The photolysis reactions of three compounds commonly used as a sunscreen agents, Parsol 1789 (1-[4-(1,1-dimethylethyl)phenyl]-3-(4-methoxyphenyl)-1,3- propanedione), Oxybenzone ((2-hydroxy-4-methoxyphenyl)phenyl-methanone) and Padimate O (2-ethylhexyl-4-(dimethylamino)benzoate), were investigated to provide a chemical background to aid in the understanding of the photosensitization of the sunscreen agents. Photolysis was carried out in cyclohexane for 70–140 h using a mercury vapor lamp (450W) without excluding oxygen.
Irradation of Parsol 1789 in cyclohexane yielded tert-butylbenzene, p-tert-butylbenzoic acid and p-methoxybenzoic acid; products obtained from the combination of the sunscreen with the solvent included the cyclohexyl esters of p-methoxybenzoic acid, p-tert-butylbenzoic acid and methanoic acid; products obtained from the solvent included cyclohexanol, cyclohexanone and dicyclohexyl ether.
Irradiation of Oxybenzone in the cyclohexane for 100 h produced no detectable products by either gas or liquid chromatographic analysis. Oxybenzone was recovered unchanged and no products were observed from the photoinitiated reaction of oxygen with the solvent.
Irradiation of Padimate O in cyclohexane yielded the ethylhexyl esters of p-aminobenzoic acid, p-monomethylaminobenzoic acid and p-dimethylamino (o/m)-methylbenzoic acid, as well as products from the photoinitiated reaction of oxygen with the solvent. 相似文献
We consider biased random walk on supercritical percolation clusters in ℤ2. We show that the random walk is transient and that there are two speed regimes: If the bias is large enough, the random
walk has speed zero, while if the bias is small enough, the speed of the random walk is positive.
Received: 20 November 2002 / Revised version: 17 January 2003
Published online: 15 April 2003
Research supported by Microsoft Research graduate fellowship.
Research partially supported by the DFG under grant SPP 1033.
Research partially supported by NSF grant #DMS-0104073 and by a Miller Professorship at UC Berkeley.
Mathematics Subject Classification (2000): 60K37; 60K35; 60G50
Key words or phrases: Percolation – Random walk 相似文献
Summary. Esterifications of acetic acid with some linear, secondary, tertiary, and benzylic alcohols mediated by catalytic amounts
of Keggin, Wells–Dawson, and Preyssler type heteropolyacids were carried out under reflux at mild reaction conditions with good to excellent yields. Among the examined
catalysts, H3PW12O40 and H14NaP5W30O110 revealed better results than other heteropolyacids. This work was performed with the aim of simplifying the esterification
process by omitting any solvents and mineral acid catalysts. Easy work-up, low cost, and acidic waste reduction, which are
all important features from the environmental and economical points of view, are distinct aspects of this protocol. Heteropolyacid
catalysts could be separated after a simple work-up and reused for several times. 相似文献
Summary. A highly efficient, selective, fast, and cheap protocol is developed for oxidation of aromatic amines and alcohols utilizing
34% hydrogen peroxide in water catalyzed by some W- and Mo-based heteropolyoxometalates. Findings showed that dodecatungstophosphoric
acid, H3PW12O40, was the most efficient catalyst in the examined oxidation reactions. This methodology may prove to be a valuable alternative
for eco-friendly green oxidation. Inherent simplicity, easy work up, and using regenerable catalysts were other key aspects
of this oxidation protocol. 相似文献
The allure of metal–organic frameworks (MOFs) in heterogeneous electrocatalysis is that catalytically active sites may be designed a priori with an unparalleled degree of control. An emerging strategy to generate coordinatively-unsaturated active sites is through the use of organic linkers that lack a functional group that would usually bind with the metal nodes. To execute this strategy, we synthesize a model MOF, Ni-MOF-74 and incorporate a fraction of 2-hydroxyterephthalic acid in place of 2,5-dihydroxyterephthalic acid. The defective MOF, Ni-MOF-74D, is evaluated vs. the nominally defect-free Ni-MOF-74 with a host of ex situ and in situ spectroscopic and electroanalytical techniques, using the oxidation of hydroxymethylfurtural (HMF) as a model reaction. The data indicates that Ni-MOF-74D features a set of 4-coordinate Ni–O4 sites that exhibit unique vibrational signatures, redox potentials, binding motifs to HMF, and consequently superior electrocatalytic activity relative to the original Ni-MOF-74 MOF, being able to convert HMF to the desired 2,5-furandicarboxylic acid at 95% yield and 80% faradaic efficiency. Furthermore, having such rationally well-defined catalytic sites coupled with in situ Raman and infrared spectroelectrochemical measurements enabled the deduction of the reaction mechanism in which co-adsorbed *OH functions as a proton acceptor in the alcohol oxidation step and carries implications for catalyst design for heterogeneous electrosynthetic reactions en route to the electrification of the chemical industry.The allure of metal–organic frameworks (MOFs) in heterogeneous electrocatalysis is that catalytically active sites may be designed a priori with an unparalleled degree of control.相似文献
Two libraries of alpha-substituted alkynes has been prepared on solid phase using a sequential Sonogashira/Nicholas reaction approach. The scope of nucleophiles in the Nicholas reaction on solid phase has been investigated, including carbon, oxygen, nitrogen, sulfur, fluoride, and hydride nucleophiles. The conditions for the reaction sequence have been optimized in terms of Lewis acid, catalyst for the Sonogashira step, temperature, reaction time, and decomplexation method, enabling the five-step sequence to be performed in 1 day. 相似文献
An on-line method for the analysis of Sb(III), Sb(V) and trimethylstiboxide (TMSbO) is presented. The separation is performed
using ion chromatography (IC) on a strong anion-exchange column with phthalic acid plus 2% acteone at pH 5 as mobile phase.
The chromatographic system is coupled to an ICP-MS as detector. The influence of different complexing agents on the chromatographic
behavior of the antimony species is studied. Rather stable complexes of Sb(III) seem to be formed with citrate and tartrate
under the experimental conditions. TMSbO forms a dianionic species with citrate in contrast to the otherwise monoanionic complex.
Received: 31 Juli 1997 / Revised: 8 December 1997 / Accepted: 11 December 1997 相似文献
Proton NMR was used to study the complexation reaction between silver ion and hexathia-18-crown-6 in a number of binary mixed solvents of dimethyl sulfoxide with acetonitrile and methanol. Formation constants for the resulting 1:1 complexes in different solvent mixtures were determined by computer fitting of the chemical shift-mole ratio data. The influence of solvent composition on the stability of the resulting complex is discussed. The exchange kinetics of Ag+-hexathia-18-crown-6 in 70-30 wt.% dimethyl sulfoxide-acetonitrile and 75-25 wt.% dimethyl sulfoxide-methanol were studied by proton NMR line-shape analysis. In both solvent mixtures, the exchange of thiacrown ether between the free and complexed sites was found to proceed via a dissociative pathway. The exchange rates and the activation parameters Ea, H, S, and G for the ligand exchange were determined and the influence of solvent properties on these parameters discussed. 相似文献