Characteristic changes in the fluorescence spectra of 1-naphthol at the gelation point during the sol-gel-xerogel transitions

The fluorescence spectra of 1-naphthol were observed during the sol-gel-xerogel transitions of two different systems as a function of time; one is in the silicon and titanium (Si:Ti = 4500:1) binary systems involving no catalysts and the silicon and lithium (Si:Li = 99:1) binary systems involving HC1 as the catalyst. During the first stage of the sol-gel reaction of the 1-naphthol system, the fluorescence spectra mainly originated from the broad ’L₂ state. The fluorescence spectrum originating from the anionic species at around 470 nm increased as the reaction proceeded. It was found that the fluorescence spectra originating from the anionic species of 1-naphthol drastically decreased in both systems just after gelation. These findings indicate that it becomes difficult for the dissociation of the excited state of 1-naphthol to give a dissociative proton to the surrounding matrix. The fluorescence-excitation spectra for the Si/Ti system indicated that the main route for the excited state of 1-naphthol to form a dissociative proton is through the excited state of the contact ion pair, while the main route in the Si/Li system is via the direct excitation of the neutral 1-naphthol and its dissociation. The observed changes in the fluorescence spectra of 1-naphthol in these sol-gel systems provide a sensitive means to monitor changes during the sol-gel transition process.     

Room-temperature phosphorescence of 6-bromo-2-naphthol included in beta-cyclodextrin in the presence of cyclohexane

The formation constant for a 1:1 binary complex between 6-bromo-2-naphthol (6B2N) and beta-cyclodextrin (CD) in aqueous solution was determined by both absorptimetric and fluorimetric methods. Room-temperature phosphorescence (RTP) was induced by adding small amounts of different apolar liquids as the third component, with cyclohexane producing the strongest enhancement effect. Microcrystals formed in the ternary system seem to be necessary for obtaining phosphorescence emission. The deoxygenation by flowing nitrogen does not improve the RTP signals, while the addition of sodium sulfite as chemical deoxygenant produces quenching of the signals. The calibration graph for 6-bromo-2-naphthol in the presence of beta-CD and cyclohexane was linear for the range of concentrations between 0.04 and 1 mug ml(-1), with a detection limit of 0.04 mug ml(-1).     

Evaluation of 1-naphthol as a convenient fluorescent probe for monitoring ethanol-induced interdigitation in lipid bilayer membrane.

In this work we have tried to evaluate the usefulness of 1-naphthol as an excited state proton transfer fluorescent probe for studying the ethanol-induced interdigitation in lipid bilayer membranes. When ethanol concentration in lipisome is progressively increased, the neutral form fluorescence of 1-naphthol is found to decrease with corresponding increase in the anionic form intensity. This behavior is in contrast to that observed in the absence of lipid where a reverse effect is noticed. Modification of lipid bilayer is known to occur in the presence of ethanol, which increases the packing density of the membrane. Due to this induction of interdigitated gel phase, redistribution of naphthol between the inner core and interfacial region of the lipid bilayer takes places, accounting for the reduction in neutral form fluorescence intensity. The partition coefficient values and the quenching studies also support the redistribution of 1-naphthol in the liposome membrane. The neutral form fluorescence of 1-naphthol successfully monitors the shift in phase transition temperature due to ethanol-induced interdigitation. It also explains the prevention of interdigitation in lipid bilayer at high cholesterol concentration.     

Assessment of ternary iron-cyclodextrin-2-naphthol complexes using NMR and fluorescence spectroscopies

Recent research has indicated that ternary complexes can be formed among carboxymethyl-beta-cyclodextrin, certain polycyclic aromatic hydrocarbons (PAHs) (e.g. anthracene and 2-naphthol), and Fe(2+) in aqueous solution. The formation of these ternary complexes has been suggested as the reason for improved reaction efficiency in iron catalyzed Fenton degradation (H(2)O(2)+Fe(2+)-->*OH+OH(-)+Fe(3+)) of PAHs and other pollutants. In the present work, several other cyclodextrins were examined to determine their ability to form similar ternary complexes with 2-naphthol and Fe(2+). Fluorescence and NMR techniques were employed in this study. Results showed that hydroxypropyl-beta-cyclodextrin, beta-cyclodextrin, and alpha-cyclodextrin were able to encapsulate 2-naphthol molecules, but their binding with Fe(2+) was weak. On the contrary, sulfated-beta-cyclodextrin has significant binding with Fe(2+), but it showed little inclusion of 2-naphthol molecules. Consequently, none of these four cyclodextrins formed significant amounts of ternary complexes in aqueous solution. The techniques used in this study provide useful methods for assessing the ability of cyclodextrins to form ternary complexes with guest compounds and metal ions.     

Rapid simultaneous analysis of 1-naphthol and 2-naphthol in water samples by derivative variable-offset synchronous fluorescence spectroscopy

Derivative variable-offset synchronous fluorescence spectroscopy is developed to improve the spectral resolution and the selectivity of fluorescence measurements. 1-naphthol and 2-naphthol are employed to evaluate the proposed coupled technique and the various spectral comparisons are conducted. Second derivative variable-offset synchronous scanning permits the rapid simultaneous identification and quantitative determination of 1-naphthol and 2-naphthol in a mixture from a single spectrum. 6.7-2000 ng/ml 1-naphthol and 3.6-500 ng/ml 2-naphthol can be quantified with 1-naphthol and 2-naphthol ratios of 40: 1-1: 10. The determination of 1-naphthol and 2-naphthol in various spiked water samples gave a mean recovery of 100.7% with a relative standard deviation of 2.8% for 1-naphthol and mean recovery of 99.7% with a relative standard deviation (RSD of 2.6% for 2-naphthol, respectively.     

Proton transfer from 2-naphthol to aliphatic amines in supercritical CO2

The proton transfer from 2-naphthol to aliphatic amines was studied in supercritical CO(2) (scCO(2)) and in cyclohexane as reference solvent, by absorption and fluorescence spectroscopy and by time-resolved emission. Irradiation of 2-naphthol in scCO(2) in the presence of ethyldiisopropylamine shows dynamic fluorescence quenching of the acidic form of 2-naphthol and emission from the basic form. Fluorescence excitation spectra show that the emission of the basic form is originated upon excitation of the acidic form. The interaction between 2-naphthol and the amines is described by the formation of a complex with proton donor-acceptor character in the ground and excited states of 2-naphthol. The acidity increase of 2-naphthol upon electronic excitation to the first excited singlet in scCO(2) is as high as in water. Proton transfer quantum yields of 0.6 can be easily achieved in scCO(2). The results have implications for carrying out acid-base catalyzed reactions in scCO(2).     

Synchronous-derivative phosphorimetric determination of 1- and 2-naphthol in irrigation water by employing beta-cyclodextrin

A room-temperature phosphorimetric (RTP) study of the inclusion process between 1- and 2-naphthol, beta-cyclodextrin (beta-CD) and 3-bromo-1-propanol as heavy atom pertuber has been performed. Experimental conditions were optimized for the formation of trimolecular complexes with lifetimes of 10.82 and 9.41 ms for 1- and 2-naphthol, respectively. A synchronous-derivative room-temperature phosphorimetric method has been proposed to the analysis of both naphthols in synthetic mixtures and irrigation water in the ratio 1:10 to 10:1; the limit of detection is 0.02 mug ml(-1) and the relative standard deviation (RSD) is about 6%.     

Microenvironmental control of photochemical reactions: II. Fluorescence quenching of naphthalene and 1,3-di-(α-naphthyl)propane by RNA and bases in aqueous methanol

The fluorescence quenching of naphthalene ( 2 ) and 1,3-di(α-naphythyl)propane ( 1 ) by RNA and bases in methanol-water (v:v = 1:1) binary solvents in the presence or absence of cyclodextrin (CD) has been investigated. The results show that both the monomer and excimer fluorescence of 1 can be quenched by these quenchers. The quenching and rates depend on the quencher and temperature. It is shown that there is a critical temperature (Tc) for each quencher. Below Tc, the excimer fluorescence spectra show vibrational structures and the Stern-Volmer plots are straight lines (for uracil and cytosine); while above the Tc, the vibrational structures disappear and the Stern-Volmer plots deviate from linearity and curve upward. The former is a static process; while the latter is a mixture of both static and dynamic processes. The addition of α-CD has no effect on the fine structure; whereas β-CD prevents the appearance of this structure efficiently. The quenching rates both for the monomer and excimer of 1 by bases except cytosine in the presence of β-CD at ambient temperature are not changed; the quenching of fluorescence of 1 by RNA in the presence of β-CD, however, is hindered. Time-resolved fluorescence study shows that the excimer fine structures appear from the zero time. The intensity of fine structures depend on the fraction of water (π) in binary solvents, and it is independent of the pH value of the solvents. It is suggested that bases and RNA induced aggregates (perhaps microcrystal) are formed, in which the motion of molecules 1 is limited.     

Effects of Si−Al composition on the fluorescence spectra of 1-naphthol during the sol-gel-xerogel transitions

A systematic study has been carried out on the characteristic changes in the fluorescence spectra of 1-naphthol doped in the sol-gel-xerogel transition systems comprised of tetraethyl orthosilicate and diisobutoxyaluminium triethylsilicate catalyzed by a small amount of HCl, NH₄OH, as well as under uncatalyzed conditions. In the systems containing large amounts of silicon, the fluorescence of 1-naphthol shifts to the red (a predominant emission from the ¹L_a state) during the first stage of the reaction. This red shift indicates an increase in the polarity of the matrix surrounding 1-naphthol. In the second stage of the reaction, the spectrum shifts to the blue (a predominant emission from the ¹L_b state), reflecting an increase in the micro-viscosity around 1-naphthol. In the systems containing relatively large amounts of aluminum, however, the spectrum just after mixing shows a larger red shift than that originating from the ¹L₂ emission. This large red-shifted fluorescence reflects the formation of a complex between 1-naphthol and the −O−Al−O−Si−O-network. The spectrum then shifted to the blue. The spectral behaviours observed indicate that there is a large and dynamic molecular-level change in the physicochemical properties of the matrix surrounding the 1-naphthol molecules during the sol-gel-xerogel transitions of the systems while the gelation phenomenon reflects macroscopic inflexibility although it is completely different from the restriction of movement at the molecular level.     

Determination of carbaryl and its metabolite 1-naphthol in water samples by fluorescence spectrophotometer after anionic surfactant micelle-mediated extraction with sodium dodecylsulfate

Anionic surfactant micelle-mediated extraction with sodium dodecylsulfate (SDS) was applied as preconcentration step prior to fluorescence spectrophotometer without further cleanup step. The obtained surfactant-rich phase was diluted to a fixed volume with water-miscible solvents. Carbaryl and its metabolite 1-naphthol were used as test compounds. The detection limits (LODs) of the method were in the microgram per liter area. Recoveries obtained from four real water samples ranged from 90.7 to 98.6%. Under the optimum experimental conditions, the method described showed a good precision, with relative standard deviations (R.S.D.) of less than 6%. According to the results, this approach reduced the viscidity of the surfactant-rich phase and made the combination of fluorescence spectrophotometer with anionic surfactant micelle-mediated extraction much easier.     

Effect of beta-cyclodextrin on the excited state proton transfer in 1-naphthol-2-sulfonate

The photophysical properties of 1-naphthol-2-sulfonate (1-NOH-2-S) in various solvents and in aqueous beta-cyclodextrin (CD) solution have been investigated. The fluorescence quantum yields in non-aqueous solvents are approximately 0.5, while in water the fluorescence quantum yield is 0.1. The fluorescence quantum yield doubled on the addition of beta-CD. In aqueous solution, proton transfer to water takes place efficiently leading to the formation of the anion form with its longer wavelength emission broad band at about 460 nm. Any environmental changes have been found to affect the rate of deprotonation and subsequently the band intensity at 460 nm. In non-aqueous solution the anion emission band disappears completely. Upon the addition of beta-CD to the aqueous solution of 1-NOH-2-S, the anion emission decreases with an increase in the intensity of the neutral form at 362 nm. Fluorescence measurements show 1:1 inclusion of 1-NOH-2-S in the beta-CD cavity with an association constant of 1915 M(-1) using Benesi-Heldbrand treatment. 1H NMR studies are used to confirm the inclusion and to provide information on the orientation of 1-NOH-2-S inside the cavity of beta-CD.     

Synthesis and photophysical processes of 9-bromo-10-naphthalen-2-yl-anthracene

A novel luminescent compound, 9-bromo-10-naphthalen-2-yl-anthracene (BNA) is synthesized by Suzuki Cross-coupling reaction of 9-bromo-anthracene and naphthalene-2-boronic acid. The structure is characterized by (1)H NMR, IR and UV-vis spectroscopy. The photophysical processes of 9-bromo-10-naphthalen-2-yl-anthracene have been carefully investigated by UV-vis absorption and fluorescence spectra. The results show that the compound emits blue and blue-violet light. The emission spectra exhibit obvious solvent effect. With the difference in polarity of solvents, The emission spectra is not only slightly blue shift with the increase of the solvent polarity but also change on the intensity of fluorescence at room temperature .The light emitting can be quenched by electron donor, N,N-dimethylaniline (DMA). On adding gradually DMA into the solution of BNA, the emission intensities of fluorescence are gradually decreased. The quenching effect follows the Stern-Volmer equation.     

锌离子对缓冲液中槲皮素和牛血清白蛋白相互作用的影响

采用荧光光谱法和紫外光谱法研究了Zn2+离子对槲皮素(Qct)和牛血清白蛋白(BSA)在pH=7.4的Tris-HCl缓冲溶液中相互作用的影响;根据荧光猝灭双倒数图计算了Qct和BSA之间的结合常数和结合位点数.结果表明,Qct和Zn2+离子都可以使BSA的荧光强度发生猝灭;Qct和BSA之间的结合常数为3.17×107L.mol-1.s-1,结合位点数为1.32.定量计算表明,加入Zn2+离子后,Qct与BSA间的结合常数显著降低、结合位点数减小,表明Zn2+离子参与了Qct与BSA的结合过程.     

Adsolubilization of 2-naphthol into adsorbed layer of PEO-PPO-PEO triblock copolymers on hydrophilic silica

Adsolubilization of 2-naphthol into an adsorbed layer of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock copolymers (Pluronics) on hydrophilic silica has been investigated. Four kinds of Pluronics (P103, P105, P123, and F108) were used in order to understand the effect of the hydrophobicity of surfactant on the adsolubilization. The order of the adsorption in the saturation level was found to be P123 approximately P103 > P105 > F108, meaning that Pluronics with higher hydrophobicity can adsorb preferentially to the silica surface. Indeed, this order was parallel to the order of the adsolubilization amount of 2-naphthol. In the case of co-addition of the Pluronics and 2-naphthol, the adsolubilization amount increased gradually at lower surfactant concentration regions, reached a maximum, and then decreased with increasing concentration of the Pluronics. The maximum amount appeared at critical polymolecular micelle concentration of each Pluronics. On the other hand, the final decrement was not observed when 2-naphthol was added after replacement of the Pluronics supernatant by the Pluronics free solution. These results suggest that adsolubilization behavior is influenced by the existence of the polymolecular micellar aggregates in the solution phase.     

Development of a novel deltamethrin sensor based on molecularly imprinted silica nanospheres embedded CdTe quantum dots

A novel procedure for the determination of deltmethrin (DM) is reported. The water-soluble CdTe quantum dots (QDs) and highly fluorescent silica molecularly imprinted nanospheres embedded CdTe QDs (CdTe-SiO2-MIPs) were prepared and characterized by fluorescence spectroscopy, UV-vis spectroscopy, TEM and IR. The fluorescence nanosensor based CdTe-SiO2-MIPs is developed. The possible quenching mechanism is discussed by DM. Under optimal conditions, the relative fluorescence intensity of CdTe-SiO2-MIPs decreased with increasing DM by a Stern-Volmer type equation in the concentration range of 0.5-35.0 μg mL(-1), the corresponding detection limit is 0.16 μg mL(-1). The developed sensor based on CdTe-SiO2-MIPs was applied to determine DM in fruit and vegetable samples.     

Isosteric heats of sorption of 1-naphthol and phenol from aqueous solutions by beta-cyclodextrin polymers

The sorption of phenol and 1-naphthol from aqueous solutions by beta-cyclodextrin polymers has been analyzed using the isosteric heat approach. This has proven to be a useful tool for comparing the interactions between the sorbents and the sorbates. With the purpose of ascertaining the role of the cyclodextrin cavities and the crosslinking network in the sorption process, analogous sucrose polymers have been prepared using the same crosslinking reagents (epichlorohydrin, succinyl chloride, 1,6-hexamethylene diisocyanate, and toluene-2,4-diisocyanate). The two studied sorbates, phenol and 1-naphthol, also show important differences in their affinities for the cyclodextrin cavities and the crosslinking networks.     

1-Naphthol as an excited state proton transfer fluorescent probe for sensing bound-water hydration of polyvinyl alcohol

When 1-naphthol incorporated polyvinyl alcohol (PVA) films are allowed to swell in water, there is a loss of fluorescence intensity of the neutral form with a concomitant increase of the anionic form fluorescence intensity. This fluorescence response due to the excited state prototropism (ESPT) of 1-naphthol is very sensitive to the initial stage of hydration of the PVA. Using an existing model of hydrogel swelling and DSC experiments, it was reasoned that 1-naphthol senses the bound-water component of PVA hydration. Thus, 1-naphthol is proposed as an ESPT fluorescent sensor for the specific sensing of bound-water hydration of PVA hydrogel.     

Spectroscopic studies on the inclusion complex of 2-naphthol-6-sulfonate with beta-cyclodextrin

The photophysical properties of 2-naphthol-6-sulfonate (2-NOH-6-S) in various solvents and in aqueous beta-cyclodextrin solution have been investigated. The fluorescence quantum yields in non-aqueous solvents are approximately 0.20+/-0.02, while in water the yield is higher. The fluorescence quantum yield in water was found to depend on the pH value of the medium and increases as the pH increase up to a pH value of 4.0 where it comes to be constant. Absorption and fluorescence measurements show 1:1 inclusion of 2-NOH-6-S in the beta-cyclodextrin cavity. The association constant of 2-NOH-6-S-beta-cyclodextrin complex based on fluorescence measurements was calculated using Benesi-Hildbrand relationship and found to be 330+/-30M(-1). (1)H NMR studies are used to confirm the inclusion and to provide information on the geometry of 2-NOH-6-S inside the cavity of beta-cyclodextrin.     

Photo-induced proton-transfer cycle of 2-naphthol in faujasite zeolitic nanocavities

The excited-state deprotonation and ground-state reprotonation of a 2-naphthol molecule encapsulated in the zeolitic nanocavity of NaX have been studied by measuring static and time-resolved spectra of fluorescence and reflectance. The excited molecule undergoes enol dissociation within 300 ps to form an isolated ion pair, which undergoes geminate recombination in 1200 ps or separation to produce the anionic species of 2-naphtholate on the time scale of 2500 ps. Ground-state reprotonation, controlled by the diffusion rate of a proton, is then followed in 0.8 ms with an activation energy of 13 kJ mol(-1).     

Synthesis and photophysics of novel 8-hydroxyquinoline aluminum metal complex with fluorene units

A novel luminescent metal complex, (MQPF)3Al2, with 8-hydroxyquinoline aluminum and 9,9-diphenylfluorene was synthesized. The optical properties were investigated by UV-vis absorption and fluorescence emission spectra. The results showed that the luminescence quantum yield of (MQPF)3Al2 was 0.612 in THF and it emitted red light with the band gap of 3.18 eV estimated from the onset absorption. The emission spectra exhibited obvious solvent effect. With the increase of polarity of solvents the fluorescence spectra changed obviously and appeared blue shift about 60 nm at room temperature. In addition, the light-emitting can be quenched by both electron donor (N,N-dimethylaniline) and electron acceptor (Fullerene), where the processes followed the Stern-Volmer equation. However, when adding 1,4-dicyanobenzene (DCB) which was a stronger electron acceptor to the solution of (MQPF)3Al2, the fluorescent intensity was increased.