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|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
de la Cruz, M O;Greenfield, M A;Hoffman, J R;Stupp, S I | 10.1021/la9030969 | null | 1155 16TH ST, NW, WASHINGTON, DC 20036 USA | 41676m16b3s442e5i2s5z243n1y5ldcx6x3d | Tunable Mechanics of Peptide Nanofiber Gels | Northwestern Univ | null | Stupp, SI (corresponding author), Northwestern Univ, Dept Mat Sci & Engn, Evanston, IL 60208 USA. | null | de la Cruz, Monica Olvera;Greenfield, Megan A;Hoffman, Jessica R;Stupp, Samuel I | Chemistry, Multidisciplinary;Chemistry, Physical;Materials Science, Multidisciplinary | null | WOS | Stupp, S I | Northwestern Univ, Chicago, IL USA;Northwestern Univ, Evanston, IL USA | 26 | gels;mechanics;Nanofiber;of;peptide;tunable | 1 | de la Cruz, Monica Olvera | AMER CHEMICAL SOC | Northwestern Univ, Dept Chem & Biol Engn, Evanston, IL 60208 USA;Northwestern Univ, Dept Chem, Evanston, IL 60208 USA;Northwestern Univ, Dept Mat Sci & Engn, Evanston, IL 60208 USA;Northwestern Univ, Feinberg Sch Med, Chicago, IL 60611 USA;Northwestern Univ, Inst Bionanotechnol Med, Chicago, IL 60611 USA | Article | Northwestern Univ | WASHINGTON | null | null | Northwestern Univ | null | Stupp, SI (corresponding author), Northwestern Univ, Dept Mat Sci & Engn, Evanston, IL 60208 USA. | 3647 | de la Cruz, Monica Olvera;Greenfield, Megan A;Hoffman, Jessica R;Stupp, Samuel I | 109 | 5 | 274,636,900,098 | null | USA | LANGMUIR | USA | null | null | Northwestern Univ, Dept Mat Sci & Engn, Evanston, IL 60208 USA | 0743-7463 | de la Cruz, M O;Greenfield, M A;Hoffman, J R;Stupp, S I | MAR 2 | s-stupp@northwestern.edu | Peptide Nanofiber Gels;tunable Mechanics | 4 | J | Chemistry;Materials Science | 10 min;100% strain;35%;42%;90%;ability;AMPHIPHILE NANOFIBERS;behavior;BINDING;CaCl2;CaCl2-PA;CaCl2-PA gels;CaCl2-PA gels form stronger intra-;CaCl2-PA gels lock;calcium-mediated ionic bridges;charged PA;charged residues;contrast;cross-linked semiflexible biopolymer networks;DEFORMATION;deformations;deformed structure;developing self-assembled;ELASTICITY;electron microscopy;exposure;fiber entanglements;GEL;gel's ability;GELATION;gels;gels encounter;growth;HCl;HCl-;HCl-PA gels;higher strains;hydrogen bonds;increasing strain amplitude HCl-;initial state;interactions;interfiber cross-links;laboratory self;large deformations;matrices;mechanical properties;mechanics;NANOFIBERS;NEUTRALIZATION;original stiffness;oscillatory rheological measurements;PAs;peptide amphiphile (PA) molecules;Peptide Nanofiber Gels;peptide segment;protonated acids;protonated carboxylic acid residues;response;result;rheological scaling behaviors;rheology;salt-mediated screening;self-assembled fibrillar networks;self-assembled nanofiber gels;SELF-ASSEMBLING BIOMATERIALS;serving;similar morphology;specific intermolecular interactions;STIFFNESS;strain sweeps;strong calcium cross-links;sustained deformation;synthetic cell scaffolds;tunable Mechanics;uncross-;viscoelastic properties;vivo | Greenfield, M A | AMPHIPHILE NANOFIBERS;BEHAVIOR;BINDING;ELASTICITY;GROWTH;MATRICES;rheology;SELF-ASSEMBLING BIOMATERIALS;STIFFNESS;VISCOELASTIC PROPERTIES | 3641 | [Hoffman, Jessica R.; de la Cruz, Monica Olvera; Stupp, Samuel I.] Northwestern Univ, Dept Mat Sci & Engn, Evanston, IL 60208 USA. [Greenfield, Megan A.; de la Cruz, Monica Olvera] Northwestern Univ, Dept Chem & Biol Engn, Evanston, IL 60208 USA. [de la Cruz, Monica Olvera; Stupp, Samuel I.] Northwestern Univ, Dept Chem, Evanston, IL 60208 USA. [Stupp, Samuel I.] Northwestern Univ, Feinberg Sch Med, Chicago, IL 60611 USA. [Stupp, Samuel I.] Northwestern Univ, Inst BioNanotechnol Med, Chicago, IL 60611 USA. | null | 10 min;100% strain;35%;42%;90%;ability;CaCl2;CaCl2-PA;CaCl2-PA gels;CaCl2-PA gels form stronger intra-;CaCl2-PA gels lock;calcium-mediated ionic bridges;charged PA;charged residues;contrast;cross-linked semiflexible biopolymer networks;deformation;deformations;deformed structure;developing self-assembled;electron microscopy;exposure;fiber entanglements;GEL;gel's ability;gelation;gels;gels encounter;HCl;HCl-;HCl-PA gels;higher strains;hydrogen bonds;increasing strain amplitude HCl-;initial state;interactions;interfiber cross-links;laboratory self;large deformations;mechanical properties;mechanics;nanofibers;neutralization;original stiffness;oscillatory rheological measurements;PAs;peptide amphiphile (PA) molecules;peptide segment;protonated acids;protonated carboxylic acid residues;response;result;rheological scaling behaviors;salt-mediated screening;self-assembled fibrillar networks;self-assembled nanofiber gels;serving;similar morphology;specific intermolecular interactions;stiffness;strain sweeps;strong calcium cross-links;sustained deformation;synthetic cell scaffolds;uncross-;vivo | 10.1002/adfm.200500161;10.1002/masy.19900390119;10.1007/s003970000124;10.1016/0301-4622(74)80046-3;10.1016/j.actbio.2005.04.002;10.1016/j.biomaterials.2008.07.049;10.1016/j.cell.2006.06.044;10.1016/j.polymer.2005.04.105;10.1016/S0006-3495(99)77113-4;10.1016/S0142-9612(97)00001-X;10.1016/S0377-0257(02)00141-6;10.1016/S0377-0257(97)00071-2;10.1021/bi00421a035;10.1021/ja028215r;10.1021/ja044863u;10.1021/ja060573x;10.1021/jp076273z;10.1021/ma010907x;10.1021/ma011964t;10.1021/nl048238z;10.1021/nl0484898;10.1021/nl0613555;10.1038/nmat1392;10.1073/pnas.072699999;10.1073/pnas.152667399;10.1073/pnas.94.25.13661;10.1083/jcb.113.1.155;10.1103/PhysRevE.60.4496;10.1103/PhysRevE.60.803;10.1103/PhysRevLett.75.4425;10.1103/PhysRevLett.82.101;10.1103/PhysRevLett.93.268106;10.1126/science.1063187;10.1126/science.1093783;10.1126/science.1106587;10.1126/science.1116995;10.1126/science.8493529;10.1152/ajpcell.2000.279.5.C1345;10.1152/japplphysiol.01121.2004;10.1529/biophysj.105.073114;10.1557/mrs2005.276 | Northwestern Univ | de la Cruz, M O;Greenfield, M A;Hoffman, J R;Stupp, S I | Greenfield, M A: Northwestern Univ, Dept Mat Sci & Engn, Evanston, IL 60208 USA | de la Cruz, Monica Olvera;Stupp, Samuel | null | 43 | null | USA | Northwestern Univ | Greenfield, Megan A | null | AMPHIPHILE NANOFIBERS;BEHAVIOR;BINDING;ELASTICITY;GROWTH;MATRICES;RHEOLOGY;SELF-ASSEMBLING BIOMATERIALS;STIFFNESS;VISCOELASTIC PROPERTIES | Greenfield, Megan A.; Hoffman, Jessica R.; de la Cruz, Monica Olvera; Stupp, Samuel I.; | null | Northwestern Univ, Dept Chem & Biol Engn, Evanston, IL 60208 USA;Northwestern Univ, Dept Chem, Evanston, IL 60208 USA;Northwestern Univ, Dept Mat Sci & Engn, Evanston, IL 60208 USA;Northwestern Univ, Feinberg Sch Med, Chicago, IL 60611 USA;Northwestern Univ, Inst Bionanotechnol Med, Chicago, IL 60611 USA | Northwestern Univ, Dept Chem & Biol Engn, Evanston, IL 60208 USA;Northwestern Univ, Dept Chem, Evanston, IL 60208 USA;Northwestern Univ, Dept Mat Sci & Engn, Evanston, IL 60208 USA;Northwestern Univ, Feinberg Sch Med, Chicago, IL 60611 USA;Northwestern Univ, Inst Bionanotechnol Med, Chicago, IL 60611 USA | null | null | 5 | 1974;1988;1990;1991;1993;1994;1995;1996;1997;1998;1999;2000;2001;2002;2003;2004;2005;2006;2008 | 185 | Northwestern Univ, Dept Mat Sci & Engn, Evanston, IL 60208 USA | Langmuir | Stupp, Samuel I | AMER CHEMICAL SOC | (PA);,;10;100%;35%;42%;90%;a;ability;acid;acids;after;allow;also;amphiphile;amplitude;and;are;as;assemble;at;behaviors;biopolymer;bonds;both;bridges;by;CaCl2;CaCl2-PA;calcium;calcium-mediated;can;carboxylic;cell;changing;charged;composed;consistent;contrast;cross-linked;cross-links;deformation;deformations;deformed;demonstrates;developed;developing;electron;encounter;entanglements;exposure;fiber;fibrillar;form;formed;from;gel;gel's;gelation;gels;HCl;HCl-;HCl-PA;here;higher;how;hydrogen;important;in;increasing;indicate;influenced;influences;inhibit;initial;interactions;interfiber;intermolecular;into;intra-;investigate;ionic;is;its;laboratory;large;lock;measurements;mechanical;mechanics;microscopy;min;modify;modulate;molecules;morphology;nanofiber;nanofibers;nearly;negatively;networks;neutralization;of;on;only;or;original;oscillatory;our;PA;pas;peptide;properties;protonated;quickly;recover;relax;report;residues;resist;respectively;respond;response;result;rheological;salt-mediated;scaffolds;scaling;scanning;screening;segment;self;self-assembled;semiflexible;series;serving;show;similar;specific;state;stiffness;strain;strains;strong;stronger;structure;suggests;sustained;sweeps;synthetic;than;that;the;their;these;this;to;uncross-;vivo;we;whereas;while;with;withstand | Northwestern Univ | The mechanical properties of self-assembled fibrillar networks are influenced by the specific intermolecular interactions that modulate fiber entanglements. We investigate how changing these interactions influences the mechanics of self-assembled nanofiber gels composed of peptide amphiphile (PA) molecules. PAs developed in our laboratory self assemble into gels of nanofibers after neutralization or salt-mediated screening of the charged residues in their peptide segment. We report here on the gelation, stiffness, and response to deformation of gels formed from a negatively charged PA and HCl or CaCl2. Scanning electron microscopy of these gels demonstrates a similar morphology, whereas the oscillatory rheological measurements indicate that the calcium-mediated ionic bridges in CaCl2-PA gels form stronger intra- and interfiber cross-links than the hydrogen bonds formed by the protonated carboxylic acid residues in HCl-PA gels. As a result, CaCl2-PA gels can withstand higher strains than HCl-PA gels. After exposure to a series of strain sweeps with increasing strain amplitude HCl- and CaCl2-PA gels both recover 42% of their original stiffness. In contrast, after sustained deformation at 100% strain, HCl-PA gels recover nearly 90% of their original stiffness after 10 min, while the CaCl2-PA gels only recover 35%. This result suggests that the hydrogen bonds formed by the protonated acids in the HCl-PA gels allow the gel to relax quickly to its initial state, while the strong calcium cross-links in the CaCl2-PA gels lock in the deformed structure and inhibit the gel's ability to recover. We also show that the rheological scaling behaviors of HCl- and CaCl2-PA gels are consistent with that of uncross- and cross-linked semiflexible biopolymer networks, respectively. The ability to modify how self-assembled fibrillar networks respond to deformations is important in developing self-assembled gels that can resist and recover from the large deformations that these gels encounter while serving as synthetic cell scaffolds in vivo. | A-7351-2012;AGV-1942-2022;B-6737-2009;N-6359-2018;X-2039-2019 | AMPHIPHILE NANOFIBERS;BEHAVIOR;BINDING;ELASTICITY;GROWTH;MATRICES;RHEOLOGY;SELF-ASSEMBLING BIOMATERIALS;STIFFNESS;VISCOELASTIC PROPERTIES | 0 | null | null | 7 | AMPHIPHILE NANOFIBERS;BEHAVIOR;BINDING;ELASTICITY;GROWTH;MATRICES;rheology;SELF-ASSEMBLING BIOMATERIALS;STIFFNESS;VISCOELASTIC PROPERTIES | WOS:000274636900098 | Northwestern Univ, Chicago, IL USA;Northwestern Univ, Evanston, IL USA | USA | 2,010 | null | 0000-0002-9802-3627 | null | null | English | null | ACTA BIOMATER;ADV FUNCT MATER;AM J PHYSIOL-CELL PH;BIOCHEMISTRY-US;BIOMATERIALS;BIOPHYS CHEM;BIOPHYS J;CELL;J AM CHEM SOC;J APPL PHYSIOL;J CELL BIOL;J NON-NEWTON FLUID;J PHYS CHEM B;MACROMOLECULES;MAKROMOL CHEM-M SYMP;Measurements;MOL BIOL CELL;MRS BULL;NANO LETT;NAT MATER;P NATL ACAD SCI USA;PHYS REV E;PHYS REV LETT;POLYMER;RHEOL ACTA;SCIENCE | de la Cruz, Monica Olvera;Greenfield, Megan A;Hoffman, Jessica R;Stupp, Samuel I | 2024-03-11
ER | Behanna, H A;Beniash, E;Bull, S R;Daniel, C;Discher, D E;Engler, A J;Georges, P C;Gerth, C;Guler, M O;Ha, B Y;Hartgerink, J D;Hvidt, S;Hwang, J J;Hyun, K;Janmey, P A;Klok, H A;Kong, H J;Langer, R;Mackintosh, F C;Macosko C. W.;Nehrer, S;Niece, K L;Ozbas, B;Paramonov, S E;Pelham, R J;Phan-Thien, N;Rajangam, K;Ryan, E A;Silva, G A;Solis, F J;Stendahl, J C;Stevens, M J;Stevens, M M;Stupp, S I;Tsonchev, S;Wan, T;Wang, H B | 556ZP | Evanston, IL USA | 222 | null | 1 | null | 19,817,454 | de la Cruz, Monica Olvera;Greenfield, Megan A;Hoffman, Jessica R;Stupp, Samuel I | LANGMUIR | Chicago, IL USA;Evanston, IL USA |