Effects of solvents and temperature on spherulites of self-assembled phloroglucinol tristearate

Yawen Yao, Sabine Rosenfeldt, Kai Zhang

PDF(3577 KB)
PDF(3577 KB)
Front. Chem. Sci. Eng. ›› 2020, Vol. 14 ›› Issue (3) : 389-396. DOI: 10.1007/s11705-019-1911-3
RESEARCH ARTICLE
RESEARCH ARTICLE

Effects of solvents and temperature on spherulites of self-assembled phloroglucinol tristearate

Author information +
History +

Abstract

Herein, phloroglucinol tristearate (PhgTS) was used to study the crystallization process due to its unique symmetric structure containing a benzene ring and three aliphatic chains. Spherulites of crystallized PhgTS from four solvents under diverse conditions were analyzed in detail and their formation process was studied. Maltese cross is shown by PhgTS spherulites obtained from aprotic solvents via polarized optical microscopy. In comparison, no Maltese cross can be observed from branch-like crystals formed from protic solvents. Independent on the microscaled morphology, lamellae were found to be the basic blocks constructing both PhgTS spherulites and branch-like crystals, which were formed predominantly by stacked PhgTS molecules. Although differential characters of the solvents did not affect the formation of lamellas, the solvents played a crucial role in the formation of self-assembled microscaled morphologies. In particular, the morphologies of spherulites were strongly affected by the concentration of PhgTS solutions, surrounding temperature and evaporation rate of solvents. Generally, a higher concentration of PhgTS led to more homogeneous spherulites, a lower evaporation rate resulted in more compact spherulites, and a higher surrounding temperature generated preferentially more ring-banded spherulites of PhgTS.

Graphical abstract

Keywords

phloroglucinol / tristearate / aprotic and protic solvent / self-assembly / spherulites

Cite this article

Download citation ▾
Yawen Yao, Sabine Rosenfeldt, Kai Zhang. Effects of solvents and temperature on spherulites of self-assembled phloroglucinol tristearate. Front. Chem. Sci. Eng., 2020, 14(3): 389‒396 https://doi.org/10.1007/s11705-019-1911-3

References

[1]
Keith H, Padden F Jr. A phenomenological theory of spherulitic crystallization. Journal of Applied Physics, 1963, 34(8): 2409–2421
CrossRef Google scholar
[2]
Shtukenberg A G, Punin Y O, Gunn E, Kahr B. Spherulites. Chemical Reviews, 2012, 112(3): 1805–1838
CrossRef Google scholar
[3]
Reddy S M M, Shanmugam G, Mandal A B. “Cross-linked fibrous” spherulites formed from a low molecular weight compound, Fmoc-functionalized phenolic amino acid. Soft Matter, 2015, 11(21): 4154–4157
CrossRef Google scholar
[4]
Samuels S L, Wilkes G L. The rheo-optical and mechanical behavior of a systematic series of hard-soft segmented urethanes. Journal of Polymer Science: Polymer Symposia, 1973, 43(1): 149–178
[5]
Lugito G, Woo E M. Interior lamellar assembly in correlation to top-surface banding in crystallized poly (ethylene adipate). Crystal Growth & Design, 2014, 14(10): 4929–4936
CrossRef Google scholar
[6]
Imai H, Oaki Y. Emergence of morphological chirality from twinned crystals. Angewandte Chemie International Edition, 2004, 43(11): 1363–1368
CrossRef Google scholar
[7]
Cui X, Rohl A L, Shtukenberg A, Kahr B. Twisted aspirin crystals. Journal of the American Chemical Society, 2013, 135(9): 3395–3398
CrossRef Google scholar
[8]
Woo E M, Lugito G, Yang C E. Analysis of crystal assembly in banded spherulites of phthalic acid upon solvent evaporation. CrystEngComm, 2016, 18(6): 977–985
CrossRef Google scholar
[9]
Atwood J. Comprehensive Supramolecular Chemistry II. 2nd Edition. Amsterdam: Elsevier, 2017, 1–10
[10]
Lehn J M, Sanders J. Supramolecular Chemistry. Concepts and Perspectives. Angewandte Chemie International Edition, 1995, 34(22): 2563
CrossRef Google scholar
[11]
Betush R J, Urban J M, Nilsson B L. Balancing hydrophobicity and sequence pattern to influence self-assembly of amphipathic peptides. Peptide Science, 2018, 110(1): e23099
CrossRef Google scholar
[12]
Payne W M, Svechkarev D, Kyrychenko A, Mohs A M. The role of hydrophobic modification on hyaluronic acid dynamics and self-assembly. Carbohydrate Polymers, 2018, 182: 132–141
CrossRef Google scholar
[13]
Shimizu T. Molecular self-assembly into one-dimensional nanotube architectures and exploitation of their functions. Bulletin of the Chemical Society of Japan, 2008, 81(12): 1554–1566
CrossRef Google scholar
[14]
Bogie P M, Holloway L R, Lyon Y, Onishi N C, Beran G J, Julian R R, Hooley R J. A Springloaded Metal-Ligand Mesocate Allows Access to Trapped Intermediates of Self-Assembly. Inorganic Chemistry, 2018, 57(7): 4155–4163
CrossRef Google scholar
[15]
Knight A S, Larsson J, Ren J M, Bou Zerdan R, Seguin S, Vrahas R, Liu J, Ren G, Hawker C J. Control of amphiphile self-assembly via bioinspired metal ion coordination. Journal of the American Chemical Society, 2018, 140(4): 1409–1414
CrossRef Google scholar
[16]
Ghosh S, Praveen V K, Ajayaghosh A. The chemistry and applications of p-gels. Annual Review of Materials Research, 2016, 46(1): 235–262
CrossRef Google scholar
[17]
Yamamoto Y. Programmed self-assembly of large p-conjugated molecules into electroactive one-dimensional nanostructures. Science and Technology of Advanced Materials, 2012, 13(3): 033001
CrossRef Google scholar
[18]
Jain A, George S J. New directions in supramolecular electronics. Materials Today, 2015, 18(4): 206–214
CrossRef Google scholar
[19]
Moulin E, Cid J J, Giuseppone N. Advances in supramolecular electronics-from randomly self-assembled nanostructures to addressable self-organized interconnects. Advanced Materials, 2013, 25(3): 477–487
CrossRef Google scholar
[20]
Cai L, Shi Y C. Self-assembly of short linear chains to A-and B-type starch spherulites and their enzymatic digestibility. Journal of Agricultural and Food Chemistry, 2013, 61(45): 10787–10797
CrossRef Google scholar
[21]
Zhou X, Zhang Q, Xu R, Chen D, Hao S, Nie F, Li H. A novel spherulitic self-assembly strategy for organic explosives: Modifying the hydrogen bonds by polymeric additives in emulsion crystallization. Crystal Growth & Design, 2018, 18(4): 2417–2423
CrossRef Google scholar
[22]
Zhang M, Chen M, Ni Z. Thermoreversible rheological responses of biscarbamates and tricarbamates in uncured epoxy composite pastes caused by their self-assembly in an epoxy matrix. Journal of Applied Polymer Science, 2018, 135(13): 46032
CrossRef Google scholar
[23]
Zhang K, Geissler A, Chen X, Rosenfeldt S, Yang Y, Förster S, Müller-Plathe F. Polymeric flower-like microparticles from self-assembled cellulose stearoyl esters. ACS Macro Letters, 2015, 4(2): 214–219
CrossRef Google scholar
[24]
Braun D E, Tocher D A, Price S L, Griesser U J. The complexity of hydration of phloroglucinol: A comprehensive structural and thermodynamic characterization. Journal of Physical Chemistry B, 2012, 116(13): 3961–3972
CrossRef Google scholar
[25]
Zhou J H, Sui Z J, Zhu J, Li P, Chen D, Dai Y C, Yuan W K. Characterization of surface oxygen complexes on carbon nanofibers by TPD, XPS and FT-IR. Carbon, 2007, 45(4): 785–796
CrossRef Google scholar
[26]
Förster S, Fischer S, Zielske K, Schellbach C, Sztucki M, Lindner P, Perlich J. Calculation of scattering-patterns of ordered nano-and mesoscale materials. Advances in Colloid and Interface Science, 2011, 163(1): 53–83
CrossRef Google scholar
[27]
El Aziz Y, Bassindale A R, Taylor P G, Stephenson R A, Hursthouse M B, Harrington R W, Clegg W. X-ray crystal structures, packing behavior, and thermal stability studies of a homologous series of n-alkyl-substituted polyhedral oligomeric silsesquioxanes. Macromolecules, 2013, 46(3): 988–1001
CrossRef Google scholar
[28]
Heeley E L, Hughes D J, El Aziz Y, Taylor P G, Bassindale A R. Linear long alkyl chain substituted POSS cages: The effect of alkyl chain length on the self-assembled packing morphology. Macromolecules, 2013, 46(12): 4944–4954
CrossRef Google scholar
[29]
Cui X, Shtukenberg A G, Freudenthal J, Nichols S, Kahr B. Circular birefringence of banded spherulites. Journal of the American Chemical Society, 2014, 136(14): 5481–5490
CrossRef Google scholar
[30]
Huang T, Kuboyama K, Fukuzumi H, Ougizawa T. PMMA/TEMPO-oxidized cellulose nanofiber nanocomposite with improved mechanical properties, high transparency and tunable birefringence. Cellulose (London, England), 2018, 25(4): 2393–2403
CrossRef Google scholar
[31]
Danjo T, Enomoto Y, Shimada H, Nobukawa S, Yamaguchi M, Iwata T. Zero birefringence films of pullulan ester derivatives. Scientific Reports, 2017, 7(1): 46342
CrossRef Google scholar

Acknowledgements

Y.Y. thanks the China Scholarship Council (CSC) for financial support. K.Z. thanks Georg-August-University of Goettingen for the Anschubfinanzierung (Funding for the Promotion of Young Academics of University of Goettingen) and Fonds der Chemischen Industrie (FCI) for the financial support. The authors declare no conflicts of interest.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-019-1911-3 and is accessible for authorized users.

RIGHTS & PERMISSIONS

2020 Higher Education Press
AI Summary AI Mindmap
PDF(3577 KB)

Accesses

Citations

Detail

Sections
Recommended

/