RESEARCH ARTICLE

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

  • Yawen Yao 1 ,
  • Sabine Rosenfeldt 2 ,
  • Kai Zhang , 1
Expand
  • 1. Wood Technology and Wood Chemistry, Georg-August-University of Goettingen, 37077 Göttingen, Germany
  • 2. Department of Chemistry and Bavarian Polymer Institute, University of Bayreuth, 95447 Bayreuth, Germany

Received date: 30 Jan 2019

Accepted date: 29 Jun 2019

Published date: 15 Jun 2020

Copyright

2020 Higher Education Press

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.

Cite this article

Yawen Yao , Sabine Rosenfeldt , Kai Zhang . Effects of solvents and temperature on spherulites of self-assembled phloroglucinol tristearate[J]. Frontiers of Chemical Science and Engineering, 2020 , 14(3) : 389 -396 . DOI: 10.1007/s11705-019-1911-3

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.
1
Keith H, Padden F Jr. A phenomenological theory of spherulitic crystallization. Journal of Applied Physics, 1963, 34(8): 2409–2421

DOI

2
Shtukenberg A G, Punin Y O, Gunn E, Kahr B. Spherulites. Chemical Reviews, 2012, 112(3): 1805–1838

DOI

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

DOI

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

DOI

6
Imai H, Oaki Y. Emergence of morphological chirality from twinned crystals. Angewandte Chemie International Edition, 2004, 43(11): 1363–1368

DOI

7
Cui X, Rohl A L, Shtukenberg A, Kahr B. Twisted aspirin crystals. Journal of the American Chemical Society, 2013, 135(9): 3395–3398

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

18
Jain A, George S J. New directions in supramolecular electronics. Materials Today, 2015, 18(4): 206–214

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

Outlines

/