Control of Regiochemistry in Photodimerization through Micellar Preorientational Effect: 2-Substituted Naphthalenes

Photodimerization of 2-substituted naphthalenes in organic solvents has been well explored. In contrast to their behavior in organic solvents, in anionic and cationic micellar media enhanced reactivity and pronounced regioselectivity are observed. Reactivity enhancement in micellar media is attributed to the local concentration effect. Enhanced reactivity in CTAC and DTAC compared to CTAB micelles is attributed to the counterion effect, and the regioselective photodimerization observed in anionic and cationic micelles leading exclusively to the cis dimer or the products derived therefrom is rationalized on the basis of the preorientational effect of micelles.

Rearrangements in the cerium(IV) and manganese(III) oxidations of substituted naphthalenes and the nih shift mechanism

Ceric ammonium sulphate oxidation of 1- and 1,4- disubstituted naphthalenes gives 2- and/or 2,3- disubstituted 1,4- naphthoquinones through migration of substituents (D, Br, Ph). Similar rearrangements are also observed in the manganese(III) oxidation and also in the anodic oxidation of these substrates. The results are consistent with the proposal that these oxidations go through the formation of radical cation followed by reaction with H2O and further oxidation of the radical to the carbocationic intermediate on the way to the corresponding 1,4-naphthoquinone. Oxidation of 1,4-diphenylnaphthalene gives 2,3-diphenyl-1,4-naphthoquinone or 4-hydroxy- 2,4- diphenyl - 1(4)R - naphthalenone. The results are in accordance with the conclusion that such rearrangements do not require prior formation of arene oxide intermediates, originally proposed for the NM shift mechanism.

Oxidation of substituted benzylic hydrocarbons and naphthalenes by peroxydisulphate in the presence of metal ions

Oxidations of various substituted benzylic hydrocarbons with peroxydisulphate in the presence of metal ion catalysts like iron, nickel, copper, cobalt, silver and cerium were examined. Among the metal ions copper (II) catalysed reaction gives products in excellent yield, whereas oxidation of naphthalene and substituted naphthalenes gives low to moderate yield of the products with peroxydisulphate- copper (II).

Naphthalenes Image microwave irradiation induced rearrangement on montmorillonite K-10

Irradiation of 4-aryl-4-alkylhex-5-en-2-ones (e.g. 1a) or 5-aryl-4-alkylhex-5-en-2-ones (e.g. 2a) adsorbed on montmorillonite K-10 in a commercial microwave oven furnishes the multialkylated naphthalenes (e.g. 3).

Isomeric identification of methylated naphthalenes using gas phase infrared spectroscopy

We report gas phase mid-infrared spectra of 1- and 2- methyl naphthalenes at 0.2 cm(-1) resolution. Assignment of observed bands have been made using scaled quantum mechanical (SQM) calculations where the force fields rather the frequencies are scaled to find a close fit between observed and calculated bands. The structure of the molecules has been optimized using B3LYP level of theory in conjunction with standard 6-311G** basis set to obtain the harmonic frequencies. Using the force constants in Cartesian coordinates from the Gaussian output, scaled force field calculations are carried out using a modified version of the UMAT program in the QCPE package. Potential energy distributions of the normal modes obtained from such calculations helped us assign the observed bands and identify the unique features of the spectra of 1- and 2-MNs which are important for their isomeric identification.

Quantitative structure-property relationships for octanol-air partition coefficients of polychlorinated naphthalenes, chlorobenzenes and p,p '-DDT

The octanol-air partition coefficient (K-OA) is a key descriptor of chemicals partitioning between the atmosphere and environmental organic phases. Quantitative structure-property relationships (QSPR) are necessary to model and predict KOA from molecular structures. Based on 12 quantum chemical descriptors computed by the PM3 Hamiltonian, using partial least squares (PLS) analysis, a QSPR model for logarithms of K-OA to base 10 (log K-OA) for polychlorinated naphthalenes (PCNs), chlorobenzenes and p,p'-DDT was obtained. The cross-validated Q(cum)(2) value of the model is 0.973, indicating a good predictive ability of the model. The main factors governing log K-OA of the PCNs, chlorobenzenes, and p,p'-DDT are, in order of decreasing importance, molecular size and molecular ability of donating/accepting electrons to participate in intermolecular interactions. The intermolecular dispersive interactions play a leading role in governing log K-OA. The more chlorines in PCN and chlorobenzene molecules, the greater the log K-OA values. Increasing E-LUMO (the energy of the lowest unoccupied molecular orbital) of the molecules leads to decreasing log K-OA values, implying possible intermolecular interactions between the molecules under study and octanol molecules. (C) 2002 Elsevier Science Ltd. All rights reserved.

Regioselective Deiodination of Thyroxine by Iodothyronine Deiodinase Mimics: An Unusual Mechanistic Pathway Involving Cooperative Chalcogen and Halogen Bonding

Iodothyronine deiodinases (IDs) are mammalian selenoenzymes that catalyze the conversion of thyroxine (T4) to 3,5,3'-triiodothyronine (T3) and 3,3',5'-triiodothyronine (rT3) by the outer- and inner-ring deiodination pathways, respectively. These enzymes also catalyze further deiodination of T3 and rT3 to produce a variety of di- and monoiodo derivatives. In this paper, the deiodinase activity of a series of pen-substituted naphthalenes having different amino groups is described. These compounds remove iodine selectively from the inner-ring of T4 and T3 to produce rT3 and 3,3'-diiodothyronine (3,3'-T2), respectively. The naphthyl-based compounds having two selenols in the pen-positions exhibit much higher deiodinase activity than those having two thiols or a thiol selenol pair. Mechanistic investigations reveal that the formation of a halogen bond between the iodine and chalcogen (S or Se) and the pen-interaction between two chalcogen atoms (chalcogen bond) are important for the deiodination reactions. Although the formation of a halogen bond leads to elongation of the C-I bond, the chalcogen bond facilitates the transfer of more electron density to the C-I sigma* orbitals, leading to a complete cleavage of the C-I bond. The higher activity of amino-substituted selenium compounds can be ascribed to the deprotonation of thiol/selenol moiety by the amino group, which not only increases the strength of halogen bond but also facilitates the chalcogen chalcogen interactions.

莱州湾区域表层沉积物中多氯化萘、多溴联苯醚和氯化石蜡的研究

本研究建立了沉积物中氯化石蜡（CPs）的分析方法，对莱州湾和该区域主要河流的表层沉积物中多氯萘（PCNs），多溴联苯醚（PBDEs）和CPs进行了分析，获得了他们在研究区域的含量水平、空间分布和单体分布模式，并初步探讨了它们在环境中的来源和迁移规律，估算了这三类污染物在莱州湾表层沉积物中的储量，初步评估了莱州湾沿岸的工业排放与人类活动对海洋生态环境的影响。 莱州湾海洋和河流沉积物PCNs的含量分别为65-470 pg/g dw，52-5100 pg/g dw，平均值分别为260 pg/g dw，1100 pg/g dw。莱州湾沉积物中PCNs的含量较低，与发达国家的背景值相当，主要河流沉积物与其他地区的近海、海湾、湖泊沉积物的含量相当。该区域的PCNs主要以5-Cl和6-Cl为主，为工业来源，主要受化工行业的影响。石化工厂热过程产生的低氯组分可能也是该区域PCNs的一个重要来源。莱州湾的PCNs主要来自水体颗粒的输入，而大气沉降来源的贡献不明显。 河流沉积物ΣPBDEs（不包括BDE-209）的含量分别为0.01- 53 ng/g dw，BDE-209的含量为0.74- 280 ng/g dw，平均值分别为4.4 ng/g dw，51 ng/g dw。在组成上，BDE-209占绝对优势，比低溴代BDEs高1-2个数量级，这是由于我国市场上十溴联苯醚是最主要的溴代阻燃剂。ΣPBDEs与亚洲一些地区含量相当，比北美和欧洲一些地区要低；BDE-209含量含量高出北美和欧洲一些地区，处于较高的水平。河流沉积物中BDE-47与-99，BDE-183与-153、-154具有很好的相关性，而且这几种单体质量分数相当，说明莱州湾区域存在五溴和八溴两种工业BDE阻燃剂来源。海洋沉积物中ΣPBDEs的含量为nd- 0.66 ng/g dw，平均值为0.32 ng/g dw，处于较低水平，BDE-209的含量为0.66- 12 ng/g dw，平均值为5.1 ng/g dw，与欧美一些地区相当，主要来自水体颗粒的输入。 本研究用电子捕获低分辨质谱（ECNI-LRMS）建立了沉积物中CPs的分析方法。该方法基于ECNI质谱对SCCP的响应与其氯含量在一定范围内呈线性关系的特性，建立SCCP的总响应因子与氯含量的工作曲线，从而建立定量方法。重点改进了传统方法中由于SCCP标准品和样品中氯含量不同所造成的响应因子的差别，不再要求标准品的含氯量与样品一致，从而提高了SCCP的分析效率与方法准确性。实验发现，当SCCP的实际氯含量在51%-63%之间时，二者线性关系良好（r2>0.96）。用不同氯含量的标准参考品测试，误差为8%-43%。仪器检测限和方法检测限分别为25-400 μg/L，20 ng/g。类似地，建立了中链氯化石蜡（MCCP）的分析方法，工作曲线的实际氯含量范围为44-57%，仪器检测限40-600 μg/L，方法检测限为6 ng/g。通过对比样品与标准品的峰形特征，严格控制保留时间来辨别SCCP与MCCP，实验证明由于二者叠加导致的误差：SCCP为8%，MCCP为14%，总体来说，用该方法得到的CPs数据是可靠的。本文所使用的净化方法能实现CPs与大部分有机氯化合物的分离。 用该方法对莱州湾的沉积物的CPs进行定量，除了两个河流样品MCCP的计算含氯量低于工作曲线以外，其他样品的SCCP和MCCP的计算氯含量都在工作曲线的范围之内。河流沉积物中SCCP和MCCP的含量分别为1-1200 ng/g dw，1-3300 ng/g dw，MCCP/SCCP均值为1.2；含量分布变化较大，一些河段受到工业排放的影响，CPs浓度高出均值1-2个数量级，MCCP/SCCP值也显著高出平均值。莱州湾区域大部分河流的CPs含量与欧洲、北美和日本一些地区相当，而一些受到点源污染的河段则处于较高的水平。河流中SCCP的质量分布在不同的站位不一样，在受到点源影响的样品中，C13的质量分数明显增大，占优势地位，可能是由MCCP携带的SCCP组分所致。MCCP的质量分布在河流和海洋中没有区别，都是C14占绝对优势。从氯取代的组分来讲，所有样品都是以6-8氯取代为主。海洋沉积物中SCCP和MCCP的含量分别为3-18 ng/g dw，1-13 ng/g dw， MCCP/SCCP均值为0.68，显著低于河流沉积物；SCCP的质量分布较为一致，都是以C10和C11为主。研究发现莱州湾区域SCCP与MCCP来源相似，但迁移规律有的不同。海洋环境中的MCCP可能主要来自水体颗粒的输入，而溶解态输入也是海洋环境中SCCP的重要来源。 对这三类污染物在莱州湾表层沉积物中的储量估算得到PCNs、ΣPBDEs、BDE-209、SCCP和MCCP在莱州湾表层0-10 cm沉积物中的储量分别为0.20t，0.25t，3.95t，6.52t，4.30t。拥有10%的渤海海域面积的莱州湾ΣPBDEs和BDE-209的储量分别占渤海海区总量的18-23%，18-32%，远远超过渤海的平均值。

Cellular-Responses To Polycyclic Aromatic-Hydrocarbons And Phenobarbital In Mytilus-Edulis

Certain polycyclic aromatic hydrocarbons and phenobarbital induced an increase in the activity of microsomal NADPH neotetrazolium reductase (linked to mixed function oxygenase systems) in the blood cells of Mytilus edulis. Phenanthrene and methylated naphthalenes caused lysosomal destabilisation which is believed to be directly related to the mechanism of cytotoxicity in the digestive cells. The use of these cytochemical techniques as indices of aromatic hydrocarbon contamination is discussed.

Biomonitoring of polybrominated diphenyl ether (PBDE) pollution: A field study

Polybrominated diphenyl ethers (PBDEs) and cytochrome P450 enzyme activities were investigated in European eels (Anguilla anguilla) collected from seven sites in a coastal lagoon in the north-western Mediterranean Sea, Orbetello lagoon (Italy). Twelve PBDE congeners were measured in muscle and two CYP1A enzyme activities, 7-ethoxyresorufin-O-deethylase (EROD) and benzo(a)pyrene monooxygenase (BP (a)PMO), were investigated in liver microsomal fraction in order to obtain insights into the health of the lagoon environment. PBDE muscle levels were low and the most abundant congeners were 2,2',4,4'-tetrabronnodiphenylether (BDE-47), 2,2',4,4',5,5'-hexaBDE (BDE-153) and 2,2',4,5'-tetraBDE (BDE-49). EROD and B(a)PMO activities were also low and no differences were observed between eels from different sites. Multivariate analysis (PCA) did not indicate correlations between PBDEs and either P450 activities. (c) 2008 Elsevier Inc. All rights reserved.

Sequential hydrocarbon biodegradation of a soil from arid coastal Australia oil-treated under laboratory controlled conditions

A general consistency in the sequential order of petroleum hydrocarbon reduction in previous biodegradation studies has led to the proposal of several molecularly based biodegradation scales. Few studies have investigated the biodegradation susceptibility of petroleum hydrocarbon products in soil media, however, and metabolic preferences can change with habitat type. A laboratory based study comprising gas chromatography–mass spectrometry (GC–MS) analysis of extracts of oil-treated soil samples incubated for up to 161 days was conducted to investigate the biodegradation of crude oil exposed to sandy soils of Barrow Island, home to both a Class ‘‘A” nature reserve and Australia’s largest on-shore oil field. Biodegradation trends of the hydrocarbon-treated soils were largely consistent with previous reports but some unusual behaviour was recognised both between and within hydrocarbon classes. For example, the n-alkanes persisted at trace levels from day 86 to 161 following the removal of typically more stable dimethyl naphthalenes and methyl phenanthrenes. The relative susceptibility to biodegradation of different di- tri- and tetramethylnaphthalene isomers also showed several features distinct from previous reports. The unique biodegradation behaviour of Barrow Is. soil likely reflects difference in microbial functioning with physiochemical variation in the environment. Correlation of molecular parameters, reduction rates of selected alkyl naphthalene isomers and CO2 respiration values with a delayed (61 d) oil-treated soil identified a slowing of biodegradation with microcosm incubation; a reduced function or population of incubated soil flora might also influence the biodegradation patterns observed.

Efficacy, safety and tolerability of terbinafine for Tinea capitis in children: Brazilian multicentric study with daily oral tablets for 1, 2 and 4 weeks

Background: Tinea capitis is a common skin disease seen predominantly in children. The standard therapies for this disease are griseofulvin and ketoconazole. Nevertheless, these drugs have drawbacks in that they are only fungistatic and require treatment for at least 6 weeks. Previous studies with oral terbinafine for the treatment of Tinea capitis have shown that this agent is effective when given for 4 weeks, comparable to an 8-week regimen with griseofulvin. To date there is no data on the use of oral terbinafine in Brazilian children. Objectives: To assess the efficacy, safety and tolerability of oral terbinafine in short-term treatments (1-, 2- and 4-week treatment) of Tinea capitis in children. Patients and methods: One hundred and thirty-two children aged 1-14 years were enrolled in this study, but only 107 were considered for the final efficacy analysis. Diagnosis included clinical assessment and examination by Wood's light. Confirmation was obtained by direct microscopy and culture for fungus. Terbinafine dosage (125 or 250 mg/day) was adjusted according to patient weight. Efficacy was evaluated both by clinical and mycological assessment. Safety and tolerability variables included data on adverse reaction and clinical laboratory evaluations. Results: Mycological evaluation in the follow-up visit at week 12 showed negative direct microscopy and culture results in 48.6, 60.5 and 69.7% patients in groups 1-, 2- and 4-week, respectively (n.s.). At week 12, 84.8% patients in group 4-week achieved clinical cure with a significant difference compared to groups 1- and 2-week, 54.3 and 60.5%, respectively (P < 0.01). Adverse reactions were present in 4.8, 6.8 and 10.9% of patients in groups 1-, 2- and 4-week, respectively. Terbinafine was not associated with clinically relevant increases in liver function tests. Conclusions: Terbinafine is an effective, well tolerated and safe antifungal agent for the treatment of Tinea capitis m children. The shorter duration of treatment resulted in lower cure rates. However, it is important to note that depending on the severity of the disease, a 1-week-only treatment can also be effective in this indication.