基于贻贝启发的水下仿生胶黏剂

海洋中的贻贝依靠丝足(Byssus)与足盘(Plaque)可以在潮湿及水下环境中快速而牢固地黏附于各种固体表面。贻贝强健的足部具有沟渠状的生理结构,通过类似于“注塑生产”的生理过程,它们可以生成丝足与足盘。贻贝将液态的蛋白质挤压到沟渠里,只需几秒钟时间,这些蛋白质就能形成一条条发丝一样纤细的丝足。每条丝足的末端都有一个黏性足盘,足盘可以牢牢地黏附在岩石及固体表面。丝足及足盘由多种黏附蛋白(Mfps)组成,且几乎每种黏附蛋白都含有L-3,4-二羟基苯丙氨酸(DOPA)成分。在过去的数十年间,科研人员基本揭示了贻贝黏附蛋白的结构及其黏附机理。DOPA的儿茶酚基团,通过氧化交联、金属螯合、氢键、静电作用、疏水作用、π-π作用、阳离子-π作用等各种共价和非共价相互作用,实现强大的界面黏接。基于贻贝黏附蛋白的结构及其黏附机理,通过使用DOPA及其类似物修饰的聚合物体系,人们得到了多种具有优秀机械性能和功能化的新型仿生多巴类水下胶黏剂。本综述首先介绍了贻贝黏附蛋白的组成特点及其黏附机理;随后分别介绍了凝聚层类胶黏剂、水凝胶类胶黏剂、智能型水下胶黏剂的结构特点及黏附机理;最后讨论了目前仿生水下胶黏剂存在的问题及未来发展前景。     

A Water‐Borne Adhesive Modeled after the Sandcastle Glue of P. californica

Polyacrylate glue protein analogs of the glue secreted by Phragmatopoma californica, a marine polycheate, were synthesized with phosphate, primary amine, and catechol sidechains with molar ratios similar to the natural glue proteins. Aqueous mixtures of the mimetic polyelectrolytes condensed into liquid complex coacervates around neutral pH. Wet cortical bone specimens bonded with the coacervates, oxidatively crosslinked through catechol sidechains, had bond strengths nearly 40% of the strength of a commercial cyanoacrylate. The unique material properties of complex coacervates may be ideal for development of clinically useful adhesives and other biomaterials.

     

邻苯二酚基团改性壳聚糖组织胶黏剂的制备和表征

分别通过1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐/N-羟基丁二酰亚胺(EDC/NHS)偶联反应和席夫碱-还原反应,并以高碘酸钠(NaIO4)为氧化交联剂,得到2种邻苯二酚接枝改性的壳聚糖基水凝胶组织胶黏剂(CHI-C和CCS)。利用红外光谱(FT-IR)、核磁共振氢谱(~1 H-NMR)、抗菌实验和黏结强度测试对壳聚糖衍生物的结构和性能进行了表征。探讨了胶黏剂配比对其成胶性能和黏结强度的影响。结果表明:此种胶黏剂的成胶时间短,邻苯二酚基团和NaIO4含量的增加均有利于凝胶形成,CHI-C的最大黏结强度为40.42kPa,CCS的最大黏结强度为15.68kPa。两种壳聚糖衍生物均具有优良的抑菌性能。     

Hydrophobically Associating Polyacrylamides Prepared by Inverse Suspension Polymerization: Synthesis,Characterization and Aqueous Solution Properties

Hydrophobically associating polyacrylamides (HAPAMs) were synthesized via inverse suspension polymerization using ammonium persulphate (APS)/tertramethylethylenediamine (TEMED) as the redox initiators, 2-methacryloyloxyethyl n-alkyl dimethyl ammonium bromide (DM-n, n = 8, 12, 16) as the hydrophobic comonomers. The structures of the copolymers were elucidated by FT-IR and ionic chromatographic analysis, respectively. The morphology and particle size of the resultant HAPAMs were characterized by scanning electronic microscope (SEM) and laser particle size analyzer, which revealed that spherical particles were formed and the particle size exhibited Gaussian distribution centered from 25 μ m to 162 μ m. Furthermore, the solution properties of the copolymers were studied with viscometry and the results showed that HAPAMs synthesized under optimal conditions exhibited an obvious viscosity enhancement in aqueous solution and excellent salt-tolerant capability in brine.     

Simple but Strong: A Mussel‐Inspired Hot Curing Adhesive Based on Polyvinyl Alcohol Backbone

The strong adhesion ability of mussel foot‐byssal proteins (Mfps) has inspired scientists to develop novel materials for strong and reversible adhesion, coating, antifouling, and many other applications. However, in many cases, the high costs and the tedious preparation steps of such bioinspired materials hamper the process to push them into practical application. Here a simple but effective way (one step) is presented to synthesize a mussel‐inspired glue from two cheap commercially available materials: polyvinyl alcohol (PVA) and 3,4‐dihydroxybenzaldehyde (DBA). This bioinspired hot curing adhesive exhibits a strong bonding ability as high as 17.3 MPa on stainless steel surfaces, which surpasses most of the commercially available adhesives.

     

木质素磺酸盐基胶黏剂的合成与表征

以双氧水(H2O2)-硫酸亚铁(FeSO4)为氧化还原引发剂,丙烯酸(AA)和马来酸酐(MAH)为单体,采用原位一步法制备了宽分子量分布的P(MAH-co-AA)。通过测定P(MAH-coAA)和木质素磺酸盐(LS)缩聚反应产物的凝胶含量,研究了P(MAH-co-AA)中单体组成、胶黏剂酸度和添加三乙醇胺(TEA)等因素对交联的影响,比较了木质素磺酸钠(LSS)和木质素磺酸铵(LSA)两种LS的反应活性。结果表明:木质素磺酸盐能代替部分多元醇与共聚物制备低成本无甲醛型木材用胶黏剂;提高共聚物P(MAH-co-AA)中MAH含量、胶黏剂酸度及采用LSA均能提高固化交联的程度。     

Characterization of Star Adhesive Sealants Based On PEG/Dextran Hydrogels

Swellable PEG amine/dextran aldehyde composite materials are emerging as a controlled, biocompatible tissue adhesive. We explain how preservation of natural tissue amines provides biocompatibility for PEG/dextran that exceeds the stringent, destructive cyanide‐based chemistry of cyanoacrylates, and adhere far better than fibrin glue. Strategic variations of material composition allow for the improvement of biocompatibility and adhesion strength. Material variations can be tailored to match the needs of specific tissue beds for an array of clinical applications. PEG/dextran cohesive properties are most responsive to variations in the PEG component (number of arms and solid content), while tissue/material adhesion strength is primarily determined by the number of aldehydes in the dextran.

     

Preparation of Biomimetic Hydrogels with Controlled Cell Adhesive Properties and Topographical Features for the Study of Muscle Cell Adhesion and Proliferation

Synthetic substrates with defined chemical and structural characteristics may potentially be prepared to mimic the living ECM to regulate cell adhesion and growth. Hydrogels with cell‐adhesive peptides (0.28 ± 0.03 nmol peptide · cm^?2, TTA‐R‐0.5; and 0.91 ± 0.12 nmol peptide · cm^?2, TTA‐R‐2.0) and/or micro‐scaled topographical patterns (10, 25, and 80 µm grooves) are prepared using enzymatic polymerization. The adherent morphology and proliferation of C2C12 skeletal myoblasts and human aortic smooth muscle cells (hAoSM) on the hydrogels are studied. The newly developed hydrogels may be useful in investigating the roles of cell adhesion and substrate surface properties in the communication of adherent cells with the ECM.

     

聚硅氧烷皮肤组织黏接材料的设计合成与性能表征

设计开发了以聚硅氧烷材料为基础的皮肤组织黏接剂, 其主要由硅氧烷预聚体、 含氢硅油交联剂和卡斯特催化剂等多组分构成. 在卡斯特催化剂作用下, 预聚体和交联剂室温下在皮肤表面原位快速固化, 其中聚硅氧烷预聚体的苯甲醛侧基与皮肤组织中广泛存在的胺基通过醛胺缩合反应实现共价黏接. 本文系统研究了聚硅氧烷预聚体的聚合度、 侧基含量及交联剂的用量等参数对该黏接剂性能的影响, 得到了最大剪切黏接强度为77.6 KPa、 室温条件下100 s内即可形成稳定黏接的组织黏接材料. 该材料还具有良好的力学相容性、 生物安全性和结构稳定性, 可满足皮肤黏接剂的基本要求, 具有较好的应用前景.     

Modification of Adhesive and Latex Properties for Starch Nanoparticle‐Based Pressure Sensitive Adhesives

Starch nanoparticle (SNP)‐based pressure sensitive adhesives (PSAs) with core‐shell particle morphology (starch nanoparticle core/acrylic polymer shell) are produced via seeded, semi‐batch emulsion polymerization at 15 wt% SNP loading (relative to total polymer weight) and 40 wt% latex solids. Crosslinker and chain transfer agent (CTA) are introduced to the acrylic shell polymer formulation at a range of concentrations according to a 3² factorial design to tailor the latex and adhesive properties of SNP‐based latexes. The crosslinker and CTA show no significant effect on polymerization kinetics, particle size, and viscosity. Latex gel content is predicted using an empirical model, which is a function of crosslinker and CTA concentration. Both the gel content and glass transition temperature strongly affect the adhesive properties (tack, peel strength, and shear strength) of the SNP‐based latex films. 3D response surfaces for the adhesive properties are constructed to facilitate the design of SNP‐based PSAs with desired properties.     

Isolation and Characterization of Cellulosic Pulp Fines and Their Interactions with Cationic Polyacrylamides

Four different types of cellulosic fines were isolated from refiner mechanical and kraft pulp samples to characterize their chemical and physical properties. The pulp fines were flocculated using four different types of cationically modified polyacrylamides. The extent of flocculation was observed with multiple light scattering apparatus. The maximum adsorption of the polyelectrolytes on the pulp fines was determined by polyelectrolyte titration. It was concluded that it is the combination of the molar mass and the charge density of a polyelectrolyte, as well as the origins and characteristics of the fines which define the adsorption and flocculation behavior. None of these properties alone could fully describe these phenomena, but the molar mass of the polyelectrolyte was the predominant factor. The most important fines characteristics were the charge properties and the microstructure.     

Influence of Particle Nucleation in Pressure Sensitive Adhesive Properties: Miniemulsion versus Emulsion Polymerization

Miniemulsion polymerization is a promising approach to produce and tailor pressure sensitive adhesives (PSAs). In this paper, a systematic comparison of the adhesive properties of latexes produced by miniemulsion and conventional emulsion polymerization is presented. Specifically, the influence of the total surfactant concentration, chain transfer agent concentration and chemical composition on the final adhesive properties of the polymer 2-ethyl hexyl acrylate/methyl methacrylate/acrylic acid was discerned using a 2³ factorial design for each polymerization method. In addition to the adhesive properties (i.e., loop tack, peel strength and shear strength), molecular weight distribution, particle size distribution (PSD) and glass transition temperature were analyzed. The results show that under the conditions used in this work, it is possible to produce PSAs using miniemulsion polymerization, a process wherein monomer droplet nucleation is the dominant particle nucleation mechanism. The use of a miniemulsion polymerization process, as opposed to the conventional emulsion technique, produced several differences such as larger particles sizes and narrower molecular weight distributions. Focusing on the PSA films that exhibited adhesive rather than cohesive failure, the PSA films generated via miniemulsion polymerization displayed higher values of loop tack and peel strength compared to those produced via conventional emulsion polymerization. Shear strength results were strongly dependent on the amount of gel content and sol molecular weight for both cases.     

Progress and Current Trends in the Synthesis of Novel Polymers with Enhanced Mucoadhesive Properties

Mucoadhesion is defined as the adherence of a synthetic or natural polymer to a mucosal membrane via physical or chemical interactions. Mucoadhesive materials are widely used to develop dosage forms for transmucosal drug delivery via ocular, nasal, esophageal, oral, vaginal, rectal, and intravesical routes of administration. This review will discuss some of the most prominent and recent synthetic methodologies employed to modify polymeric materials in order to enhance their mucoadhesive properties. This includes chemical conjugation of polymers with molecules bearing thiol‐, catechol‐, boronate‐, acrylate‐, methacrylate‐, maleimide‐, and N‐hydroxy(sulfo)succinimide ester‐ groups.     

聚氨酯/苯丙杂化乳液的合成、表征和特性及其在复膜胶中的应用

由聚氨酯(PU)预聚物、丙烯酸丁酯和苯乙烯单体的乳液聚合制备了聚氨酯-苯乙烯-丙烯酸酯(PUSA)杂化乳液,1H NMR显示所得的PU预聚物由烯烃基团封端。 TEM表明,其粒径约为150 nm,且为颜色深浅不同的两部分所组成。 随着PU含量的降低,杂化乳液的热稳定性增加。 DSC分析表明,所得杂化乳液有单一的Tg值,且处于聚氨酯和聚苯丙(PSA)乳液Tg值的中间。 当将得到的杂化乳液用于纸塑和塑塑复合时,其剥离强度分别为14.1 N/2.5 cm和12.2 N/2.5 cm。     

Biomimetic Synthesis of Nor-Cedrene and Nor-Isozizaene Sesquiterpenoids and Exploration of Their Olfactive Properties

We report the preparation of nor-bisabolyl epoxide 13 and its use as a common biomimetic intermediate for the synthesis of nor-sesquiterpenoids. Through a cationic cyclization cascade pathway, we prepared nor-isozizaenol 25 , ultimately constituting an eight-step access to this complex sesquiterpenoid from inexpensive and abundant starting materials. Using a radical cyclization cascade pathway, we prepared nor-cedryl alcohol 26 from the same intermediate. Derivatization of these two products led to the discovery of two potent woody odorants of interest in perfumery.     

Adhesive properties of hot-melt adhesives modified by radiation

Heat shrinkable tubes and tapes made of irradiated polyethylene have been produced for several years. The memory effect of such products is widely used in many industrial applications. Hot-melt adhesive is often applied to provide better sealing properties of heat shrinkable products.

Radiation grafting of hot-melt adhesives based on PP and copolymers like EVA was investigated. Several monomers were selected for radiation grafting process. Comparison of structural and mechanical properties with nonirradiated material was carried out.     

Synthesis and Evaluation of Adhesion Properties of Homogeneous and Core-Shell Pressure-Sensitive Adhesives

Summary: Pressure-Sensitive Adhesives (PSAs) are used for many applications (e.g. tapes and labels), and the market is still growing as new applications are regularly discovered. Emulsion polymerization is widely used to produce water-based PSAs. In this work, the influence of morphology, diameter and acrylic acid concentration in the particles on adhesion properties (peel, tack and shear) was studied. To do so, two series of homogeneous and core-shell latex particles of poly(butyl acrylate-2-ethyl-hexyl acrylate) with different concentrations of acrylic acid (0, 1, 3 and 5 wt%) and three different average diameters, were synthesized by means of emulsion polymerization techniques. The materials were characterized by dynamic light scattering, zeta potential and transmission electronic microscopy. The contents of acrylic acid in the polymer and dispersed medium were determined and the higher quantity of it was found within the particles. The best equilibrium between adhesion properties was found in the core-shell particles with 3 wt% of AA.     

Scalable Synthesis and Cancer Cell Cytotoxicity of Rooperol and Analogues

Plant polyphenols, such as the African potato (Hypoxis hemerocallidea)-derived bis-catechol rooperol, can display promising anticancer activity yet suffer from rapid metabolism. Embarking upon a program to systematically examine potentially more metabolically stable replacements for the catechol rings in rooperol, we report here a general, scalable synthesis of rooperol and analogues that builds on our previous synthetic approach incorporating a key Pd-catalyzed decarboxylative coupling strategy. Using this approach, we have prepared and evaluated the cancer cell cytotoxicity of rooperol and a series of analogues. While none of the analogues examined here were superior to rooperol in preventing the growth of cancer cells, analogues containing phenol or methylenedioxyphenyl replacements for one or both catechol rings were nearly as effective as rooperol.     

Copper(II) complexes containing pyridine-based and phenolate-based systems: Synthesis,characterization, DFT study,biomimetic catalytic activity of catechol oxidase and phenoxazinone synthase

A template Schiff condensation of 2,6-pyridine dicarbaldehyde or 2,6-diformyl-4- bromophenol and 1,3–diamino-2-hydroxy propane or 3,4-diaminotoluene in the presence of copper(II) salts (CuX₂) (X = Cl, Br, CH₃COO, or ClO₄) affords different types of copper(II) complexes. Depending on the employed molar ratio of the dicarbonyl compounds and diamines, different types of copper(II) complexes formed during the template condensation reaction. Structural formulation of the complexes was confirmed by elemental analysis (C, H, N, and M), physical measurements such as thermal analysis (TAG & DTG), molar conductivity, and magnetic moments in addition to spectral studies (UV–Vis, IR, and ESR). Homobinuclear in a four-coordinate square planar and five-coordinate square pyramidal and trigonal bipyramidal in monomeric structures are proposed. A mononuclear hexa-coordinate in an octahedral geometry is suggested as well. Oxidase biomimetic catalytic activity of these newly synthesized copper(II) complexes was examined toward the aerobic oxidation of 4-tert-butylcatechol (4-TBCH₂) and o-aminophenol under catalytic conditions. Both catalytic and kinetic investigations demonstrate promising oxidase catalytic activity and based on the kinetic results, probable mechanistic catalytic implications are discussed. Geometrical structures of representative copper(II) complexes were determined by optimizing their bond lengths, bond angles, dihedral angles, and the structural index (τ).