一种选择性SO2荧光探针的合成及性能

以4-(二乙氨基)水杨醛为原料,经Knoevenagel缩合反应、Vilsmeier反应以及Wittig反应得到中间体3,以2,3,3-三甲基-3H-吲哚为原料,经亲核取代得到中间体4;3与4发生缩合反应得到含半花菁结构的香豆素类SO_2荧光探针PA1,其结构经~1H NMR、~(13)C NMR和HR-MS(ESI)确证。该探针具有良好的水溶性,可以快速检测外源性SO_2,检出限为0.38μM,响应时间为3 min。探针于498 nm处的荧光强度随着SO_2浓度增加而增强,当SO_2浓度为0～120μM时,荧光强度与浓度的线性相关系数为0.998。     

一种检测HSO3-/SO32-的水溶性荧光探针

合成了一种基于半花菁类结构和碳碳双键加成原理的HSO_3~-/SO_3~(2-)荧光探针(HcyBr)。在PBS缓冲液体系中,通过紫外吸收与荧光发射光谱研究了探针对HSO_3~-/SO_3~(2-)的响应性能。探针溶液(10μmol/L)中加入HSO_3~-/SO_3~(2-)(50μmol/L)后,30 s即可完全反应,且在396 nm处的荧光强度增强近100倍。同时该强度随HSO_3~-/SO_3~(2-)浓度(0～50μmol/L)的变化具有良好的线性关系,经计算检测限为32. 5 mol/L,远低于美国EPA限定的阀值96. 2 nmol/L。另外探针对HSO_3~-/SO_3~(2-)响应后溶液由亮黄色变为无色,而加入其他的干扰物质后几乎没有颜色变化,显示了良好的抗干扰性能。探针Hcy-Br可在纯水相中特异性识别HSO_3~-/SO_3~(2-)。     

新型含羧戊基不对称五甲川菁染料的合成及蛋白标记

以磺酸基苯肼和7-甲基-8-氧代壬酸为原料合成了2,3-二甲基-3-羧戊基-3H-吲哚-5-磺酸;以2,3,3-三甲基-3H-吲哚-5-磺酸和1,3-丙磺酸内酯为原料合成了1-磺酸丙基-2,3,3-三甲基-3H-吲哚-5-磺酸;然后通过半菁合成法合成了一种新型水溶性不对称五甲川吲哚菁染料(Cy5)。产物经C18反相硅胶柱分离,收率57%,其结构经1H NMR、HRMS进行确证。并检测了目标化合物的光谱性质,初步探讨了其在生物标记方面的应用。染料具有良好的水溶性和光稳定性,水溶液的最大紫外吸收波长和最大荧光发射波长分别为646和666 nm,荧光量子产率为0.2,用n(活化菁染料)∶n(牛血清蛋白)=2∶1标记蛋白,D/P值为1.56。     

一种选择性SO2荧光探针的合成及性能研究

以4-(二乙氨基)水杨醛为原料,经Knoevenagel 缩合反应、Vilsmeier反应以及Wittig反应得到中间体3,以2,3,3-三甲基-3H-吲哚为原料,经亲核取代得到中间体4; 3与4发生缩合反应得到含半花菁结构的香豆素类SO₂荧光探针PA1,其结构经¹H NMR、 ¹³C NMR和HR-MS(ESI)确证。该探针具有良好的水溶性,可以快速检测外源性SO₂,检出限为0.38 μM,响应时间为3 min。探针于498 nm处的荧光强度随着SO₂浓度增加而增强,当SO₂浓度为0~120 μM时,荧光强度与浓度的线性相关系数为0.998。      

钠离子荧光探针的合成及应用

基于钯催化的胺化反应将1-氮杂-15-冠醚-5和6-溴-2-萘甲醛经亲核取代合成中间体M-1,并将M-1与1,2,3,3-四甲基-3H-吲哚鎓碘化物在乙醇中回流,最终合成Na~+荧光探针Probe 2。研究了该探针在不同溶剂中的紫外吸收光谱与荧光发射光谱特性,并对Probe 2在Na~+存在时的荧光光谱性能、络合比例和选择性进行了探究。Na~+浓度在1～10μmol/L范围内与Probe 2的荧光强度和初始强度的比值(F/F_0)具有良好的线性关系,线性方程为F/F0=-1. 80×10~4c~+1. 00,R~2=0. 9827。在实际样品检测中,分别应用探针Probe 2与ICP-MS检测同批样品,经统计分析,两种手段的检测结果具有良好的相关性,相关系数r=0. 9993。     

比率型SO2荧光探针的构建及细胞成像研究

本文构建了一种基于苯并吲哚季铵盐结构的荧光探针用于检测SO₂衍生物。该荧光探针能够快速、灵敏、高选择性地检测HSO₃^-和SO₃^2-,并显示出颜色和荧光变化双重响应。其比率荧光强度（I₄₆₂/I₅₈₈）与HSO₃^-的浓度（0～16 μmol/L）之间具有良好的线性关系,检测限低至12 nmol/L。¹HNMR表明该探针的响应机制为1,4-亲核加成反应。激光共聚焦荧光成像结果表明,CZBI具有良好的细胞膜通透性,并且可以通过比率荧光成像实现对细胞内SO₂衍生物的监测。     

苯并咪唑喹啉比率型pH荧光探针的合成及应用

以邻氨基苯甲酸为原料,经Skraup-Doebner-Von Miller,Knoevenagel等反应合成了2-(4-羟基苯乙烯基)-8-(1H-苯并咪唑-2-基)喹啉(探针L),通过~1HNM R,~(13)CNM R,ESI-M S对其结构进行了表征。该探针L在pH 1.0~9.0范围内对H~+有响应,pKa为6.15;且在pH 4.5~6.0范围内其荧光强度比(I_(475nm)/I_(565nm))与pH呈良好的线性关系,相关系数为0.9937。探针L对H~+响应不受其他阳离子的干扰且具有可逆性。上述结果表明2-(4-羟基苯乙烯基)-8-(1H-苯并咪唑)喹啉有望成为新型比率型pH荧光探针。     

一种罗丹明类Cu~(2+)荧光探针化合物的合成及性能研究

以罗丹明B、水合肼和咔唑为原料,合成了一种新型的荧光增强型Cu2+荧光探针,即4-(N-咔唑基)苯亚甲基罗丹明B腙(CPMRH)。用FTIR、1H NMR和13C NMR对其分子结构进行了表征,并通过荧光光谱对探针的识别性能进行了研究。研究结果表明:探针CPMRH对水溶液中的Cu2+具有良好的选择识别性,且基本不受其他金属离子的影响;探针与Cu2+络合显示粉红色,可以作为一种裸眼检测的试剂用于溶液中Cu2+的检测;当λex=520 nm时,Cu2+水溶液与探针作用可显示橙红色荧光。且Cu2+浓度在1×10-5-5×10-5mol·L-1的范围内,探针的荧光强度与Cu2+浓度呈现出较好的线性关系;Cu2+的最低检出限为5.25×10-7mol·L-1;Job’s曲线表明,探针CPMRH与Cu2+的络合比为1∶1。     

一种新型比色荧光增强型CN~-探针的合成与性能研究

设计并合成一种具有席夫碱结构的新型荧光增强型探针7-(二丁基氨基)-2'-[(2-羟基苯亚甲基)氨基]-3-甲基-1-苯基-1H-螺[色烯并[2,3-c]吡唑-4,1'-异吲哚啉]-3'-酮(SCPz-S),通过(~1H NMR、~(13)C NMR及高分辨质谱(HRMS)对其结构进行了表征.利用紫外-可见光谱和荧光光谱考察探针SCPz-S的离子识别性能,研究发现探针SCPz-S在THF/H_2O(V∶V=1930∶50,5 mmol/L Tris-HCl,pH=7.4)中对CN-具有比色和荧光上的双重响应.加入CN-后,探针SCPz-S的体系会由无色变为淡黄色,在575 nm荧光增强1060倍.探针SCPz-S拥有良好的抗干扰能力和很广的p H适用范围(pH=3~12).探针对CN-的检出限达到1.121×10~(-8) mol/L,并对其识别机理进行了研究.     

汞离子的高灵敏度裸眼识别和荧光传感探针

设计合成了一种以耐尔蓝为母体的Hg2+光学探针分子1-苯甲酰-3-{2-[9-(乙氨基)-10-甲基-9H-苯并[α]苯酚-5-胺基]乙基}硫脲盐酸盐(NBET). 在pH=7.4的Tris-HCl缓冲液中, 探针分子最大吸收波长为640 nm, 此时溶液为淡蓝色; 加入汞离子可以诱导探针分子在640 nm处的吸收降低, 并在556 nm处产生新的吸收峰, 溶液变为浅紫色, 而其它金属离子的加入未引起显著变化, 基于此可对水溶液中的痕量Hg2+进行裸眼识别. 荧光光谱显示, 汞离子可以特异性地猝灭探针分子在660 nm处的荧光发射. 该探针分子的灵敏度、选择性及荧光量子产率高, 激发/发射波长长, 可以实现水溶液中0.005 μmol/L Hg2+的荧光检测.     

A fluorescence enhanced probe for sulfur dioxide detection and fluorescence imaging in living cellsEI北大核心CSCD

基于香豆素和苯并吡啶基团,构建了用于二氧化硫(SO_(2))高效检测的荧光探针P1,其化学结构通过核磁氢谱(^(1)H NMR)、碳谱(^(13)C NMR)和高分辨质谱(HR-MS)确证。在缓冲溶液体系中,单独的探针P1具有微弱的荧光,识别SO_(2)后荧光发射强度明显增强,能够实现对SO_(2)的专一性裸眼识别,检出限为126 nmol/L。生物应用实验结果表明,该探针具有较低的细胞毒性,可用于生物活细胞中外源性SO_(2)的荧光成像。     

SO2在多组分悬浮液中的吸收反应特性

The emission of sulfur dioxide in flue gases is an important problem in industry involving combustion of coal. The wet scrubbing process using lime/limestone slurry as the scrubbing medium is currently the dominant technology for the flue gas desulfurization. Due to the presence of numerous ionic and neutral species in the slurry, the chemical reactions involved in the slurry upon absorption of sulfur dioxide are complex. In this paper, a method of measuring the sulfur dioxide absorption in multi-component suspensions was developed and the characteristics of sulfur dioxide absorption were investigated. The results show that different additives chosed in the experiment can improve the ability of SO2 absorption. As to the same additive, the improvement effect is differ with different concentration. For the magnesium hydroxide additive, its optimum concentration is 1×10-4 mol/L. Experiment results suggested that dissolved sulfur dioxide reacts mainly with the magnesium sulfite ion pair which is responsible for the increased absorption rate of SO2. However, when CO2-3 or SO24- anions are present in the solution, the catalytic effect of magnesium hydroxide precipitate on sulfur dioxide absorption reduces. According to the experiments, absorbents with better performance can be optimized to be applied in semi-dry or wet FGD process to raise SO2 removal efficiency.     

The chemistry of a ketene-sulfur dioxide adduct

We have demonstrated the formation of a reactive species from ketene and sulfur dioxide and have investigated some of its reactions. The 3 + 2 ← 5 cycloaddition reactions of this intermediate with benzylideneaniline and its derivatives gave the corresponding 2,3-diphenylthiazolidin-4-one 1,1-dioxides. The reduction of 2,3-diphenylthiazolidin-4-one 1,1-dioxide with lithium aluminum hydride yielded the corresponding thiazolidine. Aniline and its derivatives reacted with the ketene-sulfur dioxide adduct to give thioaceto-1,3-dianilide 3-oxide. o-Phenylenediamine gave [2,1,5]benzothiadiazepin-4-one 2-oxide, a derivative of a new ring system, [2,1,5]benzothiadiazepine. o-Aminophenol yielded [1,2,5]benzothiazepin-4-one 2-oxide.     

Reaction-based fluorescent probe for detecting of sulfur dioxide derivatives and hydrazine via distinct emission signals

Recently, the construction of multiple analytes responsive fluorescent probes with distinct emission signals has attracted widely attention. Thus, we have designed and synthesized a new fluorescent probe, 2-(2-hydroxyphenyl)benzothiazole dye skeleton (HBT-1), for the detection of sulfur dioxide and hydrazine. Significant fluorescence enhancements in two distinct emission bands (λ_em?=?464?nm and 498?nm) were generated when HBT-1 reacted with sulfur dioxide derivatives or hydrazine, respectively. Furthermore, the probe HBT-1 response can be saturated surpurisingly at the low concentration (100?μM), shorter reaction time for sulfur dioxide derivatives, while a longer reaction time and greater concentration (400?μM) for hydrazine. In other words, the probe HBT-1 can detect sulfur dioxide derivatives without hydrazine interference at low analyte concentrations.     

Selective oxygenation of amphiphilic thiacalix[3]pyridine Rh(I) diene complexes in both water and organic solvents

Thiacalix[3]pyridine (Py3S3) reacted with [Rh(diene)(mu-Cl)]2(diene = 1,5-cyclooctadiene (cod), 2,5-norbornadiene (nbd)) to give amphiphilic trigonal bipyramidal complexes, [Rh(Py3S3)(diene)]Cl. Sulfur bridges of the Py3S3 ligand in these complexes were selectively oxygenated by m-chloroperoxybenzoic acid in dichloromethane to give sulfinylcalix[3]pyridine complexes, [Rh(Py3(SO)3)(diene)]+, in which all three oxygen atoms of the SO groups occupy the equatorial positions. Structures of the complexes were analysed by X-ray crystallography and the oxidation reaction was investigated using 1H NMR spectroscopy and electrospray ionisation mass spectrometry showing that the oxygenation of the sulfur atoms in the ligand proceeded stepwise and further oxygenation of the SO moiety occurred only for the nbd complex having the smaller diene ligand resulting in [Rh(Py3(SO)2(SO2))(nbd)]+. On the other hand, the oxidation of [Rh(Py3S3)(cod)]+ by H2O2 in water did not result in oxygenation of the sulfur bridges but the cod ligand is hydroxygenated to give 1,4,5,6-eta4-2-hydroxycycloocta-4-ene-1,6-di-yl.     

Synthesis and structural characterization of luminescent trinuclear gold(I) complexes with dithiocarbamates

We have synthesized a series of trinuclear gold(I) complexes, namely, [Au3(mu-dpmp)(S2CNR2)nCl3-n] (n = 0-3; R = Me, CH2Ph), [Au3(mu-dpmp)(mu-S2CNR2)Cl](CF3SO3) (R = Me, CH2Ph), and [Au3(mu-dpmp)(mu-S2CNMe2)(C6F5)]X (X = Cl, CF3SO3), containing the triphosphine dpmp [bis(diphenylphosphinomethyl)phenylphosphine] and varying amounts of dithiocarbamate. NMR experiments show fluxional behavior in solution for most of these derivatives because several arrangements of the ligands are possible. The crystal structure of [(mu-dpmp)(AuCl)3] has been determined by X-ray diffraction studies; the molecule displays mirror symmetry and involves an angular arrangement of the gold atoms [Au-Au-Au 119.603(14) degrees, Au-Au 3.3709(4) A]. We have studied the optical properties of these derivatives in the solid state, finding a red shift as a function of the dithiocarbamate number and, for some derivatives, wavelength-dependent emission spectra at low temperature.     

Determination of sulfur dioxide in vitriol plant wastewater by using a polyNiMe4TAA electrochemically modified Pt microelectrode

A Pt microelectrode modified with nickel(II) polytetramethyldibenzo[b,i]tetraaza[14]annulene was prepared by electropolymerization of nickel(II) tetramethyldibenzo[b,i]tetraaza[14]annulene monomers and applied to determine sulfur dioxide in vitriol plant wastewater. For determination of SO2 with this electrochemically modified Pt microelectrode, the linear range was from 9.6 x 10(-6) to 2.4 x 10(-4) mol L-1, the sensitivity was 1.8 x 10(-4) A L mol-1, the detection limit was calculated to be 4.8 x 10(-6) mol L-1 (S/N = 3), the response time was less than 20 s and the relative standard deviation was found to be 2.1% on analyzing 4.8 x 10(-5) mol L-1 SO2 solution repeatedly (n = 7). These results demonstrated good accuracy compared with those obtained by the conventional iodimetric method.     

Ab initio and experimental studies on the hetero-Diels-Alder and cheletropic additions of sulfur dioxide to (E)-1-methoxybutadiene: a mechanism involving three molecules of SO(2)

Kinetics on the cheletropic addition of sulfur dioxide to (E)-1-methoxybutadiene (1) to give the corresponding sulfolene 2 (2-methoxy-2,5-dihydrothiophene-1,1-dioxide) gave the rate law d[2]/dt = k[1][SO(2)](x)() with x = 2.6 +/- 0.2 at 198 K. Under these conditions, no sultine 3 [(2RS,6RS)-6-methoxy-3,6-dihydro-1,2-oxathiin-2-oxide] resulting from a hetero-Diels-Alder addition was observed, and the cheletropic elimination 2 --> 1 + SO(2) did not occur. Ab initio and DFT quantum calculations confirmed that the cheletropic addition 1 + SO(2) --> 2 follows two parallel mechanisms, one involving two molecules of SO(2) and the transition structure with DeltaG(++) = 18.2 +/- 0.2 kcal/mol at 198 K (exptl); 22.5-22.7 kcal/mol [B3LYP/6-31G(d,p)], the other one involving three molecules of SO(2) with DeltaG(++) = 18.9 +/- 0.1 kcal/mol at 198 K (exptl); 19.7 kcal/mol [B3LYP/6-31G(d,p)]. The mechanism involving only one molecule of SO(2) in the transition structure requires a higher activation energy, DeltaG(++) = 25.2 kcal/mol [B3LYP/6-31G(d,p)]. Comparison of the geometries and energetics of the structures involved into the 1 + SO(2) --> 2, 3 and 1 + 2SO(2) --> 2, 3 + SO(2) reactions obtained by ab initio and DFT methods suggest that the latter calculation techniques can be used to study the cycloadditions of sulfur dioxide. The calculations predict that the hetero-Diels-Alder addition 1 + SO(2) --> 3 also prefers a mechanism in which three molecules of SO(2) are involved in the cycloaddition transition structure. At 198 K and in SO(2) solutions, the entropy cost (TDeltaS(++)) is overcompensated by the specific solvation by SO(2) in the transition structures of both the cheletropic and hetero-Diels-Alder reactions of (E)-1-methoxybutadiene with SO(2).     

Characterization of sulfurous acid, sulfite, and bisulfite aerosol systems

Acidic tropospheric aerosols contain inorganic species such as sulfurous acid (H(2)SO(3)). As the main alkaline species, ammonia (NH(3)) plays an important role in the heterogeneous neutralization of these acidic aerosols. An aerosol flow-tube apparatus was used to obtain simultaneous optical and size distribution measurements using FTIR and SMPS measurements, respectively, as a function of relative humidity and aerosol chemical composition. A novel chemiluminescence apparatus was also used to measure ammonium ion concentration [NH(4)(+)]. The interactions between ammonia and hydrated sulfur dioxide (SO(2)·H(2)O) were studied at different humidities and concentrations. SO(2)·H(2)O is an important species as it represents the first intermediate in the overall atmospheric oxidation process of sulfur dioxide to sulfuric acid (H(2)SO(4)). This complex was produced within gaseous, aqueous, and aerosol SO(2) systems. The addition of ammonia gave mainly hydrogen sulfite (SHO(3)(-)) tautomers and disulfite ions (S(2)O(5)(2-)). These species were prevalent at high humidities enhancing the aqueous nature of sulfur(IV) species. Their weak acidity is evident due to the low [NH(4)(+)] produced. Size distributions obtained correlated well with the various stages of particulate compositional development.