5-异硫氰酸酯荧光素的合成与荧光性能研究

对标题化合物的合成进行了系统研究,以4-硝基邻苯二甲酸、间苯二酚为原料,甲磺酸为缩合剂,乙酸酐为酰化剂、九水硫化钠为还原剂,经缩合、乙酰化、还原制得5-氨基荧光素,再在二硫化碳-三乙胺-铁盐体系下经异硫氰酸化制得.目标产物结构经1 HNMR、13 CNMR、MS及IR表征,并测试了其荧光性能.与文献报道醇碱皂化再还原路...     

C36二聚脂肪酸聚乙二醇聚酯硫酸酯盐的制备及性能表征

以C36二聚脂肪酸(简称二聚酸)和聚乙二醇为原料,缩聚后得到聚酯,再用氨基磺酸硫酸化,制备了新型的C36二聚脂肪酸聚乙二醇聚酯硫酸酯盐型两性高分子表面活性剂,并对其性能进行了研究。聚酯适宜的制备工艺条件是:在0.097 MPa下,n(二聚酸)∶n(聚乙二醇)=1∶1.2,催化剂w(SnC l2)=0.3%(相对于反应物总质量),反应温度200℃,反应时间6 h,酯化率达到98.11%。聚酯平均相对分子质量为613 5,相对分子质量分布系数为1.212。优化的C36二聚脂肪酸聚乙二醇聚酯硫酸酯盐的制备条件是:尿素为催化剂,n(二聚酸聚乙二醇聚酯)∶n(NH2SO3H)∶n(尿素)=1∶1.2∶1.2,反应温度130℃,反应时间2.8 h,聚酯端羟基硫酸酯酯化率达81.17%。表面性能分析结果为:产物γCMC(25℃)为3.021 mN/m,与十二烷基硫酸钠(K12)相当;CMC(25℃)为1.07 mmol/L,远低于K12;乳化性能和乳化稳定性与壬基酚聚氧乙烯醚(OP-10)相当。与K12相比,产物起泡性差但表现出很好的抑泡性能。该工作的新颖性已为河南省科学技术情报研究所2005年12月15日出具的第2005 c0006号《论文查新报告》所证实。     

硫酸铈催化丙烯酸烷氧基醚酯的合成及表征

以丙烯酸为原料,通过亲核加成反应合成了β-丙烯酰氧基丙酸,然后与乙二醇单甲醚反应,得到β-丙烯酰氧基丙酸甲氧基乙酯.讨论了不同影响因素如催化剂、阻聚剂对转化率的影响.分别用红外光谱、核磁共振氢谱、气相色谱-质谱联用等表征了产物.结果表明选择催化剂硫酸铈(用量为反应单体总质量的5%)、阻聚剂邻甲氧基酚和压缩空气的通入有利于提高酯化反应的速率和产物收率.     

月桂酸二聚甘油酯硫酸酯钠盐的制备与表面性能

以二聚甘油和月桂酸为原料进行酯化反应得到月桂酸二聚甘油酯,再与氯磺酸反应,经氢氧化钠中和制得月桂酸二聚甘油酯硫酸酯钠盐(SLDGS)。对中间体和产物进行了红外光谱分析,测定了产物在298 K下的表面化学性能。发现SLDGS水溶液的表面张力随着月桂酸酯化度的升高而增大,酯化度为25%时,最低表面张力为28.5 mN.m-1,临界胶束浓度为1.15 mmol.L-1;在煤油和苯中,当酯化度为30%时,SLDGS水溶液的乳化性能达到最大值,乳化时间为168 s;SLDGS水溶液的泡沫性能不佳。     

壳聚糖硫酸酯制备研究进展

壳聚糖是自然界广泛分布的天然高分子多糖,结构中含有活泼的羟基和氨基,可进行多种化学修饰,磺化修饰的壳聚糖具有类肝素的结构和特征反应,可为研制类肝素物质奠定基础。本文对国内外磺化壳聚糖的制备方法进行综述。     

聚酸酐硅基酯的制备与表征

以聚己二酸酐（PAA）和氯硅氧烷Si3C6H18O2C12（Si3）和Si5C10H30O4C12（Si5）为单体合成聚己二酸酐硅基酯。所得样品用1H-NMR、DSC、TGA和测特性黏数等手段对其进行了表征。考察了反应过程中反应时间、溶剂等因素的影响。所得样品用1H-NMR，DSC-TGA进行分析，结果较理想。测得多组样品特性黏数，显示所得产物具有高分子的特性。     

硫酸改性高岭土的制备及表征

为了对比高岭土改性前后的结构变化,将鄂尔多斯高岭土分别用10%、20%、30%、40%、50%的硫酸进行改性,得到酸改性高岭土样品。采用IR、XRD、SEM、BET、EDS等对样品进行表征分析。结果表明,由于硫酸的吸水性,随着酸浓度的增加,脱除高岭土中吸附水的能力越强;酸改性浓度的变化对高岭土的结构影响不大;改性后的高岭土比表面积减小,表面粗糙度增加,密集堆积,凝结成块状,有堆积孔道出现;硫酸改性会使高岭土中大量的铝被浸出。     

可生物降解聚苹果酸丁二醇酯弹性体的制备及表征

以苹果酸和1,4-丁二醇为单体通过熔融缩聚制备出来了一种新型的可生物降解弹性体材料——聚苹果酸丁二醇酯（PBM）,初步研究了材料的亲水性能和降解性能,并对材料的结构进行了初步表征。研究结果表明：PBM的聚集态结构为无定形态,透明柔软,玻璃化转变温度在0℃以下;通过调节合成单体的物质的量比,改变预聚物的后期固化时间,控制后期固化交联（反应）时间等手段,实现了降解性能可控,吸水率可调节的目标。     

Preparation and photophysical behaviors of fluorescent chitosan bearing fluorescein: Potential biomaterial as temperature/pH probes

A novel method for attaching fluorescein (via its epoxy derivative) to water‐soluble chitosan, and the temperature/pH‐sensitive qualities of fluorescence were investigated. 3‐Epoxypropoxy fluorescein (EPF) was firstly synthesized by the reaction between fluorescein and epichlorohydrin, and then water‐soluble chitosan bearing fluorescein (CS‐EPF) was prepared via ring‐opening reaction with EPF. They were characterized by the methods of ¹H NMR, MS, IR, UV–Vis, and luminescence spectra, respectively. The chemiluminescent and photophysical behaviors of EPF and CS‐EPF were studied in detail. The results showed that the fluorescent chitosan could still provide temperature and pH sensitivities similar to that of fluo‐ rescein, achieving better long‐term stability and fast equilibrium response. CS‐EPF had an excellent linear response between relative fluorescence intensity and temperature in the range of 0–60°C and two linear relationships between relative fluorescence intensity and pH in 0.0–4.14 and 8.15–13.20, respectively. This investigation may provide a convenient way to prepare low‐cost and multifunctional macromolecule biomaterial to probe pH and temperature in biological systems. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3960–3966, 2007     

Synthesis and fluorescence properties of star‐shaped polymers carrying two fluorescent moieties

A well‐defined fluorescent star‐shaped polymer containing two different fluorescent functionalities one in the main chain and another in the end group was designed and synthesized by combining atom transfer radical polymerization (ATRP) and azide‐alkyne click reaction. The star polymer with four arms was prepared from copolymerization of methyl methacrylate and 4‐(2‐(9‐anthryl))‐vinyl‐styrene using ATRP. Subsequently the end group was modified with another fluorescent moiety by click coupling. The structure of all the intermediate and final products was established through NMR spectroscopy, Fourier transform infrared spectroscopy, gel permeation chromatography, UV?visible spectroscopy and fluorescence spectroscopy. The novel hybrid polymer exhibits an attractive high fluorescence at 494 nm and over a broad range which was a combination of both the fluorescence moieties. © 2013 Society of Chemical Industry     

Preparation and characterization of fluorescent polymer magnetic particles

Magnetic iron oxide (maghemite, Fe₃O₄) particles were encapsulated with fluorescent polymer phase. The resulting fluorescent magnetic polymer particles were characterized by Fourier transform infrared spectroscopy (FTIR), thermal gravimeter analysis (TGA), reflection optical microscopy, differential scanning calorimeter (DSC), Fritsch particle sizer, scanning electron microscopy (SEM), powder X‐ray diffractometer (XRD), and vibrating sample magnetometer (VSM) measurements. FTIR and XRD confirmed the presence of iron oxide in polymer phase. The TGA and DSC measurements indicated that the magnetic polymer particles have more than 50% iron oxide content and high thermal stability. SEM and reflection optical microscopy under UV light revealed that all maghemite particles were embedded in the polymer spheres and have fluorescent characteristics. The size‐distribution analysis of prepared magnetic particles was shown that the means diameter of the particles slightly increased. According to our magnetometry data, shape of the loops evidences the ferromagnetic character of the material and no evidence of superparamagnetism was seen. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

细乳液聚合纳米乳胶荧光颜料的制备

采用细乳液聚合法制备了纳米乳胶荧光颜料,研究了溶剂黄43用量,乳化剂、助乳化剂种类和用量,引发剂用量和超声波处理时间对纳米乳胶荧光颜料性能的影响。结果表明,纳米乳胶荧光颜料较佳的制备工艺为:溶剂黄43、十六烷(HD)和过硫酸铵(APS)的质量分数分别为1.5%、1.5%和0.8%(以单体质量计),乳化剂1-烯丙氧基-3-(4-壬基苯酚)-2-丙醇聚氧乙烯(10)醚硫酸铵(DNS-86)用量为0.019 11 mol/L,超声波处理时间9 min,在该条件下制备的纳米乳胶荧光颜料的粒径为162.1 nm,具有较高的耐热和离心稳定性,纳米乳胶荧光颜料的最大荧光发射波长517 nm,最大吸收波长425 nm。     

端羟基遥爪聚异丁烯的制备与表征

使用5-叔丁基-1,3-二（2-氯代异丙基）苯/四氯化钛引发体系,通过可控活性正离子聚合反应制备了含双活性链末端的聚异丁烯,再使用1,3-丁二烯封端制备具有烯丙基氯末端结构的聚异丁烯,并结合四丁基氢氧化铵存在条件下水解的方法制备了双端羟基遥爪聚异丁烯,研究了封端时间对封端反应的影响,探讨了所得聚合物的热稳定性和低温性能。结果表明,在四丁基氢氧化铵存在条件下,由含氯链末端亲核取代方式制备所得聚合物的端羟基转化率高,反应时间短,原料便宜易得且制备工艺简便,所得产物的热稳定性及低温性能优良。     

新型荧光纤维毡的制备及性能

先以丙烯腈和丙烯酸为单体合成聚合物（Polymer-1）,用荧光染料对聚合物进行接枝改性后得到聚合物（Polymer-2）;然后将这两种聚合物通过静电纺丝法制备出纳米纤维毡。研究了单体配比对Polymer-1共聚物粘均分子质量的影响;用DSC和IR测试手段对聚合物结构进行表征,用SEM和荧光光谱分析（FS）测试手段对纳...     

Synthesis of fluorescent ABA triblock copolymer via click reaction

A hyperbranched–linear–hyperbranched (ABA) triblock copolymer containing poly(ethylene glycol) (PEG) as linear block and polyglycerol (hbPG) as hyperbranched blocks has been synthesized through a copper‐catalysed click reaction. In order to synthesize the hyperbranched block, propargyl alcohol‐initiated ring‐opening multibranching polymerization of glycidol was used to prepare hbPG with the propargyl segment in the focal point (CH?C? hbPG). Separately, PEG was functionalized at both ends using cyanuric chloride, and then the chloride groups of cyanuric chloride were substituted by azide groups. Finally, the azide‐functionalized PEG was conjugated to CH?C? hbPG via a click reaction. Substitution of the chlorine atoms of cyanuric chloride under different conditions together with click chemistry allows the synthesis of a variety of polymeric architectures. In the last step, fluorescein was attached to the block copolymer as a fluorescent probe in order to study the cell internalization of this copolymer. This type of triblock copolymer is a promising future nanomaterial for simultaneous drug delivery and cell imaging. © 2016 Society of Chemical Industry     

Preparation and photophysical properties of organic fluorescent polymers and their nanoparticles

New classes of stable organic florescent polymer nanoparticles were prepared from the corresponding tetrahydrofuran (THF) solutions, upon slow evaporation of solvent under a mild vacuum. Uniform spherical nanospheres having mean diameter of ? 500–700 nm, showed enhanced fluorescence emission in solution, but it diminished when it is destroyed using an organic base. These end‐capped fluorescent polymers are highly stabilized in the excited states at higher concentration in solution, leads no more intra‐ and intermolecular interactions among the excited molecules, because of the absence of free functional groups. The significant enhancement in fluorescence emission was attributed to the high level of molecular stacking in the fluorescent nanoparticles, when compared with micron‐sized isolated powder sample. In addition, these fluorescent polymers exhibited significant thermal properties, along with better solubility in most of common organic solvents for their future application. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5344–5350, 2006     

松香基荧光水性聚氨酯的制备及性能

以异佛尔酮二异氰酸酯（IPDI）、丙烯酸松香加成物与甲基丙烯酸2-羟乙酯酯化物（RAG）为原料,二羟甲基丙酸（DMPA）为亲水扩链剂,5,7-二羟基-4-甲基香豆素（DHMC）为荧光扩链剂,成功制备了稳定性好的松香基荧光水性聚氨酯乳液（FWPU）。采用核磁共振氢谱、红外光谱、紫外光谱等对FWPU进行了结构表征,探讨了DHMC用量、猝灭剂1,4-对苯二酚（HQ）对FWPU荧光性能的影响,测试了聚氨酯膜的紫外防护性能。结果表明,DHMC成功接枝到聚氨酯主链上,随着其用量的增加,FWPU的荧光强度逐渐增大,用量为1%时荧光强度最大（达5002）;相比于DHMC,FWPU的荧光强度明显增大;HQ对FWPU荧光猝灭效果明显。加入DHMC,聚氨酯的紫外线防护系数从6.86增加到12.27,紫外防护性能得到改善,耐水性也有一定的提高。     

基于点击化学和可逆加成-断裂链转移自由基聚合合成极性链接枝聚丁二烯

以1-硫代甘油作为改性剂、聚丁二烯为主链,通过热引发和光引发合成了侧基含有羟基的聚丁二烯,以S-1-十二烷基-S′（α-α′-二甲基-α′′乙酸）-三硫代碳酸酯作为可逆加成-断裂链转移自由基聚合试剂、偶氮二异丁腈为引发剂,合成了端羧基聚N,N-二甲基丙烯酰胺,然后将两种官能化的聚合物进行酯化反应制得聚N,N-二甲基丙烯酰胺接枝聚丁二烯。结果表明,采用光引发可以显著提高点击化学的反应效率。用核磁共振氢谱证实了产物含羟基聚丁二烯和端羧基聚N,N-二甲基丙烯酰胺以及接枝聚合物的结构,并显示通过这种方法所制备接枝聚合物的接枝链数目和长度均可控。