bluuebunny/crossref_metadata_2025 huggingface dataset:
Alkaloid Synthesis: (+)-Deoxoprosopinine (Krishna), Alkaloid (–)-205B (Micalizio), FR901483 (Huang), (+)-Ibophyllidine (Kwon), (–)-Lycoposerramine-S (Fukuyama), (±)-Crinine (Lautens)
Authors: Taber Douglass F.
Published: November 2020

Palakodety Radha Krishna of the Indian Institute of Chemical Technology observed (Synlett 2012, 2814) high stereocontrol in the addition of allyltrimethylsilane to the cyclic imine derived from 1. The product piperidine 2 was carried onto (+)-deoxoprosopinine 3. Glenn C. Micalizio of Scripps Florida condensed (J. Am. Chem. Soc. 2012, 134, 15237) the amine 4 with 5. The ensuing intramolecular dipolar cycloaddition led to 6, which was carried onto the Dendrobates alkaloid (–)-205B 7. Pei-Qiang Huang of Xiamen University showed (Org. Lett. 2012, 14, 4834) that the quaternary center of 9 could be established with high diastereoselectivity by activation of the lactam 8, then sequential addition of two different Grignard reagents. Subsequent stereoselective intramolecular aldol condensation led to FR901843 10. More recently, Professor Huang, with Hong-Kui Zhang, also of Xiamen University, published (J. Org. Chem. 2013, 78, 455) a full account of this work. In an elegant application of the power of phosphine-catalyzed intermolecular allene cycloaddition, Ohyun Kwon of UCLA added (Chem. Sci. 2012, 3, 2510) 12 to the imine 11 to give 13. The cyclization elegantly set two of the four stereogenic centers of (+)-ibophyllidine 14. Tohru Fukuyama of the University of Tokyo initiated (Angew. Chem. Int. Ed. 2012, 51, 11824) a cascade cyclization between the enone 15 and the chiral auxiliary 16. The product lactam 17 was carried onto (–)-lycoposerramine-S 18. Mark Lautens explored (J. Am. Chem. Soc. 2012, 134, 15572) the utility of the intramolecular aryne ene reaction, as illustrated by the cyclization of 19 to 20. Oxidation cleavage of the vinyl group of 20 followed by an intramolecular carbonyl ene reaction led to (±)-crinine 21.
Substituted Benzenes: The Reddy Synthesis of Isofregenedadiol
Authors: Taber Douglass F.
Published: November 2020

Jianbo Wang of Peking University (Org. Lett. 2011, 13, 4988) and Patrick Y. Toullec and Véronique Michelet of Chimie ParisTech (Org. Lett. 2011, 13, 6086) developed conditions for the electrophilic acetoxylation of a benzene derivative 1. Seung Hwan Cho and Sukbok Chang of KAIST (J. Am. Chem. Soc. 2011, 133, 16382) and Brenton DeBoef of the University of Rhode Island (J. Am. Chem. Soc. 2011, 133, 19960) devised protocols for the electrophilic imidation of a benzene derivative 3. Vladimir V. Grushin of ICIQ Tarragona devised (J. Am. Chem. Soc. 2011, 133, 10999) a simple protocol for the cyanation of a bromobenzene 6 to the nitrile 7. Hua-Jian Xu of the Hefei University of Technology (J. Org. Chem. 2011, 76, 8036) and Myung-Jong Jin of Inha University (Org. Lett. 2011, 13, 5540) established conditions for the efficient Heck coupling of a chlorobenzene 8. Jacqueline E. Milne of Amgen/Thousand Oaks reduced (J. Org. Chem. 2011, 76, 9519) the adduct from the addition of 11 to 12 to deliver the phenylacetic acid 13. Jeffrey W. Bode of ETH Zurich effected (Angew. Chem. Int. Ed. 2011, 50, 10913) Friedel-Crafts alkylation of 14 with the hydroxamate 15 to give the meta product 16. B.V. Subba Reddy of the Indian Institute of Chemical Technology, Hyderabad took advantage (Tetrahedron Lett. 2011, 52, 5926) of the directing ability of the amide to effect selective ortho acetoxylation of 17. Similarly, Frederic Fabis of the Université de Caen Basse-Normandie used (J. Org. Chem. 2011, 76, 6414) the methoxime of 19 to direct ortho bromination, leading to 20. Teck-Peng Loh of Nanyang Technological University showed (Chem. Commun. 2011, 47, 10458) that the carbamate of 21 directed ortho C–H functionalization to give the ester 23. Yoichiro Kuninobu and Kazuhiko Takai of Okayama University rearranged (Chem. Commun. 2011, 47, 10791) the allyl ester 24 directly to the ortho-allylated acid 25. Youhong Hu of the Shanghai Institute of Materia Medica (J. Org. Chem. 2011, 76, 8495) and Graham J. Bodwell of Memorial University (J. Org. Chem. 2011, 76, 9015) condensed a chromene 26 with a nucleophile 27 to give the arene 28. C.V. Ramana of the National Chemical Laboratory prepared (Tetrahedron Lett. 2011, 52, 4627) the arene 31 by condensing 29 with 30 with high regioselectivity.
Substituted Benzenes: The Subba Reddy Synthesis of 7-Desmethoxyfusarentin
Authors: Taber Douglass F.
Published: November 2020

Andrey P. A ntonchick of the Max-Planck-Institut Dortmund devised (Org. Lett. 2012, 14, 5518) a protocol for the direct amination of an arene 1 to give the amide 3. Douglass A. Klumpp of Northern University showed (Tetrahedron Lett. 2012, 53, 4779) that under strong acid conditions, an arene 4 could be carboxylated to give the amide 6. Eiji Tayama of Niigata University coupled (Tetrahedron Lett. 2012, 53, 5159) an arene 7 with the α-diazo ester 8 to give 9. Guy C. Lloyd-Jones and Christopher A. Russell of the University of Bristol activated (Science 2012, 337, 1644) the aryl silane 11 to give an intermediate that coupled with the arene 10 to give 12. Ram A. Vishwakarma and Sandip P. Bharate of the Indian Institute of Integrative Medicine effected (Tetrahedron Lett. 2012, 53, 5958) ipso nitration of an areneboronic acid 13 to give 14. Stephen L. Buchwald of MIT coupled (J. Am. Chem. Soc. 2012, 134, 11132) sodium isocyanate with the aryl chloride 15 (aryl triflates also worked well) to give the isocyanate 16, which could be coupled with phenol to give the carbamate or carried onto the unsymmetrical urea. Zhengwu Shen of the Shanghai University of Traditional Chinese Medicine used (Org. Lett. 2012, 14, 3644) ethyl cyanoacetate 18 as the donor for the conversion of the aryl bromide 17 to the nitrile 19. Kuo Chu Hwang of the National Tsig Hua University showed (Adv. Synth. Catal. 2012, 354, 3421) that under the stimulation of blue LED light the Castro-Stephens coupling of 20 with 21 proceeded efficiently at room temperature. Lutz Ackermann of the Georg-August-Universität Göttingen employed (Org. Lett. 2012, 14, 4210) a Ru catalyst to oxidize the amide 23 to the phenol 24. Both Professor Ackermann (Org. Lett. 2012, 14, 6206) and Guangbin Dong of the University of Texas (Angew. Chem. Int. Ed. 2012, 51, 13075) described related work on the ortho hydroxylation of aryl ketones. George A. Kraus of Iowa State University rearranged (Tetrahedron Lett. 2012, 53, 7072) the aryl benzyl ether 25 to the phenol 26. The synthetic utility of the triazene 27 was demonstrated (Angew. Chem. Int. Ed. 2012, 51, 7242) by Yong Huang of the Shenzen Graduate School of Peking University.
Organocatalyzed C–C Ring Construction: The Hayashi Synthesis of PGE1 Me Ester
Authors: Taber Douglass F.
Published: November 2020

Xiaohua Liu and Xiaoming Feng of Sichuan University devised (J. Org. Chem. 2013, 78, 6322) a catalyst that mediated the addition of the ylide 2 to the enone 1 to give 3. Peng-fei Xu of Lanzhou University found (Chem. Commun. 2013, 49, 4625) that the vinyl pyrrole 4 was sufficiently nucleophilic to add to 5, leading to the cyclobutane 6. Albert Moyano of the Universitat de Barcelona added (Eur. J. Org. Chem. 2013, 3103) 8 to the unsaturated aldehyde 7 to give the β-amino acid precursor 9. Eugenia Marqués-López and Mathias Christmann, now at Freie Universität Berlin effected (Synthesis 2013, 45, 1016) the intramolecular Michael cyclization of 10 to give 11. Delong Liu and Wanbin Zhang of Shanghai Jiao Tong University showed (Synthesis 2013, 45, 1612) that 12 and 13 could be combined to give the cyclopentane 14. Ismail Ibrahem and Armando Córdova of Mid Sweden University combined (Angew. Chem. Int. Ed. 2013, 52, 6050) 15 and 16 to give 17, with good control of the quaternary center. Kamal Nain Singh of Panjab University prepared (Synthesis 2013, 45, 1406) a proline-derived sulfoxide that mediated the addition of cyclohexanone 18 to 19. Intramolecular aldehyde alkylation is underdeveloped as a synthetic method. David W.C. MacMillan of Princeton University established (J. Am. Chem. Soc. 2013, 135, 9358) a single-electron transfer variant, cyclizing 21 to 22. Arianna Quintavalla of the University of Bologna effected (Adv. Synth. Catal. 2013, 355, 938) the double addition of nitromethane 24 to 23 to give 25. John Cong-Gui Zhao of the University of Texas at San Antonio reported (Chem. Eur. J. 2013, 19, 1666; J. Org. Chem. 2013, 78, 4153) parallel results (not pictured) with aryl enones as the acceptors. Bor-Cherng Hong of the National Chung Cheng University condensed (Eur. J. Org. Chem. 2013, 2472) 26 with the alcohol 27 to give 28. Again, good control of the quaternary center was observed. Marc C. Kimber of Loughborough University used (J. Org. Chem. 2013, 78, 3476) an organocatalyst to rearrange the prochiral endoperoxide 29 to the hydroxy enone, to which malonate 30 was added to give 31.
Metal-Mediated C–C Ring Construction: (+)-Shiromool (Baran)
Authors: Taber Douglass F.
Published: November 2020

Seiji Iwasa of the Toyohashi University of Technology devised (Adv. Synth. Catal. 2012, 354, 3435) a water-soluble Ru catalyst for enantioselective intramolecular cyclopropanation that could be separated from the product and recycled by simple water/ether extraction. Minoru Isobe of the National Tsing Hua University combined (Org. Lett. 2012, 14, 5274) the Nicholas and Hosomi-Sakurai reactions to close the cyclobutane ring of 4. Kazunori Koide of the University of Pittsburgh established (Tetrahedron Lett. 2012, 53, 6637) that the activity of a Ru metathesis catalyst, shut down by the presence of TBAF, could be restored by the inclusion of TMS2O. Jan Streuff of Albert-Ludwigs-Universität Freiburg demonstrated (Angew. Chem. Int. Ed. 2012, 51, 8661) that the enantiomerically pure Brintzinger complex mediated the reductive cyclization of 7 to 8. Huw M.L. Davies of Emory University prepared (J. Am. Chem. Soc. 2012, 134, 18241) the cyclopentenone 11 by the Rh-mediated addition of 10 to 9 followed by elimination. Christophe Meyer and Janine Cossy of ESPCI ParisTech showed (Angew. Chem. Int. Ed. 2012, 51, 11540) that the Rh-mediated rearrangement of 12 to 13 proceeded with substantial diastereocontrol. Jian-Hua Xie and Qi-Lin Zhou of Nankai University observed (Org. Lett. 2012, 14, 6158) that the enantioselective hydrogenation of 14 followed by Claisen rearrangement established the cyclic quaternary center of 17 with high stereocontrol. Ken Tanaka of the Tokyo University of Agriculture and Technology devised (Angew. Chem. Int. Ed. 2012, 51, 13031) the Rh-mediated addition of the enyne 18 to 19 to give the highly substituted cyclohexene 20. Daesung Lee of the University of Illinois at Chicago showed (Chem. Sci. 2012, 3, 3296) that the ring-opening/ring-closing metathesis of 21 delivered 22 with high diastereocontrol. Andreas Speicher of Saarland University cyclized (Org. Lett. 2012, 14, 4548) 23 to 24 with significant atropisomeric induction. Erick M. Carreira of the Eidgenössische Technische Hochschule Zürich effected (J. Am. Chem. Soc. 2012, 134, 20276) the polycyclization of racemic 25 to 26 with high enantiomeric excess. Medium rings are often the most difficult to construct, because of the inherent congestion across the forming ring. Phil S. Baran of Scripps/La Jolla effected (Angew. Chem. Int. Ed. 2012, 51, 11491) the cyclization of 27 to 28 as a single dominant diastereomer.
The Reisman Synthesis of (–)-Maoecrystal Z
Authors: Taber Douglass F.
Published: November 2020

(–)-Maoecrystal Z 3 was isolated as a minor constituent from the Chinese medicinal herb Isodon eriocalyx. The synthesis of 3 reported (J. Am. Chem. Soc. 2011, 133, 14964) by Sarah E. Reisman of the California Institute of Technology, featuring as a key step the cyclization of 1 to 2, is a tribute to the power of one-electron reduction for carbon–carbon bond construction. The synthesis began with a Myers alkylation to prepare 6. The amide was reduced to the alcohol with the convenient ammonia–borane complex, and the alcohol was carried on to the iodide 7. The first carbocyclic ring of 3 was prepared by classic chemistry, the condensation of dimethyl malonate 9 with mesityl oxide 8, followed by selective removal of one of the ketone carbonyls. A salt-free Wittig reaction followed by hydrolysis, resolution, and reduction then completed the synthesis of 12. Exposure of 12 to peracid led to the epoxide 13 as an inconsequential mixture of diastereomers. The one-electron Nugent/RajanBabu/Gansäuer protocol was low yielding with methyl acrylate, but dramatically improved when the trifluoroethyl acrylate 14 was used as the acceptor. The lactone 15 was formed as a single diastereomer. Alkylation of 15 with 7 followed by oxidation gave 16, which was deprotected and oxidized to give 1. The cascade cyclization of 1 presumably proceeded by initial one-electron reduction of the more accessible aldehyde. The cyclization of the resulting radical onto the alkene may have been assisted by complexation of the lactone carbonyl with the required second equivalent of SmI2. The Sm enolate so prepared was then added to the second aldehyde to give 2. This cyclization sets one quaternary and three ternary stereogenic centers. Attempted monoprotection of 2 was not successful, so the bis acetate was prepared and ozonized, and the aldehyde was condensed with Eschenmoser’s salt to give 17. Careful monohydrolysis then completed the synthesis of (–)-maoecrystal Z 3
The Carreira Synthesis of Indoxamycin B
Authors: Taber Douglass F.
Published: November 2020

Some members of the indoxamycin family show potent antineoplastic activity. The key cyclopentene-forming step in the route to indoxamycin B 3 devised (Angew. Chem. Int. Ed. 2012, 51, 3474) by Erick M. Carreira of ETH Zürich was the Pd-catalyzed cyclization of 1 to 2. The starting material for the preparation of 1 was the symmetrical methyl benzoate 4. Dissolving metal reduction followed by alkylation of the resulting ester enolate delivered the diene 5. Reduction and protection followed by allylic oxidation converted 5 into 6, which was carried onto 8 as a mixture of geometric isomers. The dissociated potassium alkoxide of 8 underwent smooth oxy-Cope rearrangement to give an enolate that was trapped as the silyl ether 1. Pd-catalyzed oxidative cyclization then completed the synthesis of 2. With the ketone 2 in hand, two challenges remained: distinguishing the two hydroxymethyl groups and functionalizing the allylic methine to construct the third quaternary center. Both problems were solved by the V-mediated epoxidation of the diol corresponding to 2. In situ, the anti-hydroxyl opened the epoxide to give the cyclic ether. Gold-mediated rearrangement of the O-propargylated enol ether 10 delivered an allene, which was selectively reduced to the alcohol 11. A second gold-mediated cyclization then completed the synthesis of 12. Indoxamycin B had been assigned as having the butenyl sidechain as the more stable endo diastereomer, so the synthesis was initially finished that way. When that product proved to not be congruent with the natural material, it seemed likely that the butenyl sidechain was in fact exo. Selective hydration of 12 gave a mixture of all four alcohol diastereomers. The two exo diastereomers were separated and oxidized to the ketone 13. Wittig olefination gave a pair of geometric isomers that were separated. The cyclic ether of the E isomer 14 was reduced to give a keto alcohol, which was oxidized to the keto aldehyde. Horner-Wadsworth-Emmons chain extension gave 15, which was carried onto indoxamycin B 3. An alternative construction of 3 by intramolecular carbene insertion into the allyic methine of 2 can be imagined.
The Thomson Synthesis of (–)-GB17
Authors: Taber Douglass F.
Published: November 2020

(–)-GB17 3 is one of the Galbulimima alkaloids, a family that shows a wide range of interesting physiological activity. Regan J. Thomson of Northwestern University devised (Angew. Chem. Int. Ed. 2012, 51, 2481) a convergent assembly of 3, a key step of which was the intramolecular Michael cyclization of 1 to 2. The hydroxy aldehyde 6 was prepared by alkylation of the dithiane 4 with 5, followed by hydrolysis. The preparation of 9, by condensation of 8 with 7 followed by hydrogenation and protection, had been reported by Lhommet. Condensation of 9 with the linchpin reagent 10 gave an intermediate keto phosphonate, which was combined with 6 to give, after oxidation, the aldehyde 1. Two new stereogenic centers are created in the course of the cyclization of 1. The authors found that the TFA salt 11 of the Hayashi catalyst delivered 2 with high diastereocontrol. Control experiments showed that the buttressing effect of the dithiane was required for the cyclization. The authors then explored the next intramolecular Michael cyclization of 13 to 14. In this cyclization, the stereogenic center at 6 is in jeopardy by elimination and readdition. Cyclization of the trans unsaturated ester led to the wrong diastereomer of 14, but cyclization of the cis ester 13, prepared by the Still-Gennari protocol, cleanly gave the desired diastereomer. The reaction worked best with the free amine. Under the conditions of the reaction the Michael addition product spontaneously cyclized to the lactam 14. The ketone of 14 was selectively enolized, then converted to its enol triflate, which under Pd-mediated reduction gave the alkene 15. Alkylation of 15 with 16 predominantly gave the diene 18. Hydrolysis of the dithiane to the ketone followed by reduction gave mainly the desired equatorial alcohol, which was cleaved oxidatively to (–)-GB17 3. Although there have been many isolated reports of the utility of intramolecular Michael addition as a synthetic method, there has been little systematic investigation. The optimization studies that are the heart of this work are a welcome addition.
The Procter Synthesis of (+)-Pleuromutilin
Authors: Taber Douglass F.
Published: November 2020

The fungal secondary metabolite (+)-pleuromutilin 3 exerts antibiotic activity by binding to the prokaryotic ribosome. Semisynthetic derivatives of 3 are used clinically. The central step of the first synthesis of (+)-pleuromutilin 3, devised (Chem. Eur. J. 2013, 19, 6718) by David J. Procter of the University of Manchester, was the SmI2-mediated reductive closure of 1 to the tricyclic 2. The starting material for the synthesis was the inexpensive dihydrocarvone 4. Ozonolysis and oxidative fragmentation following the White protocol delivered 5 in high ee. Conjugate addition with 6 followed by Pd-mediated oxidation of the resulting silyl enol ether gave the enone 7. Subsequent conjugate addition of 8 proceeded with modest but useful diastereoselectivity to give an enolate that was trapped as the triflate 9. The Sakurai addition of the derived ester 10 with 11 led to 12 and so 1 as an inconsequential 1:1 mixture of diastereomers. The SmI2-mediated cyclization of 1 proceeded with remarkable diastereocontrol to give 2. SmI2 is a one-electron reductant that is also a Lewis acid. It seems likely that one SmI2 bound to the ester and the second to the aldehyde. Electron transfer then led to the formation of the cis-fused five-membered ring, with the newly formed alkoxy constrained to be exo to maintain contact with the complexing Sm. Intramolecular aldol condensation of the resulting Sm enolate with the other aldehyde then formed the six-membered ring, with the alkoxy group again constrained by association with the Sm. Hydrogenation of 13 gave 14, which could be brought to diastereomeric purity by chromatography. Elegantly, protection of the ketone simultaneously selectively deprotected one of the two silyl ethers, thus differentiating the two secondary alcohols. Reduction of the ester to the primary alcohol then delivered the diol 15. Selective esterification of the secondary alcohol followed by thioimidazolide formation and free radical reduction completed the preparation of 16. Ketone deprotection followed by silyl ether formation and Rubottom oxidation led to the diol 17. Protection followed by the addition of 18 and subsequent hydrolysis and reduction gave the allylic alcohol 19.
Environmental Politics, Policy, and Administration in the United States
Authors: Conant James K. , Balint Peter J.
Published: November 2020

A variety of human activities produce pollutants, many of which pose risks to human health, the natural environment, and the Earth’s biosphere. These activities, however, may have important economic and social purposes. For example, coal-fired utility plants emit a range of dangerous substances from their tall smokestacks, many of which fall back to Earth hundreds of miles downwind. These pollutants make breathing difficult for people who have asthma and heart disease, and they damage forests, lakes, rivers, and the ecosystems of which they are a part. Yet, the electrical power generated at these plants is used to run factories, provide heat and air conditioning for office buildings, light homes, and sustain the Internet. Likewise, the internal combustion engines in automobiles and trucks emit harmful pollutants from their exhaust pipes that cause smog in urban areas and contribute to global climate change. Yet these vehicles give people the means to travel, conduct their social lives, commute to work, and move goods to markets. These two examples illustrate the underlying contradictions, tensions, and fault lines upon which environmental politics, policy, and administration are built. Human activities that generate pollutants create benefits and impose costs. The distribution of those benefits and costs differs by areas of the country, by sectors of the economy, and among many groups and individuals within our society. For example, oil companies, automobile manufacturers, and private utility companies that own coal-fired power plants have traditionally been among the fiercest opponents of efforts to limit pollutants that degrade air quality. Environmental groups, public health groups, and elected officials in urban areas and the states of the Northeast and West Coast have been among the strongest supporters of air pollution controls. Opponents of efforts to limit pollution generally contend that such limits lead to increased prices and lost jobs. Utility companies do incur costs when they purchase and install air pollution control equipment. Those costs are passed on to manufacturing firms, tenants in office buildings, and homeowners in the form of higher electricity bills.
Proceed with Caution, then Sue the Bastards in Michigan
Authors: Wurster Charles F.
Published: November 2020

At that first meeting on October 6, 1967, the new trustees of EDF had voted to “proceed with caution,” given the precarious position of this essentially nonorganization with no assets. It was an easy motion and it passed unanimously, but before long caution was thrown to the winds when Lew Batts described an imminent planned application of the insecticide dieldrin in western Michigan. Intended to eradicate an alleged infestation of Japanese beetles, dieldrin was to be applied to 3,000 acres in Berrien County near Lake Michigan by the Michigan and United States Departments of Agriculture. Lew wanted EDF to stop them. We already knew something about dieldrin, a chlorinated hydrocarbon relative of DDT and an environmentally destructive material, more acutely (immediately) toxic than DDT. We knew it would kill birds and mammals and could damage fish. Furthermore, Lew Batts was connected with a Michigan foundation that had more money, but less arrogance, than we did. EDF was designed to litigate, and Batts’s organization certainly was not. He guaranteed the assembled new trustees of EDF that if we would tackle the Michigan Department of Agriculture (MDA) in court to block the dieldrin application, he would support the effort with $10,000. The fat was in the fire! EDF’s trustees voted to cautiously sue the Michigan Department of Agriculture, and anybody else if necessary, to prevent the dieldrin treatment. Furthermore, several communities within the Lake Michigan watershed in western Michigan were using DDT in an attempt to control Dutch elm disease, a futile exercise with which we were very familiar (Wurster DH et al., 1965). With both of these destructive chemicals contaminating the fish, it would be difficult to separate the effects of each chemical from the other. So we decided to sue not only MDA in connection with its proposed dieldrin application, but we would add as defendants nine cities in western Michigan within the Lake Michigan watershed that were using DDT (Fremont, Muskegon, Greenville, Rockford, Lansing, East Lansing, East Grand Rapids, Holland, and Spring Lake).
The Mechanisms of Reactions Influencing Atmospheric Ozone
Authors: Calvert Jack G. , Orlando John J. , Stockwell William R. , Wallington Timothy J.
Published: November 2020

Ozone, an important trace component, is critical to life on Earth and to atmospheric chemistry. The presence of ozone profoundly impacts the physical structure of the atmosphere and meteorology. Ozone is also an important photolytic source for HO radicals, the driving force for most of the chemistry that occurs in the lower atmosphere, is essential to shielding biota, and is the only molecule in the atmosphere that provides protection from UV radiation in the 250-300 nm region. However, recent concerns regarding environmental issues have inspired a need for a greater understanding of ozone, and the effects that it has on the Earth's atmosphere. The Mechanisms of Reactions Influencing Atmospheric Ozone provides an overview of the chemical processes associated with the formation and loss of ozone in the atmosphere, meeting the need for a greater body of knowledge regarding atmospheric chemistry. Renowned atmospheric researcher Jack Calvert and his coauthors discuss the various chemical and physical properties of the earth's atmosphere, the ways in which ozone is formed and destroyed, and the mechanisms of various ozone chemical reactions in the different spheres of the atmosphere. The volume is rich with valuable knowledge and useful descriptions, and will appeal to environmental scientists and engineers alike. A thorough analysis of the processes related to tropospheric ozone, The Mechanisms of Reactions Influencing Atmospheric Ozone is an essential resource for those hoping to combat the continuing and future environmental problems, particularly issues that require a deeper understanding of atmospheric chemistry.
Mechanisms of Reactions of HO2 and RO2 Radicals
Authors: Calvert Jack G. , Orlando John J. , Stockwell William R. , Wallington Timothy J.
Published: November 2020

The peroxy radicals are an important link in the reaction chain that develops ozone in the atmosphere through their reactions with NO. This chapter explores the kinetics and mechanisms of these RO2 reactions. In Chapters III and IV, the kinetics and mechanisms of the reactions of organic compounds with the major atmospheric oxidants [HO, NO3, and O3] were discussed. The organic radicals formed in these reactions add O2 to form organic peroxy radicals (RO2). The rate coefficient for these reaction is typically of the order of (10−12–10−11) cm3 molecule−1 s−1 under tropospheric conditions. One atmosphere (1 atm) of air contains 5 × 1018 molecule cm−3 of O2, and the lifetime of organic radicals with respect to addition of O2 to give peroxy radicals is 10–100 nanoseconds. Addition of O2 is essentially the sole atmospheric fate of the organic radicals formed during the oxidation of organic compounds. As examples, consider the HO-initiated oxidation of ethane and acetone (M is a third body, such as N2, which collisionally deactivates the nascent peroxy radical): . . . HO + CH3CH3 → CH3CH2 + H2O . . . . . . CH3CH2 + O2 + M → CH3CH2O2 + M . . . . . . HO + CH3C(O)CH3 → CH3C(O)CH2 + H2O . . . . . . CH3C(O)CH2 + O2 + M → CH3C(O)CH2O2 + M . . . Because of the rapidity and exclusivity of the O2 addition to alkyl radicals, the organic peroxy radicals (CH3CH2O2 and CH3C(O)CH2O2) can be thought of as the primary products of the initial oxidation step. HO2 radicals are formed in reactions of O2 with alkoxy radicals (e.g., CH3O) and by the association reaction of H atoms with O2: . . . CH3O + O2 → CH2O + HO2 . . . . . . H + O2 + M → HO2 + M . . . Peroxy radicals (HO2 and RO2) have a rich atmospheric chemistry and undergo reactions with NO, NO2, HO2, and other peroxy radicals (R′O2). Unimolecular isomerization is also an important fate for larger organic peroxy radicals where the peroxy radical can abstract a hydrogen atom from another part of the organic moiety (the peroxy radical bites its own tail). Reactions of peroxy radicals with NO3 radicals at night, and ClO and BrO radicals in maritime environments, can also be of importance on local scales.
On the Use of Virtual Reality as an Outcome Measure in Neuropsychological Rehabilitation
Authors: Jovanovski Diana , Zakzanis Konstantine K.
Published: November 2020

Despite the prevalence of executive dysfunction across multiple neurological and psychiatric conditions, there have been few validated rehabilitative interventions targeting it. One intervention holding promise for patients with executive dysfunc­tion is Robertson’s Goal Management Training (GMT; Robertson, 1996). GMT is based on Duncan’s (1986) theory of goal neglect (or failure to execute intentions), in which disorganized behavior is attributed to impaired construction and use of “goal lists,” considered to direct behavior by controlling actions that promote or oppose task completion. GMT attempts to ameliorate goal neglect through verbally mediated, metacognitive strategies that systematically target planning abilities by teach­ing individuals to structure their intentions. Through presentations, discussions, exercises, and homework assignments, GMT trains participants to use strategies like stopping and orienting to relevant information, partitioning goals into more easily managed subgoals, encoding and retaining goals, and monitoring performance. Investigations into the efficacy of GMT have been promising in both normal older adults and in patients with acquired brain injury (ABI). In order to investigate the efficacy of GMT for older adults with cognitive complaints, van Hooren and colleagues (2007) randomly assigned 69 normal, community-dwelling adults age 55 years or older to a six-week GMT program or to a waitlist control group. After the intervention, participants from the GMT group reported significantly fewer anxiety symptoms, were significantly less annoyed by their cognitive failures, and reported improved ability to manage their executive failures as com­pared to control participants. Though this study reported positive results for subjective outcome measures, the intervention showed no effect on the Stroop Colour Word Test (Houx, Jolles, & Vreeling, 1993; Stroop, 1935). Levine and colleagues (2000) reported on 30 traumatic brain injury (TBI) patients who were randomly assigned to receive a brief trial (1-hour session) of GMT or motor skills training. Upon completion of the intervention, the GMT group, but not the motor skills group, showed significant improvement on paper-and-pencil tasks designed to mimic everyday executive tasks that are problematic for patients with goal neglect.
Teleneuropsychology
Authors: Kane Robert L. , Cullum C. Munro
Published: November 2020

The growth of telemedicine has been rapid. Initially, telemedicine was seen as a way to bring services to remote areas that lacked access to aspects of health­care delivered through traditional means. This view of telemedicine has changed. Current views toward telemedicine have broadened, with telemedicine now viewed as an effective way to deliver various health services and to bring together patients and providers to increase access to care in various locations and communities. Reimbursement has been a challenge for some aspects of telemedicine development. Initially, Medicare limited reimbursement for telehealth to designated underserved areas. This approach to telehealth reimbursement has lagged behind developments in the field and has been challenged by various groups and legislative initiatives. In April 2016, the Centers for Medicare and Medicaid Services (CMS) released its Managed Care Final Rule (Federal Register, 2016) with wording that potentially will permit reimbursement for expanded telemedicine-based services. The revised standards, in attempting to ensure that Medicaid beneficiaries have reasonable access to care, acknowledge a role for technology and telemedicine. The impact the new standards will have on the development of telemedicine throughout the United States will become evident with time. Tele-mental health has grown along with other aspects of remote healthcare delivery. Extant literature supports the use of remotely delivered telehealth for a variety of conditions and services, including remote psychiatric consultation, diagnosis, and various therapies (Myers & Turvey, 2012; Shore, 2013). However, the idea that one can provide an adequate neuropsychological evaluation remotely is newer and less intuitive, and would appear to have obvious challenges. Neuropsychological examinations frequently require the use of test stimuli that the examinee has to handle and manage, such as blocks, pencils, or other manipulatives. Some tests, such as the Wisconsin Card Sorting Test (Heaton, 2003), have been adapted for computer but not for Internet-based or remote administration. In some approaches to neuropsychological assessment, the examiner takes careful note of the specific strategies examinees employ when attempting to perform tasks. Hence, performing an examination when the examiner and the patient are in different locations can seem daunting.
Emperor Joseph’s Roots
Authors: Levy Sharon
Published: November 2020

On a May morning in 1957, ten thousand fish floated on the eastern edge of San Francisco Bay, their pale, upturned bellies bobbing on the surface of the dark water. The crowd of carcasses described an arc that stretched along the shore from Richmond’s harbor south to Point Isabel. Many striped bass, a prized game fish, were among the dead. Seth Gordon, director of California Department of Fish and Game (DFG), fielded complaints from anglers outraged by the fish kill. The Public Health Committee of the State Assembly passed a resolution admonishing DFG for its failure to enforce pollution control laws. Gordon told the committee members off. “We want to stop pollution,” he said, “but the law as it stands puts our Department in the position of a boxer going into the ring with one hand tied behind his back.” The ability to set and enforce pollution standards rested with California’s nine regional water pollution control boards. To effect any change, Gordon’s department had to prove to the boards’ satisfaction that pollution allowed by existing standards was harmful to fish, a challenge that had so far proved impossible. Responding to questions about the East Bay fish kill, he said, “We still don’t know what caused the die-off, or where it came from.” David Joseph was then starting out as a DFG biologist, armed with a doctorate in marine biology from the University of California at Los Angeles. Born in Connecticut, on a cooperative farm where his parents raised dairy cows and shade-grown tobacco with other immigrant Russian Jews, he’d grown up in Inglewood, in southern California, when the place was still a bucolic town and he could ride his horse to the beach. He’d met his wife, Marion, when they were both students at UCLA. “He was an outdoor guy,” she remembers. “He wasn’t a fisherman, he just loved the sea, loved the land. His work was always going to have something to do with protecting the environment.”
Wild Things
Authors: Levy Sharon
Published: November 2020

A group of sea otters laze at the edge of Elkhorn Slough. They float on their backs in the steel- gray water, paws folded against their chests, gazing at the small boat steered by ecologist Brent Hughes of the University of California– Santa Cruz. Hughes has documented a profound shift in the slough’s ecology, triggered by the otters. Sea otters were nearly driven to extinction by fur hunters in the 1800s, and were gone from Elkhorn Slough for a century. In 1984, when the first sea otters recolonized, Elkhorn Slough’s once bountiful eelgrass beds had dwindled to a few small, scattered patches. Now, more than thirty years after the sea otters’ return, expanding eelgrass beds grow lush beneath the water’s surface, the dense leaves sheltering juvenile fish and feeding an array of invertebrate grazers. The slough, on the central California coast, is one of the most severely polluted estuaries on the planet. Artificial fertilizer applied to 2.69 million acres of farmland in the neighboring Salinas Valley runs into its waters. The excess nutrient load causes eutrophication. It also fuels the growth of epiphytic algae that thrive on the surface of eelgrass leaves, blocking the sunlight the grass needs and smothering whole beds. The problem is common in estuaries around the globe, which receive heavy loads of nutrients from rivers draining polluted watersheds. Seagrass meadows filter contaminants from water and prevent coastal erosion in addition to acting as nurseries for fish and invertebrates. These crucial habitats are disappearing. The global distribution of seagrasses has decreased by 29 percent over the last 140 years, and 58 percent of the surviving seagrass meadows are in decline. Nutrient pollution of coastal waters had long been thought to be the main driver of this trend. But in Elkhorn Slough, the eelgrass has made a remarkable comeback even as pollution loads continued to climb. The mechanism of this welcome ecological shift was unknown until Hughes demonstrated that sea otters are the key. He began to put the pieces of the puzzle together when he went diving in Tomales Bay, an unpolluted estuary to the north. The eelgrass in Elkhorn Slough was lush and green despite intense pollution; in Tomales Bay, where there are no sea otters, the eelgrass was a dull brown, smothering under epiphytic algae.
Why Does Russia Invade Its Neighbors?
Authors: Toal Gerard
Published: November 2020

It was supposed to be China’s coming-out party, a moment in the global spotlight affirming its arrival as an economic superpower. But hours before the opening ceremonies of the 2008 Beijing Olympics, news of a war in the Caucasus flashed across the world’s TV screens. On the southern slopes of the Caucasus Mountains, the state of Georgia launched a military offensive against South Ossetia, a small breakaway territory beyond its control since the Soviet collapse. Georgia’s offensive quickly brought Russia to the defense of its local Ossetian allies. As Soviet-era tanks rolled through the Roki tunnel, the only land connection between South Ossetia and Russia, Russian aircraft bombed Georgian targets in the region and beyond. For the first time since the Cold War ended, Russia was invading a neighboring state. Instead of glowing stories about China, speculation about a new Cold War filled the front pages of the Western press. Yet within a week the war was over and a ceasefire agreed. Thereafter a rapidly moving global financial crisis displaced what seemed a harbinger of geopolitical rupture to an afterthought. As quickly as it had flared, the Russo-Georgian war disappeared, and with it talk of a return to geopolitics past. Six years later Russia was in the global spotlight as host of the XXII Olympic Winter Games in Sochi, located on the shores of the Black Sea at the western end of the Caucasus Mountains. Despite well-grounded fears of terrorism, the Olympics were a triumph for Russia and its leadership. Yet a few days later, the world recoiled in shock as Russia once again invaded a neighboring state. Responding to a perceived “fascist coup” in Kyiv, unmarked Russian military personnel seized control of the Ukrainian province of Crimea, once part of Soviet Russia and home to Russia’s Black Sea Fleet. A hastily organized referendum followed, creating the appearance of legitimacy for Russia to formally annex the province, and the city of Sevastopol, in late March 2014.
What Causes Autism?
Authors: Ellis Michael
Published: November 2020

The amount of research being done in autism spectrum disorder (ASD) has grown exponentially in recent years, leading to rapidly changing data and statistics. As a result, our understanding of autism is constantly evolving. This makes it difficult for professionals and families to keep up. However, the ever-increasing pace of new developments offers us all hope. There is hope for better understanding of ASD by professionals and for more effective treatments. And there is always hope for a “cure” or at least a plan for the prevention of autism in the generations to come. The most recent statistics speak to the urgency in solving the autism “puzzle.” There have been dramatic rises in autism since at least the late 1980s. Based on the latest available data, which are from the year 2010, the Centers for Disease Control and Prevention (CDC) estimates that 1 in 68 children in the United States has ASD, with the biggest increase in cases being among the higher-functioning patients, African Americans, and Hispanics. However, based on the data from the year 2000, the prevalence was 1 in 150. This is certainly a frightening jump in prevalence over a 10-year period. Some postulate that this is simply due to better diagnosis, although many studies do not support this. In a previous year, when the data showed that 1 in 88 children had ASD, the CDC noted that ASD was more prevalent than the childhood diseases of AIDS, cancer, and diabetes combined. Typically childhood cancer and diabetes have gotten more attention than autism, at least until recently. But this statistic helps to put the number of children and families affected by autism into perspective (1). A surprising government survey conducted in 2014 suggests that 1 in 45 U.S. children ages 3 to 17 have been diagnosed with ASD. This is quite a bit higher than the CDC’s 1-in-68 figure, but because the new data came from a parent survey, the 1-in-45 figure has not replaced the CDC’s number.
Spread of Farming, New Diseases, and Rising Civilizations: Mid- Holocene Optimum
Authors: McMichael Anthony
Published: November 2020

As The Earth Warmed after the last glacial maximum, temperatures fluctuated. About 9700 B.C.E., temperatures rose again suddenly and began to stabilize, marking the beginning of a new geological epoch, the Holocene. The landscape continued to change, but not so fast that a single generation of humans would have noticed. Ice- sheets and tundra were receding in Eurasia, and over time human groups, both hunter- gatherers and then early farmer- pastoralist communities, adjusted their ways of living to warmer conditions and different rainfall patterns. Small- scale farming and herding emerged on all nonpolar con­tinents during the period 8500 to 6000 B.C.E., predominantly in the northern hemisphere, while human numbers were creeping up. These great changes in environmental conditions and subsequent cultural practices had a profound influence on the foundations of human health and survival: food sufficiency and quality, water sup­plies, contacts with infectious agents, modes of settlement, and social relations. A new era in human ecology was looming. Farming increased food production, but the switch to dependency on a few staples decreased diversity of diets and created an annual agricul­tural regime more susceptible to climate shifts. Close contact with animals, standing water in irrigated environments, and denser set­tlements provided opportunities for microbes, pathogens, viruses, and parasites to cross species barriers and infect and spread among human populations. During the Early Holocene, from about 9700 B.C.E. to 6000 B.C.E., the earth was subjected to the competing stresses of high solar influ­ence and still massive melting ice- sheets. From around 6000 B.C.E., the majority of ice- sheet melting had abated, allowing the stabiliza­tion of the Earth’s climate into what can be called the Mid- Holocene Climatic Optimum (approx. 6000 to 3000 B.C.E.). This was a change in climate that spanned 3,000 to 4,000 years. Warming was most evi­dent in the northern hemisphere, influenced by the peaking of solar radiation at higher northern latitudes as the 23,000- year Milankovitch “wobble” cycle maximized northern sun exposure for several millen­nia. The Milankovitch cycle also drew the rain- bearing Inter- Tropical Convergence Zone (ITCZ) further north.
The Silver Lining
Authors: Lupia Arthur
Published: November 2020

There are many things that people do not know about politics, policy, and government. In some cases, this ignorance prevents them from making competent choices. It prevents them from making decisions that they would have made had they known certain facts and sought to act consistently with certain values. Such circumstances are why effective education is so important. Educators of all kinds are this book’s protagonists. Educators seek to help people make better decisions—where better refers to the decisions that people would have made had they known certain facts and sought to act consistently with certain values. All educators, however, face important constraints. There are limits on their time and energy. Money can be scarce, as can the labor of coworkers or volunteers. Also limited are prospective learners’ motivation to pay attention to new information. If educators seek to develop effective and efficient informational strategies in the face of such constraints, what information should they provide? Standing between many educators and the educational successes to which they aspire are their perceptions of learning’s net benefits. Over the years, I have met educators, or aspiring educators, who energetically imagine the benefits of conveying their expertise to others. They have strong beliefs that teaching certain facts will improve important outcomes. Many, however, have a difficult time articulating the costs that their educational endeavors will impose. Over the same period, I have met many citizens who are asked to participate in these endeavors. They have a different perspective about these endeavors. For citizens, the costs of becoming informed (e.g., money paid for tuition, the struggle to reconcile new information with old beliefs, time spent away from other activities) are real and tangible—while learning’s benefits are often perceived as uncertain. Many citizens as a result tend to be less enthusiastic about learning than educators imagine (and want) them to be. A key to increasing socially beneficial types of knowledge and competence is to become more knowledgeable about these perceptions. Politics is but one aspect of life to which citizens can devote time and energy.