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The jet stream is an important dynamic driver of climate variability in the Northern Hemisphere mid-latitudes 1-3 . Modern variability in the position of summer jet stream latitude in the North Atlantic-European sector (EU JSL) promotes dipole patterns in air pressure, temperature, precipitation and drought between northwestern and southeastern Europe. EU JSL variability and its impacts on regional climatic extremes and societal events are poorly understood, particularly before anthropogenic warming. Based on three temperature-sensitive European tree-ring records, we develop a reconstruction of interannual summer EU JSL variability over the period 1300-2004 CE (R 2  = 38.5%) and compare it to independent historical documented climatic and societal records, such as grape harvest, grain prices, plagues and human mortality. Here we show contrasting summer climate extremes associated with EU JSL variability back to 1300 CE as well as biophysical, economic and human demographic impacts, including wildfires and epidemics. In light of projections for altered jet stream behaviour and intensified climate extremes, our findings underscore the importance of considering EU JSL variability when evaluating amplified future climate risk., (© 2024. The Author(s).)

In 1977 California, authorities responded to an extreme drought with an unprecedented state order to drastically reduce domestic water usage and leave countless newly built swimming pools empty. These curved pools became "playgrounds" for inspired surfers to develop professional vertical skateboarding in the Los Angeles area. Industrial production of polyurethane, and the advent of digital photography, laser printing, and high gloss mass media further contributed to the explosive popularization of skateboarding, creating a global subculture and multibillion-dollar industry that still impacts music, fashion, and lifestyle worldwide. Our interdisciplinary investigation demonstrates that neither the timing nor the location of the origin of professional skateboarding was random. This modern case study highlights how environmental changes can affect human behavior, transform culture, and engender technical innovation in the Anthropocene., (© The Author(s) 2023. Published by Oxford University Press on behalf of National Academy of Sciences.)

Linked to major volcanic eruptions around 536 and 540 CE, the onset of the Late Antique Little Ice Age has been described as the coldest period of the past two millennia. The exact timing and spatial extent of this exceptional cold phase are, however, still under debate because of the limited resolution and geographical distribution of the available proxy archives. Here, we use 106 wood anatomical thin sections from 23 forest sites and 20 tree species in both hemispheres to search for cell-level fingerprints of ephemeral summer cooling between 530 and 550 CE. After cross-dating and double-staining, we identified 89 Blue Rings (lack of cell wall lignification), nine Frost Rings (cell deformation and collapse), and 93 Light Rings (reduced cell wall thickening) in the Northern Hemisphere. Our network reveals evidence for the strongest temperature depression between mid-July and early-August 536 CE across North America and Eurasia, whereas more localised cold spells occurred in the summers of 532, 540-43, and 548 CE. The lack of anatomical signatures in the austral trees suggests limited incursion of stratospheric volcanic aerosol into the Southern Hemisphere extra-tropics, that any forcing was mitigated by atmosphere-ocean dynamical responses and/or concentrated outside the growing season, or a combination of factors. Our findings demonstrate the advantage of wood anatomical investigations over traditional dendrochronological measurements, provide a benchmark for Earth system models, support cross-disciplinary studies into the entanglements of climate and history, and question the relevance of global climate averages., Competing Interests: Conflict of interest The authors declare that they have no conflict of interest., (Copyright © 2022 Science China Press. Published by Elsevier B.V. All rights reserved.)

Global temperatures are rising at an unprecedented rate, but environmental responses are often difficult to recognize and quantify. Long-term observations of plant phenology, the annually recurring sequence of plant developmental stages, can provide sensitive measures of climate change and important information for ecosystem services. Here, we present 419 354 recordings of the first flowering date from 406 plant species in the UK between 1753 and 2019 CE. Community-wide first flowering advanced by almost one month on average when comparing all observations before and after 1986 ( p < 0.0001). The mean first flowering time is 6 days earlier in southern than northern sites, 5 days earlier under urban than rural settings, and 1 day earlier at lower than higher elevations. Compared to trees and shrubs, the largest lifeform-specific phenological shift of 32 days is found in herbs, which are generally characterized by fast turnover rates and potentially high levels of genetic adaptation. Correlated with January-April maximum temperatures at -0.81 from 1952-2019 ( p < 0.0001), the observed trends (5.4 days per decade) and extremes (66 days between the earliest and latest annual mean) in the UK's first flowering dataset can affect the functioning and productivity of ecosystems and agriculture.

Tree-ring chronologies underpin the majority of annually-resolved reconstructions of Common Era climate. However, they are derived using different datasets and techniques, the ramifications of which have hitherto been little explored. Here, we report the results of a double-blind experiment that yielded 15 Northern Hemisphere summer temperature reconstructions from a common network of regional tree-ring width datasets. Taken together as an ensemble, the Common Era reconstruction mean correlates with instrumental temperatures from 1794-2016 CE at 0.79 (p < 0.001), reveals summer cooling in the years following large volcanic eruptions, and exhibits strong warming since the 1980s. Differing in their mean, variance, amplitude, sensitivity, and persistence, the ensemble members demonstrate the influence of subjectivity in the reconstruction process. We therefore recommend the routine use of ensemble reconstruction approaches to provide a more consensual picture of past climate variability.

To satisfy the increasing demand for wood in central Europe during medieval times, a new system of forest management was developed, one far superior to simple coppicing. The adoption of a sophisticated, Coppice-with-Standards (CWS) management practice created a two-storey forest structure that could provide fuelwood as well as construction timber. Here we present a dendrochronological study of actively managed CWS forests in northern Bavaria to detect the radial growth response to cyclical understorey harvesting in overstorey oaks (Quercus sp.), so-called standards. All modern standards exhibit rapid growth releases every circa 30 years, most likely caused by regular understorey management. We further analyse tree-ring width patterns in 2120 oak timbers from historical buildings and archaeological excavations in southern Germany and north-eastern France, dating between 300 and 2015 CE, and succeeded in identifying CWS growth patterns throughout the medieval period. Several potential CWS standards even date to the first millennium CE, suggesting CWS management has been in practice long before its first mention in historical documents. Our dendrochronological approach should be expanded routinely to indentify the signature of past forest management practices in archaeological and historical oak wood.

Climate change affects the distribution of many species, including Burgundy and Périgord truffles in central and southern Europe, respectively. The cultivation potential of these high-prized cash crops under future warming, however, remains highly uncertain. Here we perform a literature review to define the ecological requirements for the growth of both truffle species. This information is used to develop niche models, and to estimate their cultivation potential in the Czech Republic under current (2020) and future (2050) climate conditions. The Burgundy truffle is already highly suitable for cultivation on ~ 14% of agricultural land in the Czech Republic (8486 km 2 ), whereas only ~ 8% of the warmest part of southern Moravia are currently characterised by a low suitability for Périgord truffles (6418 km 2 ). Though rising temperatures under RCP8.5 will reduce the highly suitable cultivation areas by 7%, the 250 km 2 (3%) expansion under low-emission scenarios will stimulate Burgundy truffles to benefit from future warming. Doubling the moderate and expanding the highly suitable land by 352 km 2 in 2050, the overall cultivation potential for Périgord truffles will rise substantially. Our findings suggest that Burgundy and Périgord truffles could become important high-value crops for many regions in central Europe with alkaline soils. Although associated with uncertainty, long-term investments in truffle cultivation could generate a wide range of ecological and economic benefits.

In many species, decreasing body size has been associated with increasing temperatures. Although climate-induced phenotypic shifts, and evolutionary impacts, can affect the structure and functioning of marine and terrestrial ecosystems through biological and metabolic rules, evidence for shrinking body size is often challenged by (i) relatively short intervals of observation, (ii) a limited number of individuals, and (iii) confinement to small and isolated populations. To overcome these issues and provide important multi-species, long-term information for conservation managers and scientists, we compiled and analysed 222 961 measurements of eviscerated body weight, 170 729 measurements of hind foot length and 145 980 measurements of lower jaw length, in the four most abundant Alpine ungulate species: ibex ( Capra ibex ), chamois ( Rupicapra rupicapra ), red deer ( Cervus elaphus ) and roe deer ( Capreolus capreolus ). Regardless of age, sex and phylogeny, the body mass and size of these sympatric animals, from the eastern Swiss Alps, remained stable between 1991 and 2013. Neither global warming nor local hunting influenced the fitness of the wild ungulates studied at a detectable level. However, we cannot rule out possible counteracting effects of enhanced nutritional resources associated with longer and warmer growing seasons, as well as the animals' ability to migrate along extensive elevational gradients in the highly diversified alpine landscape of this study., Competing Interests: We declare we have no competing interests., (© 2020 The Authors.)

The sudden interruption of recurring larch budmoth (LBM; Zeiraphera diniana or griseana Gn.) outbreaks across the European Alps after 1982 was surprising, because populations had regularly oscillated every 8-9 years for the past 1200 years or more. Although ecophysiological evidence was limited and underlying processes remained uncertain, climate change has been indicated as a possible driver of this disruption. An unexpected, recent return of LBM population peaks in 2017 and 2018 provides insight into this insect's climate sensitivity. Here, we combine meteorological and dendrochronological data to explore the influence of temperature variation and atmospheric circulation on cyclic LBM outbreaks since the early 1950s. Anomalous cold European winters, associated with a persistent negative phase of the North Atlantic Oscillation, coincide with four consecutive epidemics between 1953 and 1982, and any of three warming-induced mechanisms could explain the system's failure thereafter: (1) high egg mortality, (2) asynchrony between egg hatch and foliage growth, and (3) upward shifts of outbreak epicentres. In demonstrating that LBM populations continued to oscillate every 8-9 years at sub-outbreak levels, this study emphasizes the relevance of winter temperatures on trophic interactions between insects and their host trees, as well as the importance of separating natural from anthropogenic climate forcing on population behaviour.

Despite being one of the most expensive gourmet foods, it remains unclear if the iconic White Truffle (Tuber magnatum Pico; hereinafter WT) accumulates radioactivity at harmful levels comparable to other fungal species. Here, we measure the active radiocaesium-137 concentration ( 137 Cs) in ten hypogeous WT fruitbodies from southern Hungary, and the soils in which they were growing. All WTs reveal non-significant 137 Cs values, thus providing an 'all clear' for WT hunters in the species' northernmost habitats, where corresponding soil samples occasionally exhibit slight 137 Cs concentrations. Our results are particularly relevant in the light of a rapidly increasing global demand for WTs and their subsequent trading extent and price inflation, because up to 600 kg of fresh fruitbodies are harvested each year in southern Hungary. Moreover, some of Europe's forest ecosystems, in which mushroom picking is common practise, are still contaminated with 137 Cs from the Chernobyl fallout more than 30 years ago, posing a serious threat to human health., (Crown Copyright © 2019. Published by Elsevier Ltd. All rights reserved.)

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

It is generally accepted that animal heartbeat and lifespan are often inversely correlated, however, the relationship between productivity and longevity has not yet been described for trees growing under industrial and pre-industrial climates. Using 1768 annually resolved and absolutely dated ring width measurement series from living and dead conifers that grew in undisturbed, high-elevation sites in the Spanish Pyrenees and the Russian Altai over the past 2000 years, we test the hypothesis of grow fast-die young. We find maximum tree ages are significantly correlated with slow juvenile growth rates. We conclude, the interdependence between higher stem productivity, faster tree turnover, and shorter carbon residence time, reduces the capacity of forest ecosystems to store carbon under a climate warming-induced stimulation of tree growth at policy-relevant timescales.

Although it has been recognized that rising temperatures and shifts in the hydrological cycle affect the depth of the seasonally thawing upper permafrost stratum, it remains unclear to what extent the frequency and intensity of wildfires, and subsequent changes in vegetation cover, influence the soil active layer on different spatiotemporal scales. Here, we use ring width measurements of the subterranean stem part of 15 larch trees from a Sphagnum bog site in Central Siberia to reconstruct long-term changes in the thickness of the active layer since the last wildfire occurred in 1899. Our approach reveals a three-step feedback loop between above- and belowground ecosystem components. After all vegetation is burned, direct atmospheric heat penetration over the first ~20 years caused thawing of the upper permafrost stratum. The slow recovery of the insulating ground vegetation reverses the process and initiates a gradual decrease of the active layer thickness. Due to the continuous spreading and thickening of the peat layer during the last decades, the upper permafrost horizon has increased by 0.52 cm/year. This study demonstrates the strength of annually resolved and absolutely dated tree-ring series to reconstruct the effects of historical wildfires on the functioning and productivity of boreal forest ecosystems at multi-decadal to centennial time-scale. In so doing, we show how complex interactions of above- and belowground components translate into successive changes in the active permafrost stratum. Our results are particularly relevant for improving long-term estimates of the global carbon cycle that strongly depends on the source and sink behavior of the boreal forest zone., (Copyright © 2018. Published by Elsevier B.V.)

The original version of this Article contained an error in the Data Availability section, which incorrectly read 'All data will be freely available via https://www.ams.ethz.ch/research.html .' The correct version states ' http://www.ams.ethz.ch/research/published-data.html ' in place of ' https://www.ams.ethz.ch/research.html '. This has been corrected in both the PDF and HTML versions of the Article.

Though tree-ring chronologies are annually resolved, their dating has never been independently validated at the global scale. Moreover, it is unknown if atmospheric radiocarbon enrichment events of cosmogenic origin leave spatiotemporally consistent fingerprints. Here we measure the 14 C content in 484 individual tree rings formed in the periods 770-780 and 990-1000 CE. Distinct 14 C excursions starting in the boreal summer of 774 and the boreal spring of 993 ensure the precise dating of 44 tree-ring records from five continents. We also identify a meridional decline of 11-year mean atmospheric radiocarbon concentrations across both hemispheres. Corroborated by historical eye-witness accounts of red auroras, our results suggest a global exposure to strong solar proton radiation. To improve understanding of the return frequency and intensity of past cosmic events, which is particularly important for assessing the potential threat of space weather on our society, further annually resolved 14 C measurements are needed.

Selective hunting can affect demographic characteristics and phenotypic traits of the targeted species. Hunting systems often involve harvesting quotas based on sex, age and/or size categories to avoid selective pressure. However, it is difficult to assess whether such regulations deter hunters from targeting larger "trophy" animals with longer horns that may have evolutionary consequences. Here, we compile 44,088 annually resolved and absolutely dated measurements of Alpine ibex (Capra ibex) horn growth increments from 8,355 males, harvested between 1978 and 2013, in the eastern Swiss Canton of Grisons. We aim to determine whether male ibex with longer horns were preferentially targeted, causing animals with early rapid horn growth to have shorter lives, and whether such hunting selection translated into long-term trends in horn size over the past four decades. Results show that medium- to longer-horned adult males had a higher probability of being harvested than shorter-horned individuals of the same age and that regulations do affect the hunters' behaviour. Nevertheless, phenotypic traits such as horn length, as well as body size and weight, remained stable over the study period. Although selective trophy hunting still occurs, it did not cause a measurable evolutionary response in Grisons' Alpine ibex populations; managed and surveyed since 1978. Nevertheless, further research is needed to understand whether phenotypic trait development is coinfluenced by other, potentially compensatory factors that may possibly mask the effects of selective, long-term hunting pressure., (© 2018 The Authors. Journal of Animal Ecology © 2018 British Ecological Society.)

Volcanic eruptions have global climate impacts, but their effect on the hydrologic cycle is poorly understood. We use a modified version of superposed epoch analysis, an eruption year list collated from multiple datasets, and seasonal paleoclimate reconstructions (soil moisture, precipitation, geopotential heights, and temperature) to investigate volcanic forcing of spring and summer hydroclimate over Europe and the Mediterranean over the last millennium. In the western Mediterranean, wet conditions occur in the eruption year and the following 3 years. Conversely, northwestern Europe and the British Isles experience dry conditions in response to volcanic eruptions, with the largest moisture deficits in post-eruption years 2 and 3. The precipitation response occurs primarily in late spring and early summer (April-July), a pattern that strongly resembles the negative phase of the East Atlantic Pattern. Modulated by this mode of climate variability, eruptions force significant, widespread, and heterogeneous hydroclimate responses across Europe and the Mediterranean.

On Mt. Etna (Italy), an enhanced Normalized Difference in Vegetation Index (NDVI) signature was detected in the summers of 2001 and 2002 along a distinct line where, in November 2002, a flank eruption subsequently occurred. These observations suggest that pre-eruptive volcanic activity may have enhanced photosynthesis along the future eruptive fissure. If a direct relation between NDVI and future volcanic eruptions could be established, it would provide a straightforward and low-cost method for early detection of upcoming eruptions. However, it is unclear if, or to what extent, the observed enhancement of NDVI can be attributed to volcanic activity prior to the subsequent eruption. We consequently aimed at determining whether an increase in ambient temperature or additional water availability owing to the rise of magma and degassing of water vapour prior to the eruption could have increased photosynthesis of Mt. Etna's trees. Using dendro-climatic analyses we quantified the sensitivity of tree ring widths to temperature and precipitation at high elevation stands on Mt. Etna. Our findings suggest that tree growth at high elevation on Mt. Etna is weakly influenced by climate, and that neither an increase in water availability nor an increase in temperature induced by pre-eruptive activity is a plausible mechanism for enhanced photosynthesis before the 2002/2003 flank eruption. Our findings thus imply that other, yet unknown, factors must be sought as causes of the pre-eruption enhancement of NDVI on Mt. Etna., Competing Interests: The authors have declared that no competing interests exist.

Provenance studies are an increasingly important analog for understanding how trees adapted to particular climatic conditions might respond to climate change. Dendrochronological analysis can illuminate differences among trees from different seed sources in terms of absolute annual growth and sensitivity to external growth factors. We analyzed annual radial growth of 567 36-year-old pitch pine (Pinus rigida Mill.) trees from 27 seed sources to evaluate their performance in a New Jersey Pine Barrens provenance experiment. Unexpectedly, missing rings were prevalent in most trees, and some years-1992, 1999, and 2006-had a particularly high frequency of missing rings across the plantation. Trees from local seed sources (<55 km away from the plantation) had a significantly smaller percentage of missing rings from 1980-2009 (mean: 5.0%), relative to northernmost and southernmost sources (mean: 9.3% and 7.9%, respectively). Some years with a high frequency of missing rings coincide with outbreaks of defoliating insects or dry growing season conditions. The propensity for missing rings synchronized annual variations in growth across all trees and might have complicated the detection of potential differences in interannual variability among seed sources. Average ring width was significantly larger in seed sources from both the southernmost and warmest origins compared to the northernmost and coldest seed sources in most years. Local seed sources had the highest average radial growth. Adaptation to local environmental conditions and disturbances might have influenced the higher growth rate found in local seed sources. These findings underscore the need to understand the integrative impact of multiple environmental drivers, such as disturbance agents and climate change, on tree growth, forest dynamics, and the carbon cycle.

Accurate modelling and prediction of the local to continental-scale hydroclimate response to global warming is essential given the strong impact of hydroclimate on ecosystem functioning, crop yields, water resources, and economic security. However, uncertainty in hydroclimate projections remains large, in part due to the short length of instrumental measurements available with which to assess climate models. Here we present a spatial reconstruction of hydroclimate variability over the past twelve centuries across the Northern Hemisphere derived from a network of 196 at least millennium-long proxy records. We use this reconstruction to place recent hydrological changes and future precipitation scenarios in a long-term context of spatially resolved and temporally persistent hydroclimate patterns. We find a larger percentage of land area with relatively wetter conditions in the ninth to eleventh and the twentieth centuries, whereas drier conditions are more widespread between the twelfth and nineteenth centuries. Our reconstruction reveals that prominent seesaw patterns of alternating moisture regimes observed in instrumental data across the Mediterranean, western USA, and China have operated consistently over the past twelve centuries. Using an updated compilation of 128 temperature proxy records, we assess the relationship between the reconstructed centennial-scale Northern Hemisphere hydroclimate and temperature variability. Even though dry and wet conditions occurred over extensive areas under both warm and cold climate regimes, a statistically significant co-variability of hydroclimate and temperature is evident for particular regions. We compare the reconstructed hydroclimate anomalies with coupled atmosphere-ocean general circulation model simulations and find reasonable agreement during pre-industrial times. However, the intensification of the twentieth-century-mean hydroclimate anomalies in the simulations, as compared to previous centuries, is not supported by our new multi-proxy reconstruction. This finding suggests that much work remains before we can model hydroclimate variability accurately, and highlights the importance of using palaeoclimate data to place recent and predicted hydroclimate changes in a millennium-long context.

Climate model projections suggest widespread drying in the Mediterranean Basin and wetting in Fennoscandia in the coming decades largely as a consequence of greenhouse gas forcing of climate. To place these and other "Old World" climate projections into historical perspective based on more complete estimates of natural hydroclimatic variability, we have developed the "Old World Drought Atlas" (OWDA), a set of year-to-year maps of tree-ring reconstructed summer wetness and dryness over Europe and the Mediterranean Basin during the Common Era. The OWDA matches historical accounts of severe drought and wetness with a spatial completeness not previously available. In addition, megadroughts reconstructed over north-central Europe in the 11th and mid-15th centuries reinforce other evidence from North America and Asia that droughts were more severe, extensive, and prolonged over Northern Hemisphere land areas before the 20th century, with an inadequate understanding of their causes. The OWDA provides new data to determine the causes of Old World drought and wetness and attribute past climate variability to forced and/or internal variability.

Vapor pressure and aqueous solubility are important parameters used to estimate the potential for transport of chemical substances in the atmosphere. For fluorotelomer alcohols (FTOHs), currently under scrutiny by environmental scientists as potential precursors of persistent perfluorocarboxylates (PFCAs), vapor pressure is the more significant property since these compounds are only very sparingly soluble in water. We have measured the vapor pressures of a homologous series of fluorotelomer alcohols, F(CF2CF2)nCH2CH2OH (n = 2-5), in the temperature range 21-250 degrees C by three independent methods: (a) a method suitable for very low vapor pressures at ambient temperatures (gas-saturation method), (b) an improved boiling point method at controlled pressures (Scott method), and (c) a novel method, requiring milligram quantities of substance, based on gas-phase NMR, a technique largely unfamiliar to chemists and holding promise for studies of relevance to environmental chemistry. The concordant values obtained indicate that recently published vapor pressure data overestimate the vapor pressure at ambient temperature, and therefore the volatility, of this series of fluorinated compounds. It was suggested that substantial intramolecular -O-H...F- hydrogen bonding between the hydroxylic proton and the two fluorines next to the ethanol moiety was responsible for their putative high volatility. Therefore, we have used gas-phase NMR, gas-phase FTIR, 2D NMR heteronuclear Overhauser effect measurements, and high-level ab initio computations to investigate the intramolecular hydrogen bonding in fluorotelomer alcohols. Our studies unequivocally show that hydrogen bonding of this type is not significant and cannot contribute to and cause unusual volatility. The substantially lower vapor pressure at ambient temperatures than previously reported resulting from our work is important in developing a valid understanding of the environmental transport behavior of this class of compounds.

The kinetics of the thermal decomposition of ammonium perfluorooctanoate (APFO) has been studied by high-temperature gas-phase nuclear magnetic resonance spectroscopy over the temperature range 196-234 degrees C. We find that APFO cleanly decomposes by first-order kinetics to give the hydrofluorocarbon 1-H-perfluoroheptane and is completely decomposed (>99%) in a matter of minutes at the upper limit of this temperature range. Based on the temperature dependence of the measured rate constants, we find that the enthalpy and entropy of activation are DeltaH++ = 150 +/- 11 kJ mol(-1) and DeltaS++ = 3 +/- 23 J mol(-)(1) deg(-1). These activation parameters may be used to calculate the rate of APFO decomposition at the elevated temperatures (350-400 degrees C) at which fluoropolymers are processed; for example, at 350 degrees C the half-life for APFO is estimated to be less than 0.2 s. Our studies provide the fundamental parameters involved in the decomposition of the ammonium salt of perfluorooctanoic acid and indicate the utility of gas-phase NMR for thermolysis studies of a variety of materials that release compounds that are volatile at the temperature of decomposition and that contain an NMR-active nucleus.

Gas-phase (1)H NMR analysis has been applied to investigate the kinetics of the unimolecular rearrangement of 2,2-dichloro-1-methylenecyclopropane (1) to (dichloromethylene)cyclopropane (2) [k(1) = 7.9 x 10(12) exp(-34.4 +/- 0.6 kcal mol(-1)/RT)], as well as for the subsequent second-order dimerization of 2 [k(2) = 2.4 x 10(6) exp(-18.5 +/- 1.1 kcal mol(-1)/RT)] to form 7,7,8,8-tetrachlorodispiro[2.0.2.2]octane (3)

A gas-phase NMR kinetic technique has been used for the first time to obtain accurate measurements of rate constants of some bimolecular, second-order cycloaddition reactions. As a test of the potential use of this technique for the study of second-order reactions, the rate constants and the activation parameters for the cyclodimerization reactions of chlorotrifluoroethylene (CTFE) and tetrafluoroethylene (TFE) were determined in the temperature range 240-340 degrees C, using a commercial high-temperature NMR probe. Obtaining excellent agreement of the results with published data, the technique was then applied to the reaction of 1,1-difluoroallene with 1,3-butadiene, the results of which indicate that the use of gas-phase NMR for reaction kinetics is particularly valuable when a reagent is available only in small amounts and in cases where there are several competing processes occurring simultaneously. The major processes observed in this reaction are regioselective [2+2] and [2+4] cycloadditions, whose rates and activation parameters were determined [k2 = 9.3 x 10(6) exp(-20.1 kcal x mol(-1)/RT) L/mol(-1) x s(-1) and k3 = 1.2 x 10(6) exp(-18.4 kcal x mol(-1)/RT) L/mol(-1) x s(-)(1), respectively] in the temperature range 130-210 degrees C.

The photochemistry of tetraphenylacetone (1) adsorbed on the external surface of a MFI zeolite (the sodium form of LZ-105) has been investigated in combination with computational chemistry, surface area measurements, EPR analysis, and classical adsorption isotherms. All of the methods are consistent with a supramolecular structural model in which 1 is first adsorbed strongly through intercalation of a single benzene ring into a hole on the LZ-105 external surface (site I) followed by a weaker binding to the external framework between the holes (site II) until a monolayer of 1 is formed. From both computational and surface area measurements, it is estimated that the site I holes on the external surface will be filled at ca. 0.3-0.5 wt %/wt loading of 1/LZ-105, which corresponds to 6.5 x 10(18) (ca. 10(-)(5) mol) of holes or molecules of 1 adsorbed in holes per gram of zeolite. The supramolecular composition of ca. 0.3-0.5% of 1 on LZ-105 characterizes a "break point" for the photochemistry and the EPR measurements, since it represents the value for saturation of the site I holes with 1. These conclusions are supported quantitatively by experimental isotherms of the adsorption of 1 on LZ-105. Photolysis of 1 intercalated in the site I holes causes fragmentation into two isomeric supramolecular diphenylmethyl (DPM) radicals, one (DMP)(in) which is adsorbed into the internal surface and becomes strongly persistent (half-life of many weeks) and the other (DMP)(ex) which diffuses on the external surface and rapidly dimerizes (less than a few minutes) to produce the radical-radical combination product tetraphenylethane (2). Photolysis of 1 adsorbed on the solid external surface produces two supramolecularly equivalent DPM radicals (DMP)(ex) that diffuse on the external surface and rapidly dimerize to produce 2, and do not produce persistent DPM radicals.

Perfluoroalkylated nanospheres have been prepared by reaction of fullerenes with a variety of fluoroalkyl radicals. The latter are generated by thermal or photochemical decomposition of fluoroalkyl iodides or fluorodiacyl peroxides. Up to 16 radicals add to C(60) to afford easily isolable fluoroalkylated derivatives. The monosubstituted radical adducts were detected by electron spin resonance in the early stages of the fluoroalkylation reactions. These spheroidal molecules are thermally quite stable, soluble in fluoroorganic solvents, chemically resistant to corrosive aqueous solutions, and more volatile than the parent fullerenes. Films of the sublimed material display properties typical for a perfluoroalkylated material.

Photochemically generated benzyl radicals react with C(60) producing radical and nonradical adducts Rn C(60) (R = C(6)H(5)CH(2)) with n = 1 to at least 15. The radical adducts with n = 3 and 5 are stable above 50 degrees C and have been identified by electron spin resonance (ESR) spectroscopy as the allylic R(3)C(60)(.) (3) and cyclopentadienyl R(5)C(60)(.) (5) radicals. The unpaired electrons are highly localized on the C(60) surface. The extraordinary stability of these radicals can be attributed to the steric protection of the surface radical sites by the surrounding benzyl substituents. Photochemically generated methyl radicals also add readily to C(60). Mass spectrometric analyses show the formation of (CH(3))nC(60) with n = 1 to at least 34.