PROJECTIONS OF INCREASED NON-MELANOMA SKIN CANCER INCIDENCE DUE TO OZONE DEPLETION

Abstract— Projections of increase in non-melanoma skin cancer incidence due to ozone layer depletion by chlorofluorocarbons are presented. Projections have been made for five different ozone depletion scenarios, based on US. Environmental Protection Agency estimates of potential worldwide industrial production and commercial applications of chlorofluorocarbons, and their eventual release into the atmosphere. The least favorable scenario, a regulatory cap on production at estimated 1990 levels, would lead to an eventual 30% ozone depletion and to an eventual doubling of skin cancer incidence by the year 2300. The most favorable scenario, a reduction in production commencing now and reaching a low production target by 1990, would limit ozone depletion to an eventual 2.8%, and increase in skin cancer to about 5%. Compared to the least favorable scenario, the most favorable one would prevent an average of about 100,000 cases of skin cancer per year in the United States between now and the year 2100.     

Proanthocyanidins from Grape Seeds Inhibit UV–Radiation‐Induced Immune Suppression in Mice: Detection and Analysis of Molecular and Cellular Targets

Ultraviolet (UV)–radiation‐induced immunosuppression has been linked with the risk of skin carcinogenesis. Approximately, 2 million new cases of skin cancers, including melanoma and nonmelanoma, diagnosed each year in the USA and therefore have a tremendous bad impact on public health. Dietary phytochemicals are promising options for the development of effective strategy for the prevention of photodamaging effects of UV radiation including the risk of skin cancer. Grape seed proanthocyanidins (GSPs) are such phytochemicals. Dietary administration of GSPs with AIN76A control diet significantly inhibits UV‐induced skin tumor development as well as suppression of immune system. UV‐induced suppression of immune system is commonly determined using contact hypersensitivity (CHS) model which is a prototype of T–cell‐mediated immune response. We present evidence that inhibition of UV‐induced suppression of immune system by GSPs is mediated through: (i) the alterations in immunoregulatory cytokines, interleukin (IL)‐10 and IL‐12, (ii) DNA repair, (iii) stimulation of effector T cells and (iv) DNA repair‐dependent functional activation of dendritic cells in mouse model. These information have important implications for the use of GSPs as a dietary supplement in chemoprevention of UV‐induced immunosuppression as well as photocarcinogenesis.     

Macrocyclization of polymers via ring‐closing metathesis and azide/alkyne‐“click”‐reactions: An approach to cyclic polyisobutylenes

The end‐to‐end cyclization of telechelic polyisobutylenes (PIB's) toward cyclic polyisobutylenes is reported, using either ring‐closing metathesis (RCM) or the azide/alkyne‐“click”‐reaction. The first approach uses bisallyl‐telchelic PIB's (M_n = 1650, 3680, 9770 g mol^?1) and Grubbs 1st‐, 2nd‐, and 3rd‐generation catalyst leading to cyclic PIB's in 60–80% yield, with narrow polydispersities (M_w/M_n = 1.25). Azide/alkyne‐“click”‐reactions of bisalkyne‐telechelic PIB's (M_n = 3840 and 9820 g mol^?1) with excess of 1,11‐diazido‐undecane leads to the formation of mixtures of linear/cyclic PIB's under formation of oligomeric cycles. Subsequent reaction of the residual azide‐moieties in the linear PIB's with excess of alkyne‐telechelic PEO enables the chromatographic removal of the resulting linear PEO‐PIB‐block copolymers by column chromatography. Thus pure cyclic PIB's can be obtained using this double‐“click”‐method, devoid of linear contaminants. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 671–680, 2010     

ULTRAVIOLET-RADIATION and SKIN CANCER. EFFECT OF AN OZONE LAYER DEPLETION

The effect of changes in the ozone layer on the incidence of skin cancer was explored using data for Norway. Attempts were made to arrive at a relationship between the "environmental effective UV-dose" and the skin cancer incidence. Norway is well suited for this purpose because of the large variation in the annual UV-dose from north to south. Furthermore we have a well developed cancer registry and a homogeneous population with regard to skin type. Four different regions of the country, each with a broadness of 1 degree in latitude (approximately 111 km), were selected (located around 69.5, 63.5, 60 and 58.5 degrees N). The annual effective UV-doses for these regions were calculated, assuming normal ozone conditions throughout the year and the action spectrum proposed by CIE, which extends up to 400 nm. The incidence rate (in the period 1970-1980) of malignant melanoma and non-melanoma skin cancer (mainly basal cell carcinoma) increased with the annual environmental UV-doses. For both these types of cancer a quadratic dose-effect relationship seems to be valid to a first approximation. The present data indicate that the incidence of skin cancer would increase by approximately 2% for each percent ozone reduction.     

On the origin of the “core‐free” morphology in microinjection‐molded HDPE

This study investigates the morphology of a high‐density polyethylene processed with microinjection molding. Previous work pointed out that a “core‐free” morphology exists for a micropart (150‐μm thick), contrasting with the well‐known “skin‐core” morphology of a conventional part (1.5‐mm thick). Local analyses are now conducted in every structural layer of these samples. Transmission electron microscopy observations reveal highly oriented crystalline lamellae perpendicular to the flow direction in the micropart. Image analysis also shows that lamellae are thinner. Wide‐angle X‐ray diffraction measurements using a microfocused beam highlight that highly oriented shish–kebab morphologies are found through the micropart thickness, with corresponding orientation function close to 0.8. For the macropart, quiescent crystallized morphologies are found with few oriented structures. Finally, the morphology within the micropart is more homogeneous, but the crystalline structures created are disturbed due to the combined effects of flow‐induced crystallization and thermal crystallization during processing. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1470–1478, 2011     

Sun Exposure over a Lifetime in Australian Adults from Latitudinally Diverse Regions

Spatio‐temporal patterns in sun exposure underlie variations in skin cancer incidence and vitamin D deficiency, indicate effectiveness of sun protection programs and provide insights into future health risks. From 558 adults across four regions of Australia (Brisbane (27°S), Newcastle (33°S), Geelong and the Western Districts of Victoria (37°S) and Tasmania (43°S)), we collected: self‐report data on time‐in‐the‐sun from age 6 years; natural skin color and ethnicity; silicone skin casts (for cumulative skin damage); and serum for vitamin D status. Ambient ultraviolet radiation (UVR) at the location of residence, with time‐in‐the‐sun, was used to calculate a “UVR dose” for each year of life. Individuals maintained their ranking compared to their peers for time‐in‐the‐sun in summer compared to winter and across ages (Spearman rho 0.24–0.84, all P < 0.001). Time‐in‐the‐sun decreased with age in all birth cohorts, and over calendar time. Summer time‐in‐the‐sun increased with increasing latitude (P < 0.001). Seasonal variation in vitamin D status had greater amplitude and vitamin D deficiency increased with increasing latitude. Temporal patterns are consistent with effectiveness of sun protection programs. Higher relative time‐in‐the‐sun persists from childhood through adulthood. Lower summer time‐in‐the‐sun in the warmest location may have implications for predictions of UVR‐related health risks of climate change.     

Explicit and implicit multi‐center integrations

We present truncated expansions of multicenter one‐electron nuclear attraction and two‐electron repulsion integrals over localized basis functions in terms of one‐ and two‐center integrals of “Coulomb,” “exchange,” and “hybrid” type. Two variants are discussed: the “Explicit Multi‐center Integrations” and the “Implicit Multi‐Center Integrations” (abbreviated as “EMCI” and “IMCI”, respectively). While EMCI also deals with individual integrals, the IMCI option is the more appealing one: it enables us to evaluate the entire matrix elements of “Restricted Hartree–Fock”‐type in a very effective and chemically meaningful way. Due to the diatomic nature of our expansions, integrations over “Slater‐Type Orbitals” become well‐feasible, too. © 2012 Wiley Periodicals, Inc.     

[Fe(H2O)5(NO)]2+, the “Brown‐Ring” Chromophore

Although the “brown‐ring” ion, [Fe(H₂O)₅(NO)]²⁺ ( 1 ), has been a research target for more than a century, this poorly stable species had never been isolated. We now report on the synthesis of crystals of a salt of 1 which allowed us to tackle the unique bonding situation on an experimental basis. As a result of the bonding analysis, two stretched, spin‐polarised π‐interactions provide the Fe–NO binding—and challenge the concept of “oxidation state”.     

Interfacial interaction in EVA‐carbon nanotube and EVA‐clay nanocomposites

Proper filler‐matrix compatibility is a key factor in view of obtaining nanocomposites with well‐dispersed nanofillers displaying enhanced properties. In this respect, polymer‐filler interaction can be improved by a proper combination of matrix and nanofiller polarities. This is explored for matrices ranging from nonpolar high density poly(ethylene) to ethylene‐vinyl acetate (EVA) copolymers with varying vinyl acetate contents, in combination with several types of organoclay or carbon nanotubes. A novel in situ characterization methodology using modulated temperature differential scanning calorimetry is presented to evaluate the matrix‐filler interaction. During quasi‐isothermal crystallization of the matrix, an “excess” contribution is observed in the recorded heat capacity signal because of reversible melting and crystallization. Its magnitude considerably decreases upon addition of nanofiller in case of strong interfacial interaction, whereas the influence is moderate in case of a less interacting matrix‐filler combination. It is suggested that the “excess heat capacity” can be used to quantify the segmental mobility of polymer chains in the vicinity of the nanofiller. Hence it provides valuable information on the strength of interaction, governed by the physical and chemical nature of matrix and filler. Heating experiments subsequent to quasi‐isothermal crystallization point at a certain degree of molecular ordering, responsible for crystal nucleation in EVA copolymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1291–1302, 2007     

Developing A “Polysulfide‐Phobic” Strategy to Restrain Shuttle Effect in Lithium–Sulfur Batteries

Inspired by hydrophobic interface, a novel design of “polysulfide‐phobic” interface was proposed and developed to restrain shuttle effect in lithium–sulfur batteries. Two‐dimensional VOPO₄ sheets with adequate active sites were employed to immobilize the polysulfides through the formation of a V?S bond. Moreover, owing to the intrinsic Coulomb repulsion between polysulfide anions, the surface anchored with polysulfides can be further evolved into a “polysulfide‐phobic” interface, which was demonstrated by the advanced time/space‐resolved operando Raman evidences. In particular, by introducing the “polysulfide‐phobic” surface design into separator fabrication, the lithium–sulfur battery performed a superior long‐term cycling stability. This work expands a novel strategy to build a “polysulfide‐phobic” surface by “self‐defense” mechanism for suppressing polysulfides shuttle, which provides new insights and opportunities to develop advanced lithium–sulfur batteries.     

On the “Wolfsberg–Helmholz Conjecture” of “Extended‐Hückel Theory”

After having reviewed some pioneer integral approximations closely related to Rüdenberg's expansions of one‐ and two‐electron orbital products, we apply the previously described “Implicit Multi‐Center Integration” techniques on Roothaan's “restricted” Fock‐matrix components over standard atomic orbital bases. The resulting compact forms are very similar to the well‐known “Wolfsberg–Helmholz Conjecture” of “Extended‐Hückel Theory,” which relates the various off‐diagonal matrix elements of “restricted” Fock‐type to their corresponding diagonal counterparts. In this way, a “nonempirical Extended‐Hückel Theory” can be created. © 2012 Wiley Periodicals, Inc.     

Cover Picture: Organocatalytic Domino Michael–Knoevenagel Condensation Reaction for the Synthesis of Optically Active 3‐Diethoxyphosphoryl‐2‐oxocyclohex‐3‐enecarboxylates (Chem. Eur. J. 13/2009)

In Buddhist imagery the gestures of the hand are very significant, which reflects the themes of asymmetry and chirality (derived from the word “hand”) found in the Full Paper by K. A. Jørgensen et al. on page 3093 ff. The professor is shown as a Buddha‐like image and is gesturing down with one hand and making the Buddhist gesture for “method and wisdom” with the other. Dice tumbling from his hand represent the organocatalytic Michael–Knoevenagel condensation domino reaction discussed in the paper, with the front die representing the cyclohexenone center of the molecule being formed. The two students standing by are making Buddhist gestures for “accomplishment” and “meditation”. Artwork by cartoonist Jorge Cham, http://www.phdcomics.com.

     

The Role of Aqueous Aerosols in the “Glyoxylate Scenario”: An Experimental Approach

The origin of life is one of the fundamental questions in science. Eschenmoser proposed the “glyoxylate scenario”, in which plausible abiotic synthesis pathways were suggested to be compatible with the constraints of prebiotic chemistry. In this proposal, the stem compound is HCN. In this work, we explore the “glyoxylate scenario” through several syntheses of HCN polymers, paying particular attention to the role of the aqueous aerosols, together with statistical methods, as a step to elucidate the synthetic problem of the origin of life. The soluble and insoluble HCN polymers synthetized were analyzed by GC‐MS. We identified, for the first time, glyoxylic acid in these polymers, together with some constituents of the reductive tricarboxylic acid cycle, amino acids and several N‐heterocycles. The findings presented herein, as the first global approach to the “glyoxylate scenario”, give full effect to this hypothesis and prove that aqueous aerosols could play an important role in this plausible scene of the origin of life.     

The reaction of triphenylarsine oxide with ethyl iodo‐acetate leading to triphenyl (carboethoxy)methylarsonium triiodide

New data are presented for some processes accompaning “retro‐Arbuzov” reaction of tertiary arsine oxides with halogen‐containing reagents. Triphenyl (carboethoxy)methylarsonium triiodide 10a was obtained in the reaction of triphenylarsine oxide 1a with excess of ethyl iodoacetate 2a . The structure of 10a was established by X‐ray single crystal diffraction. © 2004 Wiley Periodicals, Inc. Heteroatom Chem 15:482–485, 2004; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20050     

Anti‐Electrostatic Hydrogen Bonds

Ab initio and hybrid density functional techniques were employed to characterize a surprising new class of H‐bonded complexes between ions of like charge. Representative H‐bonded complexes of both anion–anion and cation–cation type exhibit appreciable kinetic stability and the characteristic theoretical, structural, and spectroscopic signatures of hydrogen bonding, despite the powerful opposition of Coulomb electrostatic forces. All such “anti‐electrostatic” H‐bond (AEHB) species confirm the dominance of resonance‐type covalency (“charge transfer”) interactions over the inessential (secondary or opposing) “ionic” or “dipole–dipole” forces that are often presumed to be essential for numerical modeling or conceptual explanation of the H‐bonding phenomenon.     

Trichloroethylene,tetrachloroethylene and carbon tetrachloride in an urban atmosphere: mixing ratios and temporal patterns

The measurement of halogenated hydrocarbons in the atmosphere is a matter of great interest owing to their adverse effects on the human health and the environment. This work is focused on the measurement of three toxic chlorinated hydrocarbons: trichloroethylene (TCE), tetrachloroethylene (PCE), and carbon tetrachloride (CTC). Moreover, CTC is a greenhouse gas and an ozone depleting gas, restricted under the Montreal Protocol. Owing to their low reactivity, the target chlorinated hydrocarbons are considered to be persistent and, thus, many measurements only address their mean mixing ratios (a concentration measure expressed as mol/mol). Consequently, most of the reported data have low temporal resolution as daily, seasonal or yearly mean mixing ratios, obtained with few measurements. In the study reported in this paper hourly measurements were performed for a long period of time: almost two years for TCE and PCE, and one year for CTC. The main objective was to study the temporal variability of the chlorinated hydrocarbons with high temporal resolution in order to identify their main sources and to enhance the understanding of their atmospheric processes. During the measurement period, March 2007–February 2008 with N?=?3290 valid data, CTC showed a mean mixing ratio of 0.16?ppbv (SD?=?0.13) with lower temporal variability than the majority of non-methane hydrocarbons (NMHCs), being very well mixed in the urban atmosphere owing to its long lifetime. TCE and PCE mean mixing ratios for the May 2006–February 2008 period, were 0.13?ppbv (SD?=?0.42, N?=?4601) and 0.25?ppbv (SD?=?0.54, N?=?4709) respectively, with a larger temporal variability. The study of the sources of TCE and PCE reveals that both compounds have industrial and/or commercial origin, but with different main sources.     

Investigations of the reactivity of “kick‐started” oxetanes in photoinitiated cationic polymerization

The ability of certain alkyl substituted epoxides to accelerate the photoinitiated cationic ring‐opening polymerizations of oxetane monomers by substantially reducing or eliminating the induction period altogether has been termed by us “kick‐starting.” In this communication, the rates of photopolymerization of several model “kick‐started” oxetane systems were quantified and compared with the analogous biscycloaliphatic epoxide monomer, 3,4‐epoxycyclohexylmethyl 3′,4′‐epoxycyclohexanecarboxylate (ERL). It has been found that the “kick‐started” systems undergo photopolymerization at rates that are at least two‐fold faster than ERL. These results suggest that “kick‐started” oxetanes could replace ERL in many applications in which high speed ultraviolet induced crosslinking photopolymerizations are carried out. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 586–593     

Potential‐Energy Surfaces,the Born–Oppenheimer Approximations,and the Franck–Condon Principle: Back to the Roots

The concept of a potential‐energy surface (PES) is central to our understanding of spectroscopy, photochemistry, and chemical kinetics. However, the terminology used in connection with the basic approximations is variously, and somewhat confusingly, represented with such phrases as “adiabatic”, “Born–Oppenheimer”, or “Born–Oppenheimer adiabatic” approximation. Concerning the closely relevant and important Franck–Condon principle (FCP), the IUPAC definition differentiates between a classical and quantum mechanical formulation. Consequently, in many publications we find terms such as “Franck–Condon (excited) state”, or a vertical transition to the “Franck–Condon point” with the “Franck–Condon geometry” that relaxes to the excited‐state equilibrium geometry. The Born–Oppenheimer approximation and the “classical” model of the Franck–Condon principle are typical examples of misused terms and lax interpretations of the original theories. In this essay, we revisit the original publications of pioneers of the PES concept and the FCP to help stimulate a lively discussion and clearer thinking around these important concepts.     

Photo‐initiated thiol–ene “click” hydrogels from RAFT‐synthesized poly(N‐isopropylacrylamide)

Despite the efficiency and robustness of the widely used copper‐catalyzed 1,3‐dipolar cycloaddition reaction, the use of copper as a catalyst is often not attractive, particularly for materials intended for biological systems. The use of photo‐initiated thiol‐ene as an alternative “click” reaction to synthesize “model networks” is investigated here. Poly(N‐isopropylacrylamide) precursors were synthesized by reversible addition fragmentation chain transfer (RAFT) polymerization and were designed to have trithiocarbonate moieties as end groups. This structure design provides opportunity for subsequent end‐group modifications in preparation for thiol‐ene “click.” Two reaction routes have been proposed and studied to yield thiol and ene moieties. The advantages and disadvantages of each reaction path were investigated to propose a simple but efficient route to prepare copper‐free “click” hydrogels. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4626–4636