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  1. Article: Coherence in Polycrystalline Thin Films of Twisted Molecular Crystals.

    Yang, Yongfan / Shtukenberg, Alexander G / Zhou, Hengyu / Ruzie, Christian / Geerts, Yves Henri / Lee, Stephanie S / Kahr, Bart

    Chemistry of materials : a publication of the American Chemical Society

    2024  Volume 36, Issue 2, Page(s) 881–891

    Abstract: Helicoidal crystallites in rhythmically banded spherulites manifest spectacular optical patterns in small molecules and polymers. It is shown that concentric optical bands indicating crystallographic orientations typically lose coherence (in-phase ... ...

    Abstract Helicoidal crystallites in rhythmically banded spherulites manifest spectacular optical patterns in small molecules and polymers. It is shown that concentric optical bands indicating crystallographic orientations typically lose coherence (in-phase twisting) with growth from the center of nucleation. Here, coherence is shown to increase as the twist period decreases for seven molecular crystals grown from the melt. This dependence was correlated to crystallite fiber thickness and length, as well as crystallite branching frequency, a parameter that was extracted from scanning electron micrographs, and supported by numerical simulations. Hole mobilities for 2,5-didodecyl-3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (DPP-C12) measured by using organic field-effect transistors demonstrated that more incoherent boundaries between optical bands in spherulites lead to higher charge transport for films with the same twist period. This was rationalized by combining our growth model with electrodynamic simulations. This work illustrates the emergence of complexity in crystallization processes (spherulite formation) that arises in the extra variable of helicoidal radial twisting. The details of the patterns analyzed here link the added complexity in crystal growth to the electronic and optical properties of the thin films.
    Language English
    Publishing date 2024-01-04
    Publishing country United States
    Document type Journal Article
    ZDB-ID 1500399-1
    ISSN 1520-5002 ; 0897-4756
    ISSN (online) 1520-5002
    ISSN 0897-4756
    DOI 10.1021/acs.chemmater.3c02740
    Database MEDical Literature Analysis and Retrieval System OnLINE

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  2. Article: ROY Crystallization on Poly(ethylene) Fibers, a Model for Bed Net Crystallography.

    Erriah, Bryan / Shtukenberg, Alexander G / Aronin, Reese / McCarthy, Derik / Brázda, Petr / Ward, Michael D / Kahr, Bart

    Chemistry of materials : a publication of the American Chemical Society

    2024  Volume 36, Issue 5, Page(s) 2432–2440

    Abstract: Many long-lasting insecticidal bed nets for protection against disease vectors consist of poly(ethylene) fibers in which insecticide is incorporated during manufacture. Insecticide molecules diffuse from within the supersaturated polymers to surfaces ... ...

    Abstract Many long-lasting insecticidal bed nets for protection against disease vectors consist of poly(ethylene) fibers in which insecticide is incorporated during manufacture. Insecticide molecules diffuse from within the supersaturated polymers to surfaces where they become bioavailable to insects and often crystallize, a process known as blooming. Recent studies revealed that contact insecticides can be highly polymorphic. Moreover, insecticidal activity is polymorph-dependent, with forms having a higher crystal free energy yielding faster insect knockdown and mortality. Consequently, the crystallographic characterization of insecticide crystals that form on fibers is critical to understanding net function and improving net performance. Structural characterization of insecticide crystals on bed net fiber surfaces, let alone their polymorphs, has been elusive owing to the minute size of the crystals, however. Using the highly polymorphous compound ROY (5-methyl-2-[(2-nitrophenyl)-amino]thiophene-3-carbonitrile) as a proxy for insecticide crystallization, we investigated blooming and crystal formation on the surface of extruded poly(ethylene) fibers containing ROY. The blooming rates, tracked from the time of extrusion, were determined by UV-vis spectroscopy after successive washes. Six crystalline polymorphs (of the 13 known) were observed on poly(ethylene) fiber surfaces, and they were identified and characterized by Raman microscopy, scanning electron microscopy, and 3D electron diffraction. These observations reveal that the crystallization and phase behavior of polymorphs forming on poly(ethylene) fibers is complex and dynamic. The characterization of blooming and microcrystals underscores the importance of bed net crystallography for the optimization of bed net performance.
    Language English
    Publishing date 2024-02-27
    Publishing country United States
    Document type Journal Article
    ZDB-ID 1500399-1
    ISSN 1520-5002 ; 0897-4756
    ISSN (online) 1520-5002
    ISSN 0897-4756
    DOI 10.1021/acs.chemmater.3c03188
    Database MEDical Literature Analysis and Retrieval System OnLINE

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  3. Article ; Online: Disrupting Crystal Growth through Molecular Recognition: Designer Therapies for Kidney Stone Prevention.

    Shtukenberg, Alexander G / Hu, Longqin / Sahota, Amrik / Kahr, Bart / Ward, Michael D

    Accounts of chemical research

    2022  Volume 55, Issue 4, Page(s) 516–525

    Abstract: Aberrant crystallization within the human body can lead to several disease states or adverse outcomes, yet much remains to be understood about the critical stages leading to these events, which can include crystal nucleation and growth, crystal ... ...

    Abstract Aberrant crystallization within the human body can lead to several disease states or adverse outcomes, yet much remains to be understood about the critical stages leading to these events, which can include crystal nucleation and growth, crystal aggregation, and the adhesion of crystals to cells. Kidney stones, which are aggregates of single crystals with physiological origins, are particularly illustrative of pathological crystallization, with 10% of the U.S. population experiencing at least one stone occurrence in their lifetimes. The human record of kidney stones is more than 2000 years old, as noted by Hippocrates in his renowned oath and much later by Robert Hooke in his treatise
    MeSH term(s) Animals ; Crystallization ; Cystine/chemistry ; Cystine/metabolism ; Cystine/therapeutic use ; Cystinuria/complications ; Cystinuria/drug therapy ; Cystinuria/metabolism ; Kidney ; Kidney Calculi/chemistry ; Kidney Calculi/etiology ; Kidney Calculi/prevention & control ; Male ; Mice
    Chemical Substances Cystine (48TCX9A1VT)
    Language English
    Publishing date 2022-01-28
    Publishing country United States
    Document type Journal Article ; Research Support, N.I.H., Extramural ; Research Support, U.S. Gov't, Non-P.H.S.
    ZDB-ID 1483291-4
    ISSN 1520-4898 ; 0001-4842
    ISSN (online) 1520-4898
    ISSN 0001-4842
    DOI 10.1021/acs.accounts.1c00631
    Database MEDical Literature Analysis and Retrieval System OnLINE

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  4. Article ; Online: Overcoming insecticide resistance in Anopheles mosquitoes by using faster-acting solid forms of deltamethrin.

    Carson, Jessica / Erriah, Bryan / Herodotou, Stephania / Shtukenberg, Alexander G / Smith, Leilani / Ryazanskaya, Svetlana / Ward, Michael D / Kahr, Bart / Lees, Rosemary Susan

    Malaria journal

    2023  Volume 22, Issue 1, Page(s) 129

    Abstract: Background: Controlling malaria-transmitting Anopheles mosquitoes with pyrethroid insecticides is becoming increasingly challenging because of widespread resistance amongst vector populations. The development of new insecticides and insecticidal ... ...

    Abstract Background: Controlling malaria-transmitting Anopheles mosquitoes with pyrethroid insecticides is becoming increasingly challenging because of widespread resistance amongst vector populations. The development of new insecticides and insecticidal formulations is time consuming and costly, however. A more active crystalline form of deltamethrin, prepared by heating the commercial crystalline form, previously was reported to be 12-times faster acting against susceptible North American Anopheles quadrimaculatus mosquitoes. Herein the potential for heat-activated deltamethrin dispersed on chalk to overcome various resistance mechanisms amongst five West African Anopheles strains is investigated, and its long-term sustained lethality evaluated.
    Methods: The more active deltamethrin form was generated in a commercial dust containing deltamethrin by heating the material as purchased. Tarsal contact bioassays were conducted to investigate its efficacy, potency, and speed of action against resistant Anopheles populations compared to the commercially available form of deltamethrin dust.
    Results: In all cases, D-Fense Dust heated to generate the more active form of deltamethrin was substantially more effective than the commercially available formulation. 100% of both Banfora M and Kisumu populations were knocked down 10 min post-exposure with no recovery afterwards. Gaoua-ara and Tiefora strains exhibited 100% knockdown within 15 min, and the VK7 2014 strain exhibited 100% knockdown within 20 min. In all cases, 100% mortality was observed 24 h post-exposure. Conversely, the commercial formulation (unheated) resulted in less than 4% mortality amongst VK7 2014, Banfora, and Gaoua-ara populations by 24 h, and Tiefora and Kisumu mosquitoes experienced 14 and 47% mortality by 24 h, respectively. The heat-activated dust maintained comparable efficacy 13 months after heating.
    Conclusions: The heat-activated form of commercial deltamethrin D-Fense Dust outperformed the material as purchased, dramatically increasing efficacy against all tested pyrethroid-resistant strains. This increase in lethality was retained for 13 months of storage under ambient conditions in the laboratory. Higher energy forms of commonly used insecticides may be employed to overcome various resistance mechanisms seen in African Anopheles mosquitoes through more rapid uptake of insecticide molecules from their respective solid surfaces. That is, resistant mosquitoes can be killed with an insecticide to which they are resistant without altering the molecular composition of the insecticide.
    MeSH term(s) Animals ; Insecticides/pharmacology ; Insecticide Resistance ; Anopheles ; Mosquito Control/methods ; Mosquito Vectors ; Pyrethrins/pharmacology ; Nitriles/pharmacology
    Chemical Substances decamethrin (2JTS8R821G) ; Insecticides ; Pyrethrins ; Nitriles
    Language English
    Publishing date 2023-04-21
    Publishing country England
    Document type Journal Article
    ZDB-ID 2091229-8
    ISSN 1475-2875 ; 1475-2875
    ISSN (online) 1475-2875
    ISSN 1475-2875
    DOI 10.1186/s12936-023-04554-x
    Database MEDical Literature Analysis and Retrieval System OnLINE

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  5. Article: Chlorfenapyr Crystal Polymorphism and Insecticidal Activity.

    Aronin, Reese / Brázda, Petr / Smith, Leilani N / Zhang, Carolyn Jin / Benedict, Jason B / Marr, Zoe Y / Rybtchinski, Boris / Weissman, Haim / Shtukenberg, Alexander G / Kahr, Bart

    Crystal growth & design

    2024  Volume 24, Issue 3, Page(s) 1284–1292

    Abstract: Four crystalline polymorphs of the proinsecticide chlorfenapyr [4-bromo-2-(4-chlorophenyl)-1-ethoxymethyl-5-trifluoromethyl- ... ...

    Abstract Four crystalline polymorphs of the proinsecticide chlorfenapyr [4-bromo-2-(4-chlorophenyl)-1-ethoxymethyl-5-trifluoromethyl-1
    Language English
    Publishing date 2024-01-17
    Publishing country United States
    Document type Journal Article
    ISSN 1528-7483
    ISSN 1528-7483
    DOI 10.1021/acs.cgd.3c01257
    Database MEDical Literature Analysis and Retrieval System OnLINE

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  6. Article: Eshelby untwisting

    Zhong, Xiaodi / Zhou, Hengyu / Li, Chao / Shtukenberg, Alexander G / Ward, Michael D / Kahr, Bart

    Chemical communications. 2021 June 3, v. 57, no. 45

    2021  

    Abstract: The concept of Eshelby untwisting, the effect of an axial screw dislocation driving an intrinsically twisted nanocrystal towards a straighter configuration more consistent with long–range translational symmetry, is introduced here. Force-field ... ...

    Abstract The concept of Eshelby untwisting, the effect of an axial screw dislocation driving an intrinsically twisted nanocrystal towards a straighter configuration more consistent with long–range translational symmetry, is introduced here. Force-field simulations of nanorods built from the enantiomorphous (space groups, P3₁21 and P3₂21) crystal structures of benzil (C₆H₅–C(O)–C(O)–C₆H₅) were previously shown to twist in opposite directions, even in the absence of dislocations. Here, both right- and left-handed screw dislocations were introduced into benzil nanorods in silico. For rods built from the P3₂21 enantiomorph, dislocations with negative Burgers vectors increased the right-handed twisting already present in the intrinsically twisted structures without dislocations, whereas dislocations with positive Burgers vectors drove the twisted structure back towards a straight configuration, untwisting. In the dynamic simulations, the P3₂21 helicoid endowed with a positive Burgers vector ultimately twisted back through the straight configuration, until a helicoid of opposite sense from that of the starting structure, was obtained. The bearing of these observations on the propensity of small crystals to adopt non-polyhedral morphologies is discussed.
    Keywords computer simulation ; nanocrystals ; nanorods
    Language English
    Dates of publication 2021-0603
    Size p. 5538-5541.
    Publishing place The Royal Society of Chemistry
    Document type Article
    Note NAL-AP-2-clean
    ZDB-ID 1472881-3
    ISSN 1364-548X ; 1359-7345 ; 0009-241X
    ISSN (online) 1364-548X
    ISSN 1359-7345 ; 0009-241X
    DOI 10.1039/d1cc01431e
    Database NAL-Catalogue (AGRICOLA)

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  7. Article: Tuning the optical isotropic point of mixed crystals of ethylenediammonium sulfate/selenate.

    Tan, Melissa / Martin, Alexander T / Shtukenberg, Alexander G / Kahr, Bart

    Journal of applied crystallography

    2020  Volume 53, Issue Pt 1, Page(s) 51–57

    Abstract: In anisotropic crystals, optical isotropic points are wavelengths where linear birefringence disappears because the refractive indices for both eigenmodes are accidentally equivalent. Here, the optical isotropic point of ethylene-diammonium selenate ( ... ...

    Abstract In anisotropic crystals, optical isotropic points are wavelengths where linear birefringence disappears because the refractive indices for both eigenmodes are accidentally equivalent. Here, the optical isotropic point of ethylene-diammonium selenate (EDSe) is tuned by generating a solid-solution series of EDSe doped with sulfate. Mueller matrix polarimetry and single-crystal X-ray diffraction are used to correlate changes in linear birefringence with the crystal composition of EDS
    Language English
    Publishing date 2020-02-01
    Publishing country United States
    Document type Journal Article
    ZDB-ID 2020879-0
    ISSN 1600-5767 ; 0021-8898
    ISSN (online) 1600-5767
    ISSN 0021-8898
    DOI 10.1107/S1600576719015863
    Database MEDical Literature Analysis and Retrieval System OnLINE

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  8. Article ; Online: Eshelby untwisting.

    Zhong, Xiaodi / Zhou, Hengyu / Li, Chao / Shtukenberg, Alexander G / Ward, Michael D / Kahr, Bart

    Chemical communications (Cambridge, England)

    2021  Volume 57, Issue 45, Page(s) 5538–5541

    Abstract: The concept of Eshelby untwisting, the effect of an axial screw dislocation driving an intrinsically twisted nanocrystal towards a straighter configuration more consistent with long-range translational symmetry, is introduced here. Force-field ... ...

    Abstract The concept of Eshelby untwisting, the effect of an axial screw dislocation driving an intrinsically twisted nanocrystal towards a straighter configuration more consistent with long-range translational symmetry, is introduced here. Force-field simulations of nanorods built from the enantiomorphous (space groups, P3
    Language English
    Publishing date 2021-05-07
    Publishing country England
    Document type Journal Article
    ZDB-ID 1472881-3
    ISSN 1364-548X ; 1359-7345 ; 0009-241X
    ISSN (online) 1364-548X
    ISSN 1359-7345 ; 0009-241X
    DOI 10.1039/d1cc01431e
    Database MEDical Literature Analysis and Retrieval System OnLINE

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  9. Article: Nanoparticle self-assembly: Enantioselective photoactivation.

    Kahr, Bart / Shtukenberg, Alexander G

    Nature materials

    2015  Volume 14, Issue 1, Page(s) 21–22

    Language English
    Publishing date 2015-01
    Publishing country England
    Document type Journal Article
    ZDB-ID 2088679-2
    ISSN 1476-4660 ; 1476-1122
    ISSN (online) 1476-4660
    ISSN 1476-1122
    DOI 10.1038/nmat4174
    Database MEDical Literature Analysis and Retrieval System OnLINE

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  10. Article: Self-Patterning Tetrathiafulvalene Crystalline Films.

    Whittaker, St John / McDowell, Merritt / Bendesky, Justin / An, Zhihua / Yang, Yongfan / Zhou, Hengyu / Zhang, Yuze / Shtukenberg, Alexander G / Kalyon, Dilhan M / Kahr, Bart / Lee, Stephanie S

    Chemistry of materials : a publication of the American Chemical Society

    2023  Volume 35, Issue 20, Page(s) 8599–8606

    Abstract: Tetrathiafulvalene (TTF) crystals grown from the melt are organized as spherulites in which helicoidal fibrils growing radially from the nucleation center twist in concert with one another. Alternating bright and dark concentric bands are apparent when ... ...

    Abstract Tetrathiafulvalene (TTF) crystals grown from the melt are organized as spherulites in which helicoidal fibrils growing radially from the nucleation center twist in concert with one another. Alternating bright and dark concentric bands are apparent when films are viewed between crossed polarizers, indicating an alternating pattern of crystallographic faces exposed at the film surface. Band-dependent reorganization of the TTF crystals was observed during exposure to methanol vapor. Crystalline growth appears on bright bands at the expense of the dark bands. After a 24 h period of exposure to methanol vapor, the original spherulites were completely restructured, and the films comprise isolated, concentric circles of crystallites whose orientations are determined by the initial TTF crystal fibril orientation. While the surface of these outgrowths appears faceted and smooth, cross-sectional SEM images revealed a semiporous inner structure, suggesting solvent-vapor-induced recrystallization. Collectively, these results show that crystal twisting can be used to rhythmically redistribute material. Crystal twisting is a common and often controllable phenomenon independent of molecular or crystal structure and therefore offers a generalizable path to spontaneous pattern formation in a wide range of materials.
    Language English
    Publishing date 2023-10-11
    Publishing country United States
    Document type Journal Article
    ZDB-ID 1500399-1
    ISSN 1520-5002 ; 0897-4756
    ISSN (online) 1520-5002
    ISSN 0897-4756
    DOI 10.1021/acs.chemmater.3c01604
    Database MEDical Literature Analysis and Retrieval System OnLINE

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