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Progress and Perspectives of Conducting Metal–Organic Frameworks for Electrochemical Energy Storage and Conversion 导电金属-有机框架电化学储能与转换研究进展与展望
Q3 Chemistry Pub Date : 2023-11-11 DOI: 10.3390/chemistry5040161
Minggui Li, Guangxun Zhang, Yuxin Shi, Huijie Zhou, Yongcai Zhang, Huan Pang
The metal–organic framework (MOF) is a kind of porous material with lattice materials. Due to its large surface area and structural diversity, it has made great progress in the fields of batteries, capacitors, electrocatalysis, etc. Conductive MOF (c-MOF) increases the conductivity based on the original advantages of the MOF, which is more suitable for the development of batteries, capacitors, electrocatalysis, and other fields. This review summarizes the preparation of c-MOF and the research progress of conductive MOFs in the field of electrochemical energy storage and conversion.
金属有机骨架(MOF)是一种具有点阵结构的多孔材料。由于其表面积大、结构多样,在电池、电容器、电催化等领域取得了很大的进展。导电性MOF (c-MOF)在MOF原有优点的基础上提高了导电性,更适合于电池、电容器、电催化等领域的发展。本文综述了c-MOF的制备及导电mof在电化学储能与转换领域的研究进展。
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引用次数: 0
Recent Advances in the Preparation and Application of DNA-Encoded Metal Nanoclusters dna编码金属纳米簇的制备及应用研究进展
Q3 Chemistry Pub Date : 2023-11-10 DOI: 10.3390/chemistry5040160
Fang Yin, Jiangtao Ren, Erkang Wang
DNA as an intriguing organic ligand has been widely employed for synthesizing metal nanoclusters and engineering their properties. This review aims to present recent progress on DNA-encoded metal (Ag, Cu, Au, Ag/Pt, Cu/Ag, etc.) nanoclusters (DNA-MNCs), focusing on their applications in the fields of analysis, logic operation, and therapy based on properties including fluorescence, electrochemiluminescence (ECL), and antibacterial and catalytic activity, and summarizes the attractive features of the latest research. The key points are briefly described as follows. (1) Analytical systems have been constructed based on fluorescence regulation, and nuclease-assisted and enzyme-free amplification strategies have been extensively adopted with fluorescent DNA-MNCs for amplified analysis. (2) DNA-MNCs may play more than one role (emitter, quencher, or catalyst) in ECL-based analytical systems. (3) Apart from antibacterial activity, DNA-MNCs also possess apparent catalytic capability, such as enzyme-like activity (i.e., nanozymes), which has been applied in colorimetric systems. (4) Reversibly regulating the catalytic activity of DNA-MNCs has been attained with DNA systems. It is believed that through in-depth investigation of the relationship between atomic structure and property, more novel DNA-MNCs will be explored and applied in the future.
DNA作为一种有趣的有机配体,已被广泛应用于金属纳米团簇的合成及其性质的工程设计。本文综述了dna编码金属(Ag、Cu、Au、Ag/Pt、Cu/Ag等)纳米簇(DNA-MNCs)的最新研究进展,重点介绍了DNA-MNCs在分析、逻辑运算和治疗等领域的应用,并从荧光、电化学发光(ECL)、抗菌和催化活性等方面综述了最新研究的亮点。要点简述如下。(1)基于荧光调控的分析系统已经建立,荧光DNA-MNCs广泛采用核酸酶辅助和无酶扩增策略进行扩增分析。(2) DNA-MNCs在基于ecl的分析系统中可能扮演不止一个角色(发射器、淬灭器或催化剂)。(3)除了抗菌活性外,DNA-MNCs还具有明显的催化能力,如酶样活性(即纳米酶),已应用于比色系统。(4) DNA系统已经实现了对DNA- mncs催化活性的可逆调节。相信通过对原子结构与性质关系的深入研究,未来将会有更多新型DNA-MNCs被探索和应用。
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引用次数: 0
Condensed DNA Nanosphere for DNA Origami Cryptography 用于DNA折纸密码学的浓缩DNA纳米球
Q3 Chemistry Pub Date : 2023-11-08 DOI: 10.3390/chemistry5040159
Rui Gao, Zhuang Cai, Jianbang Wang, Huajie Liu
Maintaining the confidentiality and integrity of the messages during a transmission is one of the most important aims of encrypted communication systems. Many achievements were made using biomolecules to improve the quality of the messages in communication. At the same time, it is still a challenge to construct cooperative communications based on the interactions between biomolecules to achieve the confidentiality and integrity of the transmitted messages. DNA-based encrypted communications have been developed, and in particular, DNA-origami-based message encryption can combine steganography and pattern encryption and exhibits extremely high confidentiality. Nevertheless, limited by biological characteristics, encrypted messages based on DNA require a strict storage environment in the process of transmission. The integrity of the message encoded in the DNA may be damaged when the DNA is in an unfriendly and hard environment. Therefore, it is particularly significant to improve the stability of DNA when it is exposed to a harsh environment during transmission. Here, we encoded the information into the DNA strands that were condensed for encryption to form a nanosphere covered with a shell of SiO2, which brings high-density messages and exhibits higher stability than separated DNA. The solid shell of SiO2 could prevent DNA from contacting the harsh environment, thereby protecting the DNA structure and maintaining the integrity of the information. At the same time, DNA nanospheres can achieve high throughput input and higher storage density per unit volume, which contribute to confusing the message strand (M-strand) with the interference strand in the stored information. Condensing DNA into the nanosphere that is used for DNA origami cryptography has the potential to be used in harsh conditions with higher confidentiality and integrity for the transmitted messages.
在传输过程中保持消息的机密性和完整性是加密通信系统最重要的目标之一。生物分子在提高信息质量方面取得了许多成就。同时,如何构建基于生物分子间相互作用的协作通信,以实现传输信息的保密性和完整性,仍然是一个挑战。基于dna的加密通信已经发展起来,特别是基于dna折纸的消息加密可以结合隐写和模式加密,具有极高的保密性。然而,受生物学特性的限制,基于DNA的加密信息在传输过程中需要严格的存储环境。当DNA处于不友好和恶劣的环境中时,其编码信息的完整性可能会受到破坏。因此,提高DNA在传播过程中暴露于恶劣环境时的稳定性就显得尤为重要。在这里,我们将信息编码到DNA链中,这些DNA链被压缩并加密,形成一个覆盖有SiO2外壳的纳米球,它带来高密度的信息,并且比分离的DNA具有更高的稳定性。SiO2的固体外壳可以防止DNA与恶劣环境接触,从而保护DNA结构,保持信息的完整性。同时,DNA纳米球可以实现高通量输入和单位体积的高存储密度,这有助于将存储信息中的信息链(m链)与干扰链混淆。将DNA压缩到纳米球中用于DNA折纸密码术,有可能在恶劣条件下使用,对传输的信息具有更高的保密性和完整性。
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引用次数: 0
Stereoselective Synthesis of a Novel Series of Dispiro-oxindolopyrrolizidines Embodying Thiazolo[3,2-a]benzimidazole Motif: A Molecular Electron Density Theory Study of the Mechanism of the [3 + 2] Cycloaddition Reaction 包含噻唑[3,2-a]苯并咪唑基序的新型双吡罗-氧吲哚吡咯利齐啶类化合物的立体选择性合成:[3 + 2]环加成反应机理的分子电子密度理论研究
Q3 Chemistry Pub Date : 2023-11-06 DOI: 10.3390/chemistry5040158
Assem Barakat, Saeed Alshahrani, Abdullah Mohammed Al-Majid, Abdullah Saleh Alamary, M. Ali, Mar Ríos-Gutiérrez
A one-pot multi-component reaction was employed for the stereoselective synthesis of a novel set of dispiro-oxindolopyrrolizidines analogs incorporating a thiazolo[3,2-a]benzimidazole scaffold based on the [3 + 2] cycloaddition (32CA) reaction approach. The desired novel dispiro-oxindolopyrrolizidines 9a–d were achieved using the 32CA reaction of new ethylene derivatives based on thiazolo[3,2-a]benzimidazole moiety seven with thiazolidine derivatives eight and different substituted isatin compounds 5a–d (R = H, Cl, NO2, and Br). The final dispiro-oxindolopyrrolizidines cycloadducts were separated, purified, and fully characterized by means of a set of spectroscopic tools including IR, HNMR, CNMR, and MS. The Molecular Electron Density Theory (MEDT) was applied to explain the mechanism and stereoselectivity in the of the key 32CA reaction step. The reactive pseudo(mono)radical electronic structure of the in situ generated azomethine ylides and the high polar character of the corresponding 32CA reactions account for the low computed activation Gibbs free energies and total endo stereoselectivity of this kinetically controlled exergonic reaction. The computed relative Gibbs free activation energies of competitive reaction paths and regioisomers ratio distribution of 80:20 justify the major formation of 9a via the most favorable ortho/endo reaction path.
采用一锅多组分反应,基于[3 + 2]环加成(32CA)反应方法,立体选择性合成了一组含噻唑[3,2- A]苯并咪唑支架的新型双吡罗-氧吲哚吡咯利齐啶类化合物。以噻唑[3,2-a]苯并咪唑片段7为基础的新型乙烯衍生物与噻唑烷衍生物8和不同取代的异丁基化合物5a-d (R = H, Cl, NO2,和Br)进行32CA反应,得到了新型双吡罗-氧吲哚吡咯利嗪类化合物9a-d。采用IR、HNMR、CNMR、ms等光谱分析手段对最终产物进行了分离、纯化和表征。应用分子电子密度理论(MEDT)解释了32CA反应关键步骤的反应机理和立体选择性。原位生成的亚甲酰基的反应性伪(单)自由基电子结构和相应的32CA反应的高极性特征导致了该动力学控制的ergergonic反应具有较低的计算激活吉布斯自由能和总内位立体选择性。计算得到的竞争反应路径的相对吉布斯自由活化能和区域异构体的比值分布为80:20,证明9a主要通过最有利的邻位/内端反应路径生成。
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引用次数: 0
Theoretical Evaluation of the Properties of Nitrogen-Doped C24 Fullerenes and Their Interactions with Two Adamantane-Derived Antivirals 氮掺杂C24富勒烯性质的理论评价及其与两种金刚烷衍生物抗病毒药物的相互作用
Q3 Chemistry Pub Date : 2023-11-02 DOI: 10.3390/chemistry5040157
Oana-Raluca Pop, Adina Căta, Ioana Maria Carmen Ienașcu
The replacement of carbon with a heteroatom within the structure of a fullerene gives the possibility of obtaining compounds with adjustable properties. The influence of aza-substitution on C24 fullerenes was investigated and a comparison of HF and DFT calculations was performed. Various substitution patterns were proposed and the characterization of C22N2 and C20N4 structures was performed. Global reactivity descriptors like chemical potential, hardness, HOMO–LUMO gap and singlet–triplet gap were computed. Aromaticity descriptors like delocalization indices and NICS(0) index were employed for the characterization of each six-membered ring of the studied fullerenes. The possible use of aza-fullerenes as drug delivery systems for two adamantane-derived antivirals was evaluated through molecular docking studies. The best results were obtained for the fullerenes with a pronounced hydrophobic character, the favored configuration of the antiviral drugs being the one oriented toward the side consisting of carbon atoms of the fullerenes.
在富勒烯的结构中用杂原子取代碳使得获得具有可调性质的化合物成为可能。研究了氮杂取代对C24富勒烯的影响,并进行了HF和DFT计算的比较。提出了不同的取代模式,并对C22N2和C20N4结构进行了表征。计算了化学势、硬度、HOMO-LUMO间隙和单重态-三重态间隙等全局反应性描述符。利用离域指数和NICS(0)指数等芳香性描述符对所研究的富勒烯的每个六元环进行表征。通过分子对接研究,评估了aza-富勒烯作为两种金刚烷衍生抗病毒药物的药物传递系统的可能性。具有明显疏水性的富勒烯获得了最好的效果,抗病毒药物的有利构型是朝向由富勒烯的碳原子组成的一侧的构型。
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引用次数: 0
Synthesis of D-Fructose-Based Bifunctional Primary Amine-Thiourea Organocatalysts and Their Applications in Asymmetric Reactions d -果糖基双功能伯胺-硫脲有机催化剂的合成及其在不对称反应中的应用
Q3 Chemistry Pub Date : 2023-10-23 DOI: 10.3390/chemistry5040156
Samson Lalhmangaihzuala, Vanlalngaihawma Khiangte, Zathang Laldinpuii, Lal Nunnemi, Joute Malsawmsanga, Gospel Lallawmzuali, Thanhming Liana, Chhakchhuak Lalhriatpuia, Zodinpuia Pachuau, Khiangte Vanlaldinpuia
The preparation of a new class of six bifunctional thiourea organocatalysts having a D-fructose scaffold and a primary amino group was demonstrated. In the present study, the novel organocatalysts exhibited excellent enantio- and moderate diastereoselectivities in the asymmetric Michael addition of aliphatic ketones and 1,3-diketone to substituted nitroolefins at room temperature. In addition, the direct asymmetric aldol reaction between cyclic aliphatic ketone and aromatic aldehydes was also studied in the presence of the saccharide-thiourea organocatalysts giving excellent yield with moderate enantioselectivity.
制备了一类具有d -果糖支架和伯胺基的新型双功能硫脲有机催化剂。在本研究中,新型有机催化剂在室温下对取代的硝基烯烃的脂肪族酮和1,3-二酮的不对称Michael加成反应表现出优异的对映选择性和中等的非对映选择性。此外,还研究了在糖硫脲有机催化剂的存在下,环脂肪酮与芳香醛之间的直接不对称醛醇反应,收率高,对映选择性适中。
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引用次数: 0
Achillea fragrantissima Essential Oil, Wild Grown in Saudi Arabia and Egypt: Detailed Comparative Chemical Profiling, and Evaluation of Allelopathic, Antioxidant, and Antibacterial Activities 沙特阿拉伯和埃及野生阿喀喇精油:详细比较化学特征,化感作用、抗氧化和抗菌活性的评价
Q3 Chemistry Pub Date : 2023-10-22 DOI: 10.3390/chemistry5040155
Ahmed M. Abd-ElGawad, Rania F. Ahmed, Abdelsamed I. Elshamy, Eslam G. Sadek, Abdulaziz M. Assaeed, Giuliano Bonanomi, Abd El-Nasser G. El Gendy, Yasser A. El-Amier
One of the biologically beneficial oils against many ailments is Achillea fragrantissima essential oil (EO). The current study focused on the comprehensive comparative chemical characterization of A. fragrantissima EOs, which were gathered from Saudi Arabia and Egypt, as well as evaluation of their allelopathic, antioxidant, and antibacterial functions. With a respective total oil mass of 96.9% and 96.1%, 40 compounds were found in the EOs from Saudi Arabia (38 compounds) and Egypt (26 compounds). Terpenes represented the main constituents including mono- (52.6% and 75.4% from Saudi Arabia and Egypt, respectively) and sesquiterpenoids (42.1% and 19.7%, respectively). The α-thujone (12.0%), myrcenyl acetate (10.3%), alloaromadendrene oxide-(1) (5.9%), artemisia ketone (4.9%), β-thujone (4.7%), lavandulol (4.2%), and santolina alcohol (4.0%) represented the main components of the overall oil of the Saudi Arabian plant-derived EO. However, the main constituents of the EO of the Egyptian plant were 4-terpineol (17.4%), myrcenyl acetate (9.1%), artemisia ketone (9.0%), α-thujone (8.6%), yomogi alcohol (6.2%), santolina alcohol (6.2%), and β-thujone (5.8%). The chemometric analysis exhibited a strong association between the two EOs from Saudi Arabia and Egypt in addition to the samples collected from Jordan. The Saudi and Egyptian A. fragrantissima’ EOs were found to have significant allelopathic potencies against the weed C. murale. The seed germination, seedling shoot growth, and root growth of C. murale were all reduced by the EO of the Saudi ecospecies by 79.9, 56.7, and 68.6%, respectively, with IC50 values of 66.5, 68.0, and 69.2 µL L−1, respectively. The two oils from Saudi Arabia and Egypt exhibited potent antioxidant activity against the DPPH free radicals, with IC50 values of 30.94 and 28.72 mg/L, respectively. In addition, the two oils from Saudi Arabia and Egypt exhibited strong abilities to scavenge ABTS radicals with respective IC50 values of 39.02 and 37.13 mg/L. Additionally, the two EOs showed a much higher antibacterial activity than the antibiotics tested against all bacterial strains, with the exception of Enterobacter cloacae. The two oils exhibited antibacterial activity against the examined strains, except Bacillus subtilis and Salmonella typhimurium, for which the Egyptian species shown greater inhibition. The results revealed that Escherichia coli and Staphylococcus epidermidis were more sensitive, while Enterobacter cloacae was more resistant.
一种对许多疾病有益的生物油是阿喀琉叶精油(EO)。本研究主要对沙特阿拉伯和埃及两种植物的化学特性进行了综合比较,并对其化感、抗氧化和抗菌功能进行了评价。在沙特阿拉伯(38种)和埃及(26种)的精油中分别发现了40种化合物,总油质量分别为96.9%和96.1%。萜类成分主要为单萜类(分别为52.6%和75.4%)和倍半萜类(分别为42.1%和19.7%)。α-图琼(12.0%)、乙酸月桂酯(10.3%)、氧化异芳香腺嘌呤(1)(5.9%)、青蒿酮(4.9%)、β-图琼(4.7%)、薰衣草醇(4.2%)和圣托里纳醇(4.0%)是沙乌地阿拉伯植物源油的主要成分。其主要成分为4-松油醇(17.4%)、乙酸月桂酯(9.1%)、青蒿酮(9.0%)、α-图琼(8.6%)、龙木醇(6.2%)、桑托里纳醇(6.2%)和β-图琼(5.8%)。化学计量学分析显示,除了从约旦收集的样品外,来自沙特阿拉伯和埃及的两个EOs之间存在很强的关联。沙乌地阿拉伯和埃及的香薷对杂草有明显的化感作用。沙乌地生态种EO对沙乌地南种子萌发、苗梢生长和根系生长的影响分别为79.9、56.7和68.6%,IC50值分别为66.5、68.0和69.2µL L−1。沙特阿拉伯和埃及两种油对DPPH自由基表现出较强的抗氧化活性,IC50值分别为30.94和28.72 mg/L。此外,沙特阿拉伯和埃及两种油对ABTS自由基的清除能力较强,IC50值分别为39.02和37.13 mg/L。此外,除了阴沟肠杆菌外,这两种EOs对所有菌株的抗菌活性都比抗生素高得多。除了枯草芽孢杆菌和鼠伤寒沙门氏菌外,这两种油对所检测的菌株都有抑菌活性,埃及种对这两种菌株的抑制作用更大。结果显示,大肠杆菌和表皮葡萄球菌对该药较为敏感,阴沟肠杆菌对该药较为耐药。
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引用次数: 0
Preparation and Application of Green Sustainable Solvent Cyrene 绿色可持续溶剂癸烯的制备及应用
Q3 Chemistry Pub Date : 2023-10-21 DOI: 10.3390/chemistry5040154
Yadong Wang, Mingfei Dai, Gang Luo, Jiajun Fan, James H. Clark, Shicheng Zhang
The bio-based solvent dihydrolevoglucosenone (Cyrene) is a green and sustainable alternative to petroleum-based dipolar aprotic solvents. Cyrene can be prepared from cellulose in a simple two-step process and can be produced in a variety of yields. Cyrene is compatible with a large number of reactions in the chemical industry and can be applied in organic chemistry, biocatalysis, materials chemistry, graphene and lignin processing, etc. It is also green, non-mutagenic and non-toxic, which makes it very promising for applications. In this paper, we have also screened all articles related to Cyrene on the Web of Science and visualised them through Cite Space.
生物基溶剂二氢左旋葡萄糖酮(昔rene)是一种绿色、可持续的石油基偶极非质子溶剂替代品。昔兰尼可以用简单的两步法从纤维素中制备,并且可以以各种产量生产。昔兰尼与化学工业中的大量反应兼容,可应用于有机化学、生物催化、材料化学、石墨烯和木质素加工等领域。它具有绿色、无突变、无毒等特点,具有广阔的应用前景。在本文中,我们还筛选了Web of Science上与Cyrene相关的所有文章,并通过Cite Space将其可视化。
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引用次数: 0
Vinyl Esters and Vinyl Sulfonates as Green Alternatives to Vinyl Bromide for the Synthesis of Monosubstituted Alkenes via Transition-Metal-Catalyzed Reactions 过渡金属催化反应合成单取代烯烃的乙烯基酯和乙烯基磺酸盐的绿色替代品
Q3 Chemistry Pub Date : 2023-10-20 DOI: 10.3390/chemistry5040153
Tomáš Tobrman
This review summarizes the applications of vinyl sulfonate and vinyl acetate as green alternatives for vinyl bromide in cross-coupling reactions. In the first part, the preparation of vinyl sulfonates and their cross-coupling reactions are briefly discussed. Then, a brief review of vinyl acetate cross-coupling reactions, including cyclization reactions, the Fujiware–Moritani reaction, and transvinylation reactions are described.
综述了乙烯基磺酸盐和醋酸乙烯酯在交叉偶联反应中作为绿色替代品的应用。第一部分简要介绍了乙烯基磺酸盐的制备及其交叉偶联反应。然后,简要回顾了醋酸乙烯酯的交叉偶联反应,包括环化反应、藤波-森谷反应和转乙烯基化反应。
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引用次数: 0
Synthesis and Characterization of a Self-Crosslinked Organic Copolymer Kappa-Carrageenan/Polyacrylamide/Cetrimide (κ-CAR/PAAm/CI) Hydrogel with Antimicrobial and Anti-Inflammatory Activities for Wound Healing 具有抗菌和抗炎伤口愈合活性的自交联有机共聚物kappa -卡拉胶/聚丙烯酰胺/西三酰胺(κ-CAR/PAAm/CI)水凝胶的合成和表征
Q3 Chemistry Pub Date : 2023-10-19 DOI: 10.3390/chemistry5040152
Fatimah A. Agili, Sahera F. Mohamed
The current study aimed to produce a material that has dual effects of healing and anti-inflammatory activity. For this purpose, a κ-carrageenan/polyacrylamide film loaded with cetrimide (κ-CAR/PAAm/CI) was developed using the manual casting technique. Definite concentrations of κ-CAR and AAm were heated at 80 °C for 2 h, and CI and glycerol were added. The solution was cast without using an initiator or crosslinker. The reaction of the sulfonic acid group -SO3H of κ-CAR with the –CONH2 group of PAAm lead to the formation of a sulfonamide (–SO2NH–) group. The characteristics of the produced films were investigated based on FT-IR, TGA, the contact angle, and mechanical properties. An improvement in the thermal stability of the κ-CAR/PAAm/CI2 film containing 1.5% CI was achieved, compared to the film with 0.5% CI (κ-CAR/PAAm/CI1). The contact angle measurement proved that the films were hydrophobic, enhanced by increasing the CI content. The tensile strength and elongation percent values are considered adequate for materials used in wound care. The κ-CAR/PAAm/CI2 (1.5% CI) film showed superior antimicrobial activity against P. aeruginosa, moderate activity against S. aureus, and low activity against E. coli. The κ-CAR/PAAm/CI2 film effectively inhibited heat-induced hemolysis and showed wound contraction activity at a level of 100% after 19 days of excision wound treatment. The prepared films may offer a promising approach for the development of effective wound dressings.
目前的研究旨在生产一种具有愈合和抗炎双重作用的材料。为此,采用人工浇铸技术制备了一种载载西三酰胺(κ-CAR/PAAm/CI)的κ-卡拉胶/聚丙烯酰胺膜。将一定浓度的κ-CAR和AAm在80℃下加热2小时,加入CI和甘油。该溶液在不使用引发剂或交联剂的情况下进行铸造。κ-CAR的磺酸基团- so3h与PAAm的- conh2基团反应生成磺酰胺(- so2nh -)基团。利用红外光谱(FT-IR)、热重分析仪(TGA)、接触角和力学性能对所制膜进行了表征。与含有0.5% CI (κ-CAR/PAAm/CI1)的膜相比,含有1.5% CI的κ-CAR/PAAm/CI2膜的热稳定性得到了改善。接触角测试证明了膜的疏水性,并随着CI含量的增加而增强。抗拉强度和延伸率值被认为是足够的材料用于伤口护理。κ-CAR/PAAm/CI2 (1.5% CI)膜对铜绿假单胞菌具有较好的抑菌活性,对金黄色葡萄球菌具有中等的抑菌活性,对大肠杆菌具有较低的抑菌活性。κ-CAR/PAAm/CI2膜有效抑制热致溶血,切除创面处理19天后创面收缩活性达到100%。所制备的膜为开发有效的伤口敷料提供了一条有前途的途径。
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引用次数: 0
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Chemistry
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