功能聚氨酯材料在生物医学工程中的研究进展及应用

讨论了提高聚氨酯材料生物相客性和生物稳定性的改性方法,如表面活性端基改性、表面接枝聚合、表面形成互穿网络、使用表面活性剂、与纳米无机材料共混,介绍了功能性聚氨酯材料在生物医学工程中的应用及研究进展,表明聚氨酯材料的功能化改性仍然是今后的发展方向。     

Inherently X-ray opaque polyurethane microspheres for biomedical applications

In this work synthesis and characterization of inherently X-ray opaque, nonresorbable polyurethane microspheres with well-calibrated particles in a defined range of sizes suitable for embolization is reported. In order to impart X-ray opacity to the polyurethane, a bifunctional monomer, namely, 4,4′-isopropylidenediphenol (BPA) was iodinated and this iodinated compound was used as one of the monomers during polyurethane synthesis. The resultant X-ray opaque polyurethane was converted into microspheres using an oil-in-water emulsion and solvent evaporation technique. Microspheres obtained had diameters in the range of 200–500?µm, were noncytotoxic and free from X-ray attenuating additives. In vivo X-ray fluoroscopic imaging carried out in a rabbit cadaver model showed that these microspheres were sufficiently X-ray opaque to be visualized under fluoroscopic conditions.     

Preliminary study on the biodegradation of adipate/phthalate polyester polyurethanes of commercial‐type by Alicycliphilus sp. BQ8

Accumulation of polyurethane (PU) waste has increased considerably due to its extensive use. Even though many efforts are being carried out to develop more biodegradable PU, the use of these new materials is far from being commercially available. Here, we analyzed the susceptibility of solid polyester polyurethanes (PS‐PU) of commercial‐type, to biodegradation by Alicycliphilus sp. BQ8, a polyurethanolytic bacterial strain. Four polyester polyols were synthesized from dipropylene glycol (DPG) or diethylene glycol (DEG), and adipic acid (ADA) or phthalic anhydride (PHA), and were combined with either 4,4′‐ and 4,2′‐methylene diphenyldiisocyanate (MDI) or 2,4‐ and 2,6‐toluene diisocyanate (TDI). Synthesized polyols and PUs were characterized. PU biodegradation was assessed by the capacity of the polymers to support bacterial growth, and by scanning electron microscopy (SEM), Fourier transformed infrared (FTIR) spectroscopy, and gas chromatography/mass spectrometry (GC‐MS) analyses. Although all the synthesized PUs supported BQ8 growth, SEM analysis showed that PHA‐based PU foams were the most affected by bacterial growth. FTIR spectroscopy and GC‐MS analyses of bacterial treated PS‐PUs showed that they were attacked at ester and urethane groups, suggesting that esterase and amidase activities are involved. Extra‐cellular and membrane bound esterase activities were detected during the five days of analysis. Our results suggest that solid PHA‐based PUs might be more susceptible than ADA‐based PUs to microbial biodegradation in the environment. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42992.     

Synthesis and in vitro biodegradation of pure octacalcium phosphate spheres

Octacalcium phosphate (OCP) is a key precursor of biological apatite in hard tissues with excellent osteoconductive and biodegradable properties for bone regeneration. OCP spherical granules are expected to be useful as drug delivery carriers, since OCP has high specific surface area. Although there have been some reports of OCP sphere preparation, methods for preparing pure OCP spheres are limited. The objective of this study is the preparation of spherical granules of pure OCP and assessment of their in vitro biodegradation in physiological conditions. We successfully prepared spherical pure OCP granules with a size of ~500 µm without any organic additives by simple immersion of α-tricalcium phosphate spherical granules in pH 5.0 acetate buffered solutions at 60°C. The granules had core-shell structure composed of OCP crystals different particle size. The spherical granules showed 20%-40% in vitro degradation in physiological conditions; however, the phase transition of OCP was not significantly observed.     

Castor oil and PEG‐based shape memory polyurethane films for biomedical applications

A series of polyurethane film were prepared from poly(ethylene glycol) with different molecular weight (PEG 1500, 3000, and 8000) and castor oil by one‐shot bulk polymerization method. Hexamethylene diisocyanate and 1,4‐buthane diol were used as diisocyanate and chain extender, respectively. In order to characterize the samples, their density, swelling ratio, water contact angle, surface free energy, gel content, thermal, and viscoelastic properties were determined. The effect of the soft segment length (SSL) and hard segment content (HSC) of all polyurethane films on their shape memory behavior such as shape fixity (R_f) and shape recovery (R_r) rates were investigated by bending test. Direct contact and MTT tests were used for assessment of cell adhesion and proliferation. The relatively high R_f and R_r values were obtained for the samples programmed at high temperature difference. R_f increased with decreasing HSC. On the other hand, R_r tended to decrease with increasing SSL. After evaluating experimental data by a nonlinear equation, it was found that HSC is more effective parameter on shape memory property than SSL. The gel content, swelling ratio, and water contact angle of the samples were dependent on both SSL and HSC in their structures. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40590.     

Recent advances in nanocellulose for biomedical applications

Nanocellulose materials have undergone rapid development in recent years as promising biomedical materials because of their excellent physical and biological properties, in particular their biocompatibility, biodegradability, and low cytotoxicity. Recently, a significant amount of research has been directed toward the fabrication of advanced cellulose nanofibers with different morphologies and functional properties. These nanocellulose fibers are widely applied in medical implants, tissue engineering, drug delivery, wound‐healing, cardiovascular applications, and other medical applications. In this review, we reflect on recent advancements in the design and fabrication of advanced nanocellulose‐based biomaterials (cellulose nanocrystals, bacterial nanocellulose, and cellulose nanofibrils) that are promising for biomedical applications and discuss material requirements for each application, along with the challenges that the materials might face. Finally, we give an overview on future directions of nanocellulose‐based materials in the biomedical field. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41719.     

Recent biomedical advances with polyampholyte polymers

Polyampholyte polymer systems are composed of varying mixtures of charged monomer subunits. These polymeric systems have gained increasing attention because it is possible to design the final material properties through careful selection of the charged monomer subunits and controlling the polymer architecture. Characteristics that have been manipulated include the hydration, mechanical properties, pH responsive swelling, temperature responsive swelling, resistance to nonspecific protein adsorption, and protein conjugation capability. This had led researchers to propose the use of polyampholyte polymers as biosensor platforms, fouling release membranes, drug delivery vehicles, and tissue engineering scaffolds. This review is focused on advances that have been made over the last 5 years to develop polyampholyte polymers for these biomedical applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40069.     

Zimbro (Juniperus communis L.) as a Promising Source of Bioactive Compounds and Biomedical Activities: A Review on Recent Trends

Plant-derived products and their extracted compounds have been used in folk medicine since early times. Zimbro or common juniper (Juniperus communis) is traditionally used to treat renal suppression, acute and chronic cystitis, bladder catarrh, albuminuria, leucorrhea, and amenorrhea. These uses are mainly attributed to its bioactive composition, which is very rich in phenolics, terpenoids, organic acids, alkaloids, and volatile compounds. In the last few years, several studies have analyzed the huge potential of this evergreen shrub, describing a wide range of activities with relevance in different biomedical discipline areas, namely antimicrobial potential against human pathogens and foodborne microorganisms, notorious antioxidant and anti-inflammatory activities, antidiabetic, antihypercholesterolemic and antihyperlipidemic effects, and neuroprotective action, as well as antiproliferative ability against cancer cells and the ability to activate inductive hepato-, renal- and gastroprotective mechanisms. Owing to these promising activities, extracts and bioactive compounds of juniper could be useful for the development of new pharmacological applications in the treatment of several acute and chronic human diseases.     

Design,Synthesis and Biological Activity of New Amides Derived from 3-Benzhydryl and 3-sec-Butyl-2,5-dioxo-pyrrolidin-1-yl-acetic Acid

The aim of this study was to design and synthesize two new series of pyrrolidine-2,5-dione-acetamides with a benzhydryl or sec-butyl group at position 3 as potential anticonvulsants. Their anticonvulsant activity was evaluated in standard animal models of epilepsy: the maximal electroshock (MES), the 6 Hz, and the subcutaneous pentylenetetrazole (scPTZ) tests. The in vivo studies revealed the most potent anticonvulsant activity for 15 (3-(sec-butyl)-1-(2-(4-(3-trifluoromethylphenyl)piperazin-1-yl)-2-oxoethyl)pyrrolidine-2,5-dione), with ED₅₀ values of 80.38 mg/kg (MES) and 108.80 mg/kg (6 Hz). The plausible mechanism of action was assessed in in vitro binding assays, in which 15 interacted effectively with voltage-gated sodium (site 2) and L-type calcium channels at a concentration of 100 μM. Subsequently, the antinociceptive activity of compounds 7 and 15 was observed in the hot plate test of acute pain. Moreover, compounds 7 , 11 and 15 demonstrated an analgesic effect in the formalin test of tonic pain. The hepatotoxic properties of the most effective compounds ( 7 , 11 and 15 ) in HepG2 cells were also investigated.     

Recent advances in shear-thinning and self-healing hydrogels for biomedical applications

Shear-thinning and self-healing hydrogels are being investigated in various biomedical applications including drug delivery, tissue engineering, and 3D bioprinting. Such hydrogels are formed through dynamic and reversible interactions between polymers or polypeptides that allow these shear-thinning and self-healing properties, including physical associations (e.g., hydrogen bonds, guest–host interactions, biorecognition motifs, hydrophobicity, electrostatics, and metal–ligand coordination) and dynamic covalent chemistry (e.g., Schiff base, oxime chemistry, disulfide bonds, and reversible Diels–Alder). Their shear-thinning properties allow for injectability, as the hydrogel exhibits viscous flow under shear, and their self-healing nature allows for stabilization when shear is removed. Hydrogels can be formulated as uniform polymer and polypeptide assemblies, as hydrogel nanocomposites, or in granular hydrogel form. This review focuses on recent advances in shear-thinning and self-healing hydrogels that are promising for biomedical applications. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48668.     

Enhanced thermal stability of biomedical thermoplastic polyurethane with the addition of cellulose nanocrystals

Freeze‐dried cellulose nanocrystals (CNCs) were dispersed in the thermoplastic polyurethane [Pellethane 2363‐55D (P55D)] by a solvent casting method to fabricate CNC‐reinforced nanocomposites. This study demonstrated that the addition of small amounts (1–5 wt %) of CNCs to P55D increased the thermal degradation temperature while maintaining a similar stiffness, strength, and elongation of the neat P55D. CNC additions to P55D did not alter the glass‐transition temperature, but the onset decomposition temperature was shifted from 286 to 327°C when 1 wt % CNCs was dispersed in the matrix. The higher onset decomposition temperature was attributed to the formation of hydrogen bonds between the hydroxyl groups on the CNC surface and urethane groups in the hard block of P55D. The ultimate tensile strength and strain to failure (ε_f) of the nanocomposites were minimally affected by additions up to 5 wt % CNCs, whereas the elastic modulus was increased by about 70%. The observation that ε_f was unchanged with the addition of up to 5 wt % CNCs suggested that the flow/sliding of the hard blocks and chains were not hindered by the presence of the CNCs during plastic deformation. The ramifications of this study was that CNC additions resulted in wider processing temperatures of P55D for various biomedical devices while maintaining a similar stiffness, strength, and elongation. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41970.     

湿固化聚氨酯热熔胶研究进展

概述了目前反应型湿固化聚氨酯热熔胶的应用和研究方向，介绍了改善热熔胶的初粘强度、韧性、耐热性等性能的方法，以及国内外在聚氨酯预聚体、增韧树脂、增粘树脂、催化剂、添加剂等方面取得的一些研究进展。     

Recent advances in amino acid-metal coordinated nanomaterials for biomedical applications

Metal and amino acid (AA),as two kinds of entities,have been widely involved in biomaterials and nano-medicines.Recently,the marriage of them has developed new nanoformulations,amino acid-metal coor-dinated nanomaterials (AMCNs),which show great biomedical application potential in cancer therapy,antibacterial applications,biomedical imaging,etc.With the respective characteristics of metal and AA with rich biological and chemical properties,AMCNs can not only act as drug carriers with specific tumor targeting ability,but also realize synergistic therapy and imaging-guided therapy.Although the design and synthesis of amino acid-metal coordinated nanomaterials have been in-depth investigated,there are few systematic reviews on their biomedical application.In this review,we give a comprehensive sum-mary of recent progresses in the design,fabrication,and biomedical applications of AMCNs.We also pro-pose the future outlooks and challenges in aforementioned field.We expect that this review would contribute some inspiration for future research and development for amino acid metal coordinated nanomaterials.     

Recent advances in small molecule fluorescent probes for simultaneous imaging of two bioactive molecules in live cells and in vivo

The interrelationships and synergistic regulations of bioactive molecules play pivotal roles in physiological and pathological processes involved in the initiation and development of some diseases,such as cancer and neurodegenerative and cardiovascular diseases.Therefore,the simultaneous,accurate and timely detection of two bioactive molecules is crucial to explore their roles and pathological mechanisms in related diseases.Fluorescence imaging associated with small molecular probes has been widely used in the imaging of bioactive molecules in living cells and in vivo due to its excellent performances,including high sensitivity and selectivity,noninvasive properties,real-time and high spatial temporal resolution.Single organic molecule fluorescent probes have been successively developed to simultaneously monitor two biomolecules to uncover their synergistic relationships in living systems.Hence,in this review,we focus on summarizing the design strategies,classifications,and bioimaging applications of dual-response fluorescent probes over the past decade.Furthermore,future research directions in this field are proposed.     

Recent advances on akermanite calcium-silicate ceramic for biomedical applications

Owing to great biocompatibility and high capacity of apatite formation, bioceramics, especially calcium silicate-based compounds, were extensively employed in orthopedic and dental uses concerning biomedical applications. Lately, akermanite (AK; Ca₂MgSi₂O₇), as a bioceramic containing Ca-, Mg- and Si, has gained an increased level of attention because of its more tunable mechanical characteristics and degradation rate. All studies indicate that this magnesium incorporating Ca-silicate ceramic has a great capacity to use as a bone graft material to fulfill the necessity of bone reconstruction. Despite the rising interest in using these materials in biomedical fields, there has not yet been an extensive overview of this bioceramic property and its potential benefits. Thus, it has been speculated that this concept and the emergence of akermanite bioactive ceramics might lead to significant upcoming advancements in the field of bone tissue engineering (BTE). Definitely, the approach still requires additional advances to considerably better respond to the vital concerns regarding the clinical application. The review tackles the present research trends on akermanite ceramics for biomedical purposes such as bone scaffold, coating materials, bone cement, and treatment of osteoporotic bone defects, commencing with recent status and shifting to upcoming developments.     

Physical and mechanical behavior of sterilized biomedical segmented polyurethanes

Changes in the physical and mechanical behavior induced by two sterilization methods, gamma irradiation and ethylene oxide, were determined on two commercial medical-grade segmented polyurethanes. The two materials have different chemical composition: one is an aromatic poly(ether urethane urea), Biospan^TM, and the other an aliphatic ether-free polyurethane, Chronoflex^TM. Properties before and after sterilization procedures were compared resulting in specific structural changes for each formulation. The thermal and mechanical properties were examined using differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), stress–strain measurements, and its hysteresis cycle. Molecular weight measurements were performed by gel permeation chromatography (GPC). Sterilized Biospan samples showed a decrease in the soft-segment glass transition temperature (T_g,s) and an increase in the soft segment crystallization heat along the quenching process. Sterilized Chronoflex materials showed the opposite behavior. The hysteresis percent and residual strain percent increased after sterilization. The same effect was observed when irradiation dose and strain level increased. Surface analysis performed by scanning electron microscopy showed magnification of original surface defects after sterilization. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1193–1203, 1997     

Abnormalities in electrical and acoustic properties of thermoplastic polyurethane

The temperature dependence of ultrasonic pulse velocity C and specific volume resistance ρ_v of crystallizing thermoplastic polyurethane (TPUR) was investigated. It was revealed that under certain conditions TPUR acquired abnormally low ρ_v values and C values uncharacteristic of polymers. An explanation for the observed abnormalities could be based on the assumption of the presence of ‘hot’ electrons in TPUR.     

Preparation and characterization of polyether‐based polyurethane dolomite composite

A polyether polyol‐based two‐component polyurethane composite was prepared by a reaction of polypropylene glycol (PPG) and diethylene glycol (DEG) used as a crosslinker. The final reaction for the preparation of composite is carried out with processed polyether polyol and diphenylmethane 4,4′‐diisocyanate (MDI). The physicochemical properties of processed polyether polyol have been measured, such as viscosity, moisture content, and hydroxyl value. The composite has been formed with loading of inorganic filler dolomite [MgCa(CO₃)₂] with different filler ratios. It shows good adhesive strength and mechanical properties. Composite samples have also been studied for the effects of acids and bases, swelling in solvents, physical and mechanical properties such as compression strength, shore hardness A and D, tensile strength, and elongation. Some electrical properties have also been studied, viz. thermal conductivity, volume resistivity, and dielectric strength. A comparison of prepared polyether‐based polyurethane composite with some conventional polymeric materials suggests their suitability for various applications. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2337–2342, 2007     

杀菌剂生物筛选离体活体兼顾的重要性

新合成的以金核霉素结构改造为主的数十种化合物,经多种病原菌的离体抑菌活性测定和盆栽防治效果测定,谈谈在杀菌剂生物筛选中采用离体活体测定相兼顾的重要性.     

离体筛选方法在杀虫剂研发中的应用

农药筛选方法在新农药开发中占有重要的地位,与传统的活体筛选方法相比,离体筛选方法具有快速、经济、方便和重复性好等优点.近年来,离体筛选方法在杀虫剂研发中得到了广泛的应用,随着分子生物学和生物技术的发展,新的杀虫剂筛选方法将不断被开发出来.