High-efficiency Synergistic Effect of Supramolecular Nanoparticles Based on Cyclodextrin-prodrug on Cancer Therapy.
Abstract A novel cyclodextrin-prodrug supramolecular nanoparticles (NPs) with cooperative-enhancing cancer therapy were constructed from a reduction-sensitive disulfide bond linked permethyl-β-cyclodextrin-camptothecin prodrug (PMCD-SS-CPT), water-soluble adamantane-porphyrin photosensitizer (aPs), and hyaluronic acid grafted by triphenylphosphine and β-cyclodextrin (TPP-HACD) through orthogonal host-guest recognition strategy, displaying uniform nanoparticles with diameter around 100 nm as revealed by DLS, TEM, SEM and AFM. Compared with 293T normal cells, the supramolecular NPs could be easily taken up...
Source: Biomacromolecules - September 18, 2020 Category: Biochemistry Authors: Dai X, Zhang B, Zhou W, Liu Y Tags: Biomacromolecules Source Type: research

Temperature responsive methylcellulose-hyaluronic hydrogel as a 3D cell culture matrix.
This study investigated the application of a temperature-responsive methylcellulose-hyaluronic acid (MC-HA) hydrogel to support 3D cell growth in vitro. Initial work focused on the preparation of hydrogels for 3D culture, followed by investigations of the biological compatibility of hydrogel components and optimisation of the cell culture environment. Evaluation of viability and proliferation of HCT116 cells cultured in the MC-HA hydrogel was used to adjust the blend composition so to design a hydrogel with optimal properties to support cell growth. Two important aspects in terms of application of the proposed polymeric ma...
Source: Biomacromolecules - September 18, 2020 Category: Biochemistry Authors: Mahboubian A, Vllasaliu D, Dorkoosh FA, Stolnik S Tags: Biomacromolecules Source Type: research

Chitin-based double-network hydrogel as potential superficial soft tissue repairing materials.
Abstract Chitin is a biopolymer which has been proved to be a candidate as biomedical materials, yet the weak mechanical properties limited their potentials seriously. In this work, a chitin-based double-network (DN) hydrogel was designed as a potential superficial repairing material. The hydrogel was synthesized through double-network (DN) strategy composing hybrid regenerated chitin nanofibers (RCNs)-poly (ethylene glycol diglycidyl ether) (PEGDE) as the first network and polyacrylamide (PAAm) as the second network. The hybrid RCNs-PEGDE/PAAm DN hydrogel was strong and tough, possessing Young's modulus (elastici...
Source: Biomacromolecules - September 16, 2020 Category: Biochemistry Authors: Huang J, Frauenlob M, Shibata Y, Wang L, Nakajima T, Nonoyama T, Tsuda M, Tanaka S, Kurokawa T, Gong JP Tags: Biomacromolecules Source Type: research

Effects of hyaluronan molecular weight on the lubrication of cartilage-emulating boundary-layers.
Abstract Osteoarthritic joints contain lower molecular weight (MW) hyaluronan (hyaluronic acid, HA) than healthy joints. To understand the relevance of this HA-size effect for joint lubrication, the friction and surface structure of cartilage-emulating surfaces with HA of different MW were studied using a surface force balance (SFB), and atomic force microscopy (AFM) . Gelatin (gel)-covered mica surfaces were coated with either high MW HA (HHA), medium MW HA (MHA) or low MW HA (LHA), and lipids of Hydrogenated Soy L-α-phosphatidylcholine (HSPC) in the form of small unilamellar vesicles, using a layer-by-laye...
Source: Biomacromolecules - September 15, 2020 Category: Biochemistry Authors: Liu Z, Lin W, Fan Y, Kampf N, Wang Y, Klein J Tags: Biomacromolecules Source Type: research

Cellulose nanofibers for encapsulation and pluripotency preservation in the early development of embryonic stem cells.
In this study, we used cellulose nanofiber (CNF) hydrogels to mimic the developing conditions required for ESCs. These plant-based hydrogels are simultaneously biocompatible and exogenous to mammalian cells, preventing remodeling and attachment. The storage modulus of these hydrogels could be fine-tuned by varying the degree of oxidation to enable selective degradation. The ESCs proliferated in the artificial environment, forming increasingly large embryoid bodies for 15 days. Unlike traditional cultures, in which ESCs begin differentiating upon the removal of the chemical inhibition, the expression of pluripotency markers...
Source: Biomacromolecules - September 15, 2020 Category: Biochemistry Authors: Das R, Fernandez JG Tags: Biomacromolecules Source Type: research

Advancing Towards 3D Printing of Bioresorbable Shape Memory Polymer Stents.
Abstract Stents have evolved significantly since their introduction to the medical field in the early 1980s, becoming widely used in percutaneous coronary interventions and following nephrological procedures. However, the current commercially available stents do not degrade and remain in the body forever, leading to problems like restenosis in cardiovascular applications or requiring removal procedures in ureteral applications. Efforts to replace metal with resorbable materials have largely been halted after the commercial failure of and safety concerns elicited by Abbott's AbsorbTM stent in 2017. Industry continu...
Source: Biomacromolecules - September 14, 2020 Category: Biochemistry Authors: Yeazel TR, Becker ML Tags: Biomacromolecules Source Type: research

Noncovalent stabilization of vesicular polyion complexes with chemically modified/single-stranded oligonucleotides and PEG-b-guanidinylated polypeptides for intracavity encapsulation of effector enzymes aimed at cooperative gene knockdown.
Abstract For the simultaneous delivery of antisense oligonucleotides and their effector enzymes into cells, nanosized vesicular polyion complexes (PICs) were fabricated from oppositely charged polyion-pairs of oligonucleotides and poly(ethylene glycol) (PEG)-b-polypeptides. First, the polyion component structures were carefully designed to facilitate multimolecular (or secondary) association of unit PICs for non-covalent (or chemical crosslinking-free) stabilization of vesicular PICs. Chemically modified, single-stranded oligonucleotides (SSOs) dramatically stabilized the multimolecular associates under physiologi...
Source: Biomacromolecules - September 14, 2020 Category: Biochemistry Authors: Kim BS, Naito M, Chaya H, Hori M, Hayashi K, Min HS, Yi Y, Kim HJ, Nagata T, Anraku Y, Kishimura A, Kataoka K, Miyata K Tags: Biomacromolecules Source Type: research

Methionine-Based pH and Oxidation Dual-Responsive Block Copolymer: Synthesis and Fabrication of Protein Nanogels.
Abstract In this paper, we synthesized a block copolymer containing pendent thioether functionalities by RAFT polymerization of tert-butyloxycarbonyl (Boc)-L-methionine-(2-methacryloylethyl)ester (Boc-METMA) monomer using a poly(ethylene glycol) (PEG)-based chain transfer agent. The deprotection of Boc groups resulted in an oxidation and pH dual-responsive cationic block copolymer PEG-b-P(METMA). The block copolymer PEG-b-P(METMA) possessing protonable amine groups was water soluble at pH 6.0. In the presence of H2O2, the micelles first became highly swollen with time and completely disassembled at last, demonstra...
Source: Biomacromolecules - September 11, 2020 Category: Biochemistry Authors: Dong S, Jiang Y, Qin G, Liu L, Zhao H Tags: Biomacromolecules Source Type: research

Click Nucleic Acid-DNA Binding Behavior: Dependence on Length, Sequence, and Ionic Strength.
Abstract Click nucleic acids (CNAs) are a new, low-cost class of xeno nucleic acid (XNA) oligonucleotides synthesized by an efficient and scalable thiol-ene polymerization. In this work, a thorough characterization of oligo(thymine) CNA-oligo(adenine) DNA ((dA)20) hybridization was performed to guide future implementation of CNAs in applications that rely on sequence specific interactions. Microscale thermophoresis (MST) provided a convenient platform to rapidly and systematically test the effects of several factors (i.e., sequence, length, and salt concentration) on the CNA-DNA dissociation constant (Kapp). Becau...
Source: Biomacromolecules - September 11, 2020 Category: Biochemistry Authors: Culver HR, Sinha J, Prieto TR, Calo CJ, Fairbanks BD, Bowman CN Tags: Biomacromolecules Source Type: research

Programing Performance of Silk Fibroin Superstrong Scaffolds by Mesoscopic Regulation among Hierarchical Structures.
Abstract To design the higher-strength natural scaffold materials, wool keratin (WK) rich with α-helix structure are used as a well-defined foreign substrate, which induce the formation of β-crystallites in silk fibroin (SF). Consequently, the macroscopic properties of silk materials (such as the rheological properties of SF hydrogels and the mechanical properties of stents) can be manipulated by governing the change in the hierarchical mesoscopic structure of silk materials. In this work, by monitoring the structure and morphology in the SF gel process, the mechanism of the effect of keratin on SF netw...
Source: Biomacromolecules - September 10, 2020 Category: Biochemistry Authors: Zhang Y, Tu H, Wu R, Patil A, Hou C, Lin Z, Meng Z, Ma L, Yu R, Yu W, Liu XY Tags: Biomacromolecules Source Type: research

Chitosan derivatives in macromolecular co-assembly nanogels with potential for biomedical applications.
In conclusion, the new synthesised polyelectrolyte nanogels, which can provide a stable environment for the encapsulated drugs, can be used as a multi-functional platform for administration of antimicrobial agents from the spectrum of antibiotics that have a very poor bio-distribution. PMID: 32909739 [PubMed - as supplied by publisher] (Source: Biomacromolecules)
Source: Biomacromolecules - September 10, 2020 Category: Biochemistry Authors: Rusu AG, Chiriac AP, Nita LE, Rosca I, Pinteala M, Mititelu-Tartau L Tags: Biomacromolecules Source Type: research

Rapid Synthesis of Silk-Like Polymers Facilitated by Microwave Irradiation and Click Chemistry.
Abstract Silk is a natural fiber that surpasses most man-made polymers in its combination of strength and toughness. Silk fibroin, the primary protein component of silk, can be synthetically mimicked by a linear copolymer with alternating rigid and soft segments. Strategies for chemical synthesis of such silk-like polymers have persistently resulted in poor sequence control, long reaction times, and low molecular weights. Here, we present a two-stage approach for rapidly synthesizing silk-like polymers with precisely defined rigid blocks. This approach utilizes solid-phase peptide synthesis to create uniform oligo...
Source: Biomacromolecules - September 9, 2020 Category: Biochemistry Authors: Sarkar A, Edson C, Tian D, Fink T, Cianciotti K, Gross RA, Bae C, Zha RH Tags: Biomacromolecules Source Type: research

Thread Size and Polymer Composition of 3D Printed and Electrospun Wound Dressings Affect Wound Healing Outcomes in an Excisional Wound Rat Model.
Abstract Thread size and polymer composition are critical properties to consider for achieving a positive healing outcome with a wound dressing. 3D printed scaffolds and electrospun mats both offer distinct advantages as replaceable wound dressings. This research aims to determine if thread size and polymer compositions of scaffolds affect skin wound healing outcomes, an aspect that has not been adequately explored. Using a modular polymer platform, four polyester direct-write 3D printed scaffolds and electrospun mats were fabricated into wound dressings. The dressings were applied to splinted, full thickness skin...
Source: Biomacromolecules - September 9, 2020 Category: Biochemistry Authors: Nun N, Cruz M, Jain T, Tseng YM, Menefee J, Jatana S, Patil PS, Leipzig ND, McDonald C, Maytin E, Joy A Tags: Biomacromolecules Source Type: research

Dual Biochemically Breakable Drug Carriers from Programmed Telechelic Homopolymers.
Lligadas G Abstract Well-defined hydrophilic telechelic dibromo poly(triethyleneglycol monomethyl ether acrylate)s were prepared by single-electron transfer living radical polymerization employing a hydrophobic difunctional initiator containing acetal and disulfide linkages. Despite the resulting homopolymers contain small hydrophobic contents (
Source: Biomacromolecules - September 8, 2020 Category: Biochemistry Authors: Moreno A, Jiménez-Alesanco A, Ronda JC, Cadiz V, Galia M, Percec V, Abián O, Lligadas G Tags: Biomacromolecules Source Type: research

Multi-stimuli-triggered shape transformation of polymeric filaments derived from dynamic covalent block copolymers.
Abstract Using dynamic polymers to achieve the morphology transformation of polymeric assemblies under different conditions is challenging. Herein, we reported diversiform shape transformations of multi-responsive polymer filaments, which were self-assembled by a new kind of amphiphilic block copolymers (PVEG-PVEA) possessing dynamic and reversible acylhydrazone bonds through re-acting of benzaldehyde-containing block copolymers poly(vinylbenzaldehyde)-b-poly(N-(4-vinylbenzyl)-N, N-diethylamine) (PVBA-PVEA) with acylhydrazine modified oligoethylene glycol. It was found that the resulting amphiphilic and dynamic PV...
Source: Biomacromolecules - September 8, 2020 Category: Biochemistry Authors: Yang G, Wang J, Yan Y, Hai Z, Hua Z, Chen G Tags: Biomacromolecules Source Type: research

Characterization of Octreotide-PLGA Binding by Isothermal Titration Calorimetry.
Abstract Cationic peptides are well known to readily bind poly(lactic-co-glycolic acids) (PLGAs) with carboxylic acid (-COOH) end-group, which poses a significant challenge to develop PLGA-based delivery system for peptide therapeutics. This binding has been considered as a critical step leading to the peptide acylation within PLGA-based formulations, which is also known to affect microencapsulation and release. Herein, we utilized nano isothermal titration calorimetry (NanoITC) to investigate the thermodynamics of peptide-PLGA binding using a model cationic octapeptide, octreotide, which contains 2 free amine gro...
Source: Biomacromolecules - September 4, 2020 Category: Biochemistry Authors: Hong JKY, Schwendeman SP Tags: Biomacromolecules Source Type: research

Multifunctional amyloid oligomeric nanoparticles for specific cell targeting and drug delivery.
Abstract Natural selection has endorsed proteins with amazing structures and functionalities that cannot be matched by synthetic means, explaining the exponential interest in developing protein-based materials. Protein self-assembly allows fabricating complex supramolecular structures from relatively simple building blocks, a bottom-up strategy naturally employed by amyloid fibrils. However, the design of amyloid inspired materials with biological activity is inherently difficult. Here we exploit a modular procedure to generate functional amyloid nanostructures with tight control of their mesoscopic properties. Th...
Source: Biomacromolecules - September 4, 2020 Category: Biochemistry Authors: Wang W, Azizyan R, Garro A, Kajava AV, Ventura S Tags: Biomacromolecules Source Type: research

Engineering nonmechanical protein-based hydrogels with highly mechanical properties: comparison with natural muscles.
Abstract The elegant elasticity and toughness of muscles that are controlled by myofilaments sliding, highly elastic spring-like property of titin and Ca2+-induced conformational change of troponin complex have been a source of inspiration to develop advanced materials for simulating elastic muscle motion. Herein, a highly stretchable protein hydrogel is developed to mimic the structure and motion of muscles through the combination of protein folding-unfolding and molecular sliding. It has shown that protein BSA is covalently crosslinked, together penetrated with alginate chains to construct polyprotein-based hydr...
Source: Biomacromolecules - September 4, 2020 Category: Biochemistry Authors: Zhao L, Zhang X, Luo Q, Hou C, Xu J, Liu J Tags: Biomacromolecules Source Type: research

Protein Vesicles Self-Assembled from Functional Globular Proteins with Different Charge and Size.
Abstract Protein vesicles can be synthesized by mixing two fusion proteins: an elastin-like polypeptide (ELP) fused to an arginine-rich leucine zipper (ZR) with a globular, soluble protein fused to a glutamate-rich leucine zipper (ZE). Currently, only fluorescent proteins have been incorporated into vesicles; however, for protein vesicles to be useful for biocatalysis, drug delivery, or biosensing, vesicles must assemble from functional proteins that span an array of properties and functionalities. In this work, the globular protein was systematically changed to determine the effects of the surface charge and size...
Source: Biomacromolecules - September 4, 2020 Category: Biochemistry Authors: Dautel DR, Champion JA Tags: Biomacromolecules Source Type: research

Fluorescence-based and Fluorescent label-free Characterization of Polymer Nanoparticle Decorated T cells.
Abstract Cells are attractive carriers for the transport and delivery of nanoparticulate cargo. The use of cell-based carriers allows to enhance control over the biodistribution of drug-loaded polymers and polymer nanoparticles. One key element in the development of cell-based delivery systems is the loading of the cell-based carrier with the nanoparticle cargo, which can be achieved either by internalization of the payload or by immobilization on the cell surface. The surface modification of cells with nanoparticles or the internalization of nanoparticles by cells is usually monitored with fluorescence-based tech...
Source: Biomacromolecules - September 1, 2020 Category: Biochemistry Authors: Thomsen T, Ayoub AB, Psaltis D, Klok HA Tags: Biomacromolecules Source Type: research

Reaction Rate Governs the Viscoelasticity and Nanostructure of Folded Protein Hydrogels.
Abstract Hydrogels constructed from folded protein domains are of increasing interest as resilient and responsive biomaterials, but their optimisation for applications requires time-consuming and costly molecular design. Here, we explore a complementary approach to control their properties by examining the influence of crosslinking rate on the structure and viscoelastic response of a model hydrogel constructed from photo-chemically crosslinked bovine serum albumin (BSA). Gelation is observed to follow a heterogeneous nucleation pathway in which BSA monomers crosslink into compact nuclei that grow into fractal perc...
Source: Biomacromolecules - September 1, 2020 Category: Biochemistry Authors: Aufderhorst-Roberts A, Hughes M, Hare A, Head DA, Kapur N, Brockwell DJ, Dougan L Tags: Biomacromolecules Source Type: research

Close packing of cellulose and chitosan in regenerated cellulose fibers improves carbon yield and structural properties of respective carbon fibers.
Abstract Low carbon yield is a major limitation for the use of cellulose-based filaments as carbon fiber precursors. The present study aims to investigate the use of an abundant biopolymer chitosan as a natural charring agent particularly on enhancing the carbon yield of the cellulose-derived carbon fiber. The ionic liquid 1,5-diazabicyclo[4.3.0]non-5-enium acetate ([DBNH]OAc) was used for direct dissolution of cellulose and chitosan, and to spin cellulose-chitosan composite fibers through a dry-jet wet spinning process (Ioncell). The homogenous distribution and tight packing of cellulose and chitosan revealed by ...
Source: Biomacromolecules - September 1, 2020 Category: Biochemistry Authors: Zahra H, Sawada D, Guizani C, Ma Y, Kumagai S, Yoshioka T, Sixta H, Hummel M Tags: Biomacromolecules Source Type: research

Spatiotemporal Self-Assembling Peptides Dictates Cancer-Selective Toxicity.
Abstract The intracellular or pericellular self-assembly of amphiphilic peptides is emerging as a potent cancer therapeutic strategy. Achieving self-assembly of amphiphilic peptides inside a cell or cellular organelle is challenging due to the complex cellular environment, which consists of many amphiphilic biomolecules that may alter the self-assembling propensity of the synthetic peptides. Herein, we show that the hydrophobic-hydrophilic balance of the amphiphilic peptides determines the self-assembling propensity, thereby controlling the cell's fate. A series of peptides were designed to target and self-assembl...
Source: Biomacromolecules - August 31, 2020 Category: Biochemistry Authors: Jin S, Jeena MT, Jana B, Moon M, Choi H, Lee E, Ryu JH Tags: Biomacromolecules Source Type: research

Structured, Composite Nanoparticles from Emulsion Polymerization - Morphological Possibilities.
The objective of the following discussion is to describe the scientific and engineering principles at play when creating these composite particles and to demonstrate how the balance of thermodynamic equilibrium conditions and kinetic limitations (chemical reaction and polymer chain diffusion) combine and/or compete to result in particular morphologies. Many examples are presented. PMID: 32862639 [PubMed - as supplied by publisher] (Source: Biomacromolecules)
Source: Biomacromolecules - August 30, 2020 Category: Biochemistry Authors: Sundberg D Tags: Biomacromolecules Source Type: research

Monomeric G-Quadruplex-Based CpG Oligodeoxynucleotides as Potent Toll-Like Receptor 9 Agonists.
Abstract Synthetic oligodeoxynucleotides (ODNs) containing unmethylated cytosine-phosphate-guanine (CpG) motifs trigger the immune response by stimulating endosomal Toll-like receptor (TLR) 9. Natural linear ODNs are susceptible to nuclease degradation, thereby limiting their clinical applications. Here, we designed monomeric G-quadruplex-based CpG ODNs (G4 CpG ODNs) containing CpG motifs in the central loop region of the G4 structure. The monomeric G4 CpG ODNs were more stable in serum than the linear ODNs. The monomeric G4 CpG ODNs containing two or three CpG motifs induced the production of immunostimulatory cy...
Source: Biomacromolecules - August 28, 2020 Category: Biochemistry Authors: Tu ATT, Hoshi K, Ikebukuro K, Hanagata N, Yamazaki T Tags: Biomacromolecules Source Type: research

Controlled Production of Elastin-like Recombinamer Polymer-based Membranes at a Liquid-liquid Interface by Click Chemistry.
-Cabello JC Abstract Diffusion of organic and inorganic molecules controls most industrial and biological processes that occur in a liquid phase. Although significant efforts have been devoted to the design and operation of large-scale purification systems, diffusion devices with adjustable biochemical characteristics have remained difficult to achieve. In this regard, micrometer-scale, bioinspired membranes with tunable diffusion properties have been engineered by covalent crosslinking of two elastin-like recombinamers (ELRs) at a liquid-liquid interface. The covalent approach selected provides the desired ELR-ba...
Source: Biomacromolecules - August 27, 2020 Category: Biochemistry Authors: Gonzalez-Perez M, González de Torre I, Alonso M, Rodríguez-Cabello JC Tags: Biomacromolecules Source Type: research

Nanoscale chemical features of the natural fibrous material wood.
We report the use of the PFIR to characterize the chemical modification of biobased native and intact wooden matrices, which has evolved into an increasingly active research field. The distribution of functional groups of wood cellulose aggregates, either in native or carboxylated states, was detected with a remarkable spatial resolution of 16 nm. Furthermore, mechanical and chemical maps of the distinct cell wall layers were obtained on polymerized wooden matrices to localize the exact position of the modified regions. These findings shall support the development and understanding of functionalized wood materials. PM...
Source: Biomacromolecules - August 27, 2020 Category: Biochemistry Authors: Gusenbauer C, Jakob DS, Xu XG, Vezenov DV, Cabane E, Konnerth J Tags: Biomacromolecules Source Type: research

Synthesis of heterofunctional polyester dendrimers with internal and external functionalities as versatile multipurpose platforms.
Malkoch M Abstract Heterofunctional dendrimers with internal and external representation of functionalities are considered as the ultimate dendritic frameworks. This is reflected by their unprecedented scaffolding, such as precise control over structure, molecular weight, number and location of different cargo across the whole dendritic skeleton. Consequently, these dendrimers with multipurpose character are the pinnacle of precision polymers and thereof are highly attractive by the scientific community as they can find use in a great number of cutting-edge applications, especially as discrete unimolecular carrier...
Source: Biomacromolecules - August 27, 2020 Category: Biochemistry Authors: García-Gallego S, Stenström P, Mesa-Antunez P, Zhang Y, Malkoch M Tags: Biomacromolecules Source Type: research

Degradable High Molecular Weight Monodisperse Dendritic Poly(ethylene glycols).
och M Abstract Poly(ethylene glycols) (PEGs) are extensively explored by the pharma industry as foundations for new therapeutic products. PEGs are typically used for their conjugation to active drugs, peptides, proteins and the like, to increase the half-life and enhance the therapeutic outcome. Considering the necessity of batch-to-batch consistency for clinical products, monodisperse PEGs are highly attractive, but are generally limited to 5 kDa as an upper molecular weight (Mw) and with an oligomer purity of 95%. By amalgamating short, monodisperse PEGs with dendritic frameworks based on bis-MPA polyesters, we ...
Source: Biomacromolecules - August 26, 2020 Category: Biochemistry Authors: Zhang Y, Mesa-Antunez P, Fortuin L, Andrén OCJ, Malkoch M Tags: Biomacromolecules Source Type: research

Aldehyde-Assisted Lignocellulose Fractionation Provides Unique Lignin Oligomers for the Design of Tunable Polyurethane Bioresins.
ers W Abstract Thanks to chemical stabilization, Aldehyde-Assisted Fractionation (AAF) of lignocellulosic biomass has recently emerged as a powerful tool for the production of largely uncondensed lignin. Depolymerization of AAF lignin via ether cleavage provides aromatic monomers at near theoretical yields based on ether cleavage as well as an oligomeric fraction that remains largely unexploited despite its unique material properties. Here, we present an in-depth analytical characterization of AAF oligomers derived from hardwood and softwood in order to elucidate their molecular structures. These bioaromatic oligo...
Source: Biomacromolecules - August 26, 2020 Category: Biochemistry Authors: Vendamme R, Behaghel de Bueren JT, Gracia-Vitoria J, Isnard F, Monga Mulunda M, Ortiz P, Wadekar M, Vanbroekhoven K, Wegmann C, Buser R, HÃ Roguel F, Luterbacher JS, Eevers W Tags: Biomacromolecules Source Type: research

Charge density as a molecular modulator of nanostructuration in intrinsically disordered protein polymers.
lo JC Abstract Intrinsically disordered protein polymers (IDPPs) have attracted a lot of attention in the development of bioengineered devices and for use as study models in molecular biology due to their biomechanical properties and stimuli-responsiveness. The present study aims to understand the effect of charge density on the self-assembly of IDPPs. To that end, a library of recombinant IDPPs based on an amphiphilic diblock design with different charge densities was bioproduced and their supramolecular assembly characterized on the nano-, meso- and microscale. Although phase transition was driven by the collaps...
Source: Biomacromolecules - August 25, 2020 Category: Biochemistry Authors: Acosta S, Poocza L, Quintanilla-Sierra L, Rodríguez-Cabello JC Tags: Biomacromolecules Source Type: research

High-resolution 3D bioprinting of photo-crosslinkable recombinant collagen to serve tissue engineering applications.
Abstract Various biopolymers including gelatin, have already been applied to serve a plethora of tissue engineering purposes. However, substantial concerns have arisen related to the safety and the reproducibility of these materials due to their animal origin and the risk associated with pathogen transmission as well as batch-to-batch variations. Therefore, researchers have been focussing their attention towards recombinant materials that can be produced in a laboratory with full reproducibility and can be designed according to specific needs (e.g. by introducing additional RGD sequences). In the present study, a ...
Source: Biomacromolecules - August 25, 2020 Category: Biochemistry Authors: Tytgat L, Dobos A, Markovic M, Van Damme L, Van Hoorick J, Bray F, Thienpont H, Ottevaere H, Dubruel P, Ovsianikov A, Van Vlierberghe S Tags: Biomacromolecules Source Type: research

Photo-Configurable, Cell-Remodelable Disulfide Crosslinked Hyaluronic Acid Hydrogels.
We report the facile and effective photo-curing and photo-remodelling of disulfide-crosslinked hyaluronic acid hydrogels, based on photo-oxidation of corresponding thiol residues and their radical-mediated photo-degradation. We find that the mechanical properties of disulfide hydrogels and the extent of their photo-remodelling can be tuned by controlling the photo-oxidation and photo-degradation reactions, respectively. This enables the photo-patterning of the mechanical properties of hydrogels, but also their self-healing and photo-mediated healing. Finally, we demonstrate the ability to encapsulate mesenchymal stromal ce...
Source: Biomacromolecules - August 24, 2020 Category: Biochemistry Authors: Wu L, Di Cio S, Azevedo HS, Gautrot JE Tags: Biomacromolecules Source Type: research

The architectural change of the shell forming block from linear to V-shaped accelerates micellar disassembly but slows the complete enzymatic degradation of the amphiphiles.
Abstract Tuning the enzymatic degradation and disassembly rates of polymeric amphiphiles and their assemblies is crucial for designing enzyme-responsive nanocarriers for controlled drug delivery applications. The common methods to control the enzymatic degradation of amphiphilic polymers are to tune the molecular weights and ratios of the hydrophilic and hydrophobic blocks. In addition, to these approaches, the architecture of the hydrophilic block can also serve as a tool to tune enzymatic degradation and disassembly. To gain deeper understanding of the effect of the molecular architecture of the hydrophilic bloc...
Source: Biomacromolecules - August 24, 2020 Category: Biochemistry Authors: Segal M, Ozery L, Slor G, Wagle SS, Ehm T, Beck R, Amir RJ Tags: Biomacromolecules Source Type: research

Raman Spectroscopy Methods to Characterize the Mechanical Response of Soft Biomaterials.
Abstract Raman spectroscopy has been used extensively to characterize the influence of mechanical deformation on microstructure changes in biomaterials. While traditional piezo-spectroscopy has been successful in assessing internal stresses of hard biomaterials by tracking prominent peak shifts, peak shifts due to applied loads are near or below the resolution limit of the spectrometer for soft biomaterials with moduli in the kilo- to mega-Pascal range. In this review, in addition to peak shifts, other spectral features (e.g., polarized intensity and intensity ratio) that provide quantitative assessments of micros...
Source: Biomacromolecules - August 24, 2020 Category: Biochemistry Authors: Zhou H, Simmons CS, Sarntinoranont M, Subhash G Tags: Biomacromolecules Source Type: research

Polyamidoamine Dendrimer Grafted with an Acid-Responsive Charge-Reversal Layer for Improved Gene Delivery.
We report on a heterogeneous dendrimer (G3-acetal-NH2) derivative possessing an acid-responsive charge-reversal layer. The synthesis of G3-acetal-NH2 starts with a polyamidoamine (PAMAM) G3 core and follows the aza-Michael addition with N-(2-(1-(allyloxy)ethoxy)ethyl)acrylamide (AEEAA) synthesized by us and the thiol-ene click chemistry with cysteamine hydrochloride in sequence. The surface of this newly formed dendrimer can turn from amine-terminated to hydroxyl-terminated due to the cleavage of the acetal groups in a weakly acidic environment. This charge conversion from 34.3 ± 2.7 mV to 18.0 ± 0.3 mV in 24...
Source: Biomacromolecules - August 21, 2020 Category: Biochemistry Authors: Wang J, Cooper RC, Yang H Tags: Biomacromolecules Source Type: research

Covalent Capture of Collagen Triple Helices Using Lysine-Aspartate and Lysine-Glutamate Pairs.
Abstract Collagen mimetic peptides (CMPs) self-assemble into a triple helix reproducing the most fundamental aspect of the collagen structural hierarchy. They are therefore important for both further understanding this complex family of proteins and use in a wide range of biomaterials and biomedical applications. CMP self-assembly is complicated by a number of factors which limit the use of CMPs including their slow rate of folding, relatively poor monomer-trimer equilibrium, and the large number of competing species possible in heterotrimeric helices. All of these problems can be solved through the formation of i...
Source: Biomacromolecules - August 21, 2020 Category: Biochemistry Authors: Hulgan SAH, Jalan AA, Li IC, Walker DR, Miller MD, Kosgei AJ, Xu W, Phillips GN, Hartgerink JD Tags: Biomacromolecules Source Type: research

Structure, Hydration and Interactions of Native and Hydrophobically Modified Phytoglycogen Nanoparticles.
Abstract Phytoglycogen is a highly branched polymer of glucose produced as soft, compact nanoparticles by sweet corn. Properties such as softness, porosity and mechanical integrity, combined with nontoxicity and biodegradability, make phytoglycogen nanoparticles ideal for applications involving the human body, ranging from skin moisturizing and rejuvenation agents in personal care formulations, to functional therapeutics in biomedicine. To further broaden the range of applications, phytoglycogen nanoparticles can be chemically modified with hydrophobic species such as octenyl succinic anhydride (OSA). Here, we pre...
Source: Biomacromolecules - August 21, 2020 Category: Biochemistry Authors: Simmons J, Nickels JD, Michalski M, Grossutti M, Shamana H, Stanley CB, Schwan AL, Katsaras J, Dutcher JR Tags: Biomacromolecules Source Type: research

Insights into Design of Biomimetic Glycerol-Grafted Polyol-Based Polymers for Ice Nucleation/Recrystallization Inhibition and Thermal Hysteresis Activity.
In this study we explore structural variations to polyol-based polymers to contrast with PVA as a control and we have identified several key structural elements for performance in IRI, THA, as well as in ice nucleation inhibition (INI). These structural features are bioinspired by the typical ice-binding plane of AFPs yet are surprisingly simple to produce with potency approaching that of typical AFPs. Key to the performance is positioning small organic functionalities with known anti-freeze properties (such as ethylene glycol) pendent to a host polymer chain with consideration of their conformational freedom. In order to ...
Source: Biomacromolecules - August 21, 2020 Category: Biochemistry Authors: Mousazadehkasin M, Tsavalas JG Tags: Biomacromolecules Source Type: research

Environment Controls Biomolecule Release from Dynamic Covalent Hydrogels.
Abstract Moldable hydrogels composed of dynamic covalent bonds are attractive biomaterials for controlled release, as the dynamic exchange of bonds in these networks enables minimally invasive application via injection. Despite the growing interest in the biomedical application of dynamic covalent hydrogels, there is a lack of fundamental understanding as to how the network design and local environment control the release of biomolecules from these materials. In this work, we fabricated boronic ester-based dynamic covalent hydrogels for the encapsulation and in vitro release of a model biologic (β-galactosida...
Source: Biomacromolecules - August 19, 2020 Category: Biochemistry Authors: Marco-Dufort B, Willi J, Vielba-Gomez F, Gatti F, Tibbitt MW Tags: Biomacromolecules Source Type: research

Introduction of enzyme-responsivity in biomaterials to achieve dynamic reciprocity in cell-material interactions.
Abstract Much effort has been made in the development of biomaterials that synthetically mimic the dynamics of the natural extracellular matrix in tissues. Most of these biomaterials specifically interact with cells, but lack the ability to adapt and truly communicate with the cellular environment. Communication between biomaterials and cells is achieved by the development of various materials with enzyme-responsive moieties, in order to respond to cellular cues. In this perspective, we discuss different enzyme-responsive systems, from surfaces to supramolecular assemblies. Additionally, we highlight their further...
Source: Biomacromolecules - August 19, 2020 Category: Biochemistry Authors: Brouns J, Dankers PYW Tags: Biomacromolecules Source Type: research

All-polysaccharide, self-healing injectable hydrogels based on chitosan and oxidized hydroxypropyl polysaccharides.
Abstract Polysaccharide-based hydrogels are attractive materials for biomedical applications for reasons that include their polyfunctionality, generally benign nature, and biodegradability. However, use of polysaccharide-based hydrogels may be limited by toxicity arising from small molecule crosslinkers, or may involve undesired chemical modification. Here, we report a green, simple, efficient strategy for preparation of polysaccharide-based, in situ forming hydrogels. The Edgar group reports in the accompanying manuscript that chemoselective oxidation of oligo(hydroxypropyl)-substituted polysaccharides introduces...
Source: Biomacromolecules - August 18, 2020 Category: Biochemistry Authors: Chen J, Nichols B, Norris A, Frazier CE, Edgar KJ Tags: Biomacromolecules Source Type: research

Supramolecular biocomposite hydrogels formed by cellulose and host-guest polymers assisted by calcium ion complexes.
Abstract Hydrogels are biocompatible polymer networks; however, they have the disadvantage for having poor mechanical properties. Herein, the mechanical properties of host-guest hydrogels were increased by adding a filler and incorporating other noncovalent interactions. Cellulose was added as a filler to the hydrogels to afford a composite. Citric acid-modified cellulose (CAC) with many carboxyl groups was used instead of conventional cellulose. The preparation was began with mixing an acrylamide-based αCD host polymer (p-αCD) and a dodecanoic acid guest polymer (p-AADA) to form supramolecular hydroge...
Source: Biomacromolecules - August 18, 2020 Category: Biochemistry Authors: Tsuchiya H, Sinawang G, Asoh TA, Osaki M, Ikemoto Y, Higuchi Y, Yamaguchi H, Harada A, Uyama H, Takashima Y Tags: Biomacromolecules Source Type: research

Thiolated PVP-Amphotericin B Complexes: An Innovative Approach toward Highly Mucoadhesive Gels for Mucosal Leishmaniasis Treatment.
h A Abstract The aim of this study was to synthesize polymeric excipients that can form mucoadhesive hydrogels containing amphotericin B (AmB) for the treatment of mucosal leishmaniasis. 2-(2-Acryloylaminoethyldisulfanyl)-nicotinic acid (ACENA) was copolymerized with N-vinyl pyrrolidone to obtain thiolated polyvinylpyrrolidone (PVP) that was then complexed with AmB to improve its solubility. The resulting structure of thiolated PVP was evaluated by 1H nuclear magnetic resonance to confirm S-protected thiol groups, and the average molecular mass was determined by size exclusion chromatography. Moreover, variants of...
Source: Biomacromolecules - August 17, 2020 Category: Biochemistry Authors: Jalil A, Asim MH, Shahzadi I, Khan M, Matuszczak B, Bernkop-Schnürch A Tags: Biomacromolecules Source Type: research

Supramolecular Hydrogels via Light-Responsive Homoternary Cross-Links.
Abstract Host-guest physical cross-linking has been used to prepare supramolecular hydrogels for various biomedical applications. More recent efforts to endow these materials with stimuli-responsivity offers an opportunity to precisely tune their function for a target use. In the context of light-responsive materials, azobenzenes are one prevailing motif. Here, an asymmetric azobenzene was explored for its ability to form homoternary complexes with the cucurbit[8]uril macrocycle, exhibiting an affinity (Keq) of 6.21 × 1010 M-2 for sequential binding, though having negative cooperativity. Copolymers were firs...
Source: Biomacromolecules - August 17, 2020 Category: Biochemistry Authors: Zou L, Addonizio CJ, Su B, Sis MJ, Braegelman AS, Liu D, Webber MJ Tags: Biomacromolecules Source Type: research

Customizing a tri-domain TRAIL variant to achieve active tumor homing and endogenous albumin-controlled release of the molecular machine in vivo.
Abstract Tumor necrosis factor-related apoptosis-inducing ligand (TRAIL) is an attractive antitumor drug candidate for precision cancer therapy due to its superior selective cytotoxicity in a variety of tumor cells. However, the clinical application of TRAIL in cancer therapy has been limited by its poor tumor-homing capacities and short half-life. Herein, we designed a tri-domain TRAIL variant, Z-ABD-TRAIL, by sequentially fusing the platelet-derived growth factor receptor beta (PDGFRβ)-specific affibody ZPDGFRβ and an albumin-binding domain (ABD) to the N-terminus of TRAIL. The fusion protein Z-ABD-TRA...
Source: Biomacromolecules - August 17, 2020 Category: Biochemistry Authors: Tao Z, Liu Y, Yang H, Feng Y, Li H, Shi Q, Li S, Cheng J, Lu X Tags: Biomacromolecules Source Type: research

Xyloglucan Structure Impacts the Mechanical Properties of Xyloglucan-Cellulose Nanocrystal Layered Films - a Buckling-Based Study.
Abstract Interactions between polysaccharides, specifically between cellulose and hemicelluloses like xyloglucan (XG), govern the mechanical properties of the plant cell wall. This work aims to understand how XG molecular weight and the removal of saccharide residues impact the elastic modulus of XG-cellulose materials. Layered sub-micrometer thick films of cellulose nanocrystals (CNCs) and XG were employed to mimic the structure of the plant cell wall and contained either (1) unmodified XG, (2) low molecular weight XG produced by ultrasonication (USXG), or (3) XG with a reduced degree of galactosylation (DGXG). T...
Source: Biomacromolecules - August 17, 2020 Category: Biochemistry Authors: Stimpson TC, Cathala B, Moreau C, Moran-Mirabal JM, Cranston ED Tags: Biomacromolecules Source Type: research

Thermo-Responsive Self-Immolative Polyglyoxylamides.
Abstract Thermo-responsive polymers with lower critical solution temperatures (LCSTs) are of significant interest for a wide range of applications from sensors to drug delivery vehicles. However, the most widely investigated LCST polymers have non-degradable backbones, limiting their applications in vivo or in the environment. Described here are thermo-responsive polymers based on a self-immolative polyglyoxylamide (PGAM) backbone. Poly(ethyl glyoxylate) was amidated with six different alkoxyalkyl amines to afford the corresponding PGAMs and their cloud point temperatures (Tcps) were studied in water and buffer. S...
Source: Biomacromolecules - August 17, 2020 Category: Biochemistry Authors: Rabiee Kenaree A, Sirianni QEA, Classen K, Gillies ER Tags: Biomacromolecules Source Type: research

Controlling Drug Absorption, Release, and Erosion of Photopatterned Protein Engineered Hydrogels.
Abstract A protein-engineered triblock copolymer hydrogel composed of two self-assembling domains (SADs) has been fabricated by a photoactivatable diazirine group followed by ultraviolet (UV)-mediated crosslinking. The photocrosslinkable protein polymer CEC-D has been patterned into various features including different micrometer-scale stripes by using lithographic techniques. The patterned hydrogels are important for encapsulation of small molecules where a photopatterned fraction of 50% is optimal for maximum absorption. Stripe-patterned CEC-D100-100 exhibits slightly lower swelling ratios, an 8.9 times lower er...
Source: Biomacromolecules - August 14, 2020 Category: Biochemistry Authors: Wang Y, Delgado-Fukushima E, Fu RX, Doerk GS, Monclare JK Tags: Biomacromolecules Source Type: research

Uncommon Structures of Oppositely Charged Hyaluronan/Surfactant Assemblies under Physiological Conditions.
Abstract Self-assembled aggregates formed by semidilute polyanion hyaluronan (hyaluronic acid, HA) and an oppositely charged surfactant tetradecyltrimethylammonium bromide (TTAB) in an aqueous phosphate-buffered saline (PBS) solution have been studied via light scattering (LS), small-angle neutron scattering (SANS), and cryogenic transmission electron microscopy (cryo-TEM). The addition of 0-20 mM TTAB to a 27.7 mM (monomer, 1 wt %) HA solution (597 kDa) in PBS buffer leads to soluble complexes until phase separation occurs near charge equilibrium (>20 mM TTAB). While the viscosity remains rather constant, alre...
Source: Biomacromolecules - August 14, 2020 Category: Biochemistry Authors: Buchold P, Ram-On M, Talmon Y, Hoffmann I, Schweins R, Gradzielski M Tags: Biomacromolecules Source Type: research