重氮树脂的合成

重氮树脂的合成曹曙光赵超曹维孝＊（北京大学化学与分子工程学院北京１００８７１）关键词重氮树脂，合成，多聚甲醛１９９７－０２－０４收稿，１９９７－０７－１４修回国家自然科学基金资助课题二苯胺重氮盐与甲醛缩合生成的重氮树脂由于其感光速度快，亲墨性好，又易...     

罗丹明B聚合物修饰单壁碳纳米管薄膜电极的制备、表征及一氧化氮活体分析应用

以单壁碳纳米管作为电极材料,基于减压过滤和电聚合方法制备了一种薄膜型一氧化氮(NO)电化学传感器。扫描电镜、红外光谱和电化学交流阻抗表征表明,减压过滤可以制备出导电性好、电分析性能优良的薄膜电极,而罗丹明B能通过电聚合在其表面形成高比表面的纳米敏感结构。这种薄膜型电化学传感器对NO具有灵敏的电化学响应,其安培氧化电流与NO浓度在7.2×10-8~2.5×10-5mol/L范围内呈良好的线性关系,检出限(S/N=3)达3.6×10-8mol/L。将该传感器紧贴在麻醉豚鼠的肝脏表面,成功实现了肝组织细胞在L-精氨酸刺激下NO释放的实时监测。     

铱与硫氰酸钾和罗丹明B的显色反应

铱的光度测定方法目前国内外报道不是很多.尤其摩尔吸光系数能达到10~5的高灵敏度方法更是少见.曾见有报道的方法有:用1,5-二苯苄巴腙的吸光光度法,Ir(Ⅳ)-氧化亚锡-2-巯基苯并噻唑的显色反应测定铱.但理想的显色剂罗丹明B(RhB)用于光度法测定铱尚未见报道.我们研究了在聚乙烯醇(PVA)存在下,离子缔合物体系;Ir(Ⅳ)-KSCN-RhB显色反应的形成条件、组成、线性范围、选择性等.试验证明,反应的适宜酸度为pH3.2～3.6(盐酸-邻苯二甲酸氢钾缓冲体系),缔合物的最大吸收波长599.3nm,摩尔吸光系数为1.58×I0~5.铱量在0～7μg/25ml时服从比耳定律.该体系的组成比为lr~(4 ):SCN~-:RhB~ =1:6:2.本法有较高的灵敏度和选择性,是水     

离子型超交联聚合物吸附罗丹明B

为了高效吸附废水中的可溶性有机染料,以4-苯胺基苯磺酸钠和苯为单体,二甲氧基甲烷为交联剂,在无水FeCl₃催化下,经过付-克反应一步合成了磺酸钠离子(―SO₃Na)修饰的超交联聚合物(HCP-SO₃Na)。通过元素分析、红外光谱、N₂吸/脱附分析、固态核磁共振波谱和热重分析对HCP-SO₃Na的结构和热性能进行了表征。结果表明,HCP-SO₃Na是一种比表面积大、热稳定性强的无定形微孔有机聚合物,比表面积为587m₂/g,微孔面积为411m₂/g。通过对阳离子染料罗丹明B(RhB)的吸附研究表明,―SO₃Na基团的引入,可增加HCP对RhB的饱和吸附量,最大吸附量达431mg/g,吸附符合准二级动力学模型和Langmuir模型,且循环吸附5次之后,吸附性能无明显降低。     

罗丹明B显色检测Fenton反应产生的羟自由基

提出Fe2 H2O2 罗丹明B分析新体系并用于羟自由基的检测。方法用Fenton反应产生羟自由基,加入显色剂罗丹明B,羟自由基使罗丹明B的颜色发生变化,通过紫外 可见分光光度计测其ΔA值的变化,可间接测定羟自由基产生的量。通过测定条件的研究,探讨了最佳实验条件。该方法稳定,可作为一种简便的筛选抗氧化剂的方法。     

取代二苯胺重氮盐、重氮树脂合成及光、热分解性质

二苯胺型重氮树脂是阴图PS版最重要的感光剂^[1],关于它的应用已有许多专利^{[2 5]}.作为一种预涂感光版,阴图PS版的贮存期要求在一年以上,从而对作为感光剂的重氮树脂的热稳定性有较高的要求,希望其热分解温度尽量高一些并能在潮热气候下性质稳定.一般来说,二苯胺重氮盐的苯环上带取代基时,有利这些性质的改善,如3-甲氧基二苯胺-4-重氮盐树脂就是一个例子,它已获得广泛的应用^[6,7].     

溴金酸-罗丹明B和氯金酸-罗丹明6G超高灵敏显色反应的研究——离心光度法测定金

本文研究了一个超高灵敏的测定金的方法,离心光度法。在Au-Br-RB体系中络合物λ_(max)=559nm,表观摩尔吸光系数ε_(559)=3.39×10~(11)L·mol~(-1)·cm~(-1),Au(Ⅲ)浓度(0.20×10~(-5)～2.5×10~(-5)μg/10 ml呈线性关系;Au-Cl-R6G体系络合物λ_(max)=531 nm,表观摩尔吸光系数ε_(531)=2.52×10~8L·mol~(-1)·cm~(-1),Au(Ⅲ)浓度(0.20×10~(-2)～2.4×10μg/10ml。呈线性(Ⅲ)关系。本法已用于某些低品位矿样中金的分析,分析结果与标准值相吻合。探讨了超高灵敏的显色反应机理。     

重氮树脂与银纳米颗粒自组装膜的图像化

从巯基乙酸包覆的银纳米颗粒(MA-AgNP)和重氮树脂(DR)由自组装方法, 制备了感光性的超薄膜. 在掩模(photomask)覆盖下对膜进行选择性曝光和紧接着的十二烷基硫酸钠水溶液显影, 未光照部分的膜被显影液完全洗脱, 而光照部分的膜不能洗脱, 从而形成清晰的图像. 用AFM和SEM对图像进行了表征.     

丁基罗丹明B-铜钨杂多酸光度法测定微量铜

在聚乙烯醇（ＰＶＡ）存在下，丁基罗丹明Ｂ（ＢＲＢ）与铜钨杂多酸形成离子缔合物。缔合物的形成条件为ｃＨ２ＳＯ４＝１．２ｍｏｌ／Ｌ，ｃＷＯ２－４＝６．１×１０－５ｍｏｌ／Ｌ，ｃＢＲＢ＝３．８×１０－５ｍｏｌ／Ｌ和ＰＶＡ０．０８％。缔合物的最大吸收波长位于５７０ｎｍ，摩尔吸光系数ε＝１．６６×１０６Ｌ·ｍｏｌ－１·ｃｍ－１，铜量在每２５ｍＬ０～０．５μｇ范围内服从比耳定律，检测限为每ｍＬ０．６５ｎｇ（ｎ＝１２），对每ｍＬ１８ｎｇＣｕ测定的ＲＳＤ为０．８５％（ｎ＝１０）。缔合物至少稳定１５０ｈ，其摩尔比为Ｃｕ∶Ｗ∶ＢＲＢ＝１∶１２∶５，红外图谱表明铜钨杂多酸具有Ｋｅｇｇｉｎ结构。考察了４０多种共存离子的影响，大多数常见元素不干扰。本法已用于天然水、自来水、降水、人发、中药和蔬菜中铜的测定，结果满意。     

具有荧光增强性能的罗丹明B衍生物的合成及其对汞离子的检测

利用汞离子可以诱导罗丹明B衍生物的螺环结构发生开环反应并产生荧光增强效果这一特性,设计并合成了两种新型的荧光化学传感器2-噻吩甲醛罗丹明B酰肼(RhBTh)和苯甲醛罗丹明B酰肼(RhBAr),并研究了二者在汞离子检测中的应用.研究结果表明,RhBTh与RhBAr对汞离子均表现出非常好的荧光增强效果,检测过程中其它金属离子不会对检测结果产生明显的干扰.二者对汞离子的检测限分别为7.8 nmol/L和12.5 nmol/L.实验表明RhBTh和RhBAr对汞离子均具有良好的灵敏度和选择性.     

Simultaneous Determination of Fluorescein, Rhodamine 6G and Rhodamine B in Turbid Solution by Polarization Variable-Angle Synchronous Fluorescence Spectrometry

Fluorescencespectron1etry,inpractice,ishardto'beappliedtomulti-componentanalysisduetothespectraloverlapofcomplexn1ixtures.MoredVer,enVironmentalsan1plesandbiologicalsamplesareoftenturbidiand'the'directdetern1intitjodsofsuchsampleswouldsufferfromthesignificantinterferenceofscatteringlight.Synchronousfluorescencespectrol11etryisbecomingpopularconcerningitssimpIicity,selectivityandsensitivityindealingwithcomplexsamples.Onedrawbacktoconventionalconstant-wavelengthsynchronousfluorescencespectromet…     

Rhodamine 101 Conjugates of Triterpenoic Amides Are of Comparable Cytotoxicity as Their Rhodamine B Analogs

Pentacyclic triterpenoic acids (betulinic, oleanolic, ursolic, and platanic acid) were selected and subjected to acetylation followed by the formation of amides derived from either piperazine or homopiperazine. These amides were coupled with either rhodamine B or rhodamine 101. All of these compounds were screened for their cytotoxic activity in SRB assays. As a result, the cytotoxicity of the parent acids was low but increased slightly upon their acetylation while a significant increase in cytotoxicity was observed for piperazinyl and homopiperazinyl amides. A tremendous improvement in cytotoxicity was observed; however, for the rhodamine B and rhodamine 101 conjugates, and compound 27, an ursolic acid derived homopiperazinyl amide holding a rhodamine 101 residue showed an EC₅₀ = 0.05 µM for A2780 ovarian cancer cells while being less cytotoxic for non-malignant fibroblasts. To date, the rhodamine 101 derivatives presented here are the first examples of triterpene derivatives holding a rhodamine residue different from rhodamine B.     

核酸与丁基罗丹明B体系的共振散射光谱

在pH1.1的条件下，丁基罗丹明B在335、380、420和440nm有4个共振散射峰，加入核酸后，共振散射峰强度大增，其散射光强度与核酸的浓度呈线性关系，YRNA、FSDNA、CTDNA的线性方程分别为I＝2.74 10.64C、I＝2.08 16.19C、I＝2.98 6.08C(mg/L），基于此建立了具有较高灵敏度、操作简单的核酸测定,针该方法用于核酸人工合成样品的测定，结果令人满意。     

A new tripodal rhodamine B derivative as a highly selective and sensitive fluorescence chemosensor for copper(II)

A new tripodal rhodamine B derivative 2 was designed and synthesized by tripodal trialdehyde and rhodamine B hydrazide for the first time. This derivative could be used as a fluorescent chemosensor for the selective and sensitive determination of copper(II) in Tris-HCl buffer and ethanol aqueous mixed media. Under the optimum conditions described herein, fluorescence enhancement at 557/577 nm was linearly related to the concentration of copper(II) in the range of 0.10 to 10.00×10⁻⁵ mol·L⁻¹, with a correlation coefficient of R ²=0.9964 (n=15) and a detection limit of 1.129×10⁻⁷ mol·L⁻¹ (the relative standard deviation for five repeated measurements at 4.00×10⁻⁵ mol·L⁻¹ Cu(II) was 2.2%). The absorbance measurements at 557 nm were linearly related to the concentration of Cu(II) in the range of 0.50 to 25.00×10⁻⁵ mol·L⁻¹, with a correlation coefficient of R ²=0.9948 (n=13) and a detection limit of 3.338×10⁻⁷mol·L⁻¹. Supported by the Foundation of the Governor of Guizhou Province, China (Grant No. 200617) and the Talented Person Foundation of Guizhou University (Grant No. 2007039)     

Dextran Fluorescent Probes Containing Sulfadiazine and Rhodamine B Groups

Fluorescent imaging has been expanded, as a non-invasive diagnostic modality for cancers, in recent years. Fluorescent probes in the near-infrared window can provide high sensitivity, resolution, and signal-to-noise ratio, without the use of ionizing radiation. Some fluorescent compounds with low molecular weight, such as rhodamine B (RhB) and indocyanine green (ICG), have been used in fluorescent imaging to improve imaging contrast and sensitivity; however, since these probes are excreted from the body quickly, they possess significant restrictions for imaging. To find a potential solution to this, this work investigated the synthesis and properties of novel macromolecular fluorescent compounds. Herein, water-soluble dextran fluorescent compounds (SD-Dextran-RhB) were prepared by the attachment of RhB and sulfadiazine (SD) derivatives to dextran carrier. These fluorescent compounds were then characterized through IR, ¹H NMR, ¹³C NMR, UV, GPC, and other methods. Assays of their cellular uptake and cell cytotoxicity and fluorescent imaging were also performed. Through this study, it was found that SD-Dextran-RhB is sensitive to acidic conditions and possesses low cell cytotoxicities compared to normal 293 cells and HepG2 and HeLa tumor cells. Moreover, SD-Dextran-RhB demonstrated good fluorescent imaging in HepG2 and HeLa cells. Therefore, SD-Dextran-RhB is suitable to be potentially applied as a probe in the fluorescent imaging of tumors.     

苯基乙酰丙酮-罗丹明B衍生物的合成及对Fe~(3+)离子的识别性质研究

通过罗丹明内酰胺与苯基乙酰丙酮一步缩合反应得到结构简单的席夫碱型罗丹明B衍生物,结构经X-ray单晶衍射、NMR、MS以及元素分析表征。在目标化合物的乙醇-水缓冲溶液中,加入Fe3+后能诱导罗丹明基团螺环结构开环,形成1:1的金属配合物,同时观察到显著的荧光增敏和吸收增强并具有较高的选择识别性能。电化学,色谱及光谱分析证实了配合物的形成。竞争实验显示识别响应为可逆过程。     

用钼酸盐和罗丹明B连续光度法测定铈和钪

聚乙烯醇存在下，铈或钪钼杂多酸与罗丹明Ｂ（ＲＢ）形成离子缔合物，最大吸收均位于５７０ｎｍ，摩尔吸光系数分别为１．１６×１０＾６和５．６２×１０＾５Ｌ．ｍｏｌ＾－１．ｃｍ＾－１，ｃｍ＾－１，０－１．２μｇ／２５ｍＬＣｅ和０－２．０μｇ／ｍＬＳｃ服从比耳定律，检测限１．５ｎｇ／ｍＬＣｅ（ｎ＝１０）和１．１ｎｇ／ｍＬＳｃ（ｎ＝９）。缔合物的摩尔比为Ｃｅ：ｍＯ：ＲＢ＝１：６：３和 Ｓｃ：Ｍｏ：ＲＢ＝１：１