scholarly journals Novel ionic liquids-based extraction method that preserves molecular structure from cutin

2020 ◽  
Author(s):  
Carlos J.S. Moreira ◽  
Artur Bento ◽  
Joana Pais ◽  
Johann Petit ◽  
Rita Escórcio ◽  
...  
Keyword(s):  
Molecular Structure ◽  
Ionic Liquids ◽  
Free Acid ◽  
Molecular Structures ◽  
Hydroxyl Groups ◽  
Relative Distribution ◽  
In Planta ◽  
X Ray Scattering ◽  
Monomeric Composition ◽  
Free Hydroxyl

AbstractThe biopolyester cutin is ubiquitous in land plants, building the polymeric matrix of the plant’s outermost defensive barrier - the cuticle. Cutin influences many biological processes in planta however due to its complexity and highly branched nature, the native structure remains partially unresolved. Our aim was to define an original workflow for the purification and systematic characterisation of the molecular structure of cutin. To purify cutin we tested the ionic liquids cholinium hexanoate and 1-butyl-3-methyl-imidazolium acetate. The ensuing polymers are highly esterified, amorphous and have the typical monomeric composition as demonstrated by solid state NMR, complemented by spectroscopic (GC-MS), thermal (DSC) and x-ray scattering (WAXS) analyses. A systematic study by solution-state NMR of cryogenically milled cutins extracted from Micro-Tom tomatoes (the wild type and the gpat6 and cus1 mutants) was undertaken. Their molecular structures, relative distribution of ester aliphatics, free acid end-groups and free hydroxyl groups, differentiating between those derived from primary and secondary esters, were solved. The acquired data demonstrate the existence of free hydroxyl groups in cutin and reveal novel insights on how the mutations impact the esterification arrangement of cutin. Compared to conventional approaches, the usage of ionic liquids for the study of plant polyesters opens new avenues since simple modifications can be applied to recover a biopolymer carrying distinct types/degrees of modifications (e.g. preservation of esters or cuticular polysaccharides), which in combination with the solution NMR methodologies developed here, constitutes now essential tools to fingerprint the multi-functionality and the structure of cutin in planta.

X-ray Scattering Studies to Investigate Triple-shape Capability of Polymer Networks Based on poly(ε-caprolactone) and poly(cyclohexyl methacrylate) Segments

2009 ◽  
Vol 1190 ◽  
Author(s):  
Wolfgang Wagermaier ◽  
Dieter Hofmann ◽  
Karl Kratz ◽  
Marc Behl ◽  
Andreas Lendlein
Keyword(s):  
Molecular Structure ◽  
Shape Memory ◽  
Polymer Networks ◽  
Molecular Structures ◽  
X Ray ◽  
Long Period ◽  
X Ray Scattering ◽  
Programming Process ◽  
Crystalline Domains ◽  
Cyclohexyl Methacrylate

AbstractThe super-molecular structure and morphology of shape-memory polymers (SMP) have an evident influence on the shape-memory effect (SME). More detailed information on these structure-function relations during the dynamic processes of programming and shape recovery are required to better understand the SME. Here we explore whether wide and small angle x-ray scattering (WAXS, SAXS) in combination with deformation experiments can help to characterize and better understand the respective materials super-molecular structure (spatial organization of chain segments in crystalline and non-crystalline regions, characterized by parameters such as crystallinity, crystallite-sizes, domain-sizes and -arrangements) and its changes upon varying mechanical loads and temperature increase as stimulus. Multiphase polymer networks based on poly(ε-caprolactone) and poly(cyclohexyl methacrylate), whose molecular structures allow formation of at least two separated domains, were investigated using WAXS and SAXS, to describe the respective super-molecular structures and morphologies and their development during cyclic, thermomechanical tensile tests reproducing key features of shape-memory programming and recovery. The creation of the triple-shape capability for this AB polymer network system is performed by a one-step process, which is similar to a conventional dual-shape programming process. It could be shown via SAXS that a long period between crystalline domains exists for these polymer networks. The value of this long period changes by some nanometers as a consequence of programming and the resulting elongation of the respective sample. Further insights could be obtained by investigating WAXS diffraction peaks, detected at different steps during the thermomechanical treatment. It could be shown that crystal sizes in this polymer system remain unaffected by the programming process, while the crystallization of the stretched samples during the cooling process leads to a spatial rearrangement (preferential orientation) of crystalline domains.

scholarly journals Gas–liquid interactions in solution

2005 ◽  
Vol 77 (3) ◽  
pp. 653-665 ◽  
Author(s):  
M. F. Costa Gomes ◽  
A. A. H. Pádua
Keyword(s):  
Molecular Structure ◽  
Computer Simulation ◽  
Ionic Liquids ◽  
Quantum Chemical ◽  
Molecular Structures ◽  
Gas Solubility ◽  
Free Energies ◽  
Solvent Interactions ◽  
Macroscopic Properties

Two approaches are followed to understand how molecular interactions influence the macroscopic properties of solutions: (1) experiment, through the determination of gas solubility, and (2) computer simulation, used to evaluate microscopic properties (structural and energetic). Examples of application of these approaches are considered in order to explain the properties of solutions containing fluorinated fluids or ionic liquids. The molecular structures and interactions are described by force fields built from ab initio quantum chemical calculations. These models allow the determination of free energies from computer simulations by using appropriate energy routes provided by statistical mechanics. The macroscopic properties related to the process of dissolution of several gases are interpreted in terms of the molecular structure of the solutions and of the solute–solvent interactions.

The synthesis and structure of silica-supported bis(h5-cyclopentadienyl)dichlorotitanium(IV) complexes

1986 ◽  
Vol 51 (7) ◽  
pp. 1430-1438 ◽  
Author(s):  
Alena Reissová ◽  
Zdeněk Bastl ◽  
Martin Čapka
Keyword(s):  
Free Surface ◽  
Hydroxyl Groups ◽  
Titanium Complex ◽  
Surface Hydroxyl ◽  
Surface Hydroxyl Groups ◽  
Free Hydroxyl ◽  
Cyclopentadienyl Anion

The title complexes have been obtained by functionalization of silica with cyclopentadienylsilanes of the type Rx(CH3)3 - xSi(CH2)nC5H5 (x = 1-3, n = 0, 1, 3), trimethylsilylation of free surface hydroxyl groups, transformation of the bonded cyclopentadienyl group to the cyclopentadienyl anion, followed by coordination of (h5-cyclopentadienyl)trichlorotitanium. The effects of single steps of the above immobilization on texture of the support, the number of free hydroxyl groups, the coverage of the surface by cyclopentadienyl groups and the degree of their utilization in anchoring the titanium complex have been investigated. ESCA study has shown that the above anchoring leads to formation of the silica-supported bis(h5-cyclopentadienyl)dichlorotitanium(IV) complex.

scholarly journals The Synthesis of Poly(Vinyl Alcohol) Grafted with Fluorinated Protic Ionic Liquids Containing Sulfo Functional Groups

Molecules ◽  
2021 ◽  
Vol 26 (14) ◽  
pp. 4158
Author(s):  
Patrycja Glińska ◽  
Andrzej Wolan ◽  
Wojciech Kujawski ◽  
Edyta Rynkowska ◽  
Joanna Kujawa
Keyword(s):  
Ionic Liquids ◽  
Vinyl Alcohol ◽  
Proton Exchange ◽  
Polymer Materials ◽  
Polymerization Reaction ◽  
Poly Vinyl Alcohol ◽  
Hydroxyl Groups ◽  
Protic Ionic Liquids ◽  
Synthesis Route ◽  
Sulfo Groups

There has been an ongoing need to develop polymer materials with increased performance as proton exchange membranes (PEMs) for middle- and high-temperature fuel cells. Poly(vinyl alcohol) (PVA) is a highly hydrophilic and chemically stable polymer bearing hydroxyl groups, which can be further altered. Protic ionic liquids (proticILs) have been found to be an effective modifying polymer agent used as a proton carrier providing PEMs’ desirable proton conductivity at high temperatures and under anhydrous conditions. In this study, the novel synthesis route of PVA grafted with fluorinated protic ionic liquids bearing sulfo groups (–SO3H) was elaborated. The polymer functionalization with fluorinated proticILs was achieved by the following approaches: (i) the PVA acylation and subsequent reaction with fluorinated sultones and (ii) free-radical polymerization reaction of vinyl acetate derivatives modified with 1-methylimidazole and sultones. These modifications resulted in the PVA being chemically modified with ionic liquids of protic character. The successfully grafted PVA has been characterized using 1H, 19F, and 13C-NMR and FTIR-ATR. The presented synthesis route is a novel approach to PVA functionalization with imidazole-based fluorinated ionic liquids with sulfo groups.

scholarly journals Vibrational resonant inelastic X-ray scattering in liquid acetic acid: a ruler for molecular chain lengths

2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Viktoriia Savchenko ◽  
Iulia Emilia Brumboiu ◽  
Victor Kimberg ◽  
Michael Odelius ◽  
Pavel Krasnov ◽  
...  
Keyword(s):  
Molecular Structure ◽  
Acetic Acid ◽  
Molecular Chain ◽  
X Ray ◽  
X Ray Scattering ◽  
Localized Excitations ◽  
Vibrational Excitations ◽  
Chain Lengths ◽  
X Ray Absorption ◽  
Ray Scattering

AbstractQuenching of vibrational excitations in resonant inelastic X-ray scattering (RIXS) spectra of liquid acetic acid is observed. At the oxygen core resonance associated with localized excitations at the O–H bond, the spectra lack the typical progression of vibrational excitations observed in RIXS spectra of comparable systems. We interpret this phenomenon as due to strong rehybridization of the unoccupied molecular orbitals as a result of hydrogen bonding, which however cannot be observed in x-ray absorption but only by means of RIXS. This allows us to address the molecular structure of the liquid, and to determine a lower limit for the average molecular chain length.

Synthesis and crystal structure analyses of tri-substituted guanidine-based copper(II) complexes

2021 ◽  
Vol 76 (3-4) ◽  
pp. 193-199
Author(s):  
Muhammad Said ◽  
Sadia Rehman ◽  
Muhammad Ikram ◽  
Hizbullah Khan ◽  
Carola Schulzke
Keyword(s):  
Crystal Structure ◽  
Solid State ◽  
Molecular Structures ◽  
Hydroxyl Groups ◽  
Synthesis And Crystal Structure ◽  
Pyramidal Geometry ◽  
Tautomeric Forms ◽  
Square Planar ◽  
Nitrogen Donor ◽  
Square Pyramidal Geometry

Abstract Three guanidine-derived tri-substituted ligands viz. N-pivaloyl-N′,N″-bis-(2-methoxyphenyl)guanidine (L1), N-pivaloyl-N′-(2-methoxyphenyl)-N″-phenylguanidine (L2) and N-pivaloyl-N′-(2-methoxyphenyl)-N″-(2-tolyl)guanidine (L3) were reacted with Cu(II) acetate to produce the corresponding complexes. The significance of the substituent on N″ for the resulting molecular structures and their packing in the solid state has been studied with respect to the structural specifics of the corresponding Cu(II) complexes. The key characteristic of the guanidine-based metal complexation with Cu(II) is the formation of an essentially square planar core with an N2O2 donor set. As an exception, in the complex of L1, the substituent’s methoxy moiety also interacts with the Cu(II) center to generate a square-pyramidal geometry. The hydroxyl groups of the imidic acid tautomeric forms of L1–L3, in addition to N″, are also bonded to Cu(II) in all three complexes rather than the nitrogen donor of the guanidine motif.

Sign in / Sign up

Export Citation Format

Share Document