Green synthesis of metal oxide nanoparticles and their catalytic activity for the reduction of aldehydes

In the present work, a green synthesis of Metal Oxide nanoparticles was demonstrated using the freshly prepared aqueous extract of the immature fruit of Cocos nucifera and the MO nanoparticles were characterized by the analytical techniques such as UV–vis, FT-IR, XRD, SEM, TEM and EDAX. Characterization techniques confirmed that the biomolecules involved in the formation of nanoparticles and also they stabilized the nanoparticles. The synthesized MO nanoparticles were used as catalysts for the reduction of aromatic aldehydes. The reduction was done at mild reaction conditions using ammonium formate as a green hydrogen donor and the corresponding alcohols were obtained in 2–24 h with excellent yields. The reduction reaction was optimized using various solvents, loading of catalyst and at different temperatures.     

The pH dependence of hairpin ribozyme catalysis reflects ionization of an active site adenine

Understanding how self-cleaving ribozymes mediate catalysis is crucial in light of compelling evidence that human and bacterial gene expression can be regulated through RNA self-cleavage. The hairpin ribozyme catalyzes reversible phosphodiester bond cleavage through a mechanism that does not require divalent metal cations. Previous structural and biochemical evidence implicated the amidine group of an active site adenosine, A38, in a pH-dependent step in catalysis. We developed a way to determine microscopic pK(a) values in active ribozymes based on the pH-dependent fluorescence of 8-azaadenosine (8azaA). We compared the microscopic pK(a) for ionization of 8azaA at position 38 with the apparent pK(a) for the self-cleavage reaction in a fully functional hairpin ribozyme with a unique 8azaA at position 38. Microscopic and apparent pK(a) values were virtually the same, evidence that A38 protonation accounts for the decrease in catalytic activity with decreasing pH. These results implicate the neutral unprotonated form of A38 in a transition state that involves formation of the 5'-oxygen-phosphorus bond.     

Chitosan and lactic acid-grafted chitosan nanoparticles as carriers for prolonged drug delivery

Nanoparticles of approximately 10nm in diameter made with chitosan or lactic acid-grafted chitosan were developed for high drug loading and prolonged drug release. A drug encapsulation efficiency of 92% and a release rate of 28% from chitosan nanoparticles over a 4-week period were demonstrated with bovine serum protein. To further increase drug encapsulation, prolong drug release, and increase chitosan solubility in solution of neutral pH, chitosan was modified with lactic acid by grafting D,L-lactic acid onto amino groups in chitosan without using a catalyst. The lactic acid-grafted chitosan nanoparticles demonstrated a drug encapsulation efficiency of 96% and a protein release rate of 15% over 4 weeks. With increased protein concentration, the drug encapsulation efficiency decreased and drug release rate increased. Unlike chitosan, which is generally soluble only in acid solution, the chitosan modified with lactic acid can be prepared from solutions of neutral pH, offering an additional advantage of allowing proteins or drugs to be uniformly incorporated in the matrix structure with minimal or no denaturization.     

Optically active amphiphilic hyperbranched polyglycerols as templates for palladium nanoparticles

We report a systematic study on the encapsulation of palladium nanoparticles in optically active amphiphilic hyperbranched polyglycerols with different optical signs and different degrees of polymerization, namely (−)-P(G₄₀C16_0.5) 1 and (+)-P(G₇₃C16_0.5) 2. Several issues have been addressed here: (a) relatively wide size distributions (1-5 nm) of palladium nanoparticles have been achieved, (b) a remarkable template effect (1, DP_n = 40, 1.2 ± 0.1 nm; 2, DP_n = 73, 2.3 ± 0.1 nm average particle size) has been observed using TEM technique, as shown by the particle size dependent on the degree of polymerization of the polymers, (c) NaBH₄ is found to be a convenient reducing agent to produce small particle size compared with gaseous hydrogen, (d) catalytic Heck reaction of 2,3-dihydrofuran and aryl triflate has been tested successfully without enantiocontrol.     

Chitosan nanoparticles for oral drug and gene delivery

Chitosan is a widely available, mucoadhesive polymer that is able to increase cellular permeability and improve the bioavailability of orally administered protein drugs. It can also be readily formed into nanoparticles able to entrap drugs or condense plasmid DNA. Studies on the formulation and oral delivery of such chitosan nanoparticles have demonstrated their efficacy in enhancing drug uptake and promoting gene expression. This review summarizes some of these findings and highlights the potential of chitosan as a component of oral delivery systems.     

Thiosemicarbazone-derivatised palladium nanoparticles as efficient catalyst for the Suzuki-Miyaura cross-coupling of aryl bromides with phenylboronic acid

Thiosemicarbazone-derivatised palladium nanoparticles with average crystallite size 16.2 nm have been prepared and characterized by XRD and SEM. The nanoparticles were found to efficiently catalyze the Suzuki-Miyaura cross-coupling of aryl bromides (from electron-rich to electron poor) with phenylboronic acid even at room temperature, and they can be recovered and reused.     

Preparation and antibacterial activity of chitosan nanoparticles

Chitosan nanoparticles, such as those prepared in this study, may exhibit potential antibacterial activity as their unique character. The purpose of this study was to evaluate the in vitro antibacterial activity of chitosan nanoparticles and copper-loaded nanoparticles against various microorganisms. Chitosan nanoparticles were prepared based on the ionic gelation of chitosan with tripolyphosphate anions. Copper ions were adsorbed onto the chitosan nanoparticles mainly by ion-exchange resins and surface chelation to form copper-loaded nanoparticles. The physicochemical properties of the nanoparticles were determined by size and zeta potential analysis, atomic force microscopy (AFM), FTIR analysis, and XRD pattern. The antibacterial activity of chitosan nanoparticles and copper-loaded nanoparticles against E. coli, S. choleraesuis, S. typhimurium, and S. aureus was evaluated by calculation of minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC). Results show that chitosan nanoparticles and copper-loaded nanoparticles could inhibit the growth of various bacteria tested. Their MIC values were less than 0.25 microg/mL, and the MBC values of nanoparticles reached 1 microg/mL. AFM revealed that the exposure of S. choleraesuis to the chitosan nanoparticles led to the disruption of cell membranes and the leakage of cytoplasm.     

Study of the controlled assembly of DNA gated PEI/Chitosan/SiO2 fluorescent sensor

In this paper, polyethylenimine (PEI) and Chitosan were simultaneously one‐step doped into silicon dioxide (SiO₂) nanoparticles to synthesize PEI/Chitosan/SiO₂ composite nanoparticles. The polymer PEI contained a large amount of amino groups, which can realize the amino functionalized SiO₂ nanoparticles. And, the good pore forming effect of Chitosan was introduced into SiO₂ nanoparticles, and the resulting composite nanoparticles also had a porous structure. In pH 7.4 phosphate buffer solution (PBS), the amino groups of PEI had positive charges, and therefore the fluorescein sodium dye molecule can be loaded into the channels of PEI/Chitosan/SiO₂ composite nanoparticles by electrostatic adsorption. Furthermore, utilizing the diversity of DNA molecular conformation, we designed a high sensitive controllable assembly of DNA gated fluorescent sensor based on PEI/Chitosan/SiO₂ composite nanoparticles as loading materials. The factors affecting the sensing performance of the sensor were investigated, and the sensing mechanism was also further studied.     

Chitosan coating does not prevent the effect of the transfer of green silver nanoparticles biosynthesized by Streptomyces malachitus into fetuses via the placenta

Green synthesized nanoparticles are more advantageous over conventionally prepared ones due to less toxicity, production cost, and environmental hazards. With the widespread of the utilization of nanoparticles, little is known about the maternal-fetal transplacental transfer of green nanoparticles. We have biosynthesized silver nanoparticles using metabolites of Streptomyces malachitus and sunlight then coated them with chitosan. These nanoparticles have been characterized and intraperitoneally administered at doses of 100 mg/kg on the 6^th, 8^th, and 10^th gestational days. On the 18^th day of pregnancy, both coated and non-coted NPs were detected in different maternal tissues, placenta, and in fetuses, as determined by estimation of silver content and observation by electron microscopy. Chitosan coating decreased the silver content in different tissues, maybe due to the larger size of coated nanoparticles that retards the transfer. The toxic effects on maternal and fetal tissues were proportional to their silver content, as determined by the liver and kidney functional analysis of pregnant rats and the ultrastructural and histopathological examination of the maternal liver, placenta and fetal liver. The present data suggest that green silver nanoparticles biosynthesized by Streptomyces malachitus cross the placenta and have toxic effects on maternal tissues, placenta, and fetus. Chitosan coating of these nanoparticles decreases the transfer, and consequently, the toxicity. However, it does not prevent this toxicity.     

壳聚糖及其在金属纳米材料制备中的应用

基于来源丰富、独特的理化性质及生物学特性的壳聚糖与金属复合成为纳米材料的研究,引起了研究者广泛的关注。人们利用生物分子或生物有机体合成的金属纳米材料反应条件温和、产物形貌可控、重复性高等特点,结合金属纳米材料的"尺寸效应"与生物分子的自身特性来提高两者的协同功能,进一步拓展研究与应用领域的发展。以下针对近年来壳聚糖、壳聚糖体系金属纳米材料的研制及应用等领域进行简要的总结、评述和展望。     

用壳聚糖作为配基载体亲和层析提纯淀粉糖化酶的研究

以自制的壳聚糖作配基载体,植物血球凝集素(PHA)作配基,通过戊二醛交联研制成一种用于淀粉糖化酶提纯的新型亲和吸附剂。对淀粉糖化酶的亲和层析研究表明:提纯倍数为1.8,酶活性收率达80％,纯度经聚丙烯酰胺凝胶等电聚焦电泳(IEF-PAGE)鉴定为一条带,没有非特异性吸附作用。具有简单、安全、快速和高收率等优点。     

壳聚糖和帕米膦酸双修饰的固体脂质纳米粒的制备

目的:制备壳聚糖和帕米膦酸双修饰的固体脂质纳米粒。方法:首先利用课题组发表的专利合成帕米膦酸修饰Brij78的新型非离子表面活性剂(Pa-Brij78),然后以壳聚糖(CS)溶液为水相,Pa-Brij78为乳化剂,E-Wax为油相,采用微乳法,利用修饰的帕米膦酸基团与壳聚糖分子链中质子化的氨基交联反应原理,通过一系列实验条件的探索,确定了最佳实验工艺条件,成功制备了壳聚糖和帕米膦酸双修饰的固体脂质纳米粒。通过动态光散射(DLS)粒径仪测定了纳米粒的粒径大小和Zeta电位;透射电子显微镜(TEM)对CS-Pa-Brij78-SLNs的形貌结构进行了表征。结果:实验结果显示,制备壳聚糖和帕米膦酸双修饰的固体脂质纳米粒的最佳条件为:p H=6.0,壳聚糖浓度分别为0.1%,0.2%;反应温度65℃,反应时间40 min,在该条件下,制备的壳聚糖和帕米膦酸双修饰的固体脂质纳米粒(CS-Pa-Brij78-SLNs)粒径分别为97.9±6.6 nm和182.4±62.2 nm,表面电位分别为(+5.21±1.4m V);(+7.94±0.80 m V),装载姜黄素时,载药量为10%,包封率在90%以上,透射电镜下观察其形态圆整,清晰可见壳聚糖包裹的电晕。结论:本文以壳聚糖(CS)溶液为水相,合成的新型非离子表面活性剂Pa-Brij78为乳化剂,E-Wax为油相,采用微乳化法,经过最佳实验条件的探索,通过一步法成功制备了稳定的壳聚糖和帕米膦酸双修饰的固体脂质纳米粒(CS-Pa-Brij78-SLNs)。     

The synthesis of chitosan-based silver nanoparticles and their antibacterial activity

Chitosan-based silver nanoparticles were synthesized by reducing silver nitrate salts with nontoxic and biodegradable chitosan. The silver nanoparticles thus obtained showed highly potent antibacterial activity toward both Gram-positive and Gram-negative bacteria, comparable with the highly active precursor silver salts. Silver-impregnated chitosan films were formed from the starting materials composed of silver nitrate and chitosan via thermal treatment. Compared with pure chitosan films, chitosan films with silver showed both fast and long-lasting antibacterial effectiveness against Escherichia coli. The silver antibacterial materials prepared in our present system are promising candidates for a wide range of biomedical and general applications.     

壳聚糖金属离子配合物吸附尿素性能研究

由于尿素吸附剂存在吸附容量低、吸附选择性差、生物相容性和血液相容性差等缺点,使人工肾和口服尿素吸附剂的应用受到限制．近几年,尿素吸附材料方面的研究进展较快,主要有：１９９０年,藤田良枝用活性炭作尿素吸附剂,吸附量为９０ｍｇ／ｇ（尿素初始浓度为２１００ｍｇ／Ｌ）,吸附容量低,且微炭粒易脱落,有造成栓塞的危险,不宜作人工肾材料［１］;１９９３年,何炳林等用交联聚丙烯酸固载化氧化β环糊精作尿素吸附材料,吸附容量较高,为８２１ｍｇ／ｇ（尿素的初始浓度为１３００ｍｇ／Ｌ）．由于其利用的是Ｓｃｈｉｆｆ…     

Study on the heterogeneous degradation of chitosan with hydrogen peroxide under the catalysis of phosphotungstic acid

The oxidative degradation of chitosan with H₂O₂ aqueous solution was carried out under the catalysis of phosphotungstic acid in heterogeneous phase. The optimal conditions of degradation were determined by orthogonal tests. The structure of the degraded product was characterized by Fourier-transform infrared spectra (FTIR), diffuse reflectance spectra (DRS) and X-ray diffraction (XRD) analysis. The mechanism of the degradation was correlated with cleavage of the glycosidic bond. The experimental results showed that chitosan can be effectively degraded with H₂O₂ under the catalysis of phosphotungstic acid.     

Probing the role of the divalent metal ion in uteroferrin using metal ion replacement and a comparison to isostructural biomimetics

Purple acid phosphatases (PAPs) are a group of heterovalent binuclear metalloenzymes that catalyze the hydrolysis of phosphomonoesters at acidic to neutral pH. While the metal ions are essential for catalysis, their precise roles are not fully understood. Here, the Fe(III)Ni(II) derivative of pig PAP (uteroferrin) was generated and its properties were compared with those of the native Fe(III)Fe(II) enzyme. The k _cat of the Fe(III)Ni(II) derivative (approximately 60 s⁻¹) is approximately 20% of that of native uteroferrin, and the Ni(II) uptake is considerably faster than the reconstitution of full enzymatic activity, suggesting a slow conformational change is required to attain optimal reactivity. An analysis of the pH dependence of the catalytic properties of Fe(III)Ni(II) uteroferrin indicates that the μ-hydroxide is the likely nucleophile. Thus, the Ni(II) derivative employs a mechanism similar to that proposed for the Ga(III)Zn(II) derivative of uteroferrin, but different from that of the native enzyme, which uses a terminal Fe(III)-bound nucleophile to initiate catalysis. Binuclear Fe(III)Ni(II) biomimetics with coordination environments similar to the coordination environment of uteroferrin were generated to provide both experimental benchmarks (structural and spectroscopic) and further insight into the catalytic mechanism of hydrolysis. The data are consistent with a reaction mechanism employing an Fe(III)-bound terminal hydroxide as a nucleophile, similar to that proposed for native uteroferrin and various related isostructural biomimetics. Thus, only in the uteroferrin-catalyzed reaction are the precise details of the catalytic mechanism sensitive to the metal ion composition, illustrating the significance of the dynamic ligand environment in the protein active site for the optimization of the catalytic efficiency. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Core-shell Au@Co-Fe hybrid nanoparticles as peroxidase mimetic nanozyme for antibacterial application

Nanozymes have been developed as alternative for enzymes to overcome practical limitations of enzymes in industry and medicine. Infectious diseases are becoming severe threat to public health. Hence, peroxidase nanozyme for combating bacteria have been designed. Core-Shell Au@Co-Fe hybrid nanoparticles (Au@Co-Fe NPs) were synthesized. The structure of Au@Co-Fe NPs was characterized by UV–vis and FT-IR spectroscopic methods. The size, zeta potential and spherical morphology of Au@Co-Fe NPs were determined by DLS, TEM and AFM techniques. Au@Co-Fe NPs has been evaluated as peroxidase mimic nanozyme. The peroxidase mimetic activity of gold nanoparticles, Co (II) and Fe (III) were measured and compared with that obtained for native HRP. The enzymatic measured activity was 50% of native horse radish peroxidase. Additionally, Au@Co-Fe NPs was evaluated as antibacterial agent against four selected standard pathogenic bacteria as Escherichia coli, Pseudomonas aeruginosa (as gram negative) and Staphylococcus aureus, and Bacillus cereus (as gram positive).     

Synthesis of biocompatible chitosan decorated silver nanoparticles biocomposites for enhanced antimicrobial and anticancer property

Numerous studies investigated the biosynthesis of silver nanoparticles (AgNPs); however, there is a large gap for the ideal time-consuming process and their cytotoxicity. Herein, for the first time, rapid AgNPs was synthesized in a short time span, using Piper betle leaf (PBL) extract by applying microwave exposure. PB-AgNPs antibacterial activity and cell compatibility were enhanced by capping with chitosan (CS@PB-AgNPs). The synthesized nanoparticles were characterized by bioanalytical techniques. PB-AgNPs expressed significant antibacterial activity against Gram-positive and Gram-negative bacterial pathogens, while hybrid CS@PB-AgNPs presented the enhanced bactericidal activity. In addition, PB-AgNPs exhibited IC₅₀ value of 140 μg/mL against RAW 264.7 macrophages and 100 μg/mL against lung cancer cells while, CS capping reduced its toxicity at IC₅₀ values of 400 μg/mL and 180 μg/mL respectively were affirmed by MTT, apoptosis and DNA damage detection. Overall it was demonstrated that CS capping could be a phenomenal finding to improve the biomedical potential of AgNPs.     

Interaction of peptide substrate outside the active site influences catalysis by CaMKII

The interaction of calcium/calmodulin-dependent protein kinase II (CaMKII) with the NR2B subunit of N-methyl-D-aspartate-type glutamate receptor is thought to be one of the important events leading to synaptic plasticity. CaMKII binds NR2B by its catalytic site and by the autophosphorylation site binding pocket (APBP), a non-catalytic site. Mutagenesis of Glu-236, a residue in the APBP of CaMKII that is likely to be interacting with NR2B, influences phosphorylation of NR2B. The phosphorylation of syntide-2, a classical catalytic site substrate of CaMKII, is influenced to a much lesser extent by this mutation. Taken together these results indicate that interaction of NR2B at the non-catalytic site of CaMKII influences catalysis. Our data suggest that kinetic models of peptide substrate phosphorylation by CaMKII should incorporate the non-catalytic mode of binding of peptides that is dependent on the sequence of the peptide.