Mechanical Properties of a Series of Macro- and Nanodimensional Organic Cocrystals Correlate with Atomic Polarizability

Rupasinghe, Thilini P.; Hutchins, Kristin M.; Bandaranayake, Bimali S.; Ghorai, Suman; Karunatilake, Chandana; Bučar, Dejan Krešimir; Swenson, Dale C.; Arnold, Mark A.; MacGillivray, Leonard R.; Tivanski, Alexei V.

doi:10.1021/jacs.5b07873

Cited by 47 publications

(58 citation statements)

References 38 publications

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“…[48, 49, 50] Our specific interest is to compare the results obtained from AFM with those provided from BLS with the expectation that the alternative mechanisms through which each technique probes the material will provide unique mechanical data, particularly for particles with a non-homogeneous interior. Nanoindentation results for the complete pS-co-NIPAM series are collected in Table V and representative force-displacement curves for all materials are provided as Supporting Information.…”

Section: Resultsmentioning

confidence: 99%

Core and surface microgel mechanics are differentially sensitive to alternative crosslinking concentrations

et al. 2017

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Microgel mechanics are central to the swelling of stimuli-responsive materials and furthermore have recently emerged as a novel design space for tuning the uptake of nanotherapeutics. Despite this importance, the techniques available to assess mechanics, at the sub-micron scale, remain limited. In this report, all mechanical moduli for a series of air-dried, polystyrene-co-poly(N-isopropylacrylamide) (pS-co-NIPAM) microgels of varying composition in monomer and crosslinker (N,N′-methylene-bisacrylamide (BIS)) mol% have been determined using Brillouin light scattering (BLS) and AFM nanoindentation. These techniques sample the material through distinct means and provide complementary nanomechanical data. An initial demonstration of this combined approach is used to evaluate size-dependent nanomechanics in pS particles of varying diameter. For the pS-co-NIPAM series, our BLS results demonstrate an increase in Young’s (E) and shear moduli with increasing NIPAM and/or BIS mol%, while the Poisson’s ratio decreased. The same rank order in E was observed from AFM and the two techniques correlate well. However, at low BIS crosslinking, an inverted particle structure persists and small increases in BIS yield a higher increase in E from AFM relative to BLS, consistent with a higher density at the particle surface. At higher BIS incorporation, the microgel reverts to a typical, dense-core structure and further increasing BIS yields changes to core-particle mechanics reflected in BLS. Lastly, at 75 mol% NIPAM, the microgels displayed a broad volume phase transition and increased crosslinking resulted in a minor, yet unexpected, increase in swelling ratio. This complementary approach offers new insight into nanomechanics critical for microgel design and application.

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Section: Resultsmentioning

confidence: 99%

Core and surface microgel mechanics are differentially sensitive to alternative crosslinking concentrations

et al. 2017

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“…[9] In crystalline solids, crystal engineering [10] principles may be gainfully employed to vary the nature and number of intermolecular interactions to derive mechanical response in ap redictable manner. [11,12] However,t his exercise solely depends on our comprehension of the structural factors and features that determinet he elastic and plastic responses of organic crystals. [13,14] In fact, assessing the generality of the design principles that lead to as pecific property is ac hallenging task;i ti s necessary to study al arge library of relateds ets of molecules with distinctc rystal packings to reach ac onverging conclusion.…”

Section: Introductionmentioning

confidence: 99%

Molecular Basis for the Mechanical Response of Sulfa Drug Crystals

SeethaLekshmi

Kiran

Ramamurty

et al. 2018

Chemistry A European J

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Comprehension of the nanomechanical response of crystalline materials requires the understanding of the elastic and plastic deformation mechanisms in terms of the underlying crystal structures. Nanoindentationd ata were combined with structurala nd computational inputs to derive am olecular-level understandingo ft he nanomechanical response in eight prototypical sulfa drug molecular crystals. The magnitude of the modulus, E,w as strongly connected to the non-covalent bond features, that is, the bond strength, the relative orientation with the measured crystal facet and their dispositioni nt he crystal lattice. Additional features derived from the currents tudy are the following. Firstly,r obust synthons well isolatedb yw eak andd ispersive interactions reduce the material stiffness;i nc ontrast, the interweaving of interactions with diverse energetics fortifies the crystal packing. Secondly, mereo bservation of layered structures with orthogonal distribution of strong and weak interactions is ap rerequisite, but inadequate, to attain higher plasticity.T hirdly,i nterlocked molecular arrangements preventl ong-range sliding of molecular planes and, hence, lead to enhanced E values. In ab roader perspective, the observations are remarkable in deriving am olecular basis of the mechanical properties of crystalline solids, which can be exploited through crystal engineering for thep urposeful design of materials with specific properties.

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“…The importance of interactions involving halogens in the absence of strong hydrogen bonds has been well established in the crystal engineering community (O'Hagan, 2008;Mondal et al, 2018). The evaluation of weak interactions involving halogens in the presence of strong hydrogen bonds has generated extensive interest in recent literature, particularly in the areas of isostructurality (Dey & Chopra, 2017), polymorphism (Prohens et al, 2012;Cruz Cabeza & Bernstein, 2014), cocrystals (Chattoraj et al, 2014;Mondal, Rao et al, 2017;Eccles et al, 2012), crystal structure prediction (Hulme et al, 2005), host-guest chemistry (Noa et al, 2016), nanoindentation (Mondal, Kiran et al, 2017;Rupasinghe et al, 2015) and supramolecular chemistry (Mondal, Yadav et al, 2017;Nagarajan et al, 2014).…”

Section: Introductionmentioning

confidence: 99%

Role of halogen-involved intermolecular interactions and existence of isostructurality in the crystal packing of —CF₃ and halogen (Cl or Br or I) substituted benzamides

Mondal

Shukla

Biswas

et al. 2018

Acta Crystallogr Sect B

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A total of 23 benzamides are obtained through a simple reaction between chloro-/bromo-/iodoaniline and trifluoromethylbenzoyl chloride and characterized using single-crystal X-ray diffraction. Crystal structures of three series of benzamides based on N-chlorophenyl-trifluoromethyl-benzamide (nine compounds), N-bromophenyl-trifluoromethyl-benzamide (six compounds), and N-iodophenyl-trifluoromethyl-benzamide (eight compounds) are prepared to analyse the halogen-mediated noncovalent interactions. The influences of Cl/Br/I and trifluoromethyl substituents on the respective interactions are examined in the presence of a strong N-HÁ Á ÁO hydrogen bond. This exercise has resulted in the documentation of frequently occurring supramolecular synthons involving halogen atoms in the crystal packing of benzamide molecules in the solid state. In the present study, a detailed quantitative evaluation has been performed on the nature, energetics, electrostatic contributions, and topological properties of short and directional intermolecular interactions derived from the electron density on halogenated benzamides in the solid state. Besides these, the occurrence of three-, two-and one-dimensional isostructurality in halogen (Cl or Br or I) substituted benzamide analogues is also investigated. A 'region of co-existence' involving halogen-based intermolecular interactions in the vicinity of the sum of the van der Waals radii has been identified. Thus, the nature of the halogen (effective size), type of interaction and the packing characteristics via presence of additional interactions establish the subtle, yet important, role of cooperativity in intermolecular interactions in crystal packing.

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Mechanical Properties of a Series of Macro- and Nanodimensional Organic Cocrystals Correlate with Atomic Polarizability

Cited by 47 publications

References 38 publications

Core and surface microgel mechanics are differentially sensitive to alternative crosslinking concentrations

Core and surface microgel mechanics are differentially sensitive to alternative crosslinking concentrations

Molecular Basis for the Mechanical Response of Sulfa Drug Crystals

Role of halogen-involved intermolecular interactions and existence of isostructurality in the crystal packing of —CF₃ and halogen (Cl or Br or I) substituted benzamides

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Mechanical Properties of a Series of Macro- and Nanodimensional Organic Cocrystals Correlate with Atomic Polarizability

Cited by 47 publications

References 38 publications

Core and surface microgel mechanics are differentially sensitive to alternative crosslinking concentrations

Core and surface microgel mechanics are differentially sensitive to alternative crosslinking concentrations

Molecular Basis for the Mechanical Response of Sulfa Drug Crystals

Role of halogen-involved intermolecular interactions and existence of isostructurality in the crystal packing of —CF3 and halogen (Cl or Br or I) substituted benzamides

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Product

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Role of halogen-involved intermolecular interactions and existence of isostructurality in the crystal packing of —CF₃ and halogen (Cl or Br or I) substituted benzamides