Silk Fibroin-Sophorolipid Gelation: Deciphering the Underlying Mechanism.

Abstract:

:Silk fibroin (SF) protein, produced by silkworm Bombyx mori, is a promising biomaterial, while sophorolipid (SL) is an amphiphilic functional biosurfactant synthesized by nonpathogenic yeast Candida bombicola. SL is a mixture of two forms, acidic (ASL) and lactonic (LSL), which when added to SF results in accelerated gelation of silk fibroin. LSL is known to have multiple biological functionalities and hence hydrogels of these green molecules have promising applications in the biomedical sector. In this work, SANS, NMR, and rheology are employed to examine the assembling properties of individual and mixed SLs and their interactions with SF to understand the mechanism that leads to rapid gelation. SANS and NMR studies show that ASL assembles to form charged micelles, while LSL forms micellar assemblies and aggregates of a mass fractal nature. ASL and LSL together form larger mixed micelles, all of which interact differently with SF. It is shown that preferential binding of LSL to SF causes rapid unfolding of the SF chain leading to the formation of intermolecular beta sheets, which trigger fast gelation. Based on the observations, a mechanism for gelation of SF in the presence of different sophorolipids is proposed.

journal_name

Biomacromolecules

journal_title

Biomacromolecules

authors

Dubey P,Kumar S,Aswal VK,Ravindranathan S,Rajamohanan PR,Prabhune A,Nisal A

doi

10.1021/acs.biomac.6b01069

subject

Has Abstract

pub_date

2016-10-10 00:00:00

pages

3318-3327

issue

10

eissn

1525-7797

issn

1526-4602

journal_volume

17

pub_type

杂志文章
  • Preparation and characterization of nanoparticles shelled with chitosan for oral insulin delivery.

    abstract::Nanoparticles (NPs) composed of chitosan (CS) and poly(gamma-glutamic acid) (gamma-PGA) were prepared by a simple ionic-gelation method for oral insulin delivery. Fourier transform infrared (FT-IR) spectra indicated that CS and gamma-PGA were ionized at pH 2.5-6.6, while X-ray diffractograms demonstrated that the crys...

    journal_title:Biomacromolecules

    pub_type: 杂志文章

    doi:10.1021/bm0607776

    authors: Lin YH,Mi FL,Chen CT,Chang WC,Peng SF,Liang HF,Sung HW

    更新日期:2007-01-01 00:00:00

  • Force spectroscopy of LFA-1 and its ligands, ICAM-1 and ICAM-2.

    abstract::Single-molecule measurements of the interaction of leukocyte function-associated antigen-1 (LFA-1), expressed on Jurkat T cells, with intercellular adhesion molecules-1 and -2 (ICAM-1 and ICAM-2) were conducted using atomic force microscopy (AFM). The force spectra (i.e., unbinding force versus loading rate) of both t...

    journal_title:Biomacromolecules

    pub_type: 杂志文章

    doi:10.1021/bm060559c

    authors: Wojcikiewicz EP,Abdulreda MH,Zhang X,Moy VT

    更新日期:2006-11-01 00:00:00

  • Candida antarctica lipase B chemically immobilized on epoxy-activated micro- and nanobeads: catalysts for polyester synthesis.

    abstract::Candida antarctica Lipase B (CALB) was covalently immobilized onto epoxy-activated macroporous poly(methyl methacrylate) Amberzyme beads (235 microm particle size, 220 A pore size) and nanoparticles (nanoPSG, diameter 68 nm) with a poly(glycidyl methacrylate) outer region. Amberzyme beads allowed CALB loading up to 0....

    journal_title:Biomacromolecules

    pub_type: 杂志文章

    doi:10.1021/bm700949x

    authors: Chen B,Hu J,Miller EM,Xie W,Cai M,Gross RA

    更新日期:2008-02-01 00:00:00

  • New design of helix bundle peptide-polymer conjugates.

    abstract::We present a new design of peptide-polymer conjugates where a polymer chain is covalently linked to the side chain of a helix bundle-forming peptide. The effect of conjugated polymer chains on the peptide structure was examined using a de novo designed three-helix bundle and a photoactive four-helix bundle. Upon attac...

    journal_title:Biomacromolecules

    pub_type: 杂志文章

    doi:10.1021/bm800113g

    authors: Shu JY,Tan C,DeGrado WF,Xu T

    更新日期:2008-08-01 00:00:00

  • Engineering interaction between bone marrow derived endothelial cells and electrospun surfaces for artificial vascular graft applications.

    abstract::The aim of this investigation was to understand and engineer the interactions between endothelial cells and the electrospun (ES) polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP) nanofiber surfaces and evaluate their potential for endothelialization. Elastomeric PVDF-HFP samples were electrospun to evaluate th...

    journal_title:Biomacromolecules

    pub_type: 杂志文章

    doi:10.1021/bm401825c

    authors: Ahmed F,Dutta NK,Zannettino A,Vandyke K,Choudhury NR

    更新日期:2014-04-14 00:00:00

  • Ultra-sub-stoichiometric "Dynamic" Bioconjugation Reduces Viscosity by Disrupting Immunoglobulin Oligomerization.

    abstract::Monoclonal antibodies (mAb) are a major focus of the pharmaceutical industry, and polyclonal immunoglobulin G (IgG) therapy is used to treat a wide variety of health conditions. As some individuals require mAb/IgG therapy their entire life, there is currently a great desire to formulate antibodies for bolus injection ...

    journal_title:Biomacromolecules

    pub_type: 杂志文章

    doi:10.1021/acs.biomac.9b00867

    authors: Gong Y,Soleymani Abyaneh H,Drossis N,Niederquell A,Kuentz M,Leroux JC,de Haan HW,Gauthier MA

    更新日期:2019-09-09 00:00:00

  • Enzymatic copolymerization alters the structure of unpolymerized mixtures of the biomimetic monomers: the amphiphilic decyl ester of L-tyrosine and L-tyrosineamide--an AFM investigation of nano- to micrometer-scale structure differences.

    abstract::Previously, we have shown that the amphiphilic decyl esters of both D- and L-tyrosine (DELT) self-assemble in aqueous solution above their critical micelle concentration values to form long rodlike structures that can be enzymatically polymerized. In the current study, we have examined the self-assembled structures of...

    journal_title:Biomacromolecules

    pub_type: 杂志文章

    doi:10.1021/bm049793y

    authors: Marx KA,Lee JS,Sung C

    更新日期:2004-09-01 00:00:00

  • Hyaluronic acid based materials for scaffolding via two-photon polymerization.

    abstract::Hydrogels are able to mimic the basic three-dimensional (3D) biological, chemical, and mechanical properties of native tissues. Since hyaluronic acid (HA) is a chief component of human extracellular matrix (ECM), it represents an extremely attractive starting material for the fabrication of scaffolds for tissue engine...

    journal_title:Biomacromolecules

    pub_type: 杂志文章

    doi:10.1021/bm401712q

    authors: Kufelt O,El-Tamer A,Sehring C,Schlie-Wolter S,Chichkov BN

    更新日期:2014-02-10 00:00:00

  • Superstrong and Tough Hydrogel through Physical Cross-Linking and Molecular Alignment.

    abstract::Hydrogels are attracting increasing attention due to their potential use in various fields. However, most of the existing hydrogels have limitations in either dissipating mechanical energy or maintaining high stretchability under deformation, thus do not possess high mechanical properties. Herein, poly(vinyl alcohol) ...

    journal_title:Biomacromolecules

    pub_type: 杂志文章

    doi:10.1021/acs.biomac.9b01223

    authors: Chen W,Li N,Ma Y,Minus ML,Benson K,Lu X,Wang X,Ling X,Zhu H

    更新日期:2019-12-09 00:00:00

  • Multiblock copolymers of L-lactide and trimethylene carbonate.

    abstract::Sequential copolymerizations of trimethylene carbonate (TMC) and l-lactide (LLA) were performed with 2,2-dibutyl-2-stanna-1,3-oxepane as a bifunctional cyclic initiator. The block lengths were varied via the monomer/initiator and via the TMC/l-lactide ratio. The cyclic triblock copolymers were transformed in situ into...

    journal_title:Biomacromolecules

    pub_type: 杂志文章

    doi:10.1021/bm049393a

    authors: Pospiech D,Komber H,Jehnichen D,Häussler L,Eckstein K,Scheibner H,Janke A,Kricheldorf HR,Petermann O

    更新日期:2005-01-01 00:00:00

  • Structural effects on the biodistribution and positron emission tomography (PET) imaging of well-defined (64)Cu-labeled nanoparticles comprised of amphiphilic block graft copolymers.

    abstract::The synthesis of poly(methyl methacrylate-co-methacryloxysuccinimide-graft-poly(ethylene glycol)) (PMMA-co-PMASI-g-PEG) via living free radical polymerization provides a convenient route to well-defined amphiphilic graft copolymers having a controllable number of reactive functional groups, variable length PEG grafts,...

    journal_title:Biomacromolecules

    pub_type: 杂志文章

    doi:10.1021/bm700541e

    authors: Pressly ED,Rossin R,Hagooly A,Fukukawa K,Messmore BW,Welch MJ,Wooley KL,Lamm MS,Hule RA,Pochan DJ,Hawker CJ

    更新日期:2007-10-01 00:00:00

  • In vitro studies of antifreeze glycoprotein (AFGP) and a C-linked AFGP analogue.

    abstract::Antifreeze glycoproteins (AFGPs) are a subclass of biological antifreezes found in deep sea Teleost fish. These compounds have the ability to depress the freezing point of the organism such that it can survive the subzero temperatures encountered in its environment. This physical property is very attractive for the cr...

    journal_title:Biomacromolecules

    pub_type: 杂志文章

    doi:10.1021/bm061044o

    authors: Liu S,Wang W,Moos Ev,Jackman J,Mealing G,Monette R,Ben RN

    更新日期:2007-05-01 00:00:00

  • Electrophoretic deposition of polymer chains: a Monte Carlo study of density profile and conformation.

    abstract::Effects of molecular weight (Lc) and field strength (E) on conformation of polymer chains and their density are investigated at the surface and bulk of a driven chain system in three dimensions with a Monte Carlo simulation. As the polymer chains deposit on the surface, a linear density gradient develops in low field....

    journal_title:Biomacromolecules

    pub_type: 杂志文章

    doi:10.1021/bm000289c

    authors: Foo GM,Pandey RB

    更新日期:2000-10-01 00:00:00

  • Self-assembling peptide inspired by a barnacle underwater adhesive protein.

    abstract::An underwater bioadhesive generally comprises a multiprotein complex that provides a molecular basis for self-assembly. We report here a new class of self-assembling peptide inspired by a 20 kDa barnacle cement protein. Studies on the chemically synthesized 24-residue peptide have revealed that (1) it underwent irreve...

    journal_title:Biomacromolecules

    pub_type: 杂志文章

    doi:10.1021/bm0612236

    authors: Nakano M,Shen JR,Kamino K

    更新日期:2007-06-01 00:00:00

  • Gelation, phase behavior, and dynamics of β-lactoglobulin amyloid fibrils at varying concentrations and ionic strengths.

    abstract::We have investigated the thermodynamic and dynamic behavior of multistranded β-lactoglobulin protein fibrils in water, by combining static, dynamic, and depolarized dynamic light scattering (SLS, DLS, DDLS), small angle neutron scattering (SANS), rheology, and cryogenic transmission electron microscopy (cryo-TEM). We ...

    journal_title:Biomacromolecules

    pub_type: 杂志文章

    doi:10.1021/bm301005w

    authors: Bolisetty S,Harnau L,Jung JM,Mezzenga R

    更新日期:2012-10-08 00:00:00

  • Binding between proteins and cationic spherical polyelectrolyte brushes: effect of pH, ionic strength, and stoichiometry.

    abstract::Cationic spherical polyelectrolyte brushes (SPBs) were synthesized by photoemulsion polymerization, consisting of a polystyrene core with a diameter around 80 nm and a poly(2-aminoethylmethacrylate hydrochloride) (PAEMH) shell with a thickness from 10 to 50 nm densely grafted on the core surface. The binding of variou...

    journal_title:Biomacromolecules

    pub_type: 杂志文章

    doi:10.1021/bm301865g

    authors: Wang S,Chen K,Li L,Guo X

    更新日期:2013-03-11 00:00:00

  • Wet-spinning of regenerated silk fiber from aqueous silk fibroin solution: discussion of spinning parameters.

    abstract::Regenerated silk fibroin (RSF) fibers were obtained by extruding a concentrated aqueous silk fibroin solution into an ammonium sulfate coagulation bath. A custom-made simplified industrial-type wet-spinning device with continuous mechanical postdraw was used. The effect of dope concentration, coagulation bath, extrusi...

    journal_title:Biomacromolecules

    pub_type: 杂志文章

    doi:10.1021/bm900840h

    authors: Yan J,Zhou G,Knight DP,Shao Z,Chen X

    更新日期:2010-01-11 00:00:00

  • Engineered polymeric nanoparticles for receptor-targeted blockage of oxidized low density lipoprotein uptake and atherogenesis in macrophages.

    abstract::Strategies to prevent the uptake of modified low density lipoproteins (LDLs) by immune cells, a major trigger of inflammation and atherogenesis, are challenged by complex interfacial factors governing LDL receptor-mediated uptake. We examine a new approach based on a family of "nanoblockers", which are designed to exa...

    journal_title:Biomacromolecules

    pub_type: 杂志文章

    doi:10.1021/bm0600872

    authors: Chnari E,Nikitczuk JS,Wang J,Uhrich KE,Moghe PV

    更新日期:2006-06-01 00:00:00

  • Thermoreversible poly(ethylene glycol)-g-chitosan hydrogel as a therapeutic T lymphocyte depot for localized glioblastoma immunotherapy.

    abstract::The outcome for glioblastoma patients remains dismal for its invariably recrudesces within 2 cm of the resection cavity. Local immunotherapy has the potential to eradicate the residual infiltrative component of these tumors. Here, we report the development of a biodegradable hydrogel containing therapeutic T lymphocyt...

    journal_title:Biomacromolecules

    pub_type: 杂志文章

    doi:10.1021/bm500502n

    authors: Tsao CT,Kievit FM,Ravanpay A,Erickson AE,Jensen MC,Ellenbogen RG,Zhang M

    更新日期:2014-07-14 00:00:00

  • Glyco-nanoparticles with sheddable saccharide shells: a unique and potent platform for hepatoma-targeting delivery of anticancer drugs.

    abstract::Reduction-sensitive shell-sheddable glyco-nanoparticles were designed and developed based on poly(ε-caprolactone)-graft-SS-lactobionic acid (PCL-g-SS-LBA) copolymer for efficient hepatoma-targeting delivery of doxorubicin (DOX). PCL-g-SS-LBA was prepared by ring-opening copolymerization of ε-caprolactone and pyridyl d...

    journal_title:Biomacromolecules

    pub_type: 杂志文章

    doi:10.1021/bm401749t

    authors: Chen W,Zou Y,Meng F,Cheng R,Deng C,Feijen J,Zhong Z

    更新日期:2014-03-10 00:00:00

  • Biomimetic hydrogels with immobilized ephrinA1 for therapeutic angiogenesis.

    abstract::The formation of a microvasculature is regulated in large part by cell-cell interactions. Ephrins and their Eph receptors mediate cell adhesion, repulsion, and migration, all critical processes in angiogenesis. (1) Here we use a covalently immobilized ephrinA1, conjugated to poly(ethylene glycol), to induce vessel for...

    journal_title:Biomacromolecules

    pub_type: 杂志文章

    doi:10.1021/bm200492h

    authors: Saik JE,Gould DJ,Keswani AH,Dickinson ME,West JL

    更新日期:2011-07-11 00:00:00

  • Structure of artificial cytoskeleton containing liposomes in aqueous solution studied by static and dynamic light scattering.

    abstract::The structure of three types of liposomes (egg yolk phosphatidylcholine (EPC) without modification and EPC vesicles containing cross-linked N-isopropylacrylamide (NIPAM) networks of low and a high concentration inside the vesicles) were analyzed by static and dynamic light scattering. Upon polymerization the network w...

    journal_title:Biomacromolecules

    pub_type: 杂志文章

    doi:10.1021/bm0200074

    authors: Stauch O,Schubert R,Savin G,Burchard W

    更新日期:2002-05-01 00:00:00

  • Electric field induced assembly of vimentin microscaffolds around metallic electrodes.

    abstract::The self-assembly properties of fibrous proteins such as collagen are frequently used to form three-dimensional scaffolds. In this study we investigated the effect of nonuniform alternating and static electric-fields on the self-assembly properties of a dilute solution of vimentin. In the presence of both types of fie...

    journal_title:Biomacromolecules

    pub_type: 杂志文章

    doi:10.1021/bm900398n

    authors: Colbourne TR,Hill IG,Kreplak L

    更新日期:2009-07-13 00:00:00

  • Three-dimensional arrangement of sugar residues along helical polypeptide backbone. 2. Synthesis of periodic N-glycosylated peptides by polymerization of tripeptide active esters containing alpha,alpha-disubstituted amino acid.

    abstract::New type of N-glycosylated peptides having periodic sequence of -[X-Gln(beta-D-GlcNAc)-Aib]- [X = L-Glu(OMe), L-Lys(Ac), L-Ala; Aib = alpha-aminoisobutyric acid] were synthesized by polymerization of glycosylated tripeptides with an active ester methods using Cl(-+)H(3)N-L-Glu(OMe)-Gln[beta-D-GlcNAc(Ac)(3)]-Aib-ONp (N...

    journal_title:Biomacromolecules

    pub_type: 杂志文章

    doi:10.1021/bm0502563

    authors: Takasu A,Horikoshi S,Hirabayashi T

    更新日期:2005-07-01 00:00:00

  • Analysis of the conserved N-terminal domains in major ampullate spider silk proteins.

    abstract::Major ampullate silk, also known as dragline silk, is one of the strongest biomaterials known. This silk is composed of two proteins, major ampullate spidroin 1 (MaSp1) and major ampullate spidroin 2 (MaSp2). Only partial cDNA sequences have been obtained for these proteins, and these sequences are toward the C-termin...

    journal_title:Biomacromolecules

    pub_type: 杂志文章

    doi:10.1021/bm050472b

    authors: Motriuk-Smith D,Smith A,Hayashi CY,Lewis RV

    更新日期:2005-11-01 00:00:00

  • HER2/neu antibody conjugated poly(amino acid)-coated iron oxide nanoparticles for breast cancer MR imaging.

    abstract::Superparamagnetic iron oxide nanoparticles are widely used as nanoprobes for magnetic resonance imaging (MRI). Water-soluble iron oxide nanoparticles were synthesized by coating iron oxide nanoparticles with a hydrophilic, biocompatible, biodegradable poly(amino acid) derivative, poly(2-hydroxyethyl aspartamide) graft...

    journal_title:Biomacromolecules

    pub_type: 杂志文章

    doi:10.1021/bm100560m

    authors: Yang HM,Park CW,Woo MA,Kim MI,Jo YM,Park HG,Kim JD

    更新日期:2010-11-08 00:00:00

  • Structure-activity relationships of antibacterial and biocompatible copolymers.

    abstract::The development of polymers that are both bactericidal and biocompatible would have many applications and are currently of research interest. Following the development of strongly bactericidal copolymers of 4-vinylpyridine and poly(ethylene glycol) methyl ether methacrylate, biocompatibility assays have been completed...

    journal_title:Biomacromolecules

    pub_type: 杂志文章

    doi:10.1021/bm1000839

    authors: Stratton TR,Howarter JA,Allison BC,Applegate BM,Youngblood JP

    更新日期:2010-05-10 00:00:00

  • Reproducing natural spider silks' copolymer behavior in synthetic silk mimics.

    abstract::Dragline silk from orb-weaving spiders is a copolymer of two large proteins, major ampullate spidroin 1 (MaSp1) and 2 (MaSp2). The ratio of these proteins is known to have a large variation across different species of orb-weaving spiders. NMR results from gland material of two different species of spiders, N. clavipe...

    journal_title:Biomacromolecules

    pub_type: 杂志文章

    doi:10.1021/bm301110s

    authors: An B,Jenkins JE,Sampath S,Holland GP,Hinman M,Yarger JL,Lewis R

    更新日期:2012-12-10 00:00:00

  • Polyol synthesis of silver nanoparticles: mechanism of reduction by alditol bearing polysaccharides.

    abstract::Alditol bearing chitosans have shown the ability to reduce silver ions in mild conditions and without addition of exogenous reducing agents. The ion reduction induces the formation of a lactone moiety on the polysaccharide (Fetizon reaction) without causing C-C bond cleavage on the polyol. The close and multivalent ar...

    journal_title:Biomacromolecules

    pub_type: 杂志文章

    doi:10.1021/bm801253c

    authors: Donati I,Travan A,Pelillo C,Scarpa T,Coslovi A,Bonifacio A,Sergo V,Paoletti S

    更新日期:2009-02-09 00:00:00

  • Effects of emulsion droplet size on the structure of electrospun ultrafine biocomposite fibers with cellulose nanocrystals.

    abstract::Electrospinning of cellulose nanocrystals (CNC)/poly(lactic acid) (PLA) emulsions has been demonstrated to be an effective dispersion and alignment method to control assembly of CNC into continuous composite ultrafine fibers. CNC-PLA nanocomposite random-fiber mats and aligned-fiber yarns were prepared by emulsion ele...

    journal_title:Biomacromolecules

    pub_type: 杂志文章

    doi:10.1021/bm400540v

    authors: Li Y,Ko FK,Hamad WY

    更新日期:2013-11-11 00:00:00