Size compatibility and concentration dependent supramolecular host–guest interactions at interfaces

AbstractThe quantification of supramolecular host–guest interactions is important for finely modulating supramolecular systems. Previously, most host–guest interactions quantified using force spectroscopic techniques have been reported in force units. However, accurately evaluating the adhesion energies of host–guest pairs remains challenging. Herein, using a surface forces apparatus, we directly quantify the interaction energies between cyclodextrin (CD)-modified surfaces and ditopic adamantane (DAd) molecules in water as a function of the DAd concentration and the CD cavity size. The adhesion energy of the β-CD–DAd complex drastically increased with increasing DAd concentration and reached saturation. Moreover, the molecular adhesion energy of a single host–guest inclusion complex was evaluated to be ~9.51 kBT. This approach has potential for quantifying fundamental information toward furthering the understanding of supramolecular chemistry and its applications, such as molecular actuators, underwater adhesives, and biosensors, which require precise tuning of specific host–guest interactions.

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Adhesion Energy Hysteresis and Friction between Ultrathin Polyglutamate Films Measured with the Surface Forces Apparatus

Macromolecules ◽

10.1021/ma00113a046 ◽

1995 ◽

Vol 28 (9) ◽

pp. 3401-3410 ◽

Cited By ~ 18

Author(s):

F.-J. Schmitt ◽

H. Yoshizawa ◽

A. Schmidt ◽

G. Duda ◽

W. Knoll ◽

...

Keyword(s):

Adhesion Energy ◽

Surface Forces ◽

Surface Forces Apparatus

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Insights into Nanoscale Wettability Effects of Low Salinity and Nanofluid Enhanced Oil Recovery Techniques

Energies ◽

10.3390/en13174443 ◽

2020 ◽

Vol 13 (17) ◽

pp. 4443

Author(s):

Dayo Afekare ◽

Jayne C. Garno ◽

Dandina Rao

Keyword(s):

Enhanced Oil Recovery ◽

Oil Recovery ◽

Adhesion Force ◽

Sio2 Nanoparticles ◽

Adhesion Energy ◽

Work Of Adhesion ◽

Wettability Alteration ◽

Low Salinity ◽

Nanoparticle Dispersions ◽

Fundamental Information

In this study, enhanced oil recovery (EOR) techniques—namely low salinity and nanofluid EOR—are probed at the nanometer-scale using an atomic force microscope (AFM). Mica substrates were used as model clay-rich rocks while AFM tips were coated to present alkyl (-CH3), aromatic (-C6H5) and carboxylic acid (-COOH) functional groups, to simulate oil media. We prepared brine formulations to test brine dilution and cation bridging effects while selected concentrations (0 to 1 wt%) of hydrophilic SiO2 nanoparticles dispersed in 1 wt% NaCl were used as nanofluids. Samples were immersed in fluid cells and chemical force mapping was used to measure the adhesion force between polar/non-polar moieties to substrates. Adhesion work was evaluated based on force-displacement curves and compared with theories. Results from AFM studies indicate that low salinity waters and nanoparticle dispersions promote nanoscale wettability alteration by significantly reducing three-phase adhesion force and the reversible thermodynamic work of adhesion, also known as adhesion energy. The maximum reduction in adhesion energy obtained in experiments was in excellent agreement with existing theories. Electrostatic repulsion and reduced non-electrostatic adhesion are prominent surface forces common to both low salinity and nanofluid EOR. Structural forces are complex in nature and may not always decrease total adhesion force and energy at high nanoparticle concentration. Wettability effects also depend on surface chemical groups and the presence of divalent Mg2+ and Ca2+ cations. This study provides fresh insights and fundamental information about low salinity and nanofluid EOR while demonstrating the application of force-distance spectroscopy in investigating EOR techniques.

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Vibrational structure analysis of cobalt fluoro-porphyrin surface coatings on gallium phosphide

Journal of Porphyrins and Phthalocyanines ◽

10.1142/s1088424618500906 ◽

2018 ◽

Vol 22 (06) ◽

pp. 461-466 ◽

Cited By ~ 2

Author(s):

Diana Khusnutdinova ◽

Anna M. Beiler ◽

Brian L. Wadsworth ◽

Sylvia K. Nanyangwe ◽

Gary F. Moore

Keyword(s):

Ftir Spectroscopy ◽

Gallium Phosphide ◽

Plane Deformation ◽

Grazing Angle ◽

Spectroscopic Techniques ◽

Step Method ◽

Pyridyl Nitrogen ◽

Surface Attachment ◽

Modified Surfaces ◽

Surface Graft

Grazing angle attenuated total reflectance Fourier transform infrared (GATR–FTIR) spectroscopy is used to characterize chemically modified gallium phosphide (GaP) surfaces containing grafted cobalt(II) porphyrins with 3-fluorophenyl substituents installed at the meso-positions. In these hybrid constructs, porphyrin surface attachment is achieved using either a two-step method involving coordination of cobalt fluoro-porphyrin metal centers to nitrogen sites on an initially applied thin-film polypyridyl surface coating, or via a direct modification strategy using a cobalt fluoro-porphyrin precursor bearing a covalently bonded 4-vinylphenyl surface attachment group at a [Formula: see text]-position. Both surface-attachment chemistries leverage the UV-induced immobilization of alkenes but result in distinct structural connectivities of the grafted porphyrin units and their associated vibrational spectra. In particular, the in-plane deformation vibrational frequency of metalloporphyrin components in samples prepared via coordination to the polymeric interface is characterized by an eight wavenumber shift to higher frequencies compared to that measured on metalloporphyrin-modified surfaces prepared using the one-step attachment method. The more rigid ring structure in the polymeric architecture is consistent with coordination of porphyrin cobalt centers to pyridyl-nitrogen sites on the surface graft. These results demonstrate the use of GATR–FTIR spectroscopy as a sensitive tool for characterizing porphyrin-modified surfaces with absorption signals that are close to the detection limits of many common spectroscopic techniques.

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Differential polarization imaging of sickled cells

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100102390 ◽

1988 ◽

Vol 46 ◽

pp. 62-63

Author(s):

Marcos F. Maestre

Keyword(s):

Optical Properties ◽

Theoretical Approach ◽

Polarized Light ◽

Polarization Microscopy ◽

Spectroscopic Techniques ◽

Polarization Imaging ◽

Circularly Polarized Light ◽

Circularly Polarized ◽

Microscopic Scale ◽

Chiral Structures

Recently we have developed a form of polarization microscopy that forms images using optical properties that have previously been limited to macroscopic samples. This has given us a new window into the distribution of structure on a microscopic scale. We have coined the name differential polarization microscopy to identify the images obtained that are due to certain polarization dependent effects. Differential polarization microscopy has its origins in various spectroscopic techniques that have been used to study longer range structures in solution as well as solids. The differential scattering of circularly polarized light has been shown to be dependent on the long range chiral order, both theoretically and experimentally. The same theoretical approach was used to show that images due to differential scattering of circularly polarized light will give images dependent on chiral structures. With large helices (greater than the wavelength of light) the pitch and radius of the helix could be measured directly from these images.

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Characterization of intergranular cuprous oxide in polycrystalline YBa2Cu3O7-x

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100106466 ◽

1988 ◽

Vol 46 ◽

pp. 880-881

Author(s):

Bradley L. Thiel ◽

Chan Han R. P. ◽

Kurosky L. C. Hutter ◽

I. A. Aksay ◽

Mehmet Sarikaya

Keyword(s):

Grain Boundary ◽

Cuprous Oxide ◽

Room Temperature ◽

Boundary Phase ◽

Spectroscopic Techniques ◽

Transition Width ◽

Practical Applications ◽

Thin Foils ◽

Superconducting Oxides

The identification of extraneous phases is important in understanding of high Tc superconducting oxides. The spectroscopic techniques commonly used in determining the origin of superconductivity (such as RAMAN, XPS, AES, and EXAFS) are surface-sensitive. Hence a grain boundary phase several nanometers thick could produce irrelevant spectroscopic results and cause erroneous conclusions. The intergranular phases present a major technological consideration for practical applications. In this communication we report the identification of a Cu2O grain boundary phase which forms during the sintering of YBa2Cu3O7-x (1:2:3 compound).Samples are prepared using a mixture of Y2O3. CuO, and BaO2 powders dispersed in ethanol for complete mixing. The pellets pressed at 20,000 psi are heated to 950°C at a rate of 5°C per min, held for 1 hr, and cooled at 1°C per min to room temperature. The samples show a Tc of 91K with a transition width of 2K. In order to prevent damage, a low temperature stage is used in milling to prepare thin foils which are then observed, using a liquid nitrogen holder, in a Philips 430T at 300 kV.

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Self Assembly in Supramolecular Systems

10.1039/9781847551863 ◽

2007 ◽

Keyword(s):

Self Assembly ◽

Supramolecular Systems

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Molecular adhesion

AccessScience ◽

10.1036/1097-8542.430100 ◽

2015 ◽

Keyword(s):

Molecular Adhesion

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Non-invasive infrared spectroscopic techniques for the characterization of medicinal plants and their constituents

Planta Medica ◽

10.1055/s-0029-1234278 ◽

2009 ◽

Vol 75 (09) ◽

Author(s):

CW Huck

Keyword(s):

Medicinal Plants ◽

Spectroscopic Techniques ◽

Non Invasive ◽

Infrared Spectroscopic

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Progressive Debonding of Multilayer Interconnect Structures

MRS Proceedings ◽

10.1557/proc-473-21 ◽

1997 ◽

Vol 473 ◽

Cited By ~ 9

Author(s):

Michael Lane ◽

Robert Ware ◽

Steven Voss ◽

Qing Ma ◽

Harry Fujimoto ◽

...

Keyword(s):

Thin Films ◽

Crack Growth ◽

Driving Force ◽

Adhesion Energy ◽

Time Dependent ◽

Multilayer Thin Films ◽

Processing Conditions ◽

Interface Morphology ◽

Entire Sample ◽

Crack Growth Velocity

ABSTRACTProgressive (or time dependent) debonding of interfaces poses serious problems in interconnect structures involving multilayer thin films stacks. The existence of such subcriticai debonding associated with environmentally assisted crack-growth processes is examined for a TiN/SiO2 interface commonly encountered in interconnect structures. The rate of debond extension is found to be sensitive to the mechanical driving force as well as the interface morphology, chemistry, and yielding of adjacent ductile layers. In order to investigate the effect of interconnect structure, particularly the effect of an adjacent ductile Al-Cu layer, on subcriticai debonding along the TiN/SiO2 interface, a set of samples was prepared with Al-Cu layer thicknesses varying from 0.2–4.0 μm. All other processing conditions remained the same over the entire sample run. Results showed that for a given crack growth velocity, the debond driving force scaled with Al-Cu layer thickness. Normalizing the data by the critical adhesion energy allowed a universal subcriticai debond rate curve to be derived.

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