CHANGES IN TRANSMISSION CHARACTERISTICS OF POLYMETHYLMETHACRYLATE AND CELLULOSE (III) ACETATE DURING EXPOSURE TO ULTRAVIOLET LIGHT

Abstract— Ultraviolet-transparent polymethylmethacrylate (PMMA) and cellulose (III) acetate (CA) (often used as a cut-off filter in UVB [280–320 nm] biological effect studies) were exposed to a 20 W Philips TL 12 lamp to examine changes in transmission characteristics due to UVB exposure. Transmission of UVB and biologically weighted UVB (UV_BE(DNA)) through PMMA were similar, 88.3 and 83.5%, respectively. The absorption characteristics of PMMA did not change with time at any of the UV irradiance levels applied. However, transmission of UVB and UVB_BE(DNA)) through new CA differed considerably: 59% versus only 11%, respectively. Also, spectral absorption characteristics changed with time due to degradation of CA, at a rate that was dependent on the incident UVB irradiance. The decrease in transmission through CA of both UVB and UV_BE(DNA) can be described by exponential functions. The CA that was wrapped around the UV lamp showed dramatic changes in UV absorption over the first few hours of use. However, when CA was placed at a longer distance from the light source initial degradation was less. It is concluded that PMMA can be applied in UV effect studies as a reasonable alternative for quartz. The CA should, however, be used with care, because the large transmission decreases that were observed strongly hamper an accurate calculation of (biologically weighted) UVB dose rates.     

Ultraviolet-B-induced cyclobutane-pyrimidine dimer formation and repair in Arctic marine macrophytes

The significance of ultraviolet-B radiation (UVBR: 280-315 nm)-induced DNA damage as a stress factor for Arctic marine macrophytes was examined in the Kongsfjord (Spitsbergen, 78 degrees 55.5'N, 11 degrees 56.0'E) in summer. UVBR penetration in the water column was monitored as accumulation of cyclobutane-pyrimidine dimers (CPD) in bare DNA. This showed that UVBR transparency of the fjord was variable, with 1% depths ranging between 4 and 8 m. In addition, induction and repair kinetics of CPD were studied in several subtidal macrophytes obtained from the Kongsfjord (5-15 m). Surface exposure experiments demonstrated CPD accumulation in Palmaria palmata, Devaleraea ramentacea, Phycodrys rubens, Coccotylus truncatus and Odonthalia dentata. In artificial light, field collected material of P. palmata, D. ramentacea, P. rubens and Laminaria saccharina showed efficient CPD repair, with only 10% of the artificially induced CPD remaining after 5 h. No significant differences in repair rate were observed among these species. CPD repair was slower or absent in O. dentata, C. truncatus and Monostroma arcticum, indicating that fast repair mechanisms such as photolyase were not continuously expressed in these species. CPD repair rates were not directly related to the vertical distribution of algae in the water column and to the reported UV sensitivity of the examined species. Dosimeter incubations showed that maximal exposure to DNA damaging wavelengths was low for all examined species. Furthermore, most species collected below the 1% depth for DNA damage displayed efficient CPD repair, suggesting that UVBR-induced CPD currently impose a minor threat for mature stages of these species growing in the Kongsfjord, Spitsbergen.     

2‐Chloro‐4,5‐dihydroimidazole,Part X. Revisiting route to N‐heteroarylimidazolidin‐2‐ones

The ureidation reactions of 2‐ and 4‐picoline N‐oxides with 2‐chloro‐4,5‐dihydroimidazole are described. A mechanism of novel thioureidation reaction of 4‐picoline N‐oxide with 2‐(4,5‐dihydro‐1H‐imidazol‐2‐ylthioxy)‐4,5‐dihydro‐1H‐imidazole is proposed. Structural assignment is confirmed by ¹H and ¹³C nmr as well as by X‐ray crystallography.     

Effect of normal variations on disease classification of Raman spectra from cervical tissue

In this paper, we examine how variations in normal tissue can influence disease classification of Raman spectra. Raman spectra from normal areas may be affected by previous disease or proximity to areas of dysplasia. Spectra were acquired in vivo from 172 patients and classified into five tissue categories: true normal (no history of disease), previous disease normal (history of disease, current normal diagnosis), adjacent normal (disease on cervix, spectra acquired from visually normal area), low grade, and high grade. Taking into account the various "normal" states of the tissue before statistical analysis led to a disease classification accuracy of 97%. These results indicate that abnormal changes significantly affect Raman spectra, even when areas are histopathologically normal. The sensitivity of Raman spectroscopy to subtle biochemical differences must be considered in order to successfully implement it in a clinical setting for diagnosing cervical dysplasia and cancer.     

Interaction and solubilization of some phenolic antioxidants in Pluronic® micelles

The solubilization of four phenolic antioxidants, namely p-hydroxybenzoic acid (PHBAA), syringic acid, sinapic acid, and quercetin in micelles of an ethylene oxide (EO)–propylene oxide (PO) triblock copolymer Pluronic^® P104 (EO₂₇–PO₆₁–EO₂₇, PPO mol wt = 3540, % PEO = 40) was examined at different temperatures, pHs, and in the presence of sodium chloride. The nano-size core–shell micelles of P104 characterized by dynamic light scattering had hydrodynamic diameter of about 18–20 nm with low polydispersity. Antioxidants induced micellization and micellar growth were observed. The critical micellar concentration (CMC), critical micellar temperature (CMT), cloud point (CP) of P104 decreased due to solubilization and interactions of antioxidants. The solubilization was favored at higher temperature, pH and in the presence of salt and follows the order PHBA > syringic acid > sinapic acid > quercetin which corresponds to the trend in their aqueous solubility. The location of antioxidant in micelles observed from NOESY spectra. Structure and hydrophobicity of antioxidants were found to be governing factors for their interaction and location in the micelles.     

Isolation of Bisphenol A-Tolerating/degrading Shewanella haliotis Strain MH137742 from an Estuarine Environment

Applied Biochemistry and Biotechnology - The human exposure to bisphenol A (BPA) occurs frequently. Once, this compound was one of the highest volume chemicals produced worldwide and used as a...     

The adiabatic‐to‐diabatic transformation angle and topological phases for strongly interacting states: Solution with four states

A few years back T. Vértesi et al. (J Phys Chem A 2005, 109, 3476) gave an elegant procedure to derive the adiabatic‐to‐diabatic transformation angle (ADT‐angle) for lowest two states, γ₁₂, in presence of their interaction with the higher states. In this article, we explicitly solved the coupled differential equations involving the ADT‐angles describing the mixing of four interacting states for the first time to get all the ADT‐angles, γ_ij's (including the γ₁₂) associated with well‐defined topological phases. In application to a suitable configuration space (CS) of a molecular system, we have demonstrated well‐defined Berry phases (Berry M. V., R Soc London Ser A 1984, 45, 392) for an isolated system with as many as four strongly interacting states. © 2012 Wiley Periodicals, Inc.     

Synthesis,Structure of Zwitterionic 2‐Amino‐N′‐(imidazolidin‐2‐ylidene)benzohydrazides,and Their Transformation into 3‐(Imidazolidin‐2‐ylideneamino)quinazolin‐4(1H)‐one Derivatives

The reaction of 2‐chloro‐4,5‐dihydroimidazole ( 5 ) with 2‐aminobenzohydrazides 6a–e led to the formation of 2‐amino‐N′‐(imidazolidin‐2‐ylidene)benzohydrazides as zwitterions 7a–e , which on treatment with carbon disulfide in the presence of triethylamine afforded 3‐(imidazolidin‐2‐ylideneamino)‐2‐thioxo‐2,3‐dihydroquinazolin‐4(1H)‐ones 8a–e . Compounds 8a–d were further converted into the corresponding 3‐(imidazolidin‐2‐ylideneamino)quinazoline‐2,4(1H,3H)‐diones 9a–d using hydrogen peroxide–sodium hydroxide solution. The structures of the compounds prepared were established by elemental analyses, IR and NMR spectra as well as X‐ray crystallographic analyses of 7e and 9a .     

MS/MS of protonated polyproline peptides: The influence of N-terminal protonation on dissociation

A unique collision-induced dissociation pattern was observed for protonated polyproline peptides of length n in which y(n-2) and/or y(n-4) ions were formed in much higher abundance than any other product ions. Cleavage occurs only at every other amide bond, such that product ions are formed only from the losses of even numbers of proline residues. Exclusive losses of even numbers of proline residues were not observed from sodiated peptides. Further study of the tandem mass spectrometry (MS/MS) patterns of protonated proline-rich peptides showed that the substitution of alanine in the second position of polyproline peptides did not prevent the dominant formation of y(n-2) and y(n-4) ions. The loss of ProAla to form the y(8) ion from (ProAlaPro(8)NH(2)+H)(+) was as abundant as the loss of ProPro from (Pro(10)NH(2)+H)(+). However, modification of the peptides that presumably affected the location of the proton on the peptide did alter the MS/MS spectra. Pro(10) and Pro(5) with blocked N-termini or with arginine substituted for the first proline residue did not form abundant y(n-2) or y(n-4) ions. MS(3) and double resonance experiments showed that dissociation of intermediate y(n) product ions can produce y(n-2) ions, but are not necessary dissociation pathway intermediates. This analysis suggests that the ionizing proton must be located at the N-terminus for the peptide ion to dissociate in this manner.     

Top-down patterning of zeolitic imidazolate framework composite thin films by deep X-ray lithography

For the first time a top-down process was used to control the spatial location of Metal-Organic Frameworks on a surface. Deep X-ray lithography was utilised to micropattern a Zeolitic Imidazolate Framework layer on a sol-gel surface, with exposure hardening the sol-gel by inducing crosslinking while leaving the frameworks intact.