DETERMINATION OF ATMOSPHERIC NITRO-POLYCYCLIC AROMATIC HYDROCARBONS AND THEIR PRECURSORS AT A HEAVY TRAFFIC ROADSIDE AND AT A RESIDENTIAL AREA IN OSAKA,JAPAN

Concentrations of nitrated polycyclic aromatic hydrocarbons (nitro-PAHs) and polycyclic aromatic hydrocarbons (PAHs) in airborne particles collected at two sites, a residential area and a roadside with high traffic density in Osaka, Japan, in summer and winter were quantified. Five nitro-PAHs, 1-nitropyrene (1-NP), 2-nitropyrene (2-NP), 2-nitrofluoranthene (2-NF), 3-nitrofluoranthene (3-NF), and 2-nitrotriphenylene (2-NTP) and five PAHs, pyrene (Py), fluoranthene (Fl), triphenylene (Tp), benzo[k]fluoranthene (B(k)F), and benzo[a]pyrene (B(a)P) were determined by high-performance liquid chromatography with chemiluminescence and fluorescence detection. At both sites, the mean concentration of 1-NP was higher in winter than in summer. On the contrary, the mean concentrations of 2-NF and 2-NP were higher in summer than in winter. Observed 2-NF/2-NP ratio in the range from 0.40 to 16 suggests that 2-NF and 2-NP were dominantly formed via OH radical initiated reaction in the atmosphere. Nitro-PAH and PAH concentrations were generally higher at a roadside area than at a residential area due to extremely higher concentration of particles at a roadside area. 1-NP/B(k)F ratio was higher at a roadside area than at a residential area, while 2-NF/B(k)F, 2-NP/B(k)F, and 2-NTP/B(k)F ratios were higher at a residential area than at a roadside area. The diurnal changes of 2-NF/B(k)F, 2-NP/B(k)F, and 2-NTP/B(k)F ratios were slightly different from those of 1-NP/B(k)F and 3-NF/B(k)F ratios. Thus, the differences in the patterns of nitro-PAHs/B(k)F ratios may be due to the disparity in formation pathways of each nitro-PAH.     

Arylene Azo-naphthol-furfuraldehyde Oligomer Dyes (Part-2)

Abstract

A series of oligomeric acid azo dyes has been prepared by coupling various aromatic diazonium salts to 1-naphthol-furfuraldehyde (1-NF) and 2-naphthol-furfuraldehyde (2-NF) oligomers. They were evaluated in terms of their softning points, yield, colour, solubility and UV-Vis spectra. Structure-property relationships are discussed and dyeings on wool, silk and nylon-6,6 assessed. Dyeings on wool, silk and nylon-6,6 resulted in yellow, orange and brown to red colourations having excellent fastness to light and washing.     

Functional polymers for colloidal applications. X. Syntheses of graft-charged naphthalene–formaldehyde condensates and their ability to disperse dyes

N-(3-sodium propylsulfonate)-α-naphthylamine–formaldehyde condensates (NAFS) and O-(3-propylsulfonate)-α-naphthol–formaldehyde condensates (NOFS) are synthesized by condensation reactions followed by ring-opening reactions. Those condensates are used as dispersants to disperse dyes in water (C. I. Navy Blue 79 and C. I. Brown 1), and can be compared to the conventional dispersants [e.g., naphthalenesulfonate–formaldehyde condensates (NSF)]. The dispersing properties of the condensates were evaluated by scanning electron microscopy (SEM), sedimentation, as well as measurments of viscosity. For NAFS or NOFS, the sulfonate groups were grafted separately on the backbone of the condensate; however, for NSF, the sulfonate groups were anchored on the backbone of the condensate. The structural effects of those condensates were demonstrated by comparing the dispersing ability of these condensates, and the conventional condensates NAFS and NOFS exhibit better dispersing abilities than NSF for the Navy Blue 79 and Brown 1 dyes. © 1996 John Wiley & Sons, Inc.     

聚丙烯催化剂内给电子体二乙酸-1,8-萘酚酯的合成与表征

以1,8-萘二酚和乙酰氯为原料,以三乙胺为吸收剂合成了二乙酸-1,8-萘酚酯,采用了红外光谱和核磁共振氢谱等分析测试手段对产品进行了结构表征并逐一归属。考察了原料配比、反应时间、反应温度及吸收剂用量等因素对二乙酸-1,8-萘酚酯收率的影响。实验结果表明,合成二乙酸-1,8-萘酚酯的最佳工艺条件为:1,8-萘二酚0.1 mol,n(1,8-萘二酚)︰n(乙酰氯)=1.0︰2.4,三乙胺吸收剂为60 mL,反应温度25℃,反应时间5.0 h,在此条件下,二乙酸-1,8-萘酚酯收率可达88.4%。     

球磨机中无溶剂高效合成1,1’-联二萘酚

球磨机中机械力化学作用下,β-萘酚经CuCl2·2H2O氧化偶联,无溶剂固态直接合成1,1’-联二萘酚,产率达91%。最佳反应条件为:球磨机转速350 r/min,n(CuCl2·2H2O)∶n(β-萘酚)=2∶1,研磨时间2 h。同时考察了其他Cu(Ⅱ)/Fe(Ⅲ)的金属盐氧化剂作用的β-萘酚的氧化偶联。     

Poly (acridine orange) film modified electrode for the determination 1-naphthol in the presence of 2-naphthol

The voltammetric behavior of 1-naphthol was studied with a poly (acridine orange) (PAO) film modified glass carbon electrode (GCE). The electrooxidation of 1-naphthol was an irreversible process with its oxidation overpotential at the PAO electrode 180 mV lower than that on the GCE. PAO electrode demonstrated electrocatalytic activity to the electrooxidation of 1-naphthol giving a greatly improved detection limit down to 8 × 10⁻⁸ mol L⁻¹(S/N = 3). At the optimal experimental condition, the oxidation peak current from the PAO electrode was linearly proportional to the concentration of 1-naphthol in the range of 2 × 10⁻⁷ to 3.2 × 10⁻⁶ mol L⁻¹ and 5.2 × 10⁻⁶ to 1.2 × 10⁻⁴ mol L⁻¹. The differences of the oxidation peak potentials between 1-naphthol and the coexisted 2-naphthol was 170 mV allowing the selective detection of 1-naphthol in a mixed solution with 2-naphthol. The detection of 1-naphthol in tap water and river water was carried out with satisfactory results.     

1-氨基-2-萘酚-4-磺酸的合成工艺研究

以 β 萘酚为原料 ,在水 醇混合溶剂存在下 ,经亚硝化、加成、磺化制得 1 氨基 2 萘酚 4 磺酸 ,考察了原料配比、混合溶剂配比、反应时间、反应温度及过滤等因素对反应的影响 ,确定了优惠工艺条件。亚硝化条件 :n(酚 )∶n(亚硝酸钠 )∶n(硫酸 ) =1∶1∶0 5 ,以 10 gβ 萘酚计 ,有机溶剂异丙醇用量 15ml,混合溶剂配比V(水 )∶V(异丙醇 ) =(1～ 1 5 )∶1。亚硝化完毕后将物料过滤 ,水洗。加成反应时间控制在 6h ,n(酚 )∶n(亚硫酸氢钠 ) =1∶2 ,碘化反应时间6h ,温度 5 0～ 6 0℃。在此条件下 ,收率达到 72 1%。     

Preparation of Silica-PAN Functionalized Nanoextractants for the Extraction of Ferbam from Various Samples

1-(2-pyridylazo)-2-naphthol modified SiO₂ nanoparticles were synthesized and evaluated as a nanoadsorbent for removing Ferbam from various environmental sources and fortified grain and vegetables samples. The 1-(2-pyridylazo)-2-naphthol modified SiO₂ nanoparticles were prepared by the sol-gel method. Nanoparticles were characterized by SEM and FT-IR. The adsorption of Ferbam was examined by the batch equilibrium technique. Conditions of the analysis such as preconcentration factor, effect of pH, sample volume, shaking time, elution conditions, and effects of interfering ions for the recovery of analyte were investigated. The equilibrium data analyzed by using the Langmuir isotherm, and the Freundlich and Temkin isotherm models, showed better agreement with the former model. The adsorption capacity of nanometer SiO₂-1-(2-pyridylazo)-2-naphthol was found to be 50.70 μmol/g at optimum pH and the detection limit (3σ) was 0.40 μg/L. The extractant showed rapid kinetic sorption. The adsorption equilibrium of Ferbam on nanometer SiO₂-1-(2-pyridylazo)-2-naphthol was achieved in 10 mins. Adsorbed Ferbam was easily eluted with 6 mL of 6 M hydrochloric acid. The maximum preconcentration factor was 58.33. The method was applied for the determination of trace amounts of Ferbam in various water samples and fortified samples.     

Iron(III)-induced activation of hydrogen peroxide for oxidation of 2-methylnaphthalene in glacial acetic acid

Simple iron(III) salts activate hydrogen peroxide to oxidize 2-methylnaphthalene to 2-methyl-1-naphthol in glacial acetic acid. 2-Methyl-1-naphthol is then oxidized to 2-methyl-1,4-naphthoquinone by hydrogen peroxide without influence of the catalyst. This is in contrast to the previous reports, which excluded the formation of 2-methyl-1-naphthol as an intermediate product in the process of 2-methylnaphthalene oxidation to 2-methyl-1,4-naphthoquinone. The process, however, mimics the microbial conversion of 2-methylnaphthalene to 2-methyl-1,4-naphthoquinone. The presence of chloride in the system causes exclusively the formation of 2-methyl-1-chloronaphthalene.     

Effect of some superplasticizers on the mechanical and physicochemical properties of blended cement pastes

Blended cement pastes made of Portland cement and fine sand (known in Egypt as El-Karnak cement) were made using a water–cement ratio of 0.25 by weight. Three pastes containing admixture (water-soluble condensates) were also prepared using a water–cement ratio of 0.25 and condensate (superplasticizer) content of 0.25% by the weight of cement; the superplasticizers used are Na-phenol sulfonate formaldehyde, Na-polystyrene sulfonate, and Na-ß-naphthol sulfonate formaldehyde condensates. All pastes were cured for various time intervals within the range of 0.02–90 days. Compressive strength tests, hydration kinetics, X-ray diffraction analysis, thermal analysis, and surface properties were studied and related as much as possible to the pore structure of the hardened pastes. © 1995 John Wiley & Sons, Inc.     

Combination of ARTP mutagenesis and color-mediated high-throughput screening to enhance 1-naphthol yield from microbial oxidation of naphthalene in aqueous system

Strain QCG of the aerobic bacteria Bacillus cereus is capable of producing 1-naphthol from naphthalene, this strain was first isolated and characterized in this study. Strain QCG was mutagenized to enhance 1-naphthol production, using atmospheric and room temperature plasma (ARTP) technology. Then, a microbial clone screening system was used to accelerate the operation. Meanwhile, a novel color-mediated high-throughput screening using 4-aminoantipyrine was performed to screen mutants. The optimal mutant strain QCG4 produced 19.58±0.34 mg∙L^‒1 1-naphthol from naphthalene that was 47.32% higher than that of the original strain (13.29±0.28 mg∙L^‒1). In addition, the optimal conditions for 1-naphthol production via whole-cell catalysis of strain QCG4 were determined to be an OD₆₀₀ of 40, 150 mg∙L^‒1 naphthalene, and 7.5% dimethyl formamide as a co-solvent at pH 7.5 and 26°C for 3 h, resulting in 41.18±0.12 mg∙L^‒1 1-naphthol, i.e., the mutant strain produces a 2.1-fold higher yield compared to the original strain.     

Methylation of 2-naphthol over molecular sieves

The mesoporous molecular sieves of the type MCM-41 with different pore openings (40, 64 and 80 Å) were used as catalysts in the gas-phase methylation of 2-naphthol by methanol at 473 K. Their catalytic activity was compared with that of BEA, SAPO-5 and SAPO-11. The molar ratio of 2-naphthol : methanol was varied from 1 : 4 to 1 : 6. The alkylation of the hydroxyl group (O-alkylation) as well as of the aromatic ring (C-alkylation) proceeded. The best yield of 2-methoxynaphthalene was achieved using MCM-41 40 Å and molar ratio 2-naphthol : methanol = 1 : 6.     

无溶剂CTAB催化制备取代2-氨基-2-色烯

在溴化十六烷基三甲基铵(CTAB)催化及无溶剂条件下,由芳亚甲基丙二腈与1-萘酚或2-萘酚发生加成、环化反应,生成相应的取代2-氨基-2-色烯。     

Mannich bases of 2-aminothiazoles

Synthesis of some new Mannich bases, 2(thiazolylaminobenzyl)-1-naphthols ( I ) and 1(thiazolylaminobenzyl)-2-naphthols ( II ) are described. Condensation of 4,5-disubstituted-2-aminothiazoles and the appropriate aldehyde with 1-naphthol gives ( I ), while condensation with 2-naphthol gives ( II ). Their structures have been ascertained by spectroscopy and by synthesis from the dibromoderivative of 2-arylidene-1-tetralone and the corresponding 2-aminothiazole.     

改善模塑料性能的苯酚改性蜜胺树脂的制备

采用苯酚对三聚氰胺-甲醛树脂(MF)进行改性,研究了3种原料(苯酚、三聚氰胺和甲醛)不同配比下的合成产物的模塑料性能,优选出低酚摩尔分数(8%)的用于模塑料加工的苯酚改性蜜胺树脂(PMF)。该树脂中甲醛与三聚氰胺的物质的量比(F1/M)为1.75∶1,甲醛与苯酚的物质的量比(F2/P)为1.7∶1,甲醛和苯酚的物质的量之和与三聚氰胺物质的量比((F1+F2+P)/M)为2.5∶1。该树脂可提高模塑料的加工性能,降低加工能量损耗,改善制品的模塑性和耐冲击性。     

Ozonolysis of 1-phenylazo-2-naphthol

The ozonolysis of 1-phenylazo-2-naphthol was studied using ozone in an oxygen stream. 1-Phenylazo-2-naphthol reacts with ozone to give benzene, chlorobenzene, phenol, o-naphthoquinone, phthalide and phthalic anhydride. The mechanism of the reaction is explained as an electrophilic attack of ozone with the hydrazone tautomer of 1-phenylazo-2-naphthol.     

柱前衍生化高效液相色谱法拆分1,1′-联-2-萘酚光学异构体

以(S)-(+)-樟脑磺酰氯作柱前手性衍生化试剂,与外消旋1,1′-联-2-萘酚反应,形成非对映异构体联二萘酚樟脑磺酸酯,再用反相高效液相色谱进行分离。结果表明,采用Zorbax XDB-C8和HypersilODS(C18)柱,流动相V(甲醇)∶V(水)分别为75∶25和85∶15,流速均为1mL/min时,分离度分别为1.86和1.74,有效地分离了两个非对映异构体。进一步水解得到光学纯(R)-1,1′-联-2-萘酚和(S)-1,1′-联-2-萘酚,ee值均达99%以上。     

1，1′-硫代双（2－萘酚）的合成

以2-萘酚为主要原料,与二氯化硫在甲苯、乙酸乙酯组成的混合溶剂中反应,合成了抗氧剂1,1′-硫代双（2-萘酚）。确定的最佳反应条件为：溶剂为由甲苯、乙酸乙酯组成的混合溶剂,甲苯、乙酸乙酯重量比为3：2,溶剂与2－萘酚重量比为8：1,2－萘酚与二氯化硫物质的量比为2：1．03,反应温度10-20℃,反应时间3h,产品收率84．7％,纯度大于99．0％。     

The photochemistry of 1-benzoyl-2-naphthol and 6-hydroxybenzanthrone and their effect on the rate of photo-oxidation of polypropylene

A comparison of the effect of two structurally similar additives, 1-benzoyl-2-naphthol and 6-hydroxybenzanthrone, on the rate of photo-oxidation of polypropylene under conditions of simulated daylight shows that while 6-hydroxybenzanthrone acts as a prodegradant, 1-benzoyl-2-naphthol is a light stabilizer. Examination of the spectroscopic and photochemical properties of 1-benzoyl-2-naphthol indicates that in fluid solution the photoexcited stabilizer is probably deactivated within the singlet manifold. In glassy solvents at 77°K, on the other hand, triplet formation does occur, but only in molecules in which the intermolecular hydrogen bond of the 1-benzoyl-2-naphthol is disrupted.     

Antioxidative efficiency of novel β-naphthol derivatives in storage assays of cracked naphtha

The types of hydrocarbons found in gasoline have great influence on the formation of gum (nonvolatile, insoluble, adhesive resin that forms sediments within fuel systems of an engine). In this study, the synthetic compound β-naphthol has been used in order to generate novel antioxidative substances: AO1 [6-N-ethyl,N-ethylamino)β-naphthol], AO2 [6-N-ethyl,N-diethylamino)-β-naphthol] and AO3 [mixture of amino-β-naphthol and 1,6-di-amino-β-naphthol]. The derived compounds were subjected to accelerated oxidative stability assays [potential gum (PG) and induction period (IP)] and to storage assays [washed gum (WG) and ASTM color] during six months with cracked naphtha provided by the petroleum refinery RPBC (Presidente Bernardes Refinery, in Cubatão, Brazil). During the PG and IP assays, the experimental amine mixture AO3 and the commercial product known as PDE were highlighted as good oxidation inhibitors, yielding average values of 39.15 mg/100 ml and 637 min, respectively. After the storage period, a better antioxidant behavior was observed for the experimental compound AO2, which provided an average WG value of 6.1 mg/100 ml.