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Mechanically interlocked molecules (MIMs) represent an exciting yet underexplored area of research in the context of carbon nanoscience. Recently, work from our group and others has shown that small carbon nanotube fragments—[n]cycloparaphenylenes ([n]CPPs) and related nanohoop macrocycles—may be integrated into mechanically interlocked architectures by leveraging supramolecular interactions, covalent tethers, or metal‐ion templates. Still, available synthetic methods are typically difficult and low yielding, and general methods that allow for the creation of a wide variety of these structures are limited. Here we report an efficient route to interlocked nanohoop structures via the active template Cu‐catalyzed azide‐alkyne cycloaddition (AT−CuAAC) reaction. With the appropriate choice of substituents, a macrocyclic precursor to 2,2′‐bipyridyl embedded [9]CPP (bipy[9]CPP) participates in the AT−CuAAC reaction to provide [2]rotaxanes in near‐quantitative yield, which can then be converted into the fully π‐conjugated catenane structures. Through this approach, two nanohoop[2]catenanes are synthesized which consist of a bipy[9]CPP catenated with either Tz[10]CPP or Tz[12]CPP (whereTzdenotes a 1,2,3‐triazole moiety replacing one phenylene ring in the [n]CPP backbone).

 

Mechanically interlocked molecules (MIMs) represent an exciting yet underexplored area of research in the context of carbon nanoscience. Recently, work from our group and others has shown that small carbon nanotube fragments—[n]cycloparaphenylenes ([n]CPPs) and related nanohoop macrocycles—may be integrated into mechanically interlocked architectures by leveraging supramolecular interactions, covalent tethers, or metal‐ion templates. Still, available synthetic methods are typically difficult and low yielding, and general methods that allow for the creation of a wide variety of these structures are limited. Here we report an efficient route to interlocked nanohoop structures via the active template Cu‐catalyzed azide‐alkyne cycloaddition (AT−CuAAC) reaction. With the appropriate choice of substituents, a macrocyclic precursor to 2,2′‐bipyridyl embedded [9]CPP (bipy[9]CPP) participates in the AT−CuAAC reaction to provide [2]rotaxanes in near‐quantitative yield, which can then be converted into the fully π‐conjugated catenane structures. Through this approach, two nanohoop[2]catenanes are synthesized which consist of a bipy[9]CPP catenated with either Tz[10]CPP or Tz[12]CPP (whereTzdenotes a 1,2,3‐triazole moiety replacing one phenylene ring in the [n]CPP backbone).

 

Eddy covariance (EC) air–sea CO₂flux measurements have been developed for large research vessels, but have yet to be demonstrated for smaller platforms. Our goal was to design and build a complete EC CO₂flux package suitable for unattended operation on a buoy. Published state-of-the-art techniques that have proven effective on research vessels, such as airstream drying and liquid water rejection, were adapted for a 2-m discus buoy with limited power. Fast-response atmospheric CO₂concentration was measured using both an off-the-shelf (“stock”) gas analyzer (EC155, Campbell Scientific, Inc.) and a prototype gas analyzer (“proto”) with reduced motion-induced error that was designed and built in collaboration with an instrument manufacturer. The system was tested on the University of New Hampshire (UNH) air–sea interaction buoy for 18 days in the Gulf of Maine in October 2020. The data demonstrate the overall robustness of the system. Empirical postprocessing techniques previously used on ship-based measurements to address motion sensitivity of CO₂analyzers were generally not effective for the stock sensor. The proto analyzer markedly outperformed the stock unit and did not require ad hoc motion corrections, yet revealed some remaining artifacts to be addressed in future designs. Additional system refinements to further reduce power demands and increase unattended deployment duration are described.

 

Vibrational spectroscopy enables critical insight into the structural and dynamic properties of molecules. Presently, the majority of theoretical approaches to spectroscopy employ wavefunction‐basedab initioor density functional methods that rely on the harmonic approximation. This approximation breaks down for large molecules with strongly anharmonic bonds or for molecules with large internuclear separations. An alternative to these methods involves generating molecular anharmonic potential energy surfaces (potentials) and using them to extrapolate the vibrational frequencies. This study examines the efficacy of density functional theory (DFT) and the correlation consistent Composite Approach (ccCA) in generating anharmonic frequencies from potentials of small main group molecules. Vibrational self‐consistent field Theory (VSCF) and post‐VSCF methods were used to calculate the fundamental frequencies of these molecules from their potentials. Functional choice, basis set selection, and mode‐coupling are also examined as factors in influencing accuracy. The absolute deviations for the calculated frequencies using potentials at the ccCA level of theory were lower than the potentials at the DFT level. With DFT resulting in bending modes that are better described than those of ccCA, a multilevel DFT:ccCA approach where DFT potentials are used for single vibrational mode potentials and ccCA is used for vibrational mode‐mode couplings can be utilized for larger polyatomic systems. The frequencies obtained with this multilevel approach using VCIPSI‐PT2 were closer to experimental frequencies than the scaled harmonic frequencies, indicating the success of utilizing post‐VSCF methods to generate more accurate representations of computed infrared spectra.

 

Multiyear periods (≥4 years) of extreme rainfall are increasing in frequency as climate continues to change, yet there is little understanding of how rainfall amount and heterogeneity in biophysical properties affect state changes in a sequence of wet and dry periods. Our objective was to examine the importance of rainfall periods, their legacies, and vegetation and soil properties to either the persistence of woody plants or a shift toward perennial grass dominance and a state reversal. We examined a 28‐year record of rainfall consisting of a sequence of multiyear periods (average, dry, wet, dry, average) for four ecosystem types in the Jornada Basin. We analyzed relationships between above ground net primary production (ANPP) and rainfall for three plant functional groups that characterize alternative states (perennial grasses, other herbaceous plants, dominant shrubs). A multimodel comparison was used to determine the relative importance of rainfall, soil, and vegetation properties. For perennial grasses, the greatest mean ANPP in mesquite‐ and tarbush‐dominated shrublands occurred in the wet period and in the dry period following the wet period in grasslands. Legacy effects in grasslands were asymmetric, where the lowest production was found in a dry period following an average period, and the greatest production occurred in a dry period following a wet period. For other herbaceous plants, in contrast, the greatest ANPP occurred in the wet period. Mesquite was the only dominant shrub species with a significant positive response in the wet period. Rainfall amount was a poor predictor of ANPP for each functional group when data from all periods were combined. Initial herbaceous biomass at the plant scale, patch‐scale biomass, and soil texture at the landscape scale improved the predictive relationships of ANPP compared with rainfall alone. Under future climate, perennial grass production is expected to benefit the most from wet periods compared with other functional groups with continued high grass production in subsequent dry periods that can shift (desertified) shrublands toward grasslands. The continued dominance by shrubs will depend on the effects that rainfall has on perennial grasses and the sequence of high‐ and low‐rainfall periods rather than the direct effects of rainfall on shrub production.

 

Laser ablation tandem mass spectrometry is a burgeoning field forin situRb‐Sr geochronology. Here, we determined simultaneous isotope ratios of⁸⁷Sr/⁸⁶Sr and⁸⁷Rb/⁸⁶Sr in metamorphic biotite from western Maine, using an ESL™ imageGEO™193 excimer laser ablation system coupled to a Thermo Scientific™ Neoma™ MC‐ICP‐MS/MS. Measurements were made on Faraday cups with Rb⁺at mass 87; Sr isotopes were reacted with SF₆gas and measured as SrF⁺at masses 103–107. Twenty‐two laser spots in biotite from a single sample yield a traditional Rb‐Sr isochron date of 289 ± 6 Ma. Time‐resolved signals reveal significant zoning in⁸⁷Sr/⁸⁶Sr and⁸⁷Rb/⁸⁶Sr within single spot analyses, which were used to construct single spot isochrons. Individual laser spots contain multiple isochronous subpopulations; some spots contain up to three distinct Rb‐Sr isochrons that are decoupled from variations in Rb/Sr. Thirty‐five isochron dates were determined using this sub‐spot approach, with⁸⁷Sr/⁸⁶Sr intercepts that systematically vary with Rb‐Sr date; two‐point isochrons were calculated for individual integrations (n= 780) based on these variable intercepts. Both methods yield age peaks at 303, 270 and 240 Ma. These data suggest that the Rb‐Sr system has the potential to record multiple heating, cooling or fluid‐alteration events spanning ~ 100 My within small domains in single biotite crystals.

 

Data associated with Figures, Tables, and population parameter samples associated with 
The population of merging compact binaries inferred using gravitational waves through GWTC-3 ,
LIGO DCC, arXiv, PRX. 
This is v2, superseding v1. Please see the README.md for more information.

LIGO Laboratory and Advanced LIGO are funded by the United States National Science Foundation (NSF) as well as the Science and Technology Facilities Council (STFC) of the United Kingdom, the Max-Planck-Society (MPS), and the State of Niedersachsen/Germany for support of the construction of Advanced LIGO and construction and operation of the GEO600 detector. Additional support for Advanced LIGO was provided by the Australian Research Council. Virgo is funded, through the European Gravitational Observatory (EGO), by the French Centre National de Recherche Scientifique (CNRS), the Italian Istituto Nazionale di Fisica Nucleare (INFN) and the Dutch Nikhef, with contributions by institutions from Belgium, Germany, Greece, Hungary, Ireland, Japan, Monaco, Poland, Portugal, Spain. The construction and operation of KAGRA are funded by Ministry of Education, Culture, Sports, Science and Technology (MEXT), and Japan Society for the Promotion of Science (JSPS), National Research Foundation (NRF) and Ministry of Science and ICT (MSIT) in Korea, Academia Sinica (AS) and the Ministry of Science and Technology (MoST) in Taiwan.