功能化荧光碳纳米点的一步法制备及其光谱研究

以肝素钠为碳源,采用水热法一步制备了表面功能化的荧光碳纳米点。利用透射电镜、红外光谱、光电子能谱及荧光发射光谱对其形貌、结构和光致发光性质进行了测试分析。研究结果表明,碳纳米点具有较为均一的尺寸和较强的荧光,并且保留了碳源中大量的官能团。制备得到的碳纳米点可应用于Cu2+的检测,显示了其作为离子传感器材料的潜在应用价值。     

Synthesis and Spectroscopic Properties of Novel Fluorescent Compounds Containing Bis-pyrazole Ring

A series of pyrazoline derivatives containing pyrazole group were synthesized and characterized by means of ¹H NMR, FT-IR, MS and elemental analysis, and their UV–vis absorption behavior and fluorescent properties were also measured. Moreover, the influence of metal ions on spectral properties of synthetic products was examined with compound A ₅ as an example. It has been found that all synthetic pyrazoline derivatives show two remarkable absorption peaks at about 260 and 360 nm and the maximum emission peak at 445–467 nm. Especially, the joined of Co²⁺ can quench the fluorescence of compound A ₅ obviously.     

金纳米粒子的电化学合成及光谱表征

采用电化学方法合成各种形状的金纳米粒子,生成的金纳米粒子形貌与施加电流有关,通过匀速递增电流电解的方法,可制备得到哑铃形,球形以及棒状金纳米粒子,采用恒电流电解方法主要获得球形及哑铃形纳米粒子。利用透射电镜、紫外-可见光谱及拉曼光谱对金纳米粒子进行相关表征。紫外-可见光谱研究发现金纳米棒出现位于近红外区间的吸收峰(985 nm),由此推测棒的长径比约为6。以结晶紫为探针分子,研究了金纳米粒子的表面增强拉曼光谱(SERS)效应,并分析得出其平躺的吸附模式。根据形貌表征的结果推断了纳米粒子的生长机理。     

非荧光硫化锌纳米簇的合成与表征

合成硫化锌纳米簇并对其进行表征, 建立一种利用硫化锌纳米簇的阳离子交换(CX)反应检测痕量生物分子的方法。采用水热法合成非荧光硫化锌纳米簇(NCCs)并对其进行表征。纳米簇的性能直接影响检测结果。通过透射电镜图像和X射线衍射可知, 纳米簇是多孔的, 可以通过快速阳离子交换反应从纳米簇中释放大量的Zn2+, 在锌响应试剂的作用下产生荧光信号进行荧光检测。其晶体的外部比内部排列松散, 有利于快速阳离子交换, 其晶体尺寸大小与加热时间有关。通过比表面积检测法测定纳米簇的表面积和孔径表明, 最小的纳米簇拥有相对较大的表面积及较高的阳离子交换效率。实验了三种释放方法(酸溶解法、阳离子交换法和微波辅助阳离子交换法)对Zn2+释放性能的影响, 结果表明, 微波辅助阳离子交换法信噪比较高, 操作简便, 可用于硫化锌纳米簇免疫测定法中。比较了Zn2+的释放效率和目标结合力与平均直径之间的关系, 结果表明纳米簇尺寸为44 nm时表现出最高的阳离子交换效率。结论: 所有这些特点, 使ZnS纳米簇阳离子交换放大器在痕量生物分子检测方面成为高度灵敏、生物相容性好、低廉环保的检测工具。     

非荧光硫化锌纳米簇的合成与表征

合成硫化锌纳米簇并对其进行表征,建立一种利用硫化锌纳米簇的阳离子交换(CX)反应检测痕量生物分子的方法。采用水热法合成非荧光硫化锌纳米簇(NCCs)并对其进行表征。纳米簇的性能直接影响检测结果。通过透射电镜图像和X射线衍射可知,纳米簇是多孔的,可以通过快速阳离子交换反应从纳米簇中释放大量的Zn2+,在锌响应试剂的作用下产生荧光信号进行荧光检测。其晶体的外部比内部排列松散,有利于快速阳离子交换,其晶体尺寸大小与加热时间有关。通过比表面积检测法测定纳米簇的表面积和孔径表明,最小的纳米簇拥有相对较大的表面积及较高的阳离子交换效率。实验了三种释放方法(酸溶解法、阳离子交换法和微波辅助阳离子交换法)对Zn2+释放性能的影响,结果表明,微波辅助阳离子交换法信噪比较高,操作简便,可用于硫化锌纳米簇免疫测定法中。比较了Zn2+的释放效率和目标结合力与平均直径之间的关系,结果表明纳米簇尺寸为44 nm时表现出最高的阳离子交换效率。结论：所有这些特点,使ZnS纳米簇阳离子交换放大器在痕量生物分子检测方面成为高度灵敏、生物相容性好、低廉环保的检测工具。     

一种新型希夫碱硼配合物的合成及表征

有机电致发光器件(OLED)已成为平板显示、照明等领域的研究热点。针对已报道的蓝光材料相对短缺,合成了一种新型希夫碱硼配合物蓝光发射材料,其可由N,N′-二(2-羟基-3-甲氧基苯甲醛)缩乙二胺[(HMOB)₂en]与醋酸硼B(Ac)₃在苯溶剂中反应制得。通过¹H NMR,¹³C NMR和红外光谱确定了其结构,并对其紫外-可见吸收光谱和荧光光谱进行了研究。¹H NMR、¹³C NMR和红外光谱表明该配合物是一种以[B(MOB)₂en]Ac分子形式存在的配合物。[B(MOB)₂en]Ac的发光与B的引入有关,B的引入增强了分子的刚性、减少了非辐射跃迁能量损失,最终得到一种较强的蓝绿光发光材料。该材料发射的峰值波长为485nm,半峰全宽为87nm,CIE坐标:x=0.2211,y=0.4172,其最佳激发峰波长为378nm。     

Synthesis and Spectroscopic Investigation of Diketopyrrolopyrrole - Spiropyran Dyad for Fluorescent Switch Application

We report the synthesis and characterization of a new fluorescent dyad SP-DPP-SP(9) via efficient palladium-catalyzed Sonogashira coupling of prop-2-yn-1-yl 3-(3′,3’dimethyl-6-nitrospiro[chromene-2,2′-indolin]-1′-yl)propanoatespiropyran, SP(8), a well known photochromic accepter, with 3,6-bis(5-bromothiophen-2-yl)-2,5-bis((R)-2-ethylhexyl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione, DPP(4), a highly fluorescent donor. Under visible light exposure the SP unit is in a closed hydrophobic form, whereas under UV irradiation it converts to a polar, hydrophilic open form named Merocyanine (MC), which is responsible for functioning of photo-switch application. The photochemistry pertaining to fluorescence switch, ‘on/off’ behaviour, of model dyad SP-DPP-SP(9) is experimentally analyzed in solution as well as in solid state in polymer matrices by photoluminescence(PL) and absorption spectroscopy. After absorption of UV light the spiropyran unit of the dyad under goes the rupture of the spiro C-O bond leading to the formation of MC. The absorption band of MC fairly overlaps to the fluorescence of DPP unit resulting quenching of fluorescence via fluorescence resonance energy transfer from exited DPP unit to ground state MC. In contrary, the fluorescence of DPP is fully regained upon transformation of MC to SP by exposure to visible light or thermal stimuli. Hence, the fluorescence intensity of dyad 9 is regulated by reversible conversion among the two states of the photochromic spiropyran units and the fluorescence resonance energy transfer (FRET) between the MC form of SP and the DPP unit. Conversely, these scrutiny of the experiment express that the design of dyad 9 is viable as efficient fluorescent switch molecule in many probable commercial applications, such as, logic gates and photonic and optical communications.     

Ga(OTf)3催化合成苯并二氮杂卓及其结构解析

以邻苯二胺和丙炔酸酯为原料,Ga(OTf)3催化一锅法合成了一类新型的1,5-苯并二氮杂卓衍生物,超声波辅助加快了反应的进行,该反应条件温和,反应时间短. 利用¹H NMR、¹³C NMR 确定了该产物的结构,并通过DEPT、¹H-¹H COSY、HMQC、HMBC等2D NMR谱,对化合物的¹H NMR和¹³C NMR数据进行了详细的归属,讨论了化合物的质谱裂解规律,进一步确证了该化合物的结构.     

生物分子包覆的荧光量子点的微波合成及表征

以N-乙酰基-L-半胱氨酸为稳定剂,采用控温控压微波辐射法在水溶液中快速合成了CdTe量子点.吸收光谱和荧光光谱表明所合成量子点具有优异的光学性能,量子产率最高可达50％左右,发射峰半峰宽最小在35nm左右,明显优于在相同实验条件下以3-巯基丙酸为稳定剂合成的CdTe量子点.透射电子镜显微镜(TEM)和X射线粉末衍射(XRD)进一步证实CdTe量子点具有较窄的粒径分布和好的晶体结构.电感耦合等离子体发射光谱(ICP-OES)分析表明量子点中重金属元素镉的含量随着荧光发射波长的增加而逐渐增大.     

酰基吡唑啉酮双席夫碱硼配合物的合成与光谱表征

合成了 3种 [B(PMαFP) 2 en]Ac ,[B(PMαFP) 2 pen]Ac ,[B(PMTHP) 2 en]Ac型硼配合物 (其中(HPMαFP) 2 en为N ,N′ 双 [( 1 苯基 3 甲基 5 氧 4 吡唑啉基 )α 呋喃次甲基 ]乙二亚胺、(HPMαFP) 2 pen为N ,N′ 双 [( 1 苯基 3 甲基 5 氧 4 吡唑啉基 )α 呋喃次甲基 ]邻苯二亚胺、(HPMTHP) 2 en为N ,N′ 双 [( 1 苯基 3 甲基 5 氧 4 吡唑啉基 ) 2 噻吩次甲基 ]乙二亚胺 )。通过元素分析 ,红外光谱 ,电子光谱 ,核磁共振谱 ,摩尔电导等对新配合物的组成、结构和性质进行了表征     

硼胁迫下不同柑橘砧木叶片物质组成及结构的FTIR表征

硼作为高等植物必需的微量元素,从缺乏到过量的范围很窄,因此缺硼和硼毒害导致作物产量及品质下降等问题一直是国内外关注的重点。以不同柑橘砧木(枳橙和枳壳)为材料,利用傅里叶红外光谱(FTIR)探讨低硼及高硼胁迫对不同砧木叶片物质组成和结构的影响及其差异。结果表明：(1)低硼及高硼胁迫均抑制了柑橘砧木地上部的生长,高硼时枳壳砧木叶片出现典型的硼中毒现象,而枳橙砧木叶片则无明显的硼毒症状,表明枳橙砧木比枳壳砧木更耐高硼胁迫;(2)低硼胁迫时,枳壳砧木叶片缺失1 153,1 053和1 028 cm-1三个特征峰,而枳橙砧木叶片仅缺失1 055 cm-1一个特征峰,且两种砧木叶片其他特征峰的相对吸光度较正常硼处理整体增加,表明缺硼导致枳壳砧木叶片纤维素糖苷及可溶性糖、核糖的结构发生变化且含量增加,仅改变枳橙砧木叶片可溶性糖的结构。因此,低硼胁迫对枳壳砧木影响大于枳橙砧木;(3)高硼胁迫时,枳壳砧木叶片1 153和1 053 cm-1两个特征峰消失,增加1 622 cm-1处特征峰;枳橙砧木叶片缺失1 024 cm-1处特征峰,且其他特征峰的相对吸光度较正常处理整体降低,表明高硼改变枳壳砧木蛋白质、可溶性糖等碳水化合物的结构且含量减少,而枳橙砧木仅核糖的结构发生变化,说明高硼对枳壳砧木叶片多糖结构的影响大于枳橙砧木。因此,枳橙砧木比枳壳砧木更耐低硼和高硼胁迫,硼对不同砧木物质组成和结构的效应差异是其中一个关键因子。     

钾硼胁迫对棉花功能叶物质成分影响的FTIR表征

钾和硼均是植物必需的营养元素,对植物的生长、发育与生理代谢等起着重要作用。棉花对钾和硼都有较高的需求量,而棉花缺钾或缺硼时有发生。以鄂抗8号品种的棉花作为研究材料,利用傅里叶变换探讨钾硼胁迫对棉花功能叶片物质成分的影响。红外光谱(FTIR)对钾硼胁迫下棉花叶片的物质成分进行研究,分析钾硼缺乏情况下叶片红外光谱的差异。结果表明：(1)缺钾处理时,1 546.86, 1 438.85, 1 153.39和1 024.17 cm-1这4个特征峰消失,且其他特征峰的相对吸光度值与正常处理相比均减小,表明缺钾时棉花功能叶片蛋白质、纤维素、可溶性糖和核糖的结构发生变化且含量降低。(2)缺硼条件下,叶片的特征峰的相对吸光度均有所升高,因而,缺硼则导致蛋白质及可溶性糖、纤维素等碳水化合物等的运输受阻而在叶片中积累。(3)钾硼同时缺乏,棉花功能叶片特征峰的位置和相对吸收强度与正常处理相比有很大差异,表现为棉花功能叶片蛋白质和可溶性糖等碳水化合物的含量升高,而核酸和多糖分子等含量下降。因此缺钾导致棉花功能叶片蛋白质、纤维素、可溶性糖和核糖结构变化的含量降低;缺硼时蛋白质及可溶性糖、纤维素等碳水化合物等在叶片中积累;缺钾缺硼时蛋白质和可溶性糖等碳水化合物含量升高,而核酸和多糖分子等含量下降。     

硼碳氮纳米管的拉曼光谱研究

对不同温度和不同催化条件下用高温热解法制备的硼碳氮(BCN)纳米管的拉曼光谱进行了分析。随着制备温度的升高,拉曼光谱中D带和G带的强度比I_D/I_G由小变大,而后又变小,说明存在一个最佳温度,在该温度下生成的BCN纳米管中B、N元素掺杂浓度最大。不同催化剂对BCN纳米管的拉曼光谱也有影响,当以钴/二茂铁和镍/二茂铁为催化剂时的I_D/I_G值比以钴、镍和钴/镍为催化剂时大,说明这时的B、N的掺杂浓度较高,纳米管的质量较好,这与透射电子显微镜观察结果一致。     

Synthesis,Spectroscopic Properties,and Biological Applications of Eight Novel Chlorinated Fluorescent Proteins-labeling Probes

Eight novel chlorinated fluorescent proteins-labeling probes with a linker and reactive group were prepared in 7 steps by the reaction of chlorinated resorcinols with 3, 6-dichloro-4-carboxyphthalic anhydride in the presence of methanesulfonic acid. Structures of target compounds and intermediates were determined via IR, MS, ¹H NMR and element analysis. The spectral properties of the chlorinated fluoresceins were studied. These fluorescent probes showed absorbance peaks at 508–536 nm and fluorescence peaks at 524–550 nm. It was found that they have absorption and emission maxima at long wavelengths and high fluorescence quantum yields. Emission spectra of chlorinated fluoresceins shifted towards long wavelength with increase in chlorine. The probes were used for fluorescence imaging of cells in order to investigate whether they can conjugate to cells. The fluorescence imaging of living cells showed that they were localized in cell nucleus. However, they were localized in cytosol of chemically fixed cells. These probes will be useful reagents for the preparation of stable fluorescent conjugates.     

杂多酸环戊二烯钒衍生物的合成、谱学性质及抗肿瘤活性

合成了杂多酸环戊二烯钒衍生物[Bu₄N]₄[(CpV)PW₁₁O₃₉](1),[Bu₄N]₄H[(CpV)SiW₁₁O₃₉](2)和[Bu₄N]₄[A-β-(η5-CpV)SiW₉V₃O₄₀](3),并通过元素分析、IR、51V和183W NMR谱进行了结构表征。结果表明配合物(1)和(2)为结合型有机金属配合物,(3)为支撑型杂多酸有机金属配合物。体外抗肿瘤活性研究表明化合物(1)对HL-60和B₁₆均具有一定的抑制作用。     

Spectroscopic and Photophysical Characterization of Fluorescent Chemosensors for Monosaccharides Based on N-Phenylboronic Acid Derivatives of 1,8-Naphthalimide

Spectroscopic and photophysical properties of two fluorescent probes for monosaccharides are presented. Probes are based on the N-phenyl-1,8-naphthalimide structure having the boronic acid group [R-B(OH)₂] in ortho in one case, and meta in the other case, positions of the N-phenyl group. Formation of the anionic form of the boronic acid group [R-B(OH)^– ₃] induced a substantial decrease of the steady-state fluorescence of both compounds. Because no change in the fluorescence lifetime from the neutral to the anionic forms is observed, static quenching resulting from photoinduced electron transfer from the anionic form of the boronic acid is used to explain the decrease of the emission intensity. Both compounds show substantial decreases of their fluorescence intensity in the presence of sugars. In addition, this decrease of the fluorescence intensity is associated with an increase of the fluorescence lifetime for the ortho derivative while no effect on the lifetime is observed for the meta derivative. Both photoinduced electron transfer and steric hindrance are discussed to correlate the observed results.     

Synthesis,Characterization, Properties,and Novel Applications of Fluorescent Nanodiamonds

In the last few years, fluorescent nanodiamonds (FNDs)  have been developed significantly as a new member in the nanocarbon family. The surface of FNDs is embedded with some crystallographic defects containing color centres which surmount the properties of other fluorochromes including up conversion and down conversion nanoparticles, quantum dots, nano tubes, fullerenes, organic dyes, silica etc. Some of the intriguing properties like inevitable photostability, inherent bio-compatibility, outstanding optical and robust mechanical properties, excellent magnetic field, and electric field sensing potentiality make FNDs appealing to some benevolent applications in numerous fields like bio-imaging, delivering drugs, fighting cancer, spin electronics, imaging of magnetic structure at nanoscale and as promising nanometric temperature sensor. The structure of FNDs has certain point defects on the surface among which negatively charged nitrogen vacancy centre (NV^?) is the most investigated color centre. The production of NV^? fluorescence nanodiamonds is the most challenging task as substitution of carbon atoms is required to create vacancies by causing irradiation from an electron beam which is followed by high temperature annealing. Thus, this review points out the relative advantages of FNDs containing negatively charged nitrogen vacancy centres produced from HPHT method or CVD method with those nanodiamonds produced through detonation process or pulsed laser ablation (PLA) method. The steps involved in the fabrication of FNDs are described along with the major challenges and struggles underwent during the process in this review. This review also summarizes the recent developments made in the functionalization and applications predominantly made in the field of biological science and it is understood that depending on the defect color centres they can exhibit different emitted wavelengths ranging from UV–visible to near infrared with broad or narrow bandwidths. This review also highlights some of the fluorescent NDs that emit stable and strong red or green photoluminescence from the defect centers of NV^? which are implanted in the crystal lattice. This critical and extensive review will be useful for the further progress in this futuristic field of FNDs.

     

镧与甘氨酸和邻菲绕啉三元配合物的合成及光谱表征

合成了三元固体配合物Ｌａ（Ｇｌｙ）３（Ｐｈｅｎ）．３Ｈ２Ｏ（Ｇｌｙ为甘氨酸,Ｐｈｅｎ为邻菲绕啉）,测定了配体和配合物的红外光谱,拉曼光谱,研究配体与镧配位的主要特征峰的变化,并利用热重－红外光谱联用技术,研究了配合物的稳定性和热分解情况。     

奥利司他的有机波谱分析

减肥药奥利司他是一种强效的特异性胃肠道脂肪酶抑制剂,应用NMR、ESI-MS、UV和IR对其结构进行了确证,采用DEPT、COSY、HMBC和HSQC技术对其 1H NMR和¹³C NMR谱的信号进行了归属.     

新型发蓝光材料的合成和光谱表征及光致和电致发光性能的研究

合成了能发射蓝光的锌的配合物.对配合物进行了元素分析、激发光谱、发射光谱、红外光谱进行了研究.利用配合物制成发光二极管的发光层,对其光致和电致发光性能进行了探讨.它能发射蓝光,波长为455 nm,亮度为37.20 cd·m-2 .