Investing in nature can improve equity and economic returns.

Sustainable development requires jointly achieving economic development to raise standards of living and environmental sustainability to secure these gains for the long run. Here, we develop a local-to-global, and global-to-local, earth-economy model that integrates the Global Trade Analysis Project (GTAP)-computable general equilibrium model of the economy with the Integrated Valuation of Ecosystem Services and Tradeoffs (InVEST) model of fine-scale, spatially explicit ecosystem services. The integrated model, GTAP-InVEST, jointly determines land use, environmental conditions, ecosystem services, market prices, supply and demand across economic sectors, trade across regions, and aggregate performance metrics like GDP. We use the integrated model to analyze the contribution of investing in nature for economic prosperity, accounting for the impact of four important ecosystem services (pollination, timber provision, marine fisheries, and carbon sequestration). We show that investments in nature result in large improvements relative to a business-as-usual path, accruing annual gains of $100 to $350 billion (2014 USD) with the largest percentage gains in the lowest-income countries. Our estimates include only a small subset of ecosystem services and could be far higher with inclusion of more ecosystem services, incorporation of ecological tipping points, and reduction in substitutability that limits economic adjustments to declines in natural capital. Our analysis highlights the need for improved environmental-economic modeling and the vital importance of integrating environmental information firmly into economic analysis and policy. The benefits of doing so are potentially very large, with the greatest percentage benefits accruing to inhabitants of the poorest countries.

Molecular Control of Triplet-Pair Spin Polarization and Its Optoelectronic Magnetic Resonance Probes.

ConspectusPreparing and manipulating pure magnetic states in molecular systems are the key initial requirements for harnessing the power of synthetic chemistry to drive practical quantum sensing and computing technologies. One route for achieving the requisite higher spin states in organic systems exploits the phenomenon of singlet fission, which produces pairs of triplet excited states from initially photoexcited singlets in molecular assemblies with multiple chromophores. The resulting spin states are characterized by total spin (quintet, triplet, or singlet) and its projection onto a specified molecular or magnetic field axis. These excited states are typically highly polarized but exhibit an impure spin population pattern. Herein, we report the prediction and experimental verification of molecular design rules that drive the population of a single pure magnetic state and describe the progress toward its experimental realization.A vital feature of this work is the close partnership among theory, chemical synthesis, and spectroscopy. We begin by presenting our theoretical framework for understanding spin manifold interconversion in singlet fission systems. This theory makes specific testable predictions about the intermolecular structure and orientation relative to an external magnetic field that should lead to pure magnetic state preparation and provides a powerful tool for interpreting magnetic spectra. We then test these predictions through detailed magnetic spectroscopy experiments on a series of new molecular architectures that meet one or more of the identified structural criteria. Many of these architectures rely on the synthesis of molecules with features unique to this effort: rigid bridges between chromophores in dimers, heteroacenes with tailored singlet/triplet-pair energy level matching, or side-group engineering to produce specific crystal structures. The spin evolution of these systems is revealed through our application and development of several magnetic resonance methods, each of which has different sensitivities and relevance in environments relevant to quantum applications.Our theoretical predictions prove to be remarkably consistent with our experimental results, though experimentally meeting all the structural prescriptions demanded by theory for true pure-state preparation remains a challenge. Our magnetic spectra agree with our model of triplet-pair behavior, including funneling of the population to the ms = 0 magnetic sublevel of the quintet under specified conditions in dimers and crystals, showing that this phenomenon is subject to control through molecular design. Moreover, our demonstration of novel and/or highly sensitive detection mechanisms of spin states in singlet fission systems, including photoluminescence (PL), photoinduced absorption (PA), and magnetoconductance (MC), points the way toward both a deeper understanding of how these systems evolve and technologically feasible routes toward experiments at the single-molecule quantum limit that are desirable for computational applications.

Triplet-pair spin signatures from macroscopically aligned heteroacenes in an oriented single crystal.

The photo-driven process of singlet fission generates coupled triplet pairs (TT) with fundamentally intriguing and potentially useful properties. The quintet 5TT0 sublevel is particularly interesting for quantum information because it is highly entangled, is addressable with microwave pulses, and could be detected using optical techniques. Previous theoretical work on a model Hamiltonian and nonadiabatic transition theory, called the JDE model, has determined that this sublevel can be selectively populated if certain conditions are met. Among the most challenging, the molecules within the dimer undergoing singlet fission must have their principal magnetic axes parallel to one another and to an applied Zeeman field. Here, we present time-resolved electron paramagnetic resonance (TR-EPR) spectroscopy of a single crystal sample of a tetracenethiophene compound featuring arrays of dimers aligned in this manner, which were mounted so that the orientation of the field relative to the molecular axes could be controlled. The observed spin sublevel populations in the paired TT and unpaired (T+T) triplets are consistent with predictions from the JDE model, including preferential 5TT0 formation at z ‖ B0, with one caveat-two 5TT spin sublevels have little to no population. This may be due to crossings between the 5TT and 3TT manifolds in the field range investigated by TR-EPR, consistent with the intertriplet exchange energy determined by monitoring photoluminescence at varying magnetic fields.

Tetracene Diacid Aggregates for Directing Energy Flow toward Triplet Pairs.

A comprehensive investigation of the solution-phase photophysics of tetracene bis-carboxylic acid [5,12-tetracenepropiolic acid (Tc-DA)] and its related methyl ester [5,12-tetracenepropynoate (Tc-DE)], a non-hydrogen-bonding counterpart, reveals the role of the carboxylic acid moiety in driving molecular aggregation and concomitant excited-state behavior. Low-concentration solutions of Tc-DA exhibit similar properties to the popular 5,12-bis((triisopropylsilyl)ethynl)tetracene, but as the concentration increases, evidence for aggregates that form excimers and a new mixed-state species with charge-transfer (CT) and correlated triplet pair (TT) character is revealed by transient absorption and fluorescence experiments. Aggregates of Tc-DA evolve further with concentration toward an additional phase that is dominated by the mixed CT/TT state which is the only state present in Tc-DE aggregates and can be modulated with the solvent polarity. Computational modeling finds that cofacial arrangement of Tc-DA and Tc-DE subunits is the most stable aggregate structure and this agrees with results from 1H NMR spectroscopy. The calculated spectra of these cofacial dimers replicate the observed broadening in ground-state absorption as well as accurately predict the formation of a near-UV transition associated with a CT between molecular subunits that is unique to the specific aggregate structure. Taken together, the results suggest that the hydrogen bonding between Tc-DA molecules and the associated disruption of hydrogen bonding with solvent produce a regime of dimer-like behavior, absent in Tc-DE, that favors excimers rather than CT/TT mixed states. The control of aggregate size and structure using distinct functional groups, solute concentration, and solvent in tetracene promises new avenues for its use in light-harvesting schemes.

Land-Use Decisions Have Substantial Air Quality Health Effects.

Understanding how best to use limited land without compromising food security, health, and beneficial ecosystem functions is a critical challenge of our time. Ecosystem service assessments increasingly inform land-use decisions but seldom include the effects of land use on air quality, the largest environmental health risk. Here, we estimate and value the air quality health effects of potential land-use policies and projected trends in the United States, alongside carbon sequestration and economic returns to land, until 2051. We show that air quality health effects are of first-order importance in land-use decisions, often larger in value than carbon sequestration and economic returns combined. When air quality is properly accounted for, policies that appeared beneficial are shown to be detrimental and vice versa. Land-use-driven air quality impacts are largely from agricultural emissions and biogenic forest emissions, although incentives for reduced deforestation remain beneficial overall. Without evaluating air quality, we are unable to determine whether land-use decisions make us better or worse off.

Revealing the Singlet Fission Mechanism for a Silane-Bridged Thienotetracene Dimer.

Tetraceno[2,3-b]thiophene is regarded as a strong candidate for singlet fission-based solar cell applications due to its mixed characteristics of tetracene and pentacene that balance exothermicity and triplet energy. An electronically weakly coupled tetraceno[2,3-b]thiophene dimer (Et2Si(TIPSTT)2) with a single silicon atom bridge has been synthesized, providing a new platform to investigate the singlet fission mechanism involving the two acene chromophores. We study the excited state dynamics of Et2Si(TIPSTT)2 by monitoring the evolution of multiexciton coupled triplet states, 1TT to 5TT to 3TT to T1 + S0, upon photoexcitation with transient absorption, temperature-dependent transient absorption, and transient/pulsed electron paramagnetic resonance spectroscopies. We find that the photoexcited singlet lifetime is 107 ps, with 90% evolving to form the TT state, and the complicated evolution between the multiexciton states is unraveled, which can be an important reference for future efforts toward tetraceno[2,3-b]thiophene-based singlet fission solar cells.

Primary immunoprevention of adult onset cancers by vaccinating against retired tissue-specific self-proteins.

Despite the enormous success of childhood prophylactic vaccination against diseases caused by pathogens, there is currently no similar preventive vaccine program against diseases confronted with age like breast cancer and ovarian cancer. With the exception of the annual influenza vaccine, current recommendations for adult vaccination are for either primary vaccines not received during childhood or for booster vaccinations to maintain the immunity against pathogens already induced during childhood. Here we describe a strategy to provide prophylactic pre-emptive immunity against the development of adult onset cancers not associated with any definitive etiopathogenic agent. We propose that safe and effective pre-emptive immunity may be induced in cancer-free subjects by vaccination against immunodominant tissue-specific self-proteins that are 'retired' from expression in normal tissues as part of the normal aging process but are expressed in tumors that emerge with age. Primary immunoprevention of adult onset cancers like breast cancer and ovarian cancer represents a great challenge and an even greater unmet need for our current healthcare.

Mediating Photochemical Reaction Rates at Lewis Acidic Rare Earths by Selective Energy Loss to 4f-Electron States.

Manifesting chemical differences in individual rare earth (RE) element complexes is challenging due to the similar sizes of the tripositive cations and the corelike 4f shell. We disclose a new strategy for differentiating between similarly sized Dy3+ and Y3+ ions through a tailored photochemical reaction of their isostructural complexes in which the f-electron states of Dy3+ act as an energy sink. Complexes RE(hfac)3(NMMO)2 (RE = Dy (2-Dy) and Y (2-Y), hfac = hexafluoroacetylacetonate, and NMMO = N-methylmorpholine-N-oxide) showed variable rates of oxygen atom transfer (OAT) to triphenylphosphine under ultraviolet (UV) irradiation, as monitored by 1H and 19F NMR spectroscopies. Ultrafast transient absorption spectroscopy (TAS) identified the excited state(s) responsible for the photochemical OAT reaction or lack thereof. Competing sensitization pathways leading to excited-state deactivation in 2-Dy through energy transfer to the 4f electron manifold ultimately slows the OAT reaction at this metal cation. The measured rate differences between the open-shell Dy3+ and closed-shell Y3+ complexes demonstrate that using established principles of 4f ion sensitization may deliver new, selective modalities for differentiating the RE elements that do not depend on cation size.

Coronavirus Disease 2019 (COVID-19) Coronary Vascular Thrombosis: Correlation with Neutrophil but Not Endothelial Activation.

Severe coronavirus disease 2019 (COVID-19) increases the risk of myocardial injury that contributes to mortality. This study used multiparameter immunofluorescence to extensively examine heart autopsy tissue of 7 patients who died of COVID-19 compared to 12 control specimens, with or without cardiovascular disease. Consistent with prior reports, no evidence of viral infection or lymphocytic infiltration indicative of myocarditis was found. However, frequent and extensive thrombosis was observed in large and small vessels in the hearts of the COVID-19 cohort, findings that were infrequent in controls. The endothelial lining of thrombosed vessels typically lacked evidence of cytokine-mediated endothelial activation, assessed as nuclear expression of transcription factors p65 (RelA), pSTAT1, or pSTAT3, or evidence of inflammatory activation assessed by expression of intracellular adhesion molecule-1 (ICAM-1), vascular cell adhesion molecule-1 (VCAM-1), tissue factor, or von Willebrand factor (VWF). Intimal EC lining was also generally preserved with little evidence of cell death or desquamation. In contrast, there were frequent markers of neutrophil activation within myocardial thrombi in patients with COVID-19, including neutrophil-platelet aggregates, neutrophil-rich clusters within macrothrombi, and evidence of neutrophil extracellular trap (NET) formation. These findings point to alterations in circulating neutrophils rather than in the endothelium as contributors to the increased thrombotic diathesis in the hearts of COVID-19 patients.

A Conceptual Framework to Integrate Biodiversity, Ecosystem Function, and Ecosystem Service Models.

Global biodiversity and ecosystem service models typically operate independently. Ecosystem service projections may therefore be overly optimistic because they do not always account for the role of biodiversity in maintaining ecological functions. We review models used in recent global model intercomparison projects and develop a novel model integration framework to more fully account for the role of biodiversity in ecosystem function, a key gap for linking biodiversity changes to ecosystem services. We propose two integration pathways. The first uses empirical data on biodiversity-ecosystem function relationships to bridge biodiversity and ecosystem function models and could currently be implemented globally for systems and taxa with sufficient data. We also propose a trait-based approach involving greater incorporation of biodiversity into ecosystem function models. Pursuing both approaches will provide greater insight into biodiversity and ecosystem services projections. Integrating biodiversity, ecosystem function, and ecosystem service modeling will enhance policy development to meet global sustainability goals.

Optical readout of singlet fission biexcitons in a heteroacene with photoluminescence detected magnetic resonance.

Molecular spin systems based on photoexcited triplet pairs formed via singlet fission (SF) are attractive as carriers of quantum information because of their potentially pure and controllable spin polarization, but developing systems that offer optical routes to readout as well as initialization is challenging. Herein, we characterize the electron spin magnetic resonance change in the photoluminescence intensity for a tailored organic molecular crystal while sweeping a microwave drive up to 10 GHz in a broadband loop structure. We observe resonant transitions for both triplet and quintet spin sublevel populations showing their optical sensitivity and revealing the zero-field parameters for each. We map the evolution of these spectra in both microwave frequency and magnetic field, producing a pattern of optically detected magnetic resonance (ODMR) peaks. Fits to these data using a suitable model suggest significant spin polarization in this system with orientation selectivity. Unusual excitation intensity dependence is also observed, which inverts the sign of the ODMR signal for the triplet features, but not for the quintet. These observations demonstrate optical detection of the spin sublevel population dictated by SF and intermolecular geometry, and highlight anisotropic and multi-scale dynamics of triplet pairs.

Lessons from intramolecular singlet fission with covalently bound chromophores.

Molecular dimers, oligomers, and polymers are versatile components in photophysical and optoelectronic architectures that could impact a variety of applications. We present a perspective on such systems in the field of singlet fission, which effectively multiplies excitons and produces a unique excited state species, the triplet pair. The choice of chromophore and the nature of the attachment between units, both geometrical and chemical, play a defining role in the dynamical scheme that evolves upon photoexcitation. Specific final outcomes (e.g., separated and uncorrelated triplet pairs) are being sought through rational design of covalently bound chromophore architectures built with guidance from recent fundamental studies that correlate structure with excited state population flow kinetics.

Gaze coordination with strides during walking in the cat.

KEY POINTS: Vision plays a crucial role in guiding locomotion in complex environments, but the coordination between gaze and stride is not well understood. The coordination of gaze shifts, fixations, constant gaze and slow gaze with strides in cats walking on different surfaces were examined. It was found that gaze behaviours are coordinated with strides even when walking on a flat surface in the complete darkness, occurring in a sequential order during different phases of the stride. During walking on complex surfaces, gaze behaviours are typically more tightly coordinated with strides, particularly at faster speeds, only slightly shifting in phase. These findings indicate that the coordination of gaze behaviours with strides is not vision-driven, but is a part of the whole body locomotion synergy; the visual environment and locomotor task modulate it. The results may be relevant to developing diagnostic tools and rehabilitation approaches for patients with locomotor deficits. ABSTRACT: Vision plays a crucial role in guiding locomotion in complex environments. However, the coordination between the gaze and stride is not well understood. We investigated this coordination in cats walking on a flat surface in darkness or light, along a horizontal ladder and on a pathway with small stones. We recorded vertical and horizontal eye movements and 3-D head movement, and calculated where gaze intersected the walkway. The coordination of gaze shifts away from the animal, gaze shifts toward, fixations, constant gaze, and slow gaze with strides was investigated. We found that even during walking on the flat surface in the darkness, all gaze behaviours were coordinated with strides. Gaze shifts and slow gaze toward started in the beginning of each forelimb's swing and ended in its second half. Fixations peaked throughout the beginning and middle of swing. Gaze shifts away began throughout the second half of swing of each forelimb and ended when both forelimbs were in stance. Constant gaze and slow gaze away occurred in the beginning of stance. However, not every behaviour occurred during every stride. Light had a small effect. The ladder and stones typically increased the coordination and caused gaze behaviours to occur 3% earlier in the cycle. At faster speeds, the coordination was often tighter and some gaze behaviours occurred 2-16% later in the cycle. The findings indicate that the coordination of gaze with strides is not vision-driven, but is a part of the whole body locomotion synergy; the visual environment and locomotor task modulate it.

Sensitizing Singlet Fission with Perovskite Nanocrystals.

The marriage of colloidal semiconductor nanocrystals and functional organic molecules has brought unique opportunities in emerging photonic and optoelectronic applications. Traditional semiconductor nanocrystals have been widely demonstrated to initiate efficient triplet energy transfer at the nanocrystal-acene interface. Herein, we report that unlike conventional semiconductor nanocrystals, lead halide perovskite nanocrystals promote an efficient Dexter-like singlet energy transfer to surface-anchored pentacene molecules rather than triplet energy transfer. Subsequently, molecular pentacene triplets are efficiently generated via singlet fission on the nanocrystal surface. Our demonstrated strategy not only unveils the obscure energy dynamics between perovskite nanocrystal and acenes, but also brings important perspectives of utilizing singlet fission throughout the solar spectrum.

Mapping Ecosystem Services to Human Well-being: a toolkit to support integrated landscape management for the SDGs.

The Sustainable Development Goals (SDGs) emphasize the global and multi-dimensional nature of sustainability and thus require improving our capacity to articulate and trace the impact of ecosystem change to measures of human well-being. Yet, the integrated nature of these goals is challenging to assess without similarly integrated assessment tools. We present a new modeling toolkit, "Mapping Ecosystem Services to Human well-being" (MESH), that integrates commonly used, stand-alone ecosystem services (ES) models from the InVEST suite of models to quantify and illustrate the trade-offs and synergies across five ecosystem services and up to 10 associated SDGs. Development of the software and its functionality were informed by a broad stakeholder consultation with ministries, non-governmental organizations and civil society groups in West Africa to identify common barriers to uptake and application of modeling tools in developing countries. In light of this process, key features included in MESH are (1) integration of multiple ecosystem service (ES) models into a common modeling framework supported by a curated base data set, (2) built-in scenario generation capacity to support policy analysis, (3) visualization of outcomes and trade-offs, and (4) mapping of ecosystem service change to SDG targets and goals. We illustrate the use of MESH in a case study in the Volta basin of West Africa comparing the effectiveness of three alternative conservation prioritization approaches: (1) land cover-based, (2) topographic-based, and (3) an ecosystem service-based approach to minimize the impact of agricultural expansion. We evaluate these approaches by linking changes in service supply to potential impacts on achievement of specific SDG goals and targets.

Psychiatric Care of the Post-September 11 Combat Veteran: A Review.

BACKGROUND: Post-September 11, 2001 combat veterans represent a growing cohort of patients with unique mental health needs, particularly around post-traumatic stress disorder (PTSD) and traumatic brain injury (TBI). The United States (US) remains engaged in conflicts around the globe, so this patient cohort will continue to grow in number. With around 40% of American combat veterans from Iraq and Afghanistan seeking mental health care outside of the Veterans Affairs, understanding the psychiatric needs of the post-September 11 combat veteran is an important goal for all psychiatrists. These patients are relevant to consultation-liaison (C-L) psychiatrists because of their high comorbidity of conditions such as TBI, obstructive sleep apnea, insomnia, and chronic pain. This article reviews the current literature on mental health care for the post-September 11 combat veteran, emphasizing PTSD and TBI treatment, and culling evidence-based recommendations from randomized controlled trials of combat veterans. Emphasis is also placed on the Veterans Affairs/Department of Defense Clinical Practice Guidelines. The authors also bring unique clinical expertise of having served on active duty as psychiatrists for the US Army, including in a combat zone, and both currently work in a Veterans Affairs Iraq and Afghanistan combat veteran mental health clinic. OBJECTIVE: This review outlines useful treatment approaches for PTSD and TBI and briefly covers the comorbid conditions of major depression, chronic pain, and substance use disorders. This review will prepare C-L psychiatrists to care for this challenging patient cohort.

Structure and photophysics of indigoids for singlet fission: Cibalackrot.

We report an investigation of structure and photophysics of thin layers of cibalackrot, a sturdy dye derived from indigo by double annulation at the central double bond. Evaporated layers contain up to three phases, two crystalline and one amorphous. Relative amounts of all three have been determined by a combination of X-ray diffraction and FT-IR reflectance spectroscopy. Initially, excited singlet state rapidly produces a high yield of a transient intermediate whose spectral properties are compatible with charge-transfer nature. This intermediate more slowly converts to a significant yield of triplet, which, however, does not exceed 100% and may well be produced by intersystem crossing rather than singlet fission. The yields were determined by transient absorption spectroscopy and corrected for effects of partial sample alignment by a simple generally applicable procedure. Formation of excimers was also observed. In order to obtain guidance for improving molecular packing by a minor structural modification, calculations by a simplified frontier orbital method were used to find all local maxima of singlet fission rate as a function of geometry of a molecular pair. The method was tested at 48 maxima by comparison with the ab initio Frenkel-Davydov exciton model.

Control of Energy Flow Dynamics between Tetracene Ligands and PbS Quantum Dots by Size Tuning and Ligand Coverage.

We have prepared a series of samples with the ligand 6,13-bistri(iso-propyl)silylethynyl tetracene 2-carboxylic acid (TIPS-Tc-COOH) attached to PbS quantum dot (QD) samples of three different sizes in order to monitor and control the extent and time scales of energy flow after photoexcitation. Fast energy transfer (∼1 ps) to the PbS QD occurs upon direct excitation of the ligand for all samples. The largest size QD maintains the microsecond exciton lifetime characteristic of the as-prepared oleate terminated PbS QDs. However, two smaller QD sizes with lowest exciton energies similar to or larger than the TIPS-Tc-COO- triplet energy undergo energy transfer between QD core and ligand triplet on nanosecond to microsecond timescales. For the intermediate size QDs in particular, energy can be recycled many times between ligand and core, but the triplet remains the dominant excited species at long times, living for ∼3 µs for fully exchanged QDs and up to 30 µs for partial ligand exchange, which is revealed as a method for controlling the triplet lifetime. A unique upconverted luminescence spectrum is observed that results from annihilation of triplets after exclusive excitation of the QD core.

An evaluation of the challenges to developing tumor BRCA1 and BRCA2 testing methodologies for clinical practice.

Ovarian cancer patients with germline or somatic pathogenic variants benefit from treatment with poly ADP ribose polymerase (PARP) inhibitors. Tumor BRCA1/2 testing is more challenging than germline testing as the majority of samples are formalin-fixed paraffin embedded (FFPE), the tumor genome is complex, and the allelic fraction of somatic variants can be low. We collaborated with 10 laboratories testing BRCA1/2 in tumors to compare different approaches to identify clinically important variants within FFPE tumor DNA samples. This was not a proficiency study but an inter-laboratory comparison to identify common issues. Each laboratory received the same tumor DNA samples ranging in genotype, quantity, quality, and variant allele frequency (VAF). Each laboratory performed their preferred next-generation sequencing method to report on the variants. No false positive results were reported in this small study and the majority of methods detected the low VAF variants. A number of variants were not detected due to the bioinformatics analysis, variant classification, or insufficient DNA. The use of hybridization capture or short amplicon methods are recommended based on a bioinformatic assessment of the data. The study highlights the importance of establishing standards and standardization for tBRCA testing particularly when the test results dictate clinical decisions regarding life extending therapies.