Remarkable decrease in stiffness of aspirin crystals upon reducing crystal size to nanoscale dimensions <i>via</i> sonochemistry

Hutchins, Kristin M.; Rupasinghe, Thilini P.; Oburn, Shalisa M.; Ray, Kamal K.; Tivanski, Alexei V.; MacGillivray, Leonard R.

doi:10.1039/c8ce00764k

Cited by 8 publications

(15 citation statements)

References 47 publications

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“…Thus, we quantitatively assessed how the RID values for different systems can be related to their mechanical properties. In particular, we quantified the elasticity of each system with round, prism, and rod morphology displaying solid or semisolid phase state using AFM nanoindentation technique. , Specifically, the approach to the surface data of the force plots that were used to determine the RID and VRD values above was also used to quantify YM. We note that the initial retract unloading data could also be used under certain circumstances.…”

Section: Results and Discussionmentioning

confidence: 99%

Correlating 3D Morphology, Phase State, and Viscoelastic Properties of Individual Substrate-Deposited Particles

et al. 2019

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Depending on the source and relative humidity, aerosols can have different compositional, morphological, and viscoelastic properties. Aerosol studies determining the relationship between these properties and their combined effect on the climate and environment are important. This work aims to correlate the 3D morphology, phase state, and viscoelastic properties of selected single-component chemical systems found in sea spray aerosol (SSA) that were substrate-deposited on a solid surface, studied with atomic force microscopy (AFM). Specifically, two inorganic salts (NaCl and MgSO4), four organic acids (malonic, glutaric, azelaic, and palmitic acids), three saccharides (glucose, sucrose, and raffinose), and lipopolysaccharide from Escherichia coli were studied. Furthermore, three inorganic–organic binary chemical mixtures (NaCl–malonic acid, NaCl–glucose, and MgSO4–glucose) at 1:3 and 3:1 mass ratio were studied. AFM imaging and force spectroscopy at 20% relative humidity were performed to record 3D height images of individual particles and measure force–distance plots, respectively. First, by utilizing combined relative indentation depth (RID) and viscoelastic response distance (VRD) data obtained from the force–distance plots, we establish quantitative framework toward differentiation of the solid, semisolid and liquid phase states of individual particles without prior knowledge of their chemical identity. Second, we show that the single particle aspect ratio (AR) of a wide range of compounds relevant to SSA is a measure of the extent of the particle spreading as a result of impaction with the solid substrate, which can be directly related to the RID and VRD results. Thus, we demonstrate that a quick height imaging and determination of a single particle AR can be used to assess the phase state. Therefore, we introduce the ability to semiquantitatively assess the phase states of individual substrate deposited particles of SSA-relevant compounds, irrespective of the microscopy technique used, which can subsequently be further validated by more quantitative AFM force spectroscopy.

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Section: Results and Discussionmentioning

confidence: 99%

Correlating 3D Morphology, Phase State, and Viscoelastic Properties of Individual Substrate-Deposited Particles

et al. 2019

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“…Thus, the elastic modulus results for nanocrystals are expected to yield an average response reflective of all planes of the bulk crystal, as previously described. 30,31,[36][37][38] The average elastic modulus and standard deviation values were 0.7 ± 0.2 and 2.1 ± 0.8 GPa for base-modified and unmodified ZIF-8 nanocrystals, respectively. Thus, in situ synthesis of ZIF-8 nanocrystals with triethylamine (Et3N) modulator resulted in a marked three-fold decrease in elastic modulus and a corresponding increase in framework flexibility compared to unmodified ZIF-8.…”

Section: Resultsmentioning

confidence: 97%

“…AFM nanoindentation showed force versus indentation depth plots that were purely elastic, enabling us to fit the stress-strain curve to the JKR elastic contact model. 30,31,[36][37][38] For a given indentation depth past 3 nm, the force applied to the solids was about three times more in the unmodified nanocrystals of ZIF-8 compared to the modified samples (Figure 2c). The average elastic moduli of the nanocrystals were statistically similar within each sample type and were combined into two separate histograms (Figure 2d).…”

Section: Resultsmentioning

confidence: 99%

“…AFM nanoindentation was performed by recording force versus vertical piezo displacement curves to generate force-indentation distance plots that were used to determine the elastic modulus (i.e., Young's modulus, stiffness, rigidity) 30,31,[36][37][38] of individual base-modified ZIF-8 nanocrystals and compared to the mechanical properties of unmodified nanocrystals. Repeated force-indentation plots were collected on eleven individual amine-modified and fourteen unmodified nanocrystals of ZIF-8 at two-four different positions in the approximate center of each crystal.…”

Section: Experimental Methodsmentioning

confidence: 99%

“…The acquisition of the force plots and corresponding data analysis were carried out as reported in our previous works. 30,31,[36][37][38] Ar gas sorption measurements were performed on modified and unmodified nanocrystals of ZIF-8 using an Autosorb iQ (Anton Paar QuantaTec, Boynton Beach, FL) with a MP (micropore) analysis station. Samples (100 mg) were activated by degassing for 12 hours at 100 °C followed by ensuring the rise in pressure was no greater than 21 mtorr/min while at activation temperature.…”

Section: Experimental Methodsmentioning

confidence: 99%

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Supramolecular Modification of a Metal-Organic Framework Increases Flexibility and Switchability: Experimental Insights into Structural Deformation of ZIF-8

Tiba

Perman

MacGillivray

et al. 2022

Preprint

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Use of chemical modulators during the synthesis of a coordination framework is an important strategy to affect and tune properties of porous materials. Herein, we introduce an approach to understanding structural modulation and deformation of soft, porous crystals in the context of gas adsorption by using atomic force microscopy (AFM) nanoindentation and physisorption analysis. Modified nanocrystals of the prototypical zeolitic-imidazolate framework-8 (ZIF-8) were generated in triethylamine (Et3N) via an in-situ supramolecular modulation method. We demonstrate that using triethylamine as a modulator results in a conspicuous decrease in elastic modulus (0.7 ± 0.2 GPa) compared to the unmodified nanocrystals of ZIF-8 (2.1 ± 0.8 GPa). Argon gas adsorption analysis also reveals that the more flexible, amine-modified framework exhibited gradual and cooperative gate-opening structural transitions (P/P0 = 0.33 ± 0.02) compared to the steep and stepwise characteristics of unmodified samples of ZIF-8 (P/P0 = 0.45 ± 0.02). The differences in Argon gas pressure-induced structural deformations correspond to the decrease in elastic modulus of base-modified nanocrystals of ZIF-8, likely a consequence of the impact of Et3N on the relative number of point defects and hydrogen bonds in the framework. Our study demonstrates how a combination of AFM nanoindentation, gas uptake, and spectroscopic characterization can be applied to understand structural and energetic changes upon adsorption in flexible framework materials.

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Semiconductor Cocrystals Based on Boron: Generated Electrical Response with π-Rich Aromatic Molecules

Ray

Campillo‐Alvarado

Morales‐Rojas

et al. 2019

Crystal Growth & Design

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Cocrystallization of a nonconductive, boron-based host with aromatic guests generates conductive cocrystals. Carrier mobilities of the cocrystals with either pyrene or tetrathiafulvalene were measured using conducting probe atomic force microscopy. The incorporation of the π-electron-rich aromatic guests results in electrically conductive cocrystals. The cocrystal with tetrathiafulvalene as a guest shows an approximately seven times higher charge carrier mobility than the cocrystal with pyrene.

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Remarkable decrease in stiffness of aspirin crystals upon reducing crystal size to nanoscale dimensions via sonochemistry

Abstract: Nano-dimensional crystals of aspirin generated through sonochemistry exhibit Young's modulus values an order of magnitude softer than macro-dimensional crystals.

Cited by 8 publications

References 47 publications

Correlating 3D Morphology, Phase State, and Viscoelastic Properties of Individual Substrate-Deposited Particles

Correlating 3D Morphology, Phase State, and Viscoelastic Properties of Individual Substrate-Deposited Particles

Supramolecular Modification of a Metal-Organic Framework Increases Flexibility and Switchability: Experimental Insights into Structural Deformation of ZIF-8

Semiconductor Cocrystals Based on Boron: Generated Electrical Response with π-Rich Aromatic Molecules

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