Effect of the degree of polymerization and etherification on the binding of acridine orange by sodium carboxymethyl cellulose

Summary The interaction between sodium carboxymethyl cellulose and acridine orange was studied by spectral method. The effect of the degree of polymerization and etherification on the binding of the dye was discussed. The binding value increases with an increase in the degree of the polymerization. The number of binding sites per unit glucose was larger than the degree of etherification. Therefore, the electrostatic interaction was probably not the predominant factor.

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Zusammenfassung Die Wechselwirkung zwischen Natriumcarboxymethylcellulose und Acridinorange wurde mit den spektroskopischen Methoden untersucht. Der Effekt des Polymerisationsgrades und des Verätherungsgrades bei der Verbindung mit Acridinorange wurde diskutiert. Die Bindungszahl nimmt mit dem Polymerisationsgrad zu. Die Zahl von den Adsorptionsstellen der Glukoseeinheit wird größer mit der Verätherung. Deshalb ist offensichtlich die elektrostatische Wechselwirkung kein vorherrschender Faktor.

     

吖啶黄荧光光度法测定腺嘌呤

碱性条件下,痕量腺嘌呤使得吖啶黄在激发波长为454 nm、发射波长为509 nm处的荧光强度明显增强,由此建立了荧光光度法测定痕量腺嘌呤的新方法.方法的线性范围为0.2～3.0×10-4 g/L,检出限为1.83×10-5 g/L,方法用于维生素B4片剂中腺嘌呤的测定,回收率为99.6%～101.4%.     

Resonance light scattering method for the determination of anionic surfactant with acridine orange

The resonance Rayleigh scattering (RRS), second-order scattering (SOS) and frequency-double scattering (FDS) spectra of sodium dodecylbenzene sulfonate (SDBS) (anionic surfactant (AS)) with acridine orange (AO) system were studied. Experimental results showed that when lambda(em) = lambda(ex) = 537 nm, the RRS peak of AO was greatly enhanced with the increase of SDBS concentration at a pH range of 1.8-4.0. The linear range of the calibration curve for SDBS was 0.028-8.71 mg L(-1) with a detection limit of 8.36 microg L(-1) when the AO concentration was 2.5 x 10(-5)mol L(-1). The method has been applied to the determination of trace amount of AS in environmental water samples with satisfactory results. In addition, when lambda(em) = 321 nm and lambda(ex) = 642 nm, the intensity of FDS was proportional to the SDBS concentration ranging from 0.014 to 8.71 mg L(-1) and the correlation coefficient was 0.993 with a detection limit of 4.31 microg L(-1); when lambda(em) = 642 nm and lambda(ex) = 321 nm, the intensity of SOS was proportional to the SDBS concentration ranging from 0.050 to 8.71 mg L(-1), and the correlation coefficient was 0.993 with a detection limit of 14.9 microg L(-1).     

吖啶染料共振瑞利散射法测定藻酸钠

在pH8.5和6.0的BR缓冲溶液中,吖啶橙(AO)和吖啶黄(AY)等碱性吖啶染料能与藻酸钠(SA)反应形成复合物,而使其共振瑞利散射RRS急剧增强并产生新的RRS光谱,其最大散射波长位于523nm(AO体系)和485nm (AY体系),藻酸钠浓度在0.075mg/L～5.0mg/L (AO体系)、0.25mg/L～3.0mg/ L(AY体系)时与散射强度(ΔI)呈直线关系,方法具有较高的灵敏度,其检出限分别为23.8ng/mL(AO体系),6.5ng/mL (AY体系).以吖啶橙体系为例研究了共存物质的影响,表明方法选择性好.用于海带提取液中藻酸钠的测定,结果满意.     

Fluorescence quenching method for the determination of sodium dodecyl sulphate with near-infrared hydrophobic dye in the presence of Triton X-100

A fluorophotometric method for the determination of anionic surfactant sodium dodecyl sulphate (SDS) was proposed. The method is based on the quenching effect of SDS on the fluorescence of near-infrared (NIR) hydrophobic dye, 2-[4'chloro-7'(3'hexadecyl-2'benzothiazolinylidene)-3',5'-(1',3'-propanediyl)-1',3',5'-heptatriene-1'-yl]-3-ethylbenzothiazolium iodide (dye I) in the presence of Triton X-100. The calibration graph is linear in the concentration range from 0 to 2 x 10(-6) mol L(-1) of SDS with a detection limit (LOD) of 8.3 x 10(-8) mol L(-1). The relative standard deviation for the determination of 7 x 10(-7) mol L(-1) SDS was 4.1%. Recoveries of 95.3-110.3% were found for the addition to 1.0 x 10(-6) mol L(-1) SDS in the analysis of environmental water samples. Preliminary research shows that the fluorescence quenching is due to the formation of dye aggregate facilitated by SDS.     

Fluorescence quenching method for determination of trace tungsten in environmental samples with dibromohydroxyphenylfluorone

A highly sensitive and selective fluorescence quenching method has been developed for the determination of trace tungsten in environmental samples using dibromohydroxyphenylfluorone (DBHPF) as an emission reagent. In the presence of 0.04?mol/L of sulphuric acid and acetyltrimethylammonium bromide, tungsten(VI) reacts with DBHPF to form a 1?:?3 red complex within 5.0?min. In order for the DBHPF–tungsten(VI) complex to form, the fluorescence intensity of the reagent solution was quenched linearly by adding 0.1 to 1.0?µg of tungsten(VI) in 25?mL of solution. This was measured at 528?nm with excitation at 495?nm. In this work, a standard addition method was investigated and used for sample analysis. The decrease in fluorescence intensity of the reagent solution (ΔF) was linear for 0?～?0.9?µg of tungsten(VI) in 25?mL of solution, and the detection limit (3?s) of the standard addition method was found to be 0.012?ng/mL of tungsten(VI). The effects of various metal and nonmetal ions were studied in detail. The experiments clearly showed that most foreign ions can be tolerated in considerable amounts; in particular, 50-fold Mo(VI), V(V), Zr(VI) and Ti(IV) do not interfere, and the selectivity of the proposed method is better than other previously described methods. Moreover, the method proposed here is very stable and simple, the fluorescence intensity of the solution can remain almost unchanged for 2.0?h at room temperature, and the method has been used successfully to determine tungsten in environmental samples.     

CdTe/CdS荧光探针测定痕量铜(Ⅱ)

以巯基乙酸为稳定剂,在水溶液中合成CdTe/CdS量子点,基于量子点与Cu2+混合后发生荧光猝灭作用,建立CdTe/CdS量子点作为荧光探针检测微量铜的新方法。在pH 4.60的HAc-NaAc缓冲溶液中,反应时间为10 min时,Cu2+质量浓度在0.01～1.00μg/mL范围与CdTe/CdS量子点的荧光猝灭程度呈良好的线性关系,相关系数为0.9978,检出限为9.90×10-3μg/mL。方法可以用于雨水、自来水和延河水中Cu2+的分析。     

Fluorescence quenching method for the determination of catechol with gold nanoparticles and tyrosinase hybrid system

<正>The determination method of catechol by fluorescence quenching was developed.The assay was based on the combination of the unique property of gold nanoparticles with tyrosinase enzymatic reaction.In the presence of tyrosinase,the fluorescence of gold nanoparticles was quenched by catechol which can be employed to detect catechol.Under the optimal conditions,a linear range 5.0×10~(-7)-1.0×10~(-3) mol L~(-1) and a detection limit 1.0×10~(-7) mol L~(-1) of catechol were obtained.o-Quinone intermediate produced from the enzymatic catalyzed oxidation of catechol was considered to play the main role in the fluorescence quenching.     

Dissipative crystallization of sodium salts of carboxymethyl cellulose

Drying dissipative patterns were observed at room temperature on a cover glass, a watch glass, and a Petri glass dish during the course of dryness of aqueous solution of sodium salts of carboxymethyl cellulose (NaCMC) having different molecular weights in the presence of sodium chloride and in their absence. Without salt, the polymers were slightly hygroscopic and did not dry up completely on the substrates. Single crystals of the NaCMC without salt were short rodlike and quite similar to those of the other polysaccharides studied hitherto, i.e., hydroxypropyl cellulose and sodium dextran sulfate. Morphology of the polymer crystals were short rods, long dendritic rods, and/or hedrite assemblies depending on location in the dried film and in the presence of sodium chloride. Spoke-like orientation of the long dendritic rods appeared on a cover glass and a watch glass especially for NaCMC of low molecular weights.     

Interaction of acridine orange and sodium poly-α, L-glutamate

Summary The interaction of acridine orange and sodium poly-, L-glutamate in the pH range of 3.8–6.8 was studied by a spectral method and viscosity measurement. From the binding data, the molar change in entropy, enthalpy and the number of binding sites on polymer were calculated. The values of S° were positive. S° for binding decreasing extensively in pH range of 5.0. These results are explained by the transition of helix coil of the polymer. The intrinsic viscosity reduction in the presence of the dye, in pH 3.8 is due to the formation of dye bridges between the polymer helix.

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Zusammenfassung Die Wechselwirkung zwischen Natriumsalz-, L-Glutamin-Säure wurde mit den Methoden der Spektroskopie und der Viskositätsmessung untersucht. Aus den Bindungsdaten wurde die molare Änderung von Entropie und Enthalpie und die Zahl der Brückenstellen des Polymeren berechnet. Die Werte von S° sind positiv. Für die Binding ergibt sich für S° eine starke Verminderung im Bereich pH 5.0. Diese ist durch die Änderung der Konformation der Polymerketten (Helix Knäuel-Umwandlung) zu erklären.

     

Dielectric behavior of aqueous solutions of sodium carboxymethyl cellulose

Measurements are reported for the dielectric loss factor of the SCMC solutions over the frequency range 2 MHz to 50 MHz as a function of concentration of SCMC, concentration of added sodium chloride, molecular weight, and temperature. The results are in general agreement with those of other workers and are interpreted in terms of ionic theories in which motion of the diffuse counterions is the dominant feature.     

Comparison of N-alkyl acridine orange dyes as fluorescence probes for the determination of cardiolipin

The phospholipid (PL), cardiolipin (CL), is found almost exclusively in the inner membrane of mitochondria and loss of CL is considered as an important indication of cell apoptosis. Previously, 10-N-nonyl acridine orange (NAO) has been used as a fluorescent probe for the visualization of CL in mitochondrial cell membranes and in solution. In this work for the determination of CL, we have synthesized two new fluorescent probes, n-tetradecyl acridine orange (C14-AO), and n-octadecyl acridine orange (C18-AO) by reacting acridine orange with the corresponding n-alkyl bromide. Using excitation and emission wavelengths at about 500 and 525 nm and varying the percentage of methanol in water as the solvent, no interaction between CL and the fluorescent probes at 75% is noted but a proportional quenching of the fluorescence signal by CL is observed at 50% or less for C14-AO and 60% or less for C18-AO. Binding efficiency of these fluorescent probes to CL is compared using dye concentrations of 5, 10, and 20 μM. C18-AO shows a better sensitivity than C14-AO and NAO, respectively, but is less selective. For C14-AO, the detection limit and limit of quantitation are 0.07 and 0.21 μM, respectively, which are better than those previously reported for NAO. One anionic PL, phosphatidic acid, shows some quenching interference to both the C14 and C18 dyes but only at concentrations above the working range for sample analysis. The CL in mitochondrial membrane samples is determined by standard addition using C14-AO. The level of CL in the outer mitochondrial membrane compared to the inner membrane is significantly increased due to the addition of cadmium chloride into the cells causing cell apoptosis.     

Fluorescence relaxation dynamics of acridine orange in nanosized micellar systems and DNA

In this paper, we report a detailed study of the fluorescence relaxation dynamics of a well-known fluorescent DNA intercalator, acridine orange (AO), in reverse micelles (RM), micelles, and DNA using picosecond resolved fluorescence spectroscopy. Solvation studies of AO in AOT reverse micelles (RM) containing water indicate the locations of AO close to the interface and those in RM containing NaOH; there are two types of AO--one in the nonpolar oil phase and the other at the interface. The bound water at the reverse micellar interface is found to be much more rigid than that at the micellar interface of sodium dodecyl sulfate (SDS) micelles. Dynamic light scattering (DLS) studies allow for the determination of the hydrodynamic radius and the overall tumbling motion of the macromolecules. Wobbling-in-cone data analysis of the temporal fluorescence anisotropy decay allows for determination of restriction on the motion of fluorophores attached to the macromolecules. This model further applied to AO-intercalated genomic DNA and synthetic oligonucleotides within their structural integrity (as confirmed through circular dichroism (CD) studies) shows that AO experiences less restriction in genomic salmon sperm DNA compared with that in synthetic oligonucleotides, and among the oligonucleotides, the ones with AT base pairs are much more rigid. This study would invoke further research on the dynamical nature of AO in restricted environments.     

Photochemistry on surfaces: Fluorescence emission of monomers and dimers and triplet state absorption of acridine orange adsorbed on microcrystalline cellulose

Prompt fluorescence as well as delayed fluorescence emission of acridine orange was detected at room temperature from samples where this dye is adsorbed on microcrystalline cellulose. Ground state absorption studies provided evidence for dimer formation of the dye when adsorbed on cellulose, and the equilibrium constant for dimerisation was determined as 1.6±0.1 × 10⁶mol⁻¹g. At low loadings of acridine orange on cellulose (<1 μmol g⁻¹) the fluorescence emission is mainly due to the monomer and is similar to that observed in ethanolic solutions where little aggregation occurs, and peaks at 530 nm. A linear dependence of the fluorescence intensity on the amount of light absorbed by the dye was established for these “diluted” samples. However, at higher loadings (>20 μmol g⁻¹), the fluorescence intensity decreases, and the emission is broad with its maximum at 620 nm, and is mainly due to the dimer. By assuming that the excited monomer and dimer of acridine orange are the only emitting species, it was possible to determine the fluorescence quantum yields for these two species when adsorbed on microcrystalline cellulose as 0.95±0.05 and 0.40±0.10, respectively. Pulsed emission studies at room temperature in the millisecond time-range also revealed monomer and dimer emissions on this longer time-scale. These are shown to be due to thermally activated delayed fluorescence arising from the triplet states of monomer and dimer acridine orange as confirmed by diffuse reflectance transient absorption studies.     

Radiation preparation and swelling behavior of sodium carboxymethyl cellulose hydrogels

Sodium carboxymethyl cellulose (CMC) is a kind of degraded polymer under γ-irradiation. However, in this work, it has been found that CMC crosslinks partially to form hydrogel by radiation technique at more than 20% CMC aqueous solution. The gel fraction increases with the dose. The crosslinking reaction of CMC is promoted in the presence of N₂ or N₂O due to the increase of free radicals on CMC backbone, but gel fraction of CMC hydrogel is not high (<40%). Some important values related to this kind of new CMC hydrogel synthesized under different conditions, such as radiation yield of crosslinking G(x), gelation dose R_g, number average molecular weight of network M_c were calculated according to the Charlesby–Pinner equation. The results indicated that although crosslinked CMC hydrogel could be prepared by radiation method, the rate of radiation degradation of CMC was faster than that of radiation crosslinking due to the character of CMC itself. Swelling dynamics of CMC hydrogel and its swelling behavior at different conditions, such as acidic, basic, inorganic salt as well as temperature were also investigated. Strong acidity, strong basicity, small amount of inorganic salts and lower temperature can reduce swelling ratio.     

Studies of surface adsorbability of sodium carboxymethyl cellulose onto nylon 6 fiber byζ-potential method

Summary The surface adsorption behavior of a polyelectrolyte, sodium carboxymethyl cellulose (Na-CMC), onto Nylon 6 fiber was studied by measuring-potential of the fiber in acidic aqueous solutions (pH 3) of the polyelectrolyte. The amount of Na-CMC adsorbed per unit area of the fiber surface was calculated from the-potential. With the increase in the Na-CMC concentration, the sign of the-potential of the fiber rapidly changed from positive to negative and thereafter the negative values approached to the saturation values, and the amount of adsorption of the polyelectrolyte (expressed in g/cm²-fiber) increased also. These results may possibly be attributed mainly to the formation of the electrostatic bond between the fiber and the Na-CMC. The maximum amount of adsorption of the polyelectrolyte,A _s , decreased with the increase in the degree of polymerization. The slope,a, of theA _s vs. molecular weight,M, curve was equal to or less than zero. It was, therefore, suggested that the polyelectrolyte lay flat on the fiber surface with the same dimension as that in the solution.

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Zusammenfassung Es wurde das Oberflächenadsorptions verhalten eines Polyelektrolyten (Natriumcarboxymethylcellulose (Na-CMC)) auf Nylon 6 Faser durch-Potential-Messungen in sauren wässerigen Lösungen (pH 3) des Polyelektrolyten untersucht. Die Menge von Na-CMC, die pro Flächeneinheit der Faseroberfläche adsorbiert wird, wurde aus den-Potentialen berechnet. Mit steigender Na-CMC-Konzentration änderte sich das Vorzeichen des-Potentials der Faser rasch von positiv zu negativ, und danach näherte sich der negative Wert einem Sättigungswert; auch die adsorbierte Menge des Polyelektrolyten (in g/cm² Faser) nahm zu. Die Ergebnisse sind wahrscheinlich auf die Ausbildung elektrostatischer Bindungen zwischen Faser und Na-CMC zurückzuführen. Die maximal adsorbierte Menge an PolyelektrolytA _s nahm mit steigendem Polymerisationsgrad ab. Die Steigung (a) derA _s vs. Molekulargewicht (M)-Kurve war gleich oder kleiner als Null. Daraus wird gefolgert, daß der Polyelektrolyt eben auf der Faseroberfläche aufliegt mit den gleichen Dimensionen wie in der Lösung.

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With 7 figures and 2 tables

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Presented at the 29th Annual Meeting of the Chemical Society of Japan, the Symposium of Interfacial Electrical Phenomena, Hiroshima, Oct. 1973.     

Tin/polypyrrole composite anode using sodium carboxymethyl cellulose binder for lithium-ion batteries

A tin nanoparticle/polypyrrole (nano-Sn/PPy) composite was prepared by chemically reducing and coating Sn nanoparticles onto the PPy surface. The composite shows a much higher surface area than the pure nano-Sn reference sample, due to the porous higher surface area of PPy and the much smaller size of Sn in the nano-Sn/PPy composite than in the pure tin nanoparticle sample. Poly(vinylidene fluoride) (PVDF) and sodium carboxymethyl cellulose (CMC) were also used as binders, and the electrochemical performance was investigated. The electrochemical results show that both the capacity retention and the rate capability are in the same order of nano-Sn/PPy-CMC > nano-Sn/PPy-PVDF > nano-Sn-CMC > nano-Sn-PVDF. Scanning electronic microscopy (SEM) and electrochemical impedance spectroscopy (EIS) results show that CMC can prevent the formation of cracks in electrodes caused by the big volume changes during the charge-discharge process, and the PPy in the composite can provide a conducting matrix and alleviate the agglomeration of Sn nanoparticles. The present results indicate that the nano-Sn/PPy composite could be suitable for the next generation of anode materials with relatively good capacity retention and rate capability.     

荧光猝灭法测定痕量亚硝酸根

基于在酸性介质中,NO-2与藏红T直接反应,使藏红T的荧光猝灭,加入强碱弱酸盐对体系有增敏作用,据此提出了荧光法测定痕量NO-2的新方法。方法的线性范围为2.8～294ng/mL,方法的检出限为2.8ng/mL。可直接用于水样及蔬菜中痕量NO-2的测定。