Spatial Analyses of Crisis Pregnancy Centers and Abortion Facilities in the United States, 2021 (Pre-Dobbs): Cross-Sectional Study.

BACKGROUND: Crisis pregnancy centers (CPCs) are religious nonprofit organizations with a primary mission of diverting people from having abortions. One CPC tactic has been to locate near abortion facilities. Despite medical groups' warnings that CPCs do not adhere to medical and ethical standards and pose risks, government support for CPCs has significantly increased. OBJECTIVE: This study aims to map CPCs, abortion facilities, and geographical areas in the United States into 4 zones based on their proximity to CPCs and abortion facilities. We sought to describe the number and percentage of reproductive-aged women living in each zone and the proximity of CPCs to abortion facilities. METHODS: Using 2021 data from CPC Map and the Advancing New Standards in Reproductive Health Abortion Facility Database, we determined the ratio of CPCs to abortion facilities. Along with census data, we categorized and mapped US block groups into 4 distinct zones based on locations of block group centroids within 15-mile (1 mile is approximately 1.609 km) radii of CPCs and abortion facilities, namely "no presence," "CPC only," "abortion facility only," and "dual presence." We calculated the number and percentage of block groups and reproductive-aged (15-49 years) women living in each zone. We calculated driving distances and drive times from abortion facilities to the nearest CPC and mapped abortion facilities with CPCs in close proximity. All analyses were conducted nationally and by region, division, and state. RESULTS: Nationally, the ratio of CPCs to abortion facilities was 3.4, and 54.9% (131,410/239,462) of block groups were categorized in the "dual presence" zone, 26.6% (63,679/239,462) as "CPC only," and 0.8% (63,679/239,462) as "abortion facility only." Most reproductive-aged women (45,150,110/75,582,028, 59.7%) lived in a "dual presence" zone, 26.1% (19,696,572/75,582,028) in a "CPC only" zone, and 0.8% (625,403/75,582,028) in an "abortion facility only" zone. The number of block groups and women classified as living in each zone varied by region, division, and state. Nationally, the median distance from abortion facilities to the nearest CPC was 2 miles, and the median drive time was 5.5 minutes. Minimum drive times were <1 minute in all but 11 states. The percentages of abortion facilities with a CPC within 0.25, 0.5, 1, and 3 miles were 14.1% (107/757), 22.6% (171/757), 36.1% (273/757), and 66.3% (502/757), respectively. CONCLUSIONS: The findings suggest that CPCs' tactic of locating near abortion facilities was largely realized before the 2022 US Supreme Court decision that overturned the federal right to abortion. Research on CPCs' locations and tactics should continue given the dynamic abortion policy landscape and risks posed by CPCs. Tailored programming to raise awareness about CPCs and help people identify and access safe sources of health care may mitigate harm. Increased regulation of CPCs and government divestment may also mitigate CPC harms.

Assessment of the exchange-hole dipole moment dispersion correction for the energy ranking stage of the seventh crystal structure prediction blind test.

The seventh blind test of crystal structure prediction (CSP) methods substantially increased the level of complexity of the target compounds relative to the previous tests organized by the Cambridge Crystallographic Data Centre. In this work, the performance of density-functional methods is assessed using numerical atomic orbitals and the exchange-hole dipole moment dispersion correction (XDM) for the energy-ranking phase of the seventh blind test. Overall, excellent performance was seen for the two rigid molecules (XXVII, XXVIII) and for the organic salt (XXXIII). However, for the agrochemical (XXXI) and pharmaceutical (XXXII) targets, the experimental polymorphs were ranked fairly high in energy amongst the provided candidate structures and inclusion of thermal free-energy corrections from the lattice vibrations was found to be essential for compound XXXI. Based on these results, it is proposed that the importance of vibrational free-energy corrections increases with the number of rotatable bonds.

Mapping Electrophile Chemoselectivity in DalPhos/Nickel N-Arylation Catalysis: The Unusual Influence of Remote Sterics.

We disclose herein our evaluation of competitive (hetero)aryl-X (X: Br>Cl>OTf) reactivity preferences in bisphosphine/Ni-catalyzed C-N cross-coupling catalysis, using furfurylamine as a prototypical nucleophile, and employing DalPhos and DPPF as representative ancillary ligands with established efficacy. Beyond this general (pseudo)halide ranking, other intriguing structure-reactivity trends were noted experimentally, including the unexpected observation that bulky alkyl (e. g., R=tBu) substitution in para-R-aryl-X electrophiles strongly discourages (pseudo)halide reactivity relative to smaller substituents (e. g., nBu, Et, Me), despite being both remote from, and having a similar electronic influence on, the reacting C-X bond; such effects on nickel oxidative addition have not been documented previously and were not observed in our comparator reactions presented herein involving palladium. Density functional theory modeling of such PhPAd-DalPhos/Ni-catalyzed C-N cross-couplings revealed the origins of competitive turnover of C-Br over C-Cl, and possible ways in which bulky para-alkyl substitution might discourage net electrophile uptake/turnover, leading to inversion of halide selectivity.

BODIPYs α-appended with distyryl-linked aryl bisboronic acids: single-step cell staining and turn-on fluorescence binding with D-glucose.

Small-molecule sensors that are selective for particular sugars are rare. The synthesis of BODIPYs appended with two boronic acid units is reported, alongside cellular staining/labelling and turn-on fluorescence binding data for carbohydrates. The structural frameworks were designed using computational methods, leaning on the chelation characteristics of bis(boronic acids) and the photophysical properties of BODIPYs. Selective binding to glucose is demonstrated via emission and absorption methods, and the challenges of using NMR data for studying carbohydrate binding are discussed. Furthermore, crystal structures, cell permeability and imaging properties of the BODIPYs appended with two boronic acid units are described. This work presents boronic-acid-appended BODIPYs as a potential framework for tunable carbohydrate sensing and chemical biology staining.

Modeling Intermolecular Interactions with Exchange-Hole Dipole Moment Dispersion Corrections to Neural Network Potentials.

Neural network potentials (NNPs) are an innovative approach for calculating the potential energy and forces of a chemical system. In principle, these methods are capable of modeling large systems with an accuracy approaching that of a high-level ab initio calculation, but with a much smaller computational cost. Due to their training to density-functional theory (DFT) data and neglect of long-range interactions, some classes of NNPs require an additional term to include London dispersion physics. In this Perspective, we discuss the requirements for a dispersion model for use with an NNP, focusing on the MLXDM (Machine Learned eXchange-Hole Dipole Moment) model developed by our groups. This model is based on the DFT-based XDM dispersion correction, which calculates interatomic dispersion coefficients in terms of atomic moments and polarizabilities, both of which can be approximated effectively using neural networks.

Porphyrin Aggregation under Homogeneous Conditions Inhibits Electrocatalysis: A Case Study on CO2 Reduction.

Metalloporphyrins are widely used as homogeneous electrocatalysts for transformations relevant to clean energy and sustainable organic synthesis. Metalloporphyrins are well-known to aggregate due to π-π stacking, but surprisingly, the influence of aggregation on homogeneous electrocatalytic performance has not been investigated previously. Herein, we present three structurally related iron meso-phenylporphyrins whose aggregation properties are different in commonly used N,N-dimethylformamide (DMF) electrolyte. Both spectroscopy and light scattering provide evidence of extensive porphyrin aggregation under conventional electrocatalytic conditions. Using the electrocatalytic reduction of CO2 to CO as a test reaction, cyclic voltammetry reveals an inverse dependence of the kinetics on the catalyst concentration. The inhibition extends to bulk performance, where up to 75% of the catalyst at 1 mM is inactive compared to at 0.25 mM. We additionally report how aggregation is perturbed by organic additives, axial ligands, and redox state. Periodic boundary calculations provide additional insights into aggregate stability as a function of metalloporphyrin structure. Finally, we generalize the aggregation phenomenon by surveying metalloporphyrins with different metals and substituents. This study demonstrates that homogeneous metalloporphyrins can aggregate severely in well-solubilizing organic electrolytes, that aggregation can be easily modulated through experimental conditions, and that the extent of aggregation must be considered for accurate catalytic benchmarking.

Validity of a common measure of intimate partner violence perpetration: Impact on study inference in trials in low- and middle-income countries.

Background: In lower-and middle-income countries (LMICs), studies of interventions to reduce intimate partner violence (IPV) perpetration are expanding yet measurement equivalence of the construct has not been established. We assessed the measurement equivalence of physical and sexual IPV perpetration used in recent trials in LMICs and tested the impact of non-invariance on trial inference. Methods: With data from three recent intervention trials among men (sample size 505-1537 across studies), we calculated tetrachoric correlations among items and used multiple-group confirmatory factor analysis to assess invariance across arms and over time. We also assessed treatment effects adjusting for covariate imbalance and using inverse probability to treatment weights to assess concordance of invariant measures with published results, where warranted. Findings: The average correlation among items was high and increased over time with several items in two studies showing correlations ≥0.85 at endline. Increases in correlation for physical IPV were concentrated in the treatment arm in two of the studies. The increase in correlation in sexual IPV differed by arm across studies. Across all studies, a correlated two-factor solution was the best fitting model according to the EFAs and CFAs. One study demonstrated measurement invariance across arms and over time. In two of the studies, longitudinal measurement non-invariance was detected in the intervention arms. In post hoc testing, one study attained invariance with a one-factor model and study inference was concordant with published findings. The other study did not attain even partial invariance. Conclusion: Common measures of physical and sexual IPV perpetration cannot be used for valid effect estimation without further refinement. The study highlights the need for an expanded item set, content validity assessments, further measurement invariance testing, and then consistent use of the item sets in future intervention trials to support accurate inference on the effectiveness of IPV perpetration prevention interventions.

Designing barrier-free metal/MoS2 contacts through electrene insertion.

Transition-metal dichalcogenides (TMDCs), including MoS2, have great potential in electronics applications. However, achieving low-resistance metal contacts is a challenge that impacts their performance in nanodevices due to strong Fermi-level pinning and the presence of a tunnelling barrier. As a solution, we explore a strategy of inserting monolayers of alkaline-earth sub-pnictide electrenes with a general formula of [M2X]+e- (M = Ca, Sr, Ba; X = N, P, As, Sb) between the TMDC and the metal. These electrenes possess two-dimensional sheets of charge on their surfaces that can be readily donated when interfaced with a TMDC semiconductor, thereby lowering its conduction band below the Fermi level and eliminating the Schottky and tunnelling barriers. In this work, density-functional theory (DFT) calculations were performed for metal/electrene/MoS2 heterojunctions for all stable M2X electrenes and both Au and Cu metals. To identify the material combinations that provide the most effective Ohmic contact, the charge transfer, band structure, and electrostatic potential were computed. Linear correlations were found between the charge donated to the MoS2 and both the electrene surface charge and work function. Overall, Ca2N appears to be the most promising electrene for achieving an Ohmic metal/MoS2 contact due to its high surface charge density.

Validity of a Common Measure of Intimate Partner Violence Perpetration: Impact on Study Inference in Trials in Low- and Middle-Income Countries.

Background: In lower-and middle-income countries (LMICs), studies of interventions to reduce intimate partner violence (IPV) perpetration are expanding, yet measurement equivalence of the IPV perpetration construct that is the primary outcome in these investigations has not been established. We assessed the measurement equivalence of physical and sexual IPV perpetration item sets used in recent trials in LMICs and tested the impact of non-invariance on trial inference. Methods: With data from three intervention trials among men (sample size 505-1537 across studies) completed in 2019, we calculated tetrachoric correlations among items and used multiple-group confirmatory factor analysis to assess invariance across arms and over time. We also assessed treatment effects adjusting for covariate imbalance and using inverse probability to treatment weights to assess concordance of invariant measures with published results, where warranted. Findings: The average correlation among items measuring IPV perpetration was high and increased by 0.03 to 0.15 for physical IPV and 0.07 to 0.17 for sexual IPV over time with several items in two studies showing correlations ≥ 0.85 at endline. Increases in the degree of correlation for physical IPV were concentrated in the treatment arm in two of the studies. The increase in correlation in sexual IPV differed by arm across studies. Across all studies, a correlated two-factor solution was the best fitting model according to the EFAs and CFAs. One study demonstrated measurement invariance across arms and over time. In two of the studies, longitudinal measurement non-invariance was detected in the intervention arms. In post hoc testing, one study attained invariance with a one-factor model and study inference was concordant with published findings. The other study did not attain even partial invariance. Conclusion: Common measures of physical and sexual IPV perpetration cannot be used validly for comparisons across treatment versus control groups over time without further refinement. The study highlights the need for an expanded item set, content validity assessments, further measurement invariance testing, and then consistent use of the item sets in future intervention trials to ensure valid inferences regarding the effectiveness of IPV perpetration prevention interventions within and across trials.

Nickel-Catalyzed O-Arylation of Primary or Secondary Aliphatic Alcohols with (Hetero)aryl Chlorides: A Comparison of Ni(I) and Ni(II) Precatalysts.

A comparative experimental and computational study examining the interplay of the ancillary ligand structure and Ni oxidation state in the Ni-catalyzed C(sp2)-O cross-coupling of (hetero)aryl chlorides and primary or secondary aliphatic alcohols is presented, focusing on PAd-DalPhos (L1)-, CyPAd-DalPhos (L2)-, PAd2-DalPhos (L3)-, and DPPF (L4)-ligated [(L)NiCl]n (n = 1 or 2) and (L)Ni(o-tol)Cl precatalysts. Both L1 and L2 were found to outperform the other ligands examined, with the latter proving to be superior overall. While Ni(II) precatalysts generally outperformed Ni(I) species, in some instances the catalytic abilities of Ni(I) precatalysts were competitive with those of Ni(II). Density-functional theory calculations indicate the favorability of a Ni(0)/Ni(II) catalytic cycle featuring turnover-limiting C-O bond reductive elimination over a Ni(I)/Ni(III) cycle involving turnover-limiting C-Cl oxidative addition.

Effect of [n]-Helicene Length on Crystal Packing.

Chiral π-conjugated organic molecules hold potential for emerging technologies as they are capable of introducing novel functionalities into electronic devices owing to their strong chiroptical properties. However, capitalizing on chiral molecules for electronic devices is reliant on their molecular packing-a factor that impacts their charge-transport properties. The solid-state behavior of molecules is sensitive to subtle differences in molecular interactions, chirality, and shape, but these relationships are not fully understood. Here, we employ crystal structure prediction (CSP) as a tool to probe the lattice-energy landscape for a family of chiral organic molecules: [n]helicenes, where n ranges from 3 to 12. Our results show excellent agreement between the CSP landscapes and experimentally reported structures. By analyzing the packing motifs within the polymorph landscapes, we begin to develop an understanding of how helicene length affects the shape and π-π stacking interactions seen in the polymorphs. Furthermore, we propose how helicene length can be used as a tool to design new functional organic electronics.

Low thermal expansion of layered electrides predicted by density-functional theory.

Layered electrides are a unique class of materials with anionic electrons bound in interstitial regions between thin, positively charged atomic layers. While density-functional theory is the tool of choice for computational study of electrides, there has to date been no systematic comparison of density functionals or dispersion corrections for their accurate simulation. There has also been no research into the thermomechanical properties of layered electrides, with computational predictions considering only static lattices. In this work, we investigate the thermomechanical properties of five layered electrides using density-functional theory to evaluate the magnitude of thermal effects on their lattice constants and cell volumes. We also assess the accuracy of five popular dispersion corrections with both planewave and numerical atomic orbital calculations.

Comparison of Density-Functional Theory Dispersion Corrections for the DES15K Database.

While density-functional theory (DFT) remains one of the most widely used tools in computational chemistry, most functionals fail to properly account for the effects of London dispersion. Hence, there are many popular post-self-consistent methods to add a dispersion correction to the DFT energy. Until now, the most popular methods have never been compared on equal footing due to not being implemented in the same electronic structure packages. In this work, we performed a large-scale benchmarking study, directly comparing the accuracy of the exchange-hole dipole moment (XDM), D3BJ, D4, TS, MBD, and MBD-NL dispersion models when applied to the recent DES15K database of nearly 15,000 molecular complexes at both expanded and compressed geometries. Our study showed similarly good performance for all dispersion methods (except TS) when applied to neutral complexes. However, they all performed worse for ionic complexes, particularly those involving dications of alkaline earth metals, due to systematic overbinding by the base PBE0 density functional. Investigation of the largest outliers also revealed that only the MBD and MBD-NL methods demonstrate surprising errors for complexes involving alkali metal cations at compressed geometries where they tended to significantly overbind. As we would expect minimal dispersion binding for such complexes, we further investigated the origins of these errors for the potential energy curve of a model cation-π complex. Overall, there is little choice between the XDM, D3BJ, D4, MBD, and MBD-NL dispersion methods for most systems. However, the MBD-based methods are not recommended for complexes involving organic species and alkali or alkaline earth metal cations, for example when modeling Li+ intercalation into graphite.

Measurement invariance of the Center for Epidemiologic Studies Scale-Depression within and across six diverse intervention trials.

Depression, a major contributor to the global burden of disease, is an outcome of interest in clinical trials. Researchers and clinicians note that depression often presents differently across cultures, posing challenges in the accurate measurement of depressive symptoms across populations. A commonly used self-administered screening tool to measure depressive symptoms, the Center for Epidemiologic Studies Scale-Depression (CES-D), has been translated into dozens of languages and used in thousands of studies, yet gaps remain in our understanding of its factor structure and invariance across studies and over time in the context of interventions. In this secondary analysis, we sampled six recent trials from lower- and middle-income countries to (a) establish the factor structure of the CES-D, (b) assess measurement invariance of the CES-D across treatment versus control arms and over time, (c) examine cross-study invariance, and (d) identify items that may be driving potential noninvariance. We performed exploratory/confirmatory factor analysis to establish the factor structure of the CES-D within each trial and used multiple group confirmatory analysis to assess within-study cross-arm/cross-time and cross-study invariance. After removal of positive affect items, a unidimensional model performed equivalently over time and across arms within trials, but exhibited noninvariance across trials, supporting prior literature describing differences in factor structure of the scale across populations. While our findings suggest that the CES-D without positive affect items is a valid measure of depressive symptoms within trials in our sample, caution is warranted in interpreting the findings of meta-analyses and multisite/multicountry studies using the CES-D as an outcome measure. (PsycInfo Database Record (c) 2023 APA, all rights reserved).

Periodic trends in the structural, electronic, and transport properties of electrenes.

Two-dimensional layered electrides are a class of atomically thin materials in which the anion is an excess electron rather than a negatively charged ion. These excess electrons form delocalized sheets of charge surrounding each layer of the material. A well-known example is Ca2N; its identification and characterization has triggered an avalanche of studies aimed at broadening applications of electrides. Ca2N is only one member of the M2X family of materials, with M being an alkaline-earth metal and X belonging to the pnictogen group, which can be exfoliated to form single- or few-layer electrenes. The goal of this study is to systematically investigate the monolayer and bilayer properties for this family of materials. Density-functional calculations reveal linear relationships between surface and interstitial charges, work functions, exfoliation energies, and Ewald energies. Using the Landauer formalism, informed by rigorous electron-phonon scattering calculations, we also investigate the electronic transport characteristics of the monolayer and bilayer electrenes. Our findings indicate that the nitrogen-based electrenes (Ca2N, Sr2N, and Ba2N) are more conductive than their counterparts involving heavier pnictogens. The results of this study highlight underlying periodic trends in electrene properties that can help identify which materials would be best suited for particular applications.

Quantitative matching of crystal structures to experimental powder diffractograms.

The identification and classification of crystal structures is fundamental in materials science, as the crystal structure is an inherent factor of what gives solid materials their properties. Being able to identify the same crystallographic form from unique origins (e.g. different temperatures, pressures, or in silico-generated) is a complex challenge. While our previous work has focused on comparison of simulated powder diffractograms from known crystal structures, herein is presented the variable-cell experimental powder difference (VC-xPWDF) method to match collected powder diffractograms of unknown polymorphs to both experimental crystal structures from the Cambridge Structural Database and in silico-generated structures from the Control and Prediction of the Organic Solid State database. The VC-xPWDF method is shown to correctly identify the most similar crystal structure to both moderate and "low" quality experimental powder diffractograms for a set of 7 representative organic compounds. Features of the powder diffractograms that are more challenging for the VC-xPWDF method are discussed (i.e. preferred orientation), and comparison with the FIDEL method showcases the advantage of VC-xPWDF provided the experimental powder diffractogram can be indexed. The VC-xPWDF method should allow rapid identification of new polymorphs from solid-form screening studies, without requiring single-crystal analysis.

Many-body dispersion in model systems and the sensitivity of self-consistent screening.

London dispersion is a weak, attractive, intermolecular force that occurs due to interactions between instantaneous dipole moments. While individual dispersion contributions are small, they are the dominating attractive force between nonpolar species and determine many properties of interest. Standard semi-local and hybrid methods in density-functional theory do not account for dispersion contributions, so a correction such as the exchange-hole dipole moment (XDM) or many-body dispersion (MBD) models must be added. Recent literature has discussed the importance of many-body effects on dispersion, and attention has turned to which methods accurately capture them. By studying systems of interacting quantum harmonic oscillators from first principles, we directly compare computed dispersion coefficients and energies from XDM and MBD and also study the influence of changing oscillator frequency. Additionally, the 3-body energy contributions for both XDM, via the Axilrod-Teller-Muto term, and MBD, via a random-phase approximation formalism, are calculated and compared. Connections are made to interactions between noble gas atoms as well as to the methane and benzene dimers and to two layered materials, graphite and MoS2. While XDM and MBD give similar results for large separations, some variants of MBD are found to be susceptible to a polarization catastrophe at short range, and the MBD energy calculation is seen to fail in some chemical systems. Additionally, the self-consistent screening formalism used in MBD is shown to be surprisingly sensitive to the choice of input polarizabilities.

XDM-corrected hybrid DFT with numerical atomic orbitals predicts molecular crystal lattice energies with unprecedented accuracy.

Molecular crystals are important for many applications, including energetic materials, organic semiconductors, and the development and commercialization of pharmaceuticals. The exchange-hole dipole moment (XDM) dispersion model has shown good performance in the calculation of relative and absolute lattice energies of molecular crystals, although it has traditionally been applied in combination with plane-wave/pseudopotential approaches. This has limited XDM to use with semilocal functional approximations, which suffer from delocalization error and poor quality conformational energies, and to systems with a few hundreds of atoms at most due to unfavorable scaling. In this work, we combine XDM with numerical atomic orbitals, which enable the efficient use of XDM-corrected hybrid functionals for molecular crystals. We test the new XDM-corrected functionals for their ability to predict the lattice energies of molecular crystals for the X23 set and 13 ice phases, the latter being a particularly stringent test. A composite approach using a XDM-corrected, 25% hybrid functional based on B86bPBE achieves a mean absolute error of 0.48 kcal mol-1 per molecule for the X23 set and 0.19 kcal mol-1 for the total lattice energies of the ice phases, compared to recent diffusion Monte-Carlo data. These results make the new XDM-corrected hybrids not only far more computationally efficient than previous XDM implementations, but also the most accurate density-functional methods for molecular crystal lattice energies to date.

DFT exchange: sharing perspectives on the workhorse of quantum chemistry and materials science.

In this paper, the history, present status, and future of density-functional theory (DFT) is informally reviewed and discussed by 70 workers in the field, including molecular scientists, materials scientists, method developers and practitioners. The format of the paper is that of a roundtable discussion, in which the participants express and exchange views on DFT in the form of 302 individual contributions, formulated as responses to a preset list of 26 questions. Supported by a bibliography of 777 entries, the paper represents a broad snapshot of DFT, anno 2022.

Controlling anisotropic properties by manipulating the orientation of chiral small molecules.

Chiral π-conjugated molecules bring new functionality to technological applications and represent an exciting, rapidly expanding area of research. Their functional properties, such as the absorption and emission of circularly polarized light or the transport of spin-polarized electrons, are highly anisotropic. As a result, the orientation of chiral molecules critically determines the functionality and efficiency of chiral devices. Here we present a strategy to control the orientation of a small chiral molecule (2,2'-dicyano[6]helicene) by the use of organic and inorganic templating layers. Such templating layers can either force 2,2'-dicyano[6]helicene to adopt a face-on orientation and self-assemble into upright supramolecular columns oriented with their helical axis perpendicular to the substrate, or an edge-on orientation with parallel-lying supramolecular columns. Through such control, we show that low- and high-energy chiroptical responses can be independently 'turned on' or 'turned off'. The templating methodologies described here provide a simple way to engineer orientational control and, by association, anisotropic functional properties of chiral molecular systems for a range of emerging technologies.