Midpoint scission of macromolecules in dilute solution in turbulent flow

Horn, Alexander; Merrill, Edward W.

doi:10.1038/312140a0

Cited by 101 publications

(72 citation statements)

References 7 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This suggests that chain scission occurs before full chain elongation and midpoint scission occurs in the partially uncoiled polymer. 120,121 The ε f still decreases with increasing molar mass of the polymer but scales with 123,143,[153][154][155] They observed that the critical strain rate for chain fracture in transient elongational flow was only weakly dependent on solvent viscosity and temperature. It was proposed that internal viscosity forces resulting from intramolecular friction between monomer units provide the predominant mechanism for bond scission.…”

Section: Elongational Fieldmentioning

confidence: 95%

Mechanically-Induced Chemical Changes in Polymeric Materials

et al. 2009

View full text Add to dashboard Cite

Polymeric materials exhibit an extraordinary range of mechanical responses (Figure 1a), which depend on the chemical and physical structure of the polymer chains. 3 Polymers are broadly categorized as thermoplastic, thermoset, or elastomer. Thermoplastic polymers consist of linear or branched chains and can be amorphous or semicrystalline. The mechanical response of thermoplastic polymers is highly influenced by the molecular mass, chain entanglements, chain alignment, and degree of crystallinity. Thermosetting polymers consist of highly cross-linked three-dimensional networks. The mechanical properties of these amorphous polymers depend on the molecular mass and the cross-link density. Elastomers (e.g., rubber) are highly deformable elastic networks that are lightly cross-linked by chemical or physical junctions. Mary M. Caruso (center) was born and raised in Tampa, FL. She received a B.S. degree in Chemistry from Elon University (Elon, NC) in 2006, where she worked under the direction of Prof. Karl D. Sienerth. Her research included the synthesis and electrochemical characterization of a novel palladium complex. She is currently pursuing her Ph.D. in Organic Chemistry at the University of Illinois at Urbana-Champaign under the guidance of Prof. Jeffrey S. Moore and Prof. Scott R. White. Her research interests include the development of new catalyst-free self-healing polymers, microencapsulation, and mechanical testing of bulk polymers. Douglas A. Davis (second from left) was born in Martin, TN. In 2004, he received his B.S. degree in Chemistry from the University of Tennessee, Knoxville, where he worked on surface enhanced Raman spectroscopy (SERS) in an electrospray plume with Professors Charles Feigerle and Kelsey Cook. He joined Prof. Jeffrey Moore's group at the University of Illinois, Urbana-Champaign in 2005 to pursue his Ph.D. in Organic Chemistry. His current research interests include designing and synthesizing mechanophores, which can be induced to undergo chemical reactions with mechanical force. Qilong Shen (third from left) was born in 1974 in Zhejiang Province, China. He received his B.S. degree in Chemistry (1996) from Nanjing University, China, and his M.S. in Chemistry (1999) from Shanghai Institute of Organic Chemistry, the Chinese Science Academy, China, under the supervision of Prof. Long Lu. After a two-year stay at the University of Massachusetts at Dartmouth with Prof. Gerald B. Hammond, he moved to Yale University, where he received his Ph.D. under the guidance of Prof. John F. Hartwig in 2007. He is currently a postdoctoral researcher with Prof. Jeffrey S. Moore at University of Illinois at Urbana-Champaign. His research interests include the discovery, development, and understanding of new transition metal-catalyzed reactions, and the mechanochemistry of polymers.

show abstract

Section: Elongational Fieldmentioning

confidence: 95%

Mechanically-Induced Chemical Changes in Polymeric Materials

et al. 2009

View full text Add to dashboard Cite

show abstract

“…ong-chain polymers undergo scission in strong flows because of the coupling of continuum-scale mechanical and atomicscale chemical processes (1,2). The interactions that connect these disparate scales are poorly understood.…”

mentioning

confidence: 99%

Universal scaling for polymer chain scission in turbulence

Vanapalli¹,

Ceccio

Solomon

2006

Proc. Natl. Acad. Sci. U.S.A.

104

View full text Add to dashboard Cite

We report that previous polymer chain scission experiments in strong flows, long analyzed according to accepted laminar flow scission theories, were in fact affected by turbulence. We reconcile existing anomalies between theory and experiment with the hypothesis that the local stress at the Kolmogorov scale generates the molecular tension leading to polymer covalent bond breakage. The hypothesis yields a universal scaling for polymer scission in turbulent flows. This surprising reassessment of over 40 years of experimental data simplifies the theoretical picture of polymer dynamics leading to scission and allows control of scission in commercial polymers and genomic DNA.bond breakage ͉ drag reduction ͉ polymer dynamics ͉ Kolmogorov cascade ͉ DNA rupture L ong-chain polymers undergo scission in strong flows because of the coupling of continuum-scale mechanical and atomicscale chemical processes (1, 2). The interactions that connect these disparate scales are poorly understood. Yet, practically, polymer chain scission is a principal determinant of the performance of operations in many fields, including turbulent drag reduction for pipelines and ships (3), microfluidic handling of polymeric fluids (4), and gene therapy using plasmid DNA (5). Alternatively, chain scission underlies technologies such as the shotgun sequencing of DNA (6) and the generation of monodisperse polymer standards (7). The design and control of polymer scission in each of these flows is driven by the scaling relationship between the strength of the flow, as quantified by the fluid strain rate, and the scission product distribution, as quantified by the molar mass of ruptured polymer chains. Since Frenkel (8) published the first treatise on polymer chain scission more than 60 years ago, this fundamental issue has remained unresolved.Scission theories for laminar flow hypothesize that the drag force, F d , experienced by the chain induces a tension that breaks the molecule if it is greater than the critical strength of a polymer covalent bond. In a purely extensional flow, for example, the maximum tension is at the midpoint (9). If the extended chain is modeled as a slender rod, then the tension induced by the drag is F d ϳ VR ϳ R 2 (10). Here is the solvent viscosity, V is the relative velocity of the solvent flowing past the rod at its half-length R and is the macroscopic fluid strain rate (ϳV͞R). Two laminar theories identify different regimes depending on the ratio of polymer relaxation time to flow residence time, the Deborah number (De). For the De Ͻ Ͻ 1 regime, such as in stagnation point flow of a cross-slot, chains are fully stretched such that R ϳ O(L), where L is the contour length of the chain (10). For the De Ͼ Ͼ 1 regime, such as in transient extensional flows generated in contraction-expansion geometries, chains adopt only a partially stretched conformation and R ϳ O(R g ), where R g is the radius of gyration (11). These viscous flow models yield distinct scaling relationships: c ϳ L Ϫ2 for De Ͻ Ͻ 1 and c ϳ L Ϫ1 for De Ͼ Ͼ 1, whe...

show abstract

“…The same experiment was repeated with DNA nanotubes having different circumferences and corresponding bond strengths, namely, the six-and ten-helix nanotubes, and the same trend was consistently observed in all nanotubes ͑see Table I and Figs. 4,7,and 8͒. Elongational flow induces the alignment of DNA nanotubes along the flow gradient. According to the scission theory presented in Appendix A, the drag force experienced by the nanotubes induces tension along the axis of the DNA nanotubes.…”

Section: Resultsmentioning

confidence: 99%

Elongational-flow-induced scission of DNA nanotubes in laminar flow

Hariadi

Yurke

2010

Phys. Rev. E

View full text Add to dashboard Cite

The length distributions of polymer fragments subjected to an elongational-flow-induced scission are profoundly affected by the fluid flow and the polymer bond strengths. In this paper, laminar elongational flow was used to induce chain scission of a series of circumference-programmed DNA nanotubes. The DNA nanotubes served as a model system for semiflexible polymers with tunable bond strength and cross-sectional geometry. The expected length distribution of fragmented DNA nanotubes was calculated from first principles by modeling the interplay between continuum hydrodynamic elongational flow and the molecular forces required to overstretch multiple DNA double helices. Our model has no-free parameters; the only inferred parameter is obtained from DNA mechanics literature, namely, the critical tension required to break a DNA duplex into two single-stranded DNA strands via the overstretching B-S DNA transition. The nanotube fragments were assayed with fluorescence microscopy at the single-molecule level and their lengths are in agreement with the scission theory.

show abstract

Midpoint scission of macromolecules in dilute solution in turbulent flow

Cited by 101 publications

References 7 publications

Mechanically-Induced Chemical Changes in Polymeric Materials

Mechanically-Induced Chemical Changes in Polymeric Materials

Universal scaling for polymer chain scission in turbulence

Elongational-flow-induced scission of DNA nanotubes in laminar flow

Contact Info

Product

Resources

About