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Collagenases and their inhibitors: a review 胶原酶及其抑制剂:综述
Pub Date : 2023-06-19 DOI: 10.1186/s42825-023-00126-6
Sijin Wu, Xuewei Zhou, Zhicheng Jin, Haiming Cheng

Hide and skin are complex tissue where the most abundant component is collagen. Matrix metalloproteinases and bacterial collagenases are two kinds of collagenases that can cleave the triple-helical domain of native fibrillar collagens. In this paper, the family members and domain composition of matrix metalloproteinases and bacterial collagenases are summarized. The catalytic mechanism of collagen hydrolysis by collagenases is described, and the methods adopted to date for investigating and regulating collagenases and their inhibitors are reviewed. Furthermore, the applications of collagenases and their inhibitors in biomedicine, food processing and the enzymatic unhairing process in the leather-making industry are presented.

Graphical Abstract

皮和皮肤是复杂的组织,其中最丰富的成分是胶原蛋白。基质金属蛋白酶和细菌胶原酶是两种能够切割天然原纤维胶原的三螺旋结构域的胶原酶。本文综述了基质金属蛋白酶和细菌胶原酶的家族成员及其结构域组成。介绍了胶原酶水解胶原的催化机理,综述了迄今为止研究和调控胶原酶及其抑制剂的方法。此外,还介绍了胶原酶及其抑制剂在生物医药、食品加工和皮革工业的酶解脱毛过程中的应用。图形抽象
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引用次数: 0
Separation, speciation and quantification of both chromium (VI) and chromium (III) in tanned leather samples: a comparative study and validation of analytical methods 鞣革样品中铬(VI)和铬(III)的分离、形态和定量:分析方法的比较研究和验证
Pub Date : 2023-06-06 DOI: 10.1186/s42825-023-00125-7
Mónica Gisel Arellano-Sánchez, Juliette Vievard, Lamia Moufarrej, Christine Devouge-Boyer, Marie Hubert-Roux, Carlos Afonso, Mélanie Mignot

In the present work, a comparative study of analytical methods for the simultaneous and quantitative determination of trivalent and hexavalent chromium is presented. For the analysis by ion chromatography-inductively coupled plasma-mass spectrometry, two different columns were tested, as well as different mobile phases and different pH of the samples. The optimized analytical method permitted the separation of Cr(III) and Cr(VI) using 75 mmol/L NH4NO3 pH 3 as chromatographic eluent. The method was validated and applied to real samples, allowing the determination of both species simultaneously, even when there is a huge difference of concentration between Cr(III) and Cr(VI). Limit of detection and limit of quantification for Cr(III) were found to be 0.016 and 0.054 (upmu)g/L (0.3 and 1.1 (upmu)g/kg), respectively, and for Cr(VI) 0.13 and 0.43 (upmu)g/L (7 and 22 (upmu)g/kg), respectively. Possible species interconversions were monitored through the use of chromium isotopic standards, which confirmed that the optimized methodology preserves chromium speciation during extraction and analysis. Fourier-transform ion cyclotron resonance-mass spectrometry permitted the structure elucidation of the complex formed during ethylenediaminetetraacetic acid extraction.

Graphical Abstract

对同时定量测定三价铬和六价铬的分析方法进行了比较研究。离子色谱-电感耦合等离子体质谱分析采用了两种不同的色谱柱、不同的流动相和不同的pH值。优化后的分析方法以75 mmol/L NH4NO3 pH 3为色谱洗脱液,可分离Cr(III)和Cr(VI)。该方法经过验证并应用于实际样品,即使Cr(III)和Cr(VI)的浓度差异很大,也可以同时测定两种物质。Cr(III)的检出限和定量限分别为0.016和0.054 (upmu) g/L(0.3和1.1 (upmu) g/kg), Cr(VI)的检出限和定量限分别为0.13和0.43 (upmu) g/L(7和22 (upmu) g/kg)。通过使用铬同位素标准来监测可能的物种相互转换,这证实了优化的方法在提取和分析过程中保留了铬的形态。傅里叶变换离子回旋共振质谱法对乙二胺四乙酸萃取过程中形成的络合物进行了结构解析。图形摘要
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引用次数: 0
Robust conductive skin hydrogel e-skin constructed by top–down strategy for motion-monitoring 基于自顶向下运动监测策略构建的鲁棒导电皮肤水凝胶电子皮肤
Pub Date : 2023-05-31 DOI: 10.1186/s42825-023-00123-9
Jiachang Liu, Xin Fan, Didier Astruc, Haibin Gu

The construction of biomass-based conductive hydrogel e-skins with high mechanical properties is the research hotspot and difficulty in the field of biomass materials. Traditional collagen-based conductive hydrogels, constructed by the typical “bottom–up” strategy, normally have the incompatible problem between high mechanical property and high collagen content, and the extraction of collagen is often necessary. To solve these problems, inspired by the high mechanical properties and high collagen content of animal skins, this work proposed a “top–down” construction strategy, in which the extraction of collagen was unnecessary and the skin collagen skeleton (SCS) with the 3D network structure woven by natural collagen fibers in goatskin was preserved and used as the basic framework of hydrogel. Following a four-step route, namely, pretreatment → soaking in AgNPs (silver nanoparticles) solution → soaking in the mixed solution containing HEA (2-hydroxyethyl methacrylate) and AlCl3 → polymerization, this work successfully achieved the fabrication of a new skin-based conductive hydrogel e-skin with high mechanical properties (tensile strength of 2.97 MPa, toughness of 6.23 MJ·m−3 and breaking elongation of 428%) by using goatskin as raw material. The developed skin hydrogel (called PH@Ag) possessed a unique structure with the collagen fibers encapsulated by PHEA, and exhibited satisfactory adhesion, considerable antibacterial property, cytocompatibility, conductivity (3.06 S·m−1) and sensing sensitivity (the maximum gauge factor of 5.51). The PH@Ag e-skin could serve as strain sensors to accurately monitor and recognize all kinds of human motions such as swallowing, frowning, walking, and so on, and thus is anticipated to have considerable application prospect in many fields including flexible wearable electronic devices, health and motion monitoring.

Graphical abstract

构建具有高力学性能的生物质基导电水凝胶电子皮是目前生物质材料领域的研究热点和难点。传统的以胶原蛋白为基础的导电水凝胶,采用典型的“自下而上”策略构建,通常存在高力学性能与高胶原含量不相容的问题,并且往往需要提取胶原蛋白。为了解决这些问题,本工作受到动物皮肤高力学性能和高胶原含量的启发,提出了一种“自上而下”的构建策略,即不需要提取胶原蛋白,保留山羊皮中天然胶原纤维编织的具有三维网络结构的皮肤胶原蛋白骨架(SCS),并将其作为水凝胶的基本框架。采用预处理→AgNPs(银纳米粒子)溶液浸泡→含HEA(2-羟乙基甲基丙烯酸酯)和AlCl3的混合溶液浸泡→聚合的四步工艺流程,成功制备了以山羊皮为原料,具有高力学性能(抗拉强度2.97 MPa,韧性6.23 MJ·m−3,断裂伸长率428%)的新型皮肤基导电水凝胶电子皮肤。制备的皮肤水凝胶(PH@Ag)具有独特的结构,其胶原纤维被PHEA包裹,具有良好的粘附性、良好的抗菌性能、细胞相容性、电导率(3.06 S·m−1)和传感灵敏度(最大测量因子为5.51)。PH@Ag电子皮肤可作为应变传感器,准确监测和识别人体吞咽、皱眉、行走等各种动作,在柔性可穿戴电子设备、健康、运动监测等领域具有广阔的应用前景。图形抽象
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引用次数: 14
Valorization of sustainable vegetable oil deodorizer distillate as a novel fatliquor 可持续植物油脱臭馏出物作为新型加脂剂的研究
Pub Date : 2023-05-30 DOI: 10.1186/s42825-023-00124-8
El-Shahat H. A. Nashy, Adel Gabr Abdel-Razek, Minar Mahmoud M. Hassanein, Ghada A. Abo-Elwafa, Hamed Elsayed

The deodorizer distillate (DD) is a byproduct of vegetable oil processing industry and is rich in functional bioactive components. This study aimed to employ phosphorylation modification for DD to produce a new sustainable fatliquor. The bioactive ingredients in DD, namely fatty acids, sterols, and tocopherols, were determined by using HPLC and GLC. The results revealed that the DD sample contained a high percentage of unsaturated fatty acids (72.3%) and high levels of γ and δ-tocopherols (54.8% and 31.60%, respectively). Mechanical parameters (tensile strength, elongation at break, and tear strength) of leather were improved after being treated with the prepared fatliquor emulsion. Eventually, SEM showed that the texture of the fatliquored leather had been remarkably enhanced. Moreover, the fatliquored leather possessed effective antibacterial effect against the specified +ve, −ve bacteria, and Candida albicans microorganisms. The strength, fullness, soft handle, and elasticity of leather were all improved, and the grain of leather was protected from becoming loose after drying.

Graphical Abstract

除臭馏出物是植物油加工业的副产品,含有丰富的功能性生物活性成分。本研究旨在对DD进行磷酸化修饰,制备一种新型的可持续加脂剂。采用高效液相色谱法和GLC法测定了DD中的生物活性成分脂肪酸、甾醇和生育酚。结果表明,DD样品中不饱和脂肪酸含量高(72.3%),γ和δ-生育酚含量高(分别为54.8%和31.60%)。经加脂剂乳液处理后,皮革的力学参数(抗拉强度、断裂伸长率和撕裂强度)得到改善。最后,扫描电镜显示,加脂皮革的质地明显增强。此外,加脂皮革对特定的+ve、- ve细菌和白色念珠菌具有有效的抗菌作用。皮革的强度、饱满度、手感柔软、弹性都得到了提高,而且皮革的纹路在干燥后不会变松。图形抽象
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引用次数: 2
Self-assembly fabrication of lignin-derived carbon with dual heteroatoms doping for high-performance supercapacitor 双杂原子掺杂木质素衍生碳自组装制备高性能超级电容器
Pub Date : 2023-05-12 DOI: 10.1186/s42825-023-00122-w
Zehong Chen, Haihong Lai, Hao Zhuo, Yu Lin Zhong, Linxin Zhong, Xinwen Peng

Renewable and low-cost biomass is an ideal sustainable alternative to petroleum-based resources, but producing biomass-based carbon electrode with high performances remains a challenge. Herein, we propose a facile self-assembly strategy to fabricate a biomass-derived N, S co-doping carbon electrode from lignosulfonate without any activation or template process. Taking advantage of the coordination between Fe ions and lignosulfonate, the resultant carbon exhibits a spherical structure with abundant graphitized nanosheets, leading to a high specific surface area with rational pore structure, which are beneficial to the electron/ion transport and storage. The high contents of doping N (8.47 wt%) and S (2.56 wt%) significantly boost the electrochemical performances. As a supercapacitor electrode, the carbon material displays high specific capacitance of 390 F g−1, excellent cycling stability and high energy density of 14.7 W h kg−1 at a power density of 450 W kg−1. This study provides a potential strategy for synthesizing cost-effective heteroatom-doped carbon materials from biomass with abundant functional groups and heteroatom sources, such as chitosan, collagen, and gelatin.

Graphical Abstract

可再生和低成本的生物质是石油基资源的理想可持续替代品,但生产高性能的生物质基碳电极仍然是一个挑战。在此,我们提出了一种简单的自组装策略,以木质素磺酸盐制备生物质来源的N, S共掺杂碳电极,无需任何活化或模板过程。利用铁离子与木质素磺酸盐之间的配位作用,合成的碳具有丰富的石墨化纳米片的球形结构,具有较高的比表面积和合理的孔结构,有利于电子/离子的传递和储存。高含量的N (8.47 wt%)和S (2.56 wt%)显著提高了电化学性能。作为超级电容器电极,碳材料具有390 F g−1的高比电容、优异的循环稳定性和在450 W kg−1的功率密度下14.7 W h kg−1的高能量密度。本研究为从具有丰富官能团和杂原子来源的生物质中合成具有成本效益的杂原子掺杂碳材料提供了一种潜在的策略,如壳聚糖、胶原蛋白和明胶。图形抽象
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引用次数: 1
Advancing collagen-based biomaterials for oral and craniofacial tissue regeneration 推进口腔和颅面组织再生的胶原基生物材料
Pub Date : 2023-05-06 DOI: 10.1186/s42825-023-00120-y
Bo Zhang, Yunxiang He, Jialing Liu, Jiaojiao Shang, Chider Chen, Tianyi Wang, Mei Chen, Yifei Li, Guidong Gong, Jie Fang, Zhihe Zhao, Junling Guo

The oral and craniofacial region consists of various types of hard and soft tissues with the intricate organization. With the high prevalence of tissue defects in this specific region, it is highly desirable to enhance tissue regeneration through the development and use of engineered biomaterials. Collagen, the major component of tissue extracellular matrix, has come into the limelight in regenerative medicine. Although collagen has been widely used as an essential component in biomaterial engineering owing to its low immunogenicity, high biocompatibility, and convenient extraction procedures, there is a limited number of reviews on this specific clinic sector. The need for mechanical enhancement and functional engineering drives intensive efforts in collagen-based biomaterials concentrating on therapeutical outcomes and clinical translation in oral and craniofacial tissue regeneration. Herein, we highlighted the status quo of the design and applications of collagen-based biomaterials in oral and craniofacial tissue reconstruction. The discussion expanded on the inspiration from the leather tanning process on modifications of collagen-based biomaterials and the prospects of multi-tissue reconstruction in this particular dynamic microenvironment. The existing findings will lay a new foundation for the optimization of current collagen-based biomaterials for rebuilding oral and craniofacial tissues in the future.

Graphical Abstract

口腔和颅面区由各种类型的软组织和硬组织组成,组织复杂。由于这一特定区域组织缺陷的高发性,通过开发和使用工程生物材料来增强组织再生是非常可取的。胶原蛋白作为组织细胞外基质的主要组成部分,在再生医学领域受到广泛关注。尽管胶原蛋白因其低免疫原性、高生物相容性和方便的提取程序而被广泛用作生物材料工程的重要成分,但关于这一特定临床领域的综述数量有限。对机械增强和功能工程的需求推动了基于胶原蛋白的生物材料在口腔和颅面组织再生中的治疗效果和临床转化的密集努力。本文重点介绍了胶原基生物材料在口腔和颅面组织重建中的设计和应用现状。讨论扩展了从皮革鞣制过程中对胶原基生物材料改性的启发,以及在这种特殊的动态微环境中多组织重建的前景。这些发现将为今后优化现有的胶原基生物材料用于口腔和颅面组织的重建奠定新的基础。图形抽象
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引用次数: 2
Correction to Competing Interests 更正竞争利益
Pub Date : 2023-05-06 DOI: 10.1186/s42825-023-00121-x
Collagen and Leather
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引用次数: 0
Wearable synthetic leather-based high-performance X-ray shielding materials enabled by the plant polyphenol- and hierarchical structure-facilitated dispersion 可穿戴的合成皮革为基础的高性能x射线屏蔽材料,由植物多酚和分层结构实现,有利于分散
Pub Date : 2023-04-21 DOI: 10.1186/s42825-023-00119-5
Linping Yan, Jibo Zhou, Hao Li, Rui Zhong, Junxin Zhuang, Xiaohui Xu, Yaping Wang, Xuepin Liao, Bi Shi

Effective protection against X-ray is the premise of utilizing the X-ray, thus it is critical to develop novel X-ray shielding materials with both low density and high X-ray attenuation efficiency. As the even distribution of high-Z element components is of great significance for increasing the attenuation efficiency of X-ray shielding materials, in this study, the microfiber membrane (MFM), a type of synthetic leather featuring hierarchical structure was chosen to provide large surface area for the dispersion of rare earth (RE) element. Meanwhile, plant polyphenol was utilized to achieve the stable loading and uniform dispersion of the Ce or Er into MFM. Benefiting from the assistance of polyphenol and hierarchical structure of MFM, the even dispersion of RE element was successfully realized. The resultant shielding materials displayed approximately 10% superior X-ray attenuation efficiency compared to that without polyphenol, and an averagely 9% increment in X-ray attenuation efficiency than that without hierarchical structure. Moreover, the obtained composite with a thickness of 2.8 mm displayed superior X-ray shielding performance compared to 0.25 mm lead sheet in 16–83 keV and retained an ultralow density of 1.4 g cm–3. Our research results would shed new light on the manufacture of high-performance X-ray shielding materials with excellent X-ray shielding performance.

Graphical Abstract

有效防护x射线是利用x射线的前提,因此开发低密度、高x射线衰减效率的新型x射线屏蔽材料至关重要。由于高z元素组分的均匀分布对提高x射线屏蔽材料的衰减效率具有重要意义,因此本研究选择了一种具有分层结构的合成革——超纤维膜(MFM),为稀土(RE)元素的分散提供了较大的表面积。同时,利用植物多酚实现了Ce或Er在MFM中的稳定加载和均匀分散。利用多酚的辅助和MFM的层次化结构,成功地实现了稀土元素的均匀分散。所得屏蔽材料的x射线衰减效率比不含多酚的材料高约10%,比不含分层结构的材料平均提高9%。此外,与0.25 mm铅板相比,2.8 mm厚度的复合材料在16-83 keV下具有更好的x射线屏蔽性能,并保持了1.4 g cm-3的超低密度。我们的研究成果将为研制具有优异x射线屏蔽性能的高性能x射线屏蔽材料提供新的思路。图形抽象
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引用次数: 1
High-strength collagen/delphinidin film incorporated with Vaccinium oxycoccus pigment for active and intelligent food packaging 含有氧化牛痘色素的高强度胶原蛋白/飞燕草蛋白薄膜,用于活性和智能食品包装
Pub Date : 2023-04-13 DOI: 10.1186/s42825-023-00118-6
Simiao Yin, Yuanzhi Zhang, Xiaoxia Zhang, Keyu Tao, Guoying Li

This study developed an active and intelligent collagen-based packaging film with high strength for visually monitoring the freshness of fish. The results of scanning electron microscopy and atomic force microscopy showed that the film based on cross-linked collagen/delphinidin catalyzed by laccase exhibited a denser layer structure and a rougher surface. The dry and wet tensile strengths of the laccase-catalyzed collagen/delphinidin film (Col/Dp-LA film) increased by 41.74 MPa and 13.13 MPa in comparison with that of the pure collagen film, respectively. Moreover, the Col/Dp-LA film presented good antioxidant and barrier properties demonstrated by the results of free radical scavenging rate, light transmission rate, and water vapor permeability. The intelligent collagen-based film was obtained by incorporating Vaccinium oxycoccus pigment into the Col/Dp-LA film, which could change color under different pH values. When applied to the preservation of fish fillets, the film could release Dp to minimize oxidative rancidity and prolong the shelf life of the fish for 2 days. Meanwhile, the film showed visual color changes from purplish-red to greyish-blue after the fish spoilage. These results indicated that the collagen film treated with delphinidin, laccase, and Vaccinium oxycoccus pigment has potential application value in the field of active and intelligent food packaging.

Graphical Abstract

本研究开发了一种高强度的活性智能胶原蛋白包装薄膜,用于鱼类新鲜度的视觉监测。扫描电镜和原子力显微镜结果表明,漆酶催化的交联胶原/飞鸽苷膜层结构致密,表面粗糙。漆酶催化的胶原/飞燕草苷膜(Col/Dp-LA膜)的干、湿拉伸强度分别比纯胶原膜提高41.74 MPa和13.13 MPa。此外,通过自由基清除率、透光率和水蒸气透气性等测试结果表明,Col/Dp-LA膜具有良好的抗氧化和屏障性能。在Col/Dp-LA膜中加入氧化球蓝色素,获得了在不同pH值下可变色的智能胶原基膜。应用于鱼片保鲜时,可释放Dp,减少氧化酸味,延长鱼片保质期2天。同时,影片显示鱼变质后的视觉颜色由紫红色变为灰蓝色。这些结果表明,用飞燕草苷、漆酶和氧化牛痘色素处理的胶原膜在活性和智能食品包装领域具有潜在的应用价值。图形抽象
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引用次数: 3
Key mechanism of enzymatic dehairing technology for leather-making: permeation behaviors of protease into animal hide and the mechanism of charge regulation 酶法脱毛制革技术的关键机理:蛋白酶对兽皮的渗透行为及电荷调节机制
Pub Date : 2023-03-16 DOI: 10.1186/s42825-023-00117-7
Mengchu Gao, Jinzhi Song, Xu Zhang, Chunxiao Zhang, Biyu Peng, Sadaqat Ali Chattha

Enzymes have been widely used as alternatives to conventional chemicals in cleaner leather processes due to their advantages of meeting increasing environmental demands. Especially, enzymatic unhairing based on protease has been applied to leather-making for a long time, however, it still has the key problem of slow permeation in the animal hide, resulting in slow unhairing rate, poor hair removal effect, excessive proteolysis of hide collagen, and decreased leather quality. Aiming at the key problem of bio-unhairing technology, fluorescent labeling technique and confocal laser scanning microscopy were used to investigate the protease permeation behaviors into the animal hide based on well-prepared labeled proteases, as well as the quantitative analysis of the protease amount in different hide layers. The results show that the protease mainly permeates the bovine hide through transfollicular routes from the hair side, and although the intercellular-interfibrillar pathway also exists, it does not play an important role. Additionally, the protease permeation behaviors into the hide are greatly impacted by the charge states of the hide and protease proteins, depending on the isoelectric points (pI) of the proteins and solution pH values. When the solution pH is not between the pI values of the two proteins, the similarly charged protease can quickly and deeply penetrate the hide because of the electrostatic repulsion. The established mechanism provides a theoretical basis for developing an efficient enzymatic unhairing technology for leather-making, and this can also be applied to other processes involving the enzyme permeation into the hide or leather.

Graphical Abstract

由于酶具有满足日益增长的环境要求的优点,酶已被广泛用于清洁皮革工艺中作为传统化学品的替代品。特别是以蛋白酶为基础的酶解脱毛技术在制革中应用已久,但其在兽皮中的渗透速度慢,导致脱毛速度慢,脱毛效果差,兽皮胶原蛋白水解过度,皮革质量下降。针对生物脱毛技术的关键问题,采用荧光标记技术和激光共聚焦扫描显微镜技术,在制备好的标记蛋白酶的基础上,研究了蛋白酶对兽皮的渗透行为,并定量分析了不同兽皮层中蛋白酶的含量。结果表明,蛋白酶主要从毛侧经毛囊途径渗透到牛皮中,虽然也存在细胞间-纤维间途径,但并不起重要作用。此外,蛋白酶在皮革中的渗透行为很大程度上受到皮革和蛋白酶蛋白的电荷状态的影响,这取决于蛋白质的等电点(pI)和溶液pH值。当溶液的pH值不在两种蛋白质的pI值之间时,由于静电斥力的作用,带类似电荷的蛋白酶可以迅速而深入地渗透到皮中。所建立的机制为开发高效的皮革酶脱毛技术提供了理论基础,也可应用于涉及酶渗透到皮革或皮革中的其他工艺。图形抽象
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引用次数: 0
期刊
Journal of Leather Science and Engineering
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