Towards the Application of Supramolecular Self-Associating Amphiphiles as Next-Generation Delivery Vehicles

Herein, we present a series of supramolecular self-associating amphiphilic (SSA) salts and establish the potential for these molecular constructs to act as next-generation solution-state molecular delivery vehicles. We characterise the self-association of these SSAs, both alone and when co-formulated with a variety of drug(like) competitive guest species. Single crystal X-ray diffraction studies enable the observation of hydrogen-bonded self-association events in the solid state, whilst high resolution mass spectrometry confirms the presence of anionic SSA dimers in the gas-phase. These same anionic SSA dimeric species are also identified within a competitive organic solvent environment (DMSO-d6/0.5% H2O). However, extended self-associated aggregates are observed to form under aqueous conditions (H2O/5.0% EtOH) in both the absence and presence of these competitive guest species. Finally, through the completion of these studies, we present a framework to support others in the characterisation of such systems.

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Synthesis and characterization of meso-to-meso directly linked porphyrin-diazaporphyrin triads

Journal of Porphyrins and Phthalocyanines ◽

10.1142/s1088424618500633 ◽

2018 ◽

Vol 22 (09n10) ◽

pp. 814-820

Author(s):

Yingying Jia ◽

Ling Xu ◽

Bangshao Yin ◽

Mingbo Zhou ◽

Jianxin Song

Keyword(s):

Nickel Complex ◽

High Resolution Mass Spectrometry ◽

Dihedral Angles ◽

X Ray Diffraction ◽

Extinction Coefficients ◽

X Ray ◽

H Nmr ◽

First Time ◽

Molar Extinction Coefficients

Beginning with 5,10,15-triarylporphyrin-nickel complex, five meso-to-meso directly linked porphyrin-diazaporphyrin triads were successfully prepared for the first time through a series of reactions including formylation via Vilsmeier–Haack reaction, condensation with pyrrole, bromination with [Formula: see text]-Bromosuccinimide (NBS), oxidation with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), metal-templated cyclization of dibromodipyrrin-metal complexes with NaN[Formula: see text] and demetalization. All these triads were comprehensively characterized by [Formula: see text]H NMR, high-resolution mass spectrometry and UV-vis absorption. In addition, the structure of compound 6Ni was unambiguously determined by X-ray diffraction analysis, which showed that the two dihedral angles are both 86.65 (4)[Formula: see text] between each mean plane of porphyrin and that of central diazaporphyrin The UV-vis absorption spectra disclosed that the longest wavelengths of Soret bands and Q bands for these triads were observed at 429 and 642 nm, respectively. In contrast to diazaporphyrin-porphyrin dyads, diazaporphyrin dimers and diazaporphyrin monomers reported previously the molar extinction coefficients, particularly for triad 8Ni are much higher.

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A Conformational Analysis of the Spirocyclic Quaternary Ammonium Cation [(CH2)4N(CH2)4]+ in its Bromide and Picrate Salts

Zeitschrift für Naturforschung B ◽

10.1515/znb-2004-0303 ◽

2004 ◽

Vol 59 (3) ◽

pp. 259-263 ◽

Cited By ~ 10

Author(s):

Uwe Monkowius ◽

Stefan Nogai ◽

Hubert Schmidbaur

Keyword(s):

Gas Phase ◽

Quaternary Ammonium ◽

Point Group ◽

High Yield ◽

X Ray Diffraction ◽

X Ray ◽

Quaternary Ammonium Cations ◽

Twist Conformation ◽

Twist Form ◽

Group D

High-yield syntheses of the bromide (1a) and picrate salts (1b) of the 5-azonia-spiro[4]nonane cation [(CH2)4N(CH2)4]+ are reported. In the single crystal X-ray diffraction analyses of the two salts the spirocyclic quaternary ammonium cations have their five-membered rings in envelop and twist conformations modified by packing forces. The conformation found experimentally for 1a has C2-symmetry as predicted for the gas phase by quantum-chemical calculations (RI-DFT, RI-MP2), but the five-membered rings are intermediate between the expected envelop and the twist form. For 1b, both of the two independent cations can be described as a combination of rings in an envelop and a twist conformation. According to the NMR spectra, in solution the cations are highly flexible and pseudosymmetrical (point group D2d)

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Polysulfonylamine, CXXV [1]. Neue Komplexe von Disulfonylaminen mit Kronenethern - im voraus entworfen oder zufällig entdeckt / Polysulfonylamines, CXXV [1]. New Complexes of Disulfonylam ines with Crown Ethers - Preconceived or Discovered by Serendipity

Zeitschrift für Naturforschung B ◽

10.1515/znb-2000-3-412 ◽

2000 ◽

Vol 55 (3-4) ◽

pp. 299-316 ◽

Cited By ~ 2

Author(s):

Dagmar Henschel ◽

Karna Wijaya ◽

Oliver Moers ◽

Armand Blaschette ◽

Peter G. Jones

Keyword(s):

Hydrogen Bonds ◽

X Ray Diffraction ◽

Ladder Structure ◽

Triclinic Space Group ◽

One Dimensional ◽

X Ray ◽

Bonding System ◽

Supramolecular Aggregate ◽

Guest Species ◽

The One

Abstract In a study aim ed at the „deconstruction“ of the supramolecular aggregate 3(18C6) · 2HN( SO2Me)2 (1,18C6 = 18-crown-6), which is known to display a ladder structure with two isotactic [18C6 - Me SO2N(H)SO2Me···)∞ polymers forming the uprights and symmetrically N - H···O bonded 18C6 rings providing the rungs, the following crystalline complexes were isolated and (except for 2b) characterized by low-temperature X-ray diffraction: 18C6-ClN (SO2Me)2 (2a, triclinic, space group P1̅, Z = 2), 18C6-PhN (SO2Me)2 (2b), 18C6 -MeN(SO2Me)2 (3, monoclinic, P21/c, Z = 8), Bz18C6-HN(SO2Me)2 (4, Bz18C6 = benzo-18-crown-6, monoclinic, P21/n, Z = 4), 18C6-2 MeN (SO2Me)2 (5, triclinic, P1̅, Z = 1), 18C6-Me2SO- HN( SO2Me) (SO2Ph) (13, triclinic, P1̅, Z = 2), and 18C6-H2OMe2SO·2HN(SO2Me)2 (14, triclinic, P1̅, Z = 2). Each of the one-dimensional polymers 2a (syndiotactic), 3 (disyndiotactic) and 4 (isotactic) mimics a single upright of 1; in contrast to 1 and 2a, where the intra-catemer connectivity solely relies on S - Me ··· crow n and crown ··· O = S hydrogen bonds, this bonding system is reinforced in 3 by N -Me ··· crown and in 4 by N - H ··· crown hydrogen bonds. Complex 5 is monomeric and matches a fragment formally extruded from the catemer 3; moreover, 3 and 5 represent a rare case of two structurally characterized 18C6 complexes containing the same uncharged guest species in distinct molecular ratios. The surprising structure of the quaternary adduct 14 exhibits an [18C6 ··· MeSO2N(H)SO2Me ··· ]∞ chain, which can be regarded both as an isolated, though unmodified upright from the ladder 1 and, being syndiotactic, as a stereochemical analogue of 2a; the potentially rung-forming *NH functions in the chain are blocked by hydrogenbonded side chains of the type * N - H ··· water ··· sulfoxide ··· H - N (SO2Me)2. The ternary complex 13 consists of chains [18C6 ··· Me2SO ··· H - N (SO2Ph)SO2Me···]∞ and is not closely related to the other structures

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ChemInform Abstract: Molecular Structures of Some (Dimethylamino)halosilanes in the Gas Phase by Electron Diffraction and the Crystal and Molecular Structures of Mono- and Dichloro(dimethylamino)silane by X-Ray Diffraction at Low Temperatures.

ChemInform ◽

10.1002/chin.198814045 ◽

1988 ◽

Vol 19 (14) ◽

Author(s):

D. G. ANDERSON ◽

A. J. BLAKE ◽

S. CRADOCK ◽

E. A. V. EBSWORTH ◽

D. W. H. RANKIN ◽

...

Keyword(s):

Electron Diffraction ◽

Gas Phase ◽

Low Temperatures ◽

Molecular Structures ◽

X Ray Diffraction ◽

X Ray ◽

Crystal And Molecular Structures

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Molecular structure of trimethylamine–gallane, Me3N·GaH3: ab initio calculations, gas-phase electron diffraction and single-crystal X-ray diffraction studies †

Journal of the Chemical Society Dalton Transactions ◽

10.1039/a806289g ◽

1998 ◽

pp. 3685-3692 ◽

Cited By ~ 24

Author(s):

Paul T. Brain ◽

Helen E. Brown ◽

Anthony J. Downs ◽

Tim M. Greene ◽

Emma Johnsen ◽

...

Keyword(s):

Molecular Structure ◽

Electron Diffraction ◽

Ab Initio Calculations ◽

Single Crystal ◽

Ab Initio ◽

Gas Phase ◽

X Ray Diffraction ◽

X Ray ◽

Gas Phase Electron Diffraction

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Phase Characterization and Grain Size Effects of Nanophase Y2O3, ZrO2 and Y2O3-ZrO2 Composites Produced by the Gas-Phase Condensation Technique

MRS Proceedings ◽

10.1557/proc-286-61 ◽

1992 ◽

Vol 286 ◽

Author(s):

C. M. Foster ◽

G. R. Bai ◽

J. C. Parker ◽

M. N. Ali

Keyword(s):

Grain Size ◽

Raman Scattering ◽

Gas Phase ◽

Size Effects ◽

Structural Evolution ◽

Deposition Process ◽

X Ray Diffraction ◽

X Ray ◽

Nanophase Materials ◽

Phase Characterization

ABSTRACTNanophase (n-) ZrO2 was produced in its pure and partially stabilized form by the gas-phase condensation method. The material was examined by x-ray diffraction and Raman scattering to obtain information on the structural evolution of the material during sintering. Two types of Y2O3 doped ZrO2 nanophase materials were made one by co-deposition of n-Y2O3 and n-ZrO2 in a consecutive manner and the second by mechanically mixing n-Y2O3 and n-ZrO2. We have determined that the co-deposition process is the most effect means of doping the n-ZrO2.

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Synthesis, Crystal Structure and Magnetic Properties of a Copper(II) p-Formylbenzoate Complex

Zeitschrift für Naturforschung B ◽

10.5560/znb.2012-0209 ◽

2012 ◽

Vol 67 (11) ◽

pp. 1185-1190 ◽

Cited By ~ 1

Author(s):

Jin-Li Qi ◽

Wei Xu ◽

Yue-Qing Zheng

Keyword(s):

Room Temperature ◽

Magnetic Measurements ◽

X Ray Diffraction ◽

Complex Molecules ◽

Triclinic Space Group ◽

X Ray ◽

Cell Dimensions ◽

Ferromagnetic Interactions ◽

Aqueous Conditions ◽

Discrete Complex

A new Cu(II) complex was prepared at room temperature from the reaction of p-formylbenzoic acid, phenanthroline, CuCl2⋅2H2O, and NaOH under ethanolic aqueous conditions. The complex has been characterized by X-ray diffraction, IR spectroscopy, TG-DTA analyses, and magnetic measurements. Single-crystal X-ray diffraction analysis indicated that the complex crystallizes in the triclinic space group P1̄ with the cell dimensions a=7.875(2), b=10.724(2), c=15.317(3) Å , α =102.65(3), β =93.71(3), γ =107:64(3)°. The Cu atoms are in the environment of distorted CuN2O3 tetragonal pyramids. These discrete complex molecules are packed through intermolecular π...π-stacking interactions and C-H...O hydrogen bonds forming a supramolecular structure. The title complex obeys the Curie-Weiss law with a Curie constant C=0:53 cm3 K mol-1 and a Weiss constant θ = -0:27 K. The shape of the xmT curve is characteristic of weak ferromagnetic interactions between the Cu(II) centers from 300 to 7 K, while there are weak antiferromagnetic interactions below 7 K.

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Biobased Poly(ethylene furanoate) Polyester/TiO2 Supported Nanocomposites as Effective Photocatalysts for Anti-inflammatory/Analgesic Drugs

Molecules ◽

10.3390/molecules24030564 ◽

2019 ◽

Vol 24 (3) ◽

pp. 564 ◽

Cited By ~ 6

Author(s):

Anastasia Koltsakidou ◽

Zoi Terzopoulou ◽

George Kyzas ◽

Dimitrios Bikiaris ◽

Dimitra Lambropoulou

Keyword(s):

High Resolution Mass Spectrometry ◽

Transformation Products ◽

Solvent Evaporation Method ◽

X Ray Diffraction ◽

Analgesic Drug ◽

Ion Release ◽

Scanning Calorimetry ◽

X Ray ◽

Anti Inflammatory ◽

Poly Ethylene

In the present study, polymer supported nanocomposites, consisting of bio-based poly(ethylene furanoate) polyester and TiO2 nanoparticles, were prepared and evaluated as effective photocatalysts for anti-inflammatory/analgesic drug removal. Nanocomposites were prepared by the solvent evaporation method containing 5, 10, 15, and 20 wt% TiO2 and characterized using Fourier Transform Infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). Thin films of them have been prepared by the melt press and optimization of the photocatalytic procedure was conducted for the most efficient synthesized photocatalyst. Finally, mineralization was evaluated by means of Total organic carbon (TOC) reduction and ion release, while the transformation products (TPs) generated during the photocatalytic procedure were identified by high-resolution mass spectrometry.

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