ◽

Fluorescent Sensors ◽

29Si Nmr ◽

Polyhedral Oligomeric Silsesquioxanes ◽

New Materials ◽

Thermal Stabilities

This study reports a novel series of imidazolium ionic liquids (ILs) based on polyhedral oligomeric silsesquioxanes (POSS) towards effective detection of metal ions, especially Fe3+ ion. 1H, 13C, 29Si NMR, high resolution mass spectra (HRMS) and Fourier transform infrared spectra (FTIR) were applied to confirm the structures of the ILs based on POSS (ILs-POSS). The three ILs-POSS were synthesized via a green chemistry approach—a thiol-ene “click” reaction without metal ions as catalysts. Furthermore, the spherical vesicle structures of the ILs-POSS were observed and caused by self-assembly behaviors. Through comprehensive characterizations, these ILs-POSS have performed excellent thermal stabilities and low glass transition temperatures. In addition, we found it very meaningful that the limits of detection (LODs) of the three ILs-POSS for the detection of the Fe3+ ion were 7.91 × 10−8 M, 1.2 × 10−7 M, and 1.2 × 10−7 M, respectively. These data illustrate that these ILs-POSS have great potential for the detection of the Fe3+ ion. In conclusion, this study not only prepared novel ILs-POSS, but also provided new materials as fluorescent sensors in the detection of Fe3+.

Download Full-text

Preparation of protic ionic liquids containing cyclic oligosiloxane frameworks

RSC Advances ◽

10.1039/c7ra00656j ◽

2017 ◽

Vol 7 (17) ◽

pp. 10575-10582 ◽

Cited By ~ 8

Author(s):

T. Hirohara ◽

T. Kai ◽

J. Ohshita ◽

Y. Kaneko

Keyword(s):

Ionic Liquids ◽

Protic Ionic Liquids ◽

Thermal Stabilities ◽

Hydrolytic Condensation ◽

Condensation Method

Protic ionic liquids containing cyclic oligosiloxane frameworks, which were prepared by the hydrolytic condensation method, exhibited relatively high thermal stabilities.

Download Full-text

Influence of Flexible Side-Chains on the Breathing Phase Transition of Pillared Layer MOFs: A Force Field Investigation

10.26434/chemrxiv.11720679.v1 ◽

2020 ◽

Author(s):

Julian Keupp ◽

Johannes P. Dürholt ◽

Rochus Schmid

Keyword(s):

First Principles ◽

Good Accuracy ◽

Field Investigation ◽

Square Lattice ◽

Side Chain ◽

Second Step ◽

Side Chains ◽

Dynamics Simulations ◽

Complex Phenomena ◽

Closed Pore

The prototypical pillared layer MOFs, formed by a square lattice of paddle- wheel units and connected by dinitrogen pillars, can undergo a breathing phase transition by a “wine-rack” type motion of the square lattice. We studied this not yet fully understood behavior using an accurate first principles parameterized force field (MOF-FF) for larger nanocrystallites on the example of Zn 2 (bdc) 2 (dabco) [bdc: benzenedicarboxylate, dabco: (1,4-diazabicyclo[2.2.2]octane)] and found clear indi- cations for an interface between a closed and an open pore phase traveling through the system during the phase transformation [Adv. Theory Simul. 2019, 2, 11]. In conventional simulations in small supercells this mechanism is prevented by periodic boundary conditions (PBC), enforcing a synchronous transformation of the entire crystal. Here, we extend this investigation to pillared layer MOFs with flexible side-chains, attached to the linker. Such functionalized (fu-)MOFs are experimen- tally known to have different properties with the side-chains acting as fixed guest molecules. First, in order to extend the parameterization for such flexible groups, 1a new parametrization strategy for MOF-FF had to be developed, using a multi- structure force based fit method. The resulting parametrization for a library of fu-MOFs is then validated with respect to a set of reference systems and shows very good accuracy. In the second step, a series of fu-MOFs with increasing side-chain length is studied with respect to the influence of the side-chains on the breathing behavior. For small supercells in PBC a systematic trend of the closed pore volume with the chain length is observed. However, for a nanocrystallite model a distinct interface between a closed and an open pore phase is visible only for the short chain length, whereas for longer chains the interface broadens and a nearly concerted trans- formation is observed. Only by molecular dynamics simulations using accurate force fields such complex phenomena can be studied on a molecular level.

Download Full-text

Effects of Amino Acid Side-Chain Length and Chemical Structure on Anionic Polyglutamic and Polyaspartic Acid Cellulose-Based Polyelectrolyte Brushes

Polymers ◽

10.3390/polym13111789 ◽

2021 ◽

Vol 13 (11) ◽

pp. 1789

Author(s):

Dmitry Tolmachev ◽

George Mamistvalov ◽

Natalia Lukasheva ◽

Sergey Larin ◽

Mikko Karttunen

Keyword(s):

Glutamic Acid ◽

Chain Length ◽

Chemical Structure ◽

Side Chain ◽

Side Chains ◽

Side Chain Length ◽

Polyelectrolyte Brushes ◽

Grafting Density ◽

The Difference ◽

Cellulose Surface

We used atomistic molecular dynamics (MD) simulations to study polyelectrolyte brushes based on anionic α,L-glutamic acid and α,L-aspartic acid grafted on cellulose in the presence of divalent CaCl2 salt at different concentrations. The motivation is to search for ways to control properties such as sorption capacity and the structural response of the brush to multivalent salts. For this detailed understanding of the role of side-chain length, the chemical structure and their interplay are required. It was found that in the case of glutamic acid oligomers, the longer side chains facilitate attractive interactions with the cellulose surface, which forces the grafted chains to lie down on the surface. The additional methylene group in the side chain enables side-chain rotation, enhancing this effect. On the other hand, the shorter and more restricted side chains of aspartic acid oligomers prevent attractive interactions to a large degree and push the grafted chains away from the surface. The difference in side-chain length also leads to differences in other properties of the brush in divalent salt solutions. At a low grafting density, the longer side chains of glutamic acid allow the adsorbed cations to be spatially distributed inside the brush resulting in a charge inversion. With an increase in grafting density, the difference in the total charge of the aspartic and glutamine brushes disappears, but new structural features appear. The longer sides allow for ion bridging between the grafted chains and the cellulose surface without a significant change in main-chain conformation. This leads to the brush structure being less sensitive to changes in salt concentration.

Download Full-text

Ion conformation and orientational order in a dicationic ionic liquid crystal studied by solid-state nuclear magnetic resonance spectroscopy

Scientific Reports ◽

10.1038/s41598-021-85021-y ◽

2021 ◽

Vol 11 (1) ◽

Author(s):

Debashis Majhi ◽

Sergey V. Dvinskikh

Keyword(s):

Ionic Liquid ◽

Ionic Liquids ◽

Liquid Crystals ◽

Bond Order ◽

Van Der Waals ◽

Orientational Order ◽

Smectic Phase ◽

Side Chains ◽

Dicationic Ionic Liquid ◽

Ionic Liquid Crystals

AbstractIonic liquids crystals belong to a special class of ionic liquids that exhibit thermotropic liquid-crystalline behavior. Recently, dicationic ionic liquid crystals have been reported with a cation containing two single-charged ions covalently linked by a spacer. In ionic liquid crystals, electrostatic and hydrogen bonding interactions in ionic sublayer and van der Waals interaction in hydrophobic domains are the main forces contributing to the mesophase stabilization and determining the molecular orientational order and conformation. How these properties in dicationic materials are compared to those in conventional monocationic analogs? We address this question using a combination of advanced NMR methods and DFT analysis. Dicationic salt 3,3′-(1,6-hexanediyl)bis(1-dodecylimidazolium)dibromide was studied. Local bond order parameters of flexible alkyl side chains, linker chain, and alignment of rigid polar groups were analyzed. The dynamic spacer effectively “decouples” the motion of two ionic moieties. Hence, local order and alignment in dicationic mesophase were similar to those in analogous single-chain monocationic salts. Bond order parameters in the side chains in the dicationic smectic phase were found consistently lower compared to double-chain monocationic analogs, suggesting decreasing contribution of van der Waals forces. Overall dication reorientation in the smectic phase was characterized by low values of orientational order parameter S. With increased interaction energy in the polar domain the layered structure is stabilized despite less ordered dications. The results emphasized the trends in the orientational order in ionic liquid crystals and contributed to a better understanding of interparticle interactions driving smectic assembly in this and analogous ionic mesogens.

Download Full-text

Unusual Structural Features in the Adduct of Dirhodium Tetraacetate with Lysozyme

International Journal of Molecular Sciences ◽

10.3390/ijms22031496 ◽

2021 ◽

Vol 22 (3) ◽

pp. 1496

Author(s):

Domenico Loreto ◽

Giarita Ferraro ◽

Antonello Merlino

Keyword(s):

Anticancer Agents ◽

Structural Features ◽

Side Chain ◽

Side Chains ◽

Valuable Insight ◽

Experimental Conditions ◽

Egg White Lysozyme ◽

Potential Applications ◽

Model Protein ◽

Hen Egg White

The structures of the adducts formed upon reaction of the cytotoxic paddlewheel dirhodium complex [Rh2(μ-O2CCH3)4] with the model protein hen egg white lysozyme (HEWL) under different experimental conditions are reported. Results indicate that [Rh2(μ-O2CCH3)4] extensively reacts with HEWL:it in part breaks down, at variance with what happens in reactions with other proteins. A Rh center coordinates the side chains of Arg14 and His15. Dimeric Rh–Rh units with Rh–Rh distances between 2.3 and 2.5 Å are bound to the side chains of Asp18, Asp101, Asn93, and Lys96, while a dirhodium unit with a Rh–Rh distance of 3.2–3.4 Å binds the C-terminal carboxylate and the side chain of Lys13 at the interface between two symmetry-related molecules. An additional monometallic fragment binds the side chain of Lys33. These data, which are supported by replicated structural determinations, shed light on the reactivity of dirhodium tetracarboxylates with proteins, providing useful information for the design of new Rh-containing biomaterials with an array of potential applications in the field of catalysis or of medicinal chemistry and valuable insight into the mechanism of action of these potential anticancer agents.

Download Full-text