Environmental concerns have and will continue to have a significant role in determining how chemistry is carried out. Chemists will be challenged to develop new, efficient synthetic processes that ...have the fewest possible steps leading to a target molecule, the goal being to decrease the amount of waste generated and reduce energy use. Along this path, chemists will need to develop highly selective reactions with atom-economical pathways producing nontoxic byproduct. In this context, C–H bond activation and functionalization is an extremely attractive method. Indeed, for most organic transformations, the presence of a reactive functionality is required. In Total Synthesis, the “protection and deprotection” approach with such reactive groups limits the overall yield of the synthesis, involves the generation of significant chemical waste, costs energy, and in the end is not as green as one would hope. In turn, if a C–H bond functionalization were possible, instead of the use of a prefunctionalized version of the said C–H bond, the number of steps in a synthesis would obviously be reduced. In this case, the C–H bond can be viewed as a dormant functional group that can be activated when necessary during the synthetic strategy. One issue increasing the challenge of such a desired reaction is selectivity. The cleavage of a C–H bond (bond dissociation requires between 85 and 105 kcal/mol) necessitates a high-energy species, which could quickly become a drawback for the control of chemo-, regio-, and stereoselectivity. Transition metal catalysts are useful reagents for surmounting this problem; they can decrease the kinetic barrier of the reaction yet retain control over selectivity. Transition metal complexes also offer important versatility in having distinct pathways that can lead to activation of the C–H bond. An oxidative addition of the metal in the C–H bond, and a base-assisted metal–carbon bond formation in which the base can be coordinated (or not) to the metal complexes are possible. These different C–H bond activation modes provide chemists with several synthetic options. In this Account, we discuss recent discoveries involving the versatile NHC–gold(I) and NHC–copper(I) hydroxide complexes (where NHC is N-heterocyclic carbene) showing interesting Brønsted basic properties for C–H bond activation or C–H bond functionalization purposes. The simple and easy synthesis of these two complexes involves their halide-bearing relatives reacting with simple alkali metal hydroxides. These complexes can react cleanly with organic compounds bearing protons with compatible pK a values, producing only water as byproduct. It is a very simple protocol indeed and may be sold as a C–H bond activation, although the less flashy “metalation reaction” also accurately describes the process. The synthesis of these complexes has led us to develop new organometallic chemistry and catalysis involving C–H bond activation (metalation) and subsequent C–H bond functionalization. We further highlight applications with these reactions, in areas such as photoluminescence and biological activities of NHC–gold(I) and NHC–copper(I) complexes.
The spectrum of the hydrogen atom has played a central part in fundamental physics over the past 200 years. Historical examples of its importance include the wavelength measurements of absorption ...lines in the solar spectrum by Fraunhofer, the identification of transition lines by Balmer, Lyman and others, the empirical description of allowed wavelengths by Rydberg, the quantum model of Bohr, the capability of quantum electrodynamics to precisely predict transition frequencies, and modern measurements of the 1S-2S transition by Hänsch to a precision of a few parts in 10
. Recent technological advances have allowed us to focus on antihydrogen-the antimatter equivalent of hydrogen. The Standard Model predicts that there should have been equal amounts of matter and antimatter in the primordial Universe after the Big Bang, but today's Universe is observed to consist almost entirely of ordinary matter. This motivates the study of antimatter, to see if there is a small asymmetry in the laws of physics that govern the two types of matter. In particular, the CPT (charge conjugation, parity reversal and time reversal) theorem, a cornerstone of the Standard Model, requires that hydrogen and antihydrogen have the same spectrum. Here we report the observation of the 1S-2S transition in magnetically trapped atoms of antihydrogen. We determine that the frequency of the transition, which is driven by two photons from a laser at 243 nanometres, is consistent with that expected for hydrogen in the same environment. This laser excitation of a quantum state of an atom of antimatter represents the most precise measurement performed on an anti-atom. Our result is consistent with CPT invariance at a relative precision of about 2 × 10
.
The observation of hyperfine structure in atomic hydrogen by Rabi and co-workers and the measurement of the zero-field ground-state splitting at the level of seven parts in 10
are important ...achievements of mid-twentieth-century physics. The work that led to these achievements also provided the first evidence for the anomalous magnetic moment of the electron, inspired Schwinger's relativistic theory of quantum electrodynamics and gave rise to the hydrogen maser, which is a critical component of modern navigation, geo-positioning and very-long-baseline interferometry systems. Research at the Antiproton Decelerator at CERN by the ALPHA collaboration extends these enquiries into the antimatter sector. Recently, tools have been developed that enable studies of the hyperfine structure of antihydrogen-the antimatter counterpart of hydrogen. The goal of such studies is to search for any differences that might exist between this archetypal pair of atoms, and thereby to test the fundamental principles on which quantum field theory is constructed. Magnetic trapping of antihydrogen atoms provides a means of studying them by combining electromagnetic interaction with detection techniques that are unique to antimatter. Here we report the results of a microwave spectroscopy experiment in which we probe the response of antihydrogen over a controlled range of frequencies. The data reveal clear and distinct signatures of two allowed transitions, from which we obtain a direct, magnetic-field-independent measurement of the hyperfine splitting. From a set of trials involving 194 detected atoms, we determine a splitting of 1,420.4 ± 0.5 megahertz, consistent with expectations for atomic hydrogen at the level of four parts in 10
. This observation of the detailed behaviour of a quantum transition in an atom of antihydrogen exemplifies tests of fundamental symmetries such as charge-parity-time in antimatter, and the techniques developed here will enable more-precise such tests.
Antihydrogen, a positron bound to an antiproton, is the simplest anti-atom. Its structure and properties are expected to mirror those of the hydrogen atom. Prospects for precision comparisons of the ...two, as tests of fundamental symmetries, are driving a vibrant programme of research. In this regard, a limiting factor in most experiments is the availability of large numbers of cold ground state antihydrogen atoms. Here, we describe how an improved synthesis process results in a maximum rate of 10.5 ± 0.6 atoms trapped and detected per cycle, corresponding to more than an order of magnitude improvement over previous work. Additionally, we demonstrate how detailed control of electron, positron and antiproton plasmas enables repeated formation and trapping of antihydrogen atoms, with the simultaneous retention of atoms produced in previous cycles. We report a record of 54 detected annihilation events from a single release of the trapped anti-atoms accumulated from five consecutive cycles.Antihydrogen studies are important in testing the fundamental principles of physics but producing antihydrogen in large amounts is challenging. Here the authors demonstrate an efficient and high-precision method for trapping and stacking antihydrogen by using controlled plasma.
Physicists have long wondered whether the gravitational interactions between matter and antimatter might be different from those between matter and itself. Although there are many indirect ...indications that no such differences exist and that the weak equivalence principle holds, there have been no direct, free-fall style, experimental tests of gravity on antimatter. Here we describe a novel direct test methodology; we search for a propensity for antihydrogen atoms to fall downward when released from the ALPHA antihydrogen trap. In the absence of systematic errors, we can reject ratios of the gravitational to inertial mass of antihydrogen >75 at a statistical significance level of 5%; worst-case systematic errors increase the minimum rejection ratio to 110. A similar search places somewhat tighter bounds on a negative gravitational mass, that is, on antigravity. This methodology, coupled with ongoing experimental improvements, should allow us to bound the ratio within the more interesting near equivalence regime.
Arboviruses (arthropod-borne-viruses) are an emerging global health threat that are rapidly spreading as climate change, international business transport, and landscape fragmentation impact local ...ecologies. Since its initial detection in 1999, West Nile virus has shifted from being a novel to an established arbovirus in the United States of America. Subsequently, more than 25,000 cases of West Nile neuro-invasive disease have been diagnosed, cementing West Nile virus as an arbovirus of public health importance. Given its novelty in the United States of America, high-risk ecologies are largely underdefined making targeted population-level public health interventions challenging. Using the Centers for Disease Control and Prevention ArboNET neuroinvasive West Nile virus data from 2000–2021, this study aimed to predict neuroinvasive West Nile virus human cases at the county level for the contiguous USA using a spatio-temporal Bayesian negative binomial regression model. The model includes environmental, climatic, and demographic factors, as well as the distribution of host species. An integrated nested Laplace approximation approach was used to fit our model. To assess model prediction accuracy, annual counts were withheld, forecasted, and compared to observed values. The validated models were then fit to the entire dataset for 2022 predictions. This proof-of-concept mathematical, geospatial modelling approach has proven utility for national health agencies seeking to allocate funding and other resources for local vector control agencies tackling West Nile virus and other notifiable arboviral agents.
Summary
The change in soil carbon (C) stock over a 19–31‐year period (mean 25 years) has been measured at 179 sites on a 20‐km grid across Scotland. Sampling was by horizon from a profile pit. ...Although soil bulk density determinations were absent at the first sampling time, we used bulk density values from the second sampling time calibrated against NIR spectra to predict the missing values. There was no detectable change in overall total soil C stock (mean ± standard error, to a depth of 100 cm), which was 266 ± 15 and 270 ± 15 t C ha−1 for the first and second sampling times, respectively, or generally in C stock within specific vegetation or soil types. The exception was for soils under woodland, excluding those on deep peat, which exhibited a significant (P = 0.05) gain of 1.0 t C ha−1 year−1. Soils under woodland (mainly coniferous plantation) also showed a significant (P = 0.04) increase in C content (g kg−1), a significant decrease in bulk density (P = 0.006) and an increase in the thickness of the Litter‐Fermentation‐Humus (LFH) layer (P = 0.06). Recalculating the C stock to a depth of 15 cm showed a significant increase in overall C stock (when deep peat sites were excluded) as well as specifically in moorland and woodland soils, suggesting that had we sampled only to 15 cm, we would have reached a different conclusion. Both improved grassland soils and those initially under arable cultivation showed a significant decrease in C content. However, the mean thickness of Ap horizons increased from 29 to 32 cm, with a concomitant decrease in C content and a slight increase in bulk density; this we ascribe to deeper ploughing between the sample periods. In the context of possible soil C losses, we can be 95% confident that the mean loss does not exceed 0.2% year−1 and 99% confident that it does not exceed 0.4% year−1.
The bigger the better: The new well‐defined Pd(IPr*)(cin)Cl pre‐catalyst is described (see scheme). This complex proves to be highly active in the Suzuki–Miyaura cross‐coupling for the synthesis of ...tetra‐ortho‐substituted biaryls under mild conditions. IPr* is reported as the largest N‐heterocyclic carbene (NHC) to date for Pd(NHC)(cin)Cl complexes, explaining the high reactivity observed for this complex in this challenging transformation.
Aims/hypothesis Obesity is the dominant cause of insulin resistance. In adult humans it is characterised by a combination of adipocyte hypertrophy and, to a lesser extent, adipocyte hyperplasia. As ...hypertrophic adipocytes secrete more leptin and less adiponectin, the plasma leptin:adiponectin ratio (LAR) has been proposed as a potentially useful measure of insulin resistance and vascular risk. We sought to assess the usefulness of the LAR as a measure of insulin resistance in non-diabetic white adults. Methods Leptin and adiponectin levels were measured in 2,097 non-diabetic individuals from the Ely and European Group for the Study of Insulin Resistance (EGIR) Relationship between Insulin Sensitivity and Cardiovascular Risk (RISC) study cohorts. LAR was compared with fasting insulin and HOMA-derived insulin sensitivity (HOMA-S) in all individuals and with the insulin sensitivity index (M/I) from hyperinsulinaemic-euglycaemic clamp studies in 1,226 EGIR RISC participants. Results The LAR was highly correlated with HOMA-S in men (r = −0.58, p = 4.5 × 10⁻³³ and r = −0.65, p = 1.1 × 10⁻⁶⁶ within the Ely and EGIR RISC study cohorts, respectively) and in women (r = −0.51, p = 2.8 × 10⁻³⁶ and r = −0.61, p = 2.5 × 10⁻⁷³). The LAR was also strongly correlated with the clamp M/I value (r = −0.52, p = 4.5 × 10⁻³⁸ and r = −0.47, p = 6.6 × 10⁻⁴⁰ in men and women, respectively), similar to correlations between HOMA-S and the M/I value. Conclusions/interpretation The leptin:adiponectin ratio is a useful measure of insulin resistance in non-diabetic white adults. These data highlight the central role of adipocyte dysfunction in the pathogenesis of insulin resistance. Given that variations between fasting and postprandial leptin and adiponectin levels tend to be small, the leptin to adiponectin ratio might also have potential value in assessing insulin sensitivity in the non-fasted state.
We present multi-model global datasets of nitrogen and sulfate deposition covering time periods from 1850 to 2100, calculated within the Atmospheric Chemistry and Climate Model Intercomparison ...Project (ACCMIP). The computed deposition fluxes are compared to surface wet deposition and ice core measurements. We use a new dataset of wet deposition for 2000–2002 based on critical assessment of the quality of existing regional network data. We show that for present day (year 2000 ACCMIP time slice), the ACCMIP results perform similarly to previously published multi-model assessments. For this time slice, we find a multi-model mean deposition of approximately 50 Tg(N) yr−1 from nitrogen oxide emissions, 60 Tg(N) yr−1 from ammonia emissions, and 83 Tg(S) yr−1 from sulfur emissions. The analysis of changes between 1980 and 2000 indicates significant differences between model and measurements over the United States but less so over Europe. This difference points towards a potential misrepresentation of 1980 NH3 emissions over North America. Based on ice core records, the 1850 deposition fluxes agree well with Greenland ice cores, but the change between 1850 and 2000 seems to be overestimated in the Northern Hemisphere for both nitrogen and sulfur species. Using the Representative Concentration Pathways (RCPs) to define the projected climate and atmospheric chemistry related emissions and concentrations, we find large regional nitrogen deposition increases in 2100 in Latin America, Africa and parts of Asia under some of the scenarios considered. Increases in South Asia are especially large, and are seen in all scenarios, with 2100 values more than double their 2000 counterpart in some scenarios and reaching > 1300 mg(N) m−2 yr−1 averaged over regional to continental-scale regions in RCP 2.6 and 8.5, ~ 30–50% larger than the values in any region currently (circa 2000). However, sulfur deposition rates in 2100 are in all regions lower than in 2000 in all the RCPs. The new ACCMIP multi-model deposition dataset provides state-of-the-science, consistent and evaluated time slice (spanning 1850–2100) global gridded deposition fields for use in a wide range of climate and ecological studies.
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