Cleavable ester-linked magnetic nanoparticles for labeling of 5 solvent-exposed primary amine groups

羧酸配体金属Co配合物的合成、结构及磁性刘航诚;阿娜尔古丽·吾甫尔;潘言亮;孙佳仪;张朔;王多志【期刊名称】《合成化学》【年(卷),期】2024(32)6【摘要】羧酸配体配合物在气体吸附/分离、催化、光学和磁学等众多领域均有潜在的应用价值。

以5-氨基间苯二甲酸(5-H_(2)AIPC)和吡嗪甲酸(2-HPC) 2种羧酸作为配体,在溶剂热条件下与氯化钴反应,合成2种新型金属钴配合物{[Co_(2)(μ_(3)-OH_(-))_(2)(5-HAIPC)(2-PC)]}_n(1)和{[Co_(2)Cl_(2)(2-PC)_(2)(H_(2)O)_(3)]}_n(2)。

通过X-射线单晶衍射、红外光谱和热重分析对配合物1和2的结构进行了表征。

X-射线单晶衍射结果表明:配合物1属于C2/c空间群,由椅式四核簇经5-氨基间苯二甲酸和吡嗪甲酸2种配体连接形成三维框架结构。

配合物2属于P2_1/c空间群,由配体吡嗪甲酸与金属中心Co2连接形成无限延伸的一维链,配体吡嗪甲酸与Co1连接形成二维层状结构,金属中心Co1和Co2通过配体连接进而通过氢键组装成1个三维超分子结构。

对2种配合物的磁性进行测试研究,结果表明:配合物1和2均呈反铁磁性。

【总页数】9页(P542-550)【作者】刘航诚;阿娜尔古丽·吾甫尔;潘言亮;孙佳仪;张朔;王多志【作者单位】新疆大学化学学院【正文语种】中文【中图分类】O622.5【相关文献】1.由联苯三羧酸配体构筑的零维四核镍(Ⅱ)配合物和一维锰(Ⅱ)配位聚合物的合成、晶体结构及磁性质2.两个包含联苯三羧酸配体的铜(Ⅱ)和锰(Ⅱ)配合物的合成、晶体结构及磁性质3.以吡啶-2,5-二羧酸或噻吩-2,5-二羧酸为配体的过渡金属配合物的合成、晶体结构及性质4.由吡啶-三羧酸配体构筑的锌(Ⅱ)和锰(Ⅱ)配合物的合成、晶体结构、荧光及磁性质5.基于含双吡唑的四羧酸配体构筑的Fe(Ⅱ)/Co(Ⅱ)同构配合物的合成、晶体结构及磁性质因版权原因，仅展示原文概要，查看原文内容请购买。

聚合物包覆的超顺磁性Fe3O4纳米粒子万守荣1，郑月娥1，刘源钦1，阎虎生1，刘克良21南开大学高分子化学研究所，天津3000712军事医学科学院毒物药物研究所，北京100850关键词：磁性纳米颗粒，磁流体，纳米材料，聚（甲基）丙烯酸甘油单酯稳定地分散于载液中的超顺磁性纳米粒子如Fe3O4称磁流体。

磁流体广泛用于细胞分离、药物控释、免疫试验、磁共振诊断增强剂和肿瘤热疗等[1,2]。

在磁流体的应用中其关键性能之一是其磁性纳米粒子的表面性能（如生物相容性等）和表面功能基（用于固载配体等）。

由于铁磁性的纳米粒子具有非常高的表面能，纳米粒子有很高的聚集的倾向。

因此磁流体中的铁磁性的纳米粒子必须有稳定剂才能稳定存在，常用的稳定剂有双电层稳定剂[3]和有机表面活性剂[4]，这些稳定剂稳定的磁流体由于其稳定性较低，在某些应用中磁性纳米粒子会聚集。

也有用天然或合成聚合物作为稳定剂制备磁流体[5,6]。

本文采用丙烯酸甘油单酯和甲基丙烯酸甘油单酯的均聚物或含聚丙烯酸甘油单酯（PGA）或聚甲基丙烯酸甘油单酯（PGMA）的二嵌段共聚物作为稳定剂，合成了非常稳定的水基磁流体，在这些磁流体中，聚丙烯酸甘油单酯或聚甲基丙烯酸甘油单酯吸附于Fe3O4纳米粒子表面上，而嵌段共聚物的另一段伸展向水相中，这样可通过改变伸展向水相中的这一段聚合物，来合成磁性纳米粒子具有特定表面特性或特定功能基的磁流体。

PGA和PGMA是分别通过酸性水解其前体聚合物－聚丙烯酸-2,2-二甲基-1,3-二氧戊烷-4-甲基酯(PSA)和聚甲基丙烯酸-2,2-二甲基-1,3-二氧戊烷-4-甲基酯(PSMA)得到，PSA 和PSMA通过ATRP合成。

嵌段共聚物聚丙烯酸－聚丙烯酸甘油单酯（PAA-b-PGA）、聚甲基丙烯酸-2-(N,N-二甲氨基)乙基酯－聚甲基丙烯酸甘油单酯（PDMAEMA-b-PGMA）、聚乙二醇单甲醚－聚丙烯酸甘油单酯（MPEG-b-PGA）分别通过其前体聚合物聚丙烯酸叔丁酯－聚丙烯酸-2,2-二甲基-1,3-二氧戊烷-4-甲基酯、聚甲基丙烯酸-2-(N,N-二甲氨基)乙基酯－聚甲基丙烯酸-2,2-二甲基-1,3-二氧戊烷-4-甲基酯、聚乙烯醇单甲醚－聚丙烯酸-2,2-二甲基-1,3-二氧戊烷-4-甲基酯的脱保护而得到，这几种前体嵌段共聚物都是通过ATRP法合成的。

Magnetic Separation TechnologyPowering reliability for nucleic acid captureDynabeads® MyOne™ SILANEMagnetic Separation TechnologyNucleic acid capture Dynabeads® magnetic separation technology Rapid and automatable protocols→Absolute consistency reduces assay variability→One bead, numerous possibilities for nucleic acid capture →Dynal® was founded in 1986, and is built on the Norwegian invention of bead-based mag-netic separation technology. The making of spherical polystyrene magnetic beads of exactly the same size allowed researchers to get results that were previously unattainable.Dynabeads® are well established as the gold-standard magnetic separation method, and are integrated in more than 25,000 automated assay platforms worldwide. Their qual-ity is renowned in academia as well as in the diagnostic industry, and they meet important criteria for OEM use in biotech and IVD. The attraction is simply magnetisk!*A new solution for sample preparationMethods for nucleic acid capture by adsorption to a silica-like surface have been around for decades. Magnetic particles are now the material of choice with system manufacturers, as magnetic separation is easy to adapt to automated processes.Invitrogen’s Dynal® division has developed a new solution for rapid and reliable nucleic acid capture. Dynabeads® MyOne™ SILANE are uniform, monosized magnetic beads, 1 μm in diameter (Figures 1 and 2). They are composed of highly cross-linked polystyrene combined with evenly distributed magnetic material and an optimized silica-like surface chemistry.20 µm A2 µm B Figure 1—No compromises on reproducibility. A. Magnetic particles from other suppliers often have a random size and surface area. B.Dynabeads® MyOne™ SILANE are monosized 1 µm magnetic beads with a large and well-defined surface area, which translates to highly reproducible results in your applications.* Magnetisk is the Norwegian word for magnetic.23Figure 2—Dynabeads® are monosized. The graph shows size frequency distribu-tion of Dynabeads® MyOne™ SILANE (red) and magnetic particles from four alternative suppliers, as analyzed by flow particle image analysis on a Sysmex FPIA-3000 (Malvern Instruments Ltd.). The second peak for Dynabeads® at 2 µm represents doublets. Monosized Dynabeads® ensure optimal, predict-able behavior in automated systems. Minimal variation within and between lots allows for standardized and reproducible processes.% S i z e d i s t r i b u t i o n510152025Size (µm)Their small size and defined surface area offer excellent reaction kinetics. These new Dynabeads® have an increased magnetic strength compared to the traditional Dynabeads® portfolio (Figure 3). This ensures rapid magnetic mobility and efficient isolation even in viscous samples. Combined with a low sedimentation rate, these qualities make the beads particularly well suited for automated molecular applications.Dynabeads® MyOne™ SILANE offer enhanced performance beyond the capabilities provided by alternative magnetic separa-tion systems. The product has been developed to meet the high requirements of solid-phase sample preparation for diagnostic and biotech OEM customers.One bead, numerous possibilitiesThe protocol is simple, scalable, and automatable (Figure 4). Dueto their versatile silica-like surface chemistry, the Dynabeads® serve as a flexible platform product for capture of nucleic acids:Genomic DNA (Figures 5 and 6) →Viral DNA/RNA (Figures 7, 8, and 9) →Total RNA→Other nucleic acids (e.g., bacterial DNA)→Dynabeads® are compatible with a variety of buffer systems (Figure 10). Specific buffers and protocols are available for selected applications. We are eager to help further optimize buffers and pro-tocols on an OEM level, to meet the needs of your specific assay.Figure 3—More iron means shorter assay times. Dynabeads® MyOne™ SILANE have an increased iron content compared to the traditional Dynabeads® port-folio (MyOne™, M-270, and M-280). The tightly controlled bead size and iron content ensure consistent high performance and high magnetic mobility. Combined with a slow sedimentation time, this allows for shorter assay times and improved capture efficiency even in highly viscous samples.100150200250300350400450500m g F e /g D y n a b e a d s ®50Dynabeads ®M-280Dynabeads ®M-270Dynabeads ®MyOne ™Dynabeads ®MyOne ™ SILANE4Magnetic Separation TechnologyFigure 5—Linear yields and high integrity of genomic DNA from blood. A. gDNA was isolated from varying amounts of human whole blood (150–350 μl) containing known numbers of WBCs. Yield was measured spectrophotometrically. B. The isolated gDNA is of high integrity. 10 μl (1/10th) of the gDNA isolated from different starting volumes of blood (100–350 μl), was loaded onto the gel. MW: molecular weight marker (λ DNA ladder).ABFigure 4—Quick and automatable magnetic separation protocol. The illustration shows the simple steps (lyse, bind, wash, and elute) of the automatable protocol for nucleic acid capture from a variety of biological samples using Dynabeads® MyOne™ SILANE.200 µl 300 µl 350 µl 100 µl MWBlood volume (µl)g D N A y i e l d (µg )246810120Starting sample containingnucleic acidsLyse and bind WashElute5Figure 6—Benchmarking yield and purity. gDNA was isolated from whole blood following respective suppliers’ protocols. Dynabeads® and the alternative magnetic particles provide comparable high yields (μg/106 WBC). Dynabeads® consistently show good yield and purity with a high level of reproducibility.g D N A p u r i t y a n d y i e l dcolumnmagnetic particleMyOne™ SILANE10234657Figure 7—Sensitive detection of HBV virus. Known amounts of HBV were spiked into 200 µl serum samples: 4,000 (blue), 400 (red), and 40 (black) copies. The isolated HBV DNA was eluted in 100 µl, of which 10 µl was used for qPCR. Only Dynabeads® MyOne™ SILANE enabled HBV detection in the most dilute samples.®MyOne ™ SILANE50100150200250# H B V c o p i e s d e t e c t e d f r o m s p i k e d s e r u mFigure 9—Sensitive and reproducible isolation of lentivirus RNA. Dynabeads® MyOne™ SILANE (4 different batches) were used to isolate lentivirus RNA from spiked human plasma samples. The extractions were done on an automated iPrep™ Purification Instrument (Invitrogen). Positive control: manual extraction using the PureLink™ Viral RNA/DNA Mini Kit (Invitrogen). Following reverse transcription and qPCR analysis, outstanding reproducibility is seen across all batches.Figure 8—Linear scalability of HBV isolation procedure. HBV DNA was isolated from patient serum heavily infected with HBV, using the Dynabeads® SILANE Viral NA Kit automated protocol on a Precision System Science platform. Theisolated HBV DNA was analyzed using quantitative PCR.1502025C tC t5010152535203040HBV serial dilution factor6Magnetic Separation TechnologyDynabeads® make good business senseDynabeads® MyOne™ SILANE hold reputable Dynal® high stan-dards, with unique batch-to-batch reproducibility. Quality is built into the product during comprehensive R&D and process devel-opment. Here are some of the many advantages offered:One bead suitable for all nucleic acid sample preparations→(using application-specific buffers and protocols)Higher reproducibility than with magnetic particles from→alternative suppliersSuperior sensitivity, allowing for low detection limits →Predictable binding capacity→Highly consistent dynamic range→Excellent integrity and purity of isolated nucleic acids →Flexible sample, reaction, and elution volumes →Quick protocols with reduced manual handling→Integration of sample preparation into open and closed→automated systemsInspired by the Norwegian invention of bead-based magnetic sep-aration technology and driven by your needs and challenges, we are committed to delivering absolute consistency and to offering the safest choice for nucleic acid capture. It’s simply magnetisk !Figure 10—Dynabeads® can be used with different buffer systems. The graphs show (A) specific yield and (B) purity (A 260/A 280) of DNA isolated using alternative magnetic particles and buffer systems. Human serum (100 μl) spiked with 5 µg of λ DNA ladder was used as a model system. Yield and purity were measured spectrophoto-metrically. Comparable results are seen with an RNA ladder (not shown). Dynabeads® MyOne™ SILANE (red) outperforms the alternative magnetic particles (blue, purple, and yellow). Note that Dynabeads® MyOne™ SILANE give better yield and purity than other suppliers’ separation products in their buffer systems.I s o l a t e d D N A (% o f t o t a l D N A )buffer system ® buffer system buffer system buffer system 200406080120100A 260/A 2801.51.31.71.92.12.32.5buffer system ® buffer systembuffer system buffer system ABOrdering InformationProduct Quantity* Cat. no.Dynabeads® MyOne™ SILANEManufactured under validated production processes. Can be supplied in bulk quantities. 5 ml (40 mg/ml) 370-02D Dynabeads® SILANE Viral NAContains Dynabeads MyOne™ SILANE and specific buffers optimized for sensitive isolation 96 isolations 370-11D of viral DNA/RNA from human serum/plasma samples.Dynabeads® SILANE Genomic DNAContains Dynabeads MyOne™ SILANE and specific buffers optimized for predictable isolation 96 isolations 370-12D of gDNA from human whole blood.*Alternative product formats are available.Dynabeads® for specific capture of nucleic acids A comprehensive range of Dynabeads® for specific capture of nucleic acids is also available, with different bead sizes and surface functionalities. Some Dynabeads® are precoated with streptavidin, allowing for capture of biotinylated nucleic acids in a wide variety of protocols. Other Dynabeads® have a specific surface chemistry for coupling of nucleic acids (e.g., hybridization probes/primers) and/or other ligands.Custom developmentWe are able to work with our customers to further optimize buffers and protocols and to develop, improve, or automate nucleic acid capture. Validation and customization on an OEM level are also available.If you would like to discuss a potential collabora-tion or OEM agreement, please contact us by email at ivd@.7 ©2008 Invitrogen Corporation. All rights reserved. These products may be covered by one or more Limited Use Label Licenses (see Invitrogen catalog or ). By use of these products you accept theterms and conditions of all applicable Limited Use Label Licenses. For research use only. Not intended for any animal or human therapeutic or diagnostic use, unless otherwise stated. B-075596-r1 0308。

AsianToxicologyResearchdoi:10.53388/ATR2021110103

1Submitamanuscript:https://www.tmrjournals.com/atr

Nanotoxicity:toxicityofmetalnanoparticlesYifeiWu1,2,DongyunZhao1,2,Ebuka-OlisaemekaNwafor3，PengLu2*

1Graduateschool,AnhuiUniversityofTraditionalChineseMedicine,Hefei,Anhui230012,China;2Departmentofpharmacy,SuzhouTCMHospitalAffiliatedtoNanjingUniversityofChineseMedicine,Suzhou,Jiangsu215009,China;3StateKeyLaboratoryofComponent-BasedChineseMedicine,TianjinUniversityofTraditionalChineseMedicine,Tianjin301617,China.*Correspondingto:PengLu.SuzhouTCMHospitalAffiliatedtoNanjingUniversityofChineseMedicine,No.18,YangsuRoad,GusuDistrict,Suzhou,Jiangsu215009,China.Email:****************.

Abbreviations:SNPs,silvernanoparticles;NPs,nanoparticles.Competinginterests:Theauthorsdeclarethattheyhavenoconflictofinterest.Citation:WuYF,ZhaoDY,NwaforEO,LuP.Nanotoxicity:toxicityofmetalnanoparticles.AsianToxicolRes.2021;3(4):18.doi:10.53388/ATR2021110103.