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Organic co-crystals have emerged as a promising class of semiconductors for next-generation optoelectronic devices due to their unique photophysical properties. This paper presents a joint experimental-theoretical study comparing the crystal structure, spectroscopy, and electronic structure of two charge transfer co-crystals. Reported herein is a novel co-crystal Npe:TCNQ, formed from 4-(1-naphthylvinyl)pyridine (Npe) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) via molecular self-assembly. This work also presents a revised study of the co-crystal composed of Npe and 1,2,4,5-tetracyanobenzene (TCNB) molecules, Npe:TCNB, herein reported with a higher-symmetry (monoclinic) crystal structure than previously published. Npe:TCNB and Npe:TCNQ dimer clusters are used as theoretical model systems for the co-crystals; the geometries of the dimers are compared to geometries of the extended solids, which are computed with periodic boundary conditions density functional theory. UV-Vis absorption spectra of the dimers are computed with time-dependent density functional theory and compared to experimental UV-Vis diffuse reflectance spectra. Both Npe:TCNB and Npe:TCNQ are found to exhibit neutral character in the S 0 state and ionic character in the S 1 state. The high degree of charge transfer in the S 1 state of both Npe:TCNB and Npe:TCNQ is rationalized by analyzing the changes in orbital localization associated with the S 1 transitions.

The environmentally benign metal-organic framework (MOF) CUK-1 based on 2,4-pyridine dicarboxylate has been prepared for the first time using Mn(II) as the inorganic node and water as the only solvent. Mn-CUK-1 shows reversible and efficient capture of H 2 O, SO 2 , and H 2 S. Compared to previously studied Co(II) and Mg(II) versions of the same MOF, Mn-CUK-1 also exhibited unique temperature-induced structural flexibility due to organic linker torsion, as detailed by variable-temperature single-crystal X-ray diffraction studies. Owing to this inherent solid-state flexibility, Mn-CUK-1 showed stepwise adsorption for polar gases, which induce structural deformations upon adsorption, while the nonpolar guest adsorbates were reversibly sorbed in a more classical manner. Notably, Mn-CUK-1 demonstrates the highest reported H 2 S capacity-to-surface area ratio among MOFs that are chemically stable toward this reactive acidic molecule. Moreover, Mn-CUK-1 displays exceptional structural stability in the presence of high relative humidity and corrosive gases and shows soft crystalline behavior triggered by changes in both the adsorption temperature and guest molecule identity.

A combined experimental and theoretical study of H 2 adsorption was carried out in Co-CUK-1 and Mg-CUK-1, two isostructural metal-organic frameworks (MOFs) that consist of M 2+ ions (M = Co and Mg) coordinated to pyridine-2,4-dicarboxylate (pdc 2- ) and OH - ligands. These MOFs possess saturated metal centers in distorted octahedral environments and narrow pore sizes and display high chemical and thermal stability. Previous experimental studies revealed that Co-CUK-1 exhibits a H 2 uptake of 183 cm 3 g -1 at 77 K/1.0 atm [ Angew. Chem., Int. Ed. 2007, 46, 272-275, DOI: 10.1002/anie.200601627], while that for Mg-CUK-1 under the same conditions is 240 cm 3 g -1 on the basis of the experimental measurements carried out herein. The theoretical H 2 adsorption isotherms are in close agreement with the corresponding experimental measurements for simulations using electrostatic and polarizable potentials of the adsorbate. Through simulated annealing calculations, it was found that the primary binding site for H 2 in both isostructural analogues is localized proximal to the center of the aromatic rings belonging to the pdc 2- linkers. Inelastic neutron scattering (INS) spectroscopic studies of H 2 adsorbed in both MOFs revealed a rotational tunnelling transition occurring at around 8 meV in the corresponding spectra; this peak represents H 2 adsorbed at the primary binding site. Two-dimensional quantum rotation calculations for H 2 localized at the primary and secondary binding sites in both MOFs yielded rotational energy levels that are in agreement with the transitions observed in the INS spectra. Even though both M-CUK-1 analogues possess different metal ions, they exhibit similar electrostatic environments, modeled structures at H 2 saturation, and rotational potentials for H 2 adsorbed at the most favorable adsorption site. Overall, this study demonstrates how important molecular-level details of the H 2 adsorption mechanism inside MOF micropores can be derived from a combination of experimental measurements and theoretical calculations using two stable and isostructural MOFs with saturated metal centers and small pore windows as model systems.

The highly unfavorable thermodynamics of direct aluminum hydrogenation can be overcome by stabilizing alane within a nanoporous bipyridine-functionalized covalent triazine framework (AlH 3 @CTF-bipyridine). This material and the counterpart AlH 3 @CTF-biphenyl rapidly desorb H 2 between 95 and 154 °C, with desorption complete at 250 °C. Sieverts measurements, 27 Al MAS NMR and 27 Al{ 1 H} REDOR experiments, and computational spectroscopy reveal that AlH 3 @CTF-bipyridine dehydrogenation is reversible at 60 °C under 700 bar hydrogen, >10 times lower pressure than that required to hydrogenate bulk aluminum. DFT calculations and EPR measurements support an unconventional mechanism whereby strong AlH 3 binding to bipyridine results in single-electron transfer to form AlH 2 (AlH 3 ) n clusters. The resulting size-dependent charge redistribution alters the dehydrogenation/rehydrogenation thermochemistry, suggesting a novel strategy to enable reversibility in high-capacity metal hydrides., (© 2021 Wiley-VCH GmbH.)

A large-pore version of Mg-CUK-1, a water-stable metal-organic framework (MOF) with 1-D channels, was synthesized in basic water. Mg-CUK-1L has a BET surface area of 2896 m 2 g -1 and shows stark selectivity for CO 2 sorption over N 2 , O 2 , H 2 , and CH 4 . It displays reversible, multistep gated sorption of CO 2 below 0.33 atm. The dehydrated single-crystal structure of Mg-CUK-1L confirms retention of the open-channel structure. The MOF can be loaded with organic molecules by immersion in hot melts, providing single crystals suitable for X-ray diffraction. trans -Azobenzene fills the channels in a 2 × 2 arrangement. Solid-state UV-vis spectroscopy reveals that azobenzene molecules undergo reversible trans - cis isomerization, despite being close-packed; this surprising result is confirmed by DFT-simulated UV-vis spectra.

In the wake of the Deepwater Horizon disaster, much has been learned about the biological, ecological, physical, and chemical conditions of the Gulf of Mexico. In parallel, the research community has also gained insight about the social and organizational structures and processes necessary for oil spill response and subsequent marine and coastal restoration. However, even with these lessons from both the Deepwater Horizon and previous spills, including 1989's Exxon Valdez and the Ixtoc 1 in 1979, our understanding of how to avoid future crises has not advanced at the same pace as offshore oil and gas development. We argue that this progress deficit indicates a continued devaluing of marine and coastal resources. We believe that we must, instead, advance a proactive conservation ethic based on the precautionary principle and an appropriately placed burden of proof-strategies that will help reduce our reliance on costly restoration and protect marine and coastal ecosystems., (© The Author(s) 2019. Published by Oxford University Press on behalf of the American Institute of Biological Sciences.)

ACM-1 is the first example of an organoarsine metal-organic framework (MOF), prepared using a new pyridyl-functionalized triarylarsine ligand coordinated to Ni(II) nodes. ACM-1 has micropores that are decorated with cis-diarsine coordination pockets. Postsynthetic metalation of ACM-1 with AuCl under facile conditions studied by single-crystal X-ray diffraction reveals the installation of dimeric Au 2 Cl 2 complexes via the formation of As-Au bonds. The Au(I) dimers display exceptionally short aurophilic bonds (2.76 Å) induced by the rigidity of the MOF, which acts as a unique solid-state ligand.

Light-emitting electrochemical cells (LEECs) from ionic transition-metal complexes (iTMCs) offer the potential for high-efficiency electroluminescence in a simple, single-layer device. However, LEECs typically rely on the use of rare metal complexes. This has limited their cost effectiveness and put constraints on their applicability. With a view to leveraging the efficient emission of these complexes while mitigating costs, we describe here a host/guest LEEC strategy that relies on the use of carbazole (Cz)-based organic small-molecule hosts and iTMC guests. Three cationic host molecules were prepared via the coupling of 1-(4-bromophenyl)-2-phenylbenzimidazole (PBI-Br) with Cz. This has allowed a comparison between the hosts bearing methoxy (PBI-CzOMe) and tert-butyl (PBI-Cz tBu) substituents, as well as an unsubstituted analogue (PBI-CzH). Cyclic voltammetry and UV-visible absorption revealed that all three host materials have wide band gaps characterized by reversible oxidation and irreversible reduction events. On the basis of electronic structure calculations, the host highest occupied molecular orbital (HOMO) resides primarily on the Cz moiety, whereas the lowest unoccupied molecular orbital (LUMO) is located primarily on the phenyl-benzimidazolium unit. Photoluminescence analysis of thin-film blends of PBI-CzH with iTMC guests confirmed that the emission was blue-shifted relative to pristine iTMC films, which is consistent with what was seen in dilute dichloromethane solution. LEEC devices were prepared based on thin films of the pristine hosts, pristine guests, and 90%/10% (w/w) host/guest blends. Among these host/guest blends, LEECs based on PBI-CzH displayed the best performance, particularly when an iridium complex was used as the guest. The system in question yielded a luminance maximum of 624 cd/m 2 at an external quantum efficiency of 3.80%. This result stands in contrast to what is seen with typical organic light-emitting diode host studies, where tert-butyl substitution of the host generally leads to a better performance. To rationalize the present observations, the host materials were subject to single-crystal X-ray diffraction analysis. The resulting structures revealed clear head-to-tail interactions in the case of both PBI-CzH and PBI-CzOMe. No such interactions were evident in the case of PBI-Cz tBu. Furthermore, PBI-CzH showed a relatively smaller spacing between the successive HOMO and successive LUMO levels relative to PBI-CzOMe and PBI-Cz tBu, a finding consistent with more favorable charge transport and energy transfer. The results presented here can help inform the design and preparation of host materials suitable for use in single-layer iTMC LEECs.

PCM-101 is a phosphine coordination material comprised of tris(p-carboxylato)triphenylphosphine and secondary pillaring groups coordinated to [M 3 (OH)] 5+ nodes (M=Co, Ni). PCM-101 has a unique topology in which R 3 P: sites are arranged directly trans to one another, with a P⋅⋅⋅P separation distance dictated by the pillars. Post-synthetic coordination of soft metals to the P: sites proceeds at room temperature to provide X-ray quality crystals that permit full structural resolution. Addition of AuCl groups forces a large distortion of the parent framework. In contrast, CuBr undergoes insertion directly between the trans-P sites to form dimers that mimic solution-phase complexes, but that are geometrically strained due to steric pressure exerted by the MOF scaffold. The metalated materials are active in heterogeneous hydroaddition catalysis under mild conditions, yielding different major products compared to their molecular counterparts., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Florida manatees (Trichechus manatus latirostris) possess an unusual suite of adaptations to accommodate both a fully aquatic lifestyle and an herbivorous diet, including a low metabolic rate and a very limited thermoneutral zone. Their relatively high lower critical temperature of around 20 °C suggests strong sensitivity to cold, thereby limiting their distribution to tropical and subtropical waters. "Cold stress syndrome" affects and kills Florida manatees every year during intense or prolonged cold weather, posing one of the major threats to manatees. However, knowledge regarding manatee thermoregulation is sparse, but essential for effective conservation and management of this threatened species. We measured heat flux in two captive Florida manatees at multiple times of the year, at 41 sites distributed across the entire body surface of each manatee. Heat flux differed significantly between individuals, and among body sites and times of the year. The pectoral flippers and axillae were identified as areas with highest heat exchange. Despite exposure to constant water temperature throughout the year, the manatees in this study had significantly lower heat flux in winter than in summer. We used the measured heat flux values to calculate total heat dissipation in individual manatees. The values estimated this way correspond well with the low metabolic rates estimated in previous studies, confirming the reliability of our novel approach. Our method provides simple and useful options for enhancing manatee welfare by monitoring the animals' thermal state during potentially stressful activities such as during medical treatment, capture restraints and transportation.

The effect of pH on the spectral and redox properties of model GFP synthetic chromophores (Cros) in a universal buffer system was investigated. The Cro hydroxy-derivatives demonstrated a Nernst-type electrochemical dependence of the anodic potential within the pH 2-8 range. Analogous studies on various fluorescent proteins were unsuccessful.

We used southwestern Florida as a case study to lay the groundwork for an intended and organized decision-making process for managing warm-water habitat needed by endangered manatees to survive winters in Florida. Scientists and managers have prioritized (a) projecting how the network of warm-water sites will change over the next 50 years as warmed industrial discharges may expire and as flows of natural springs are reduced through redirection of water for human uses, and (b) mitigating such changes to prevent undue consequences to manatees. Given the complexities introduced by manatee ecology; agency organizational structure; shifting public demands; fluctuating resource availability; and managing within interacting cultural, social, political, and environmental contexts, it was clear that a structured decision process was needed. To help promote such a process, we collected information relevant to future decisions including maps of known and suspected warm-water sites and prototyped a characterization of sites and networks. We propose steps that would lead to models that might serve as core tools in manatee/warm-water decision-making, and we summarized topics relevant for informed decision-making (e.g., manatee spatial cognition, risk of cold-stress morbidity and mortality, and human dimensions). A major impetus behind this effort is to ensure proactively that robust modeling tools are available well in advance of the anticipated need for a critical management decision.

To survive cold winter periods most, if not all, Florida manatees rely on warm-water refuges in the southern two-thirds of the Florida peninsula. Most refuges are either warm-water discharges from power plant and natural springs, or passive thermal basins that temporarily trap relatively warm water for a week or more. Strong fidelity to one or more refuges has created four relatively discrete Florida manatee subpopulations. Using statewide winter counts of manatees from 1999 to 2011, we provide the first attempt to quantify the proportion of animals using the three principal refuge types (power plants, springs, and passive thermal basins) statewide and for each subpopulation. Statewide across all years, 48.5% of all manatees were counted at power plant outfalls, 17.5% at natural springs, and 34.9 % at passive thermal basins or sites with no known warm-water features. Atlantic Coast and Southwest Florida subpopulations comprised 82.2% of all manatees counted (45.6% and 36.6%, respectively) with each subpopulation relying principally on power plants (66.6% and 47.4%, respectively). The upper St. Johns River and Northwest Florida subpopulations comprised 17.8% of all manatees counted with almost all animals relying entirely on springs (99.2% and 88.6% of those subpopulations, respectively). A record high count of 5,076 manatees in January 2010 revealed minimum sizes for the four subpopulations of: 230 manatees in the upper St. Johns River; 2,548 on the Atlantic Coast; 645 in Northwest Florida; and 1,774 in Southwest Florida. Based on a comparison of carcass recovery locations for 713 manatees killed by cold stress between 1999 and 2011 and the distribution of known refuges, it appears that springs offer manatees the best protection against cold stress. Long-term survival of Florida manatees will require improved efforts to enhance and protect manatee access to and use of warm-water springs as power plant outfalls are shut down.

Fatty acid signature analysis (FASA) is an important tool by which marine mammal scientists gain insight into foraging ecology. Fatty acid profiles (resulting from FASA) represent a potential biomarker to assess exposure to natural and anthropogenic stressors. Florida manatees are well studied, and an excellent necropsy program provides a basis against which to assess this budding tool. Results using samples from 54 manatees assigned to four cause-of-death categories indicated that those animals exposed to or that died due to brevetoxin exposure (red tide, or RT samples) demonstrate a distinctive hepatic fatty acid profile. Discriminant function analysis indicated that hepatic fatty acids could be used to classify RT versus non-RT liver samples with reasonable certainty. A discriminant function was derived based on 8 fatty acids which correctly classified 100% of samples from a training dataset (10 RT and 25 non-RT) and 85% of samples in a cross-validation dataset (5 RT and 13 non-RT). Of the latter dataset, all RT samples were correctly classified, but two of thirteen non-RT samples were incorrectly classified. However, the "incorrect" samples came from manatees that died due to other causes during documented red tide outbreaks; thus although the proximal cause of death was due to watercraft collisions, exposure to brevetoxin may have affected these individuals in ways that increased their vulnerability. This use of FASA could: a) provide an additional forensic tool to help scientists and managers to understand cause of death or debilitation due to exposure to red tide in manatees; b) serve as a model that could be applied to studies to improve assessments of cause of death in other marine mammals; and c) be used, as in humans, to help diagnose metabolic disorders or disease states in manatees and other species., (Copyright © 2010 Elsevier B.V. All rights reserved.)

Knowledge of mammalian diversity is still surprisingly disparate, both regionally and taxonomically. Here, we present a comprehensive assessment of the conservation status and distribution of the world's mammals. Data, compiled by 1700+ experts, cover all 5487 species, including marine mammals. Global macroecological patterns are very different for land and marine species but suggest common mechanisms driving diversity and endemism across systems. Compared with land species, threat levels are higher among marine mammals, driven by different processes (accidental mortality and pollution, rather than habitat loss), and are spatially distinct (peaking in northern oceans, rather than in Southeast Asia). Marine mammals are also disproportionately poorly known. These data are made freely available to support further scientific developments and conservation action.

Relative to many other mammals, little is known about the functional morphology of the four extant species of the order Sirenia. In this study, 166 Florida manatee (Trichechus manatus latirostris) carcasses fresh enough to collect detailed anatomical information were examined to describe the gross anatomy of the diaphragm. Our results show that the Florida manatee's diaphragm differs from those of other mammals in that it: lies in a dorsal plane, rather than in the more typical transverse plane; is located dorsal to the heart and does not attach to the sternum; and attaches medially at the "I"-shaped central tendon to bony projections extending ventrally from the vertebral bodies, forming two distinct hemidiaphragms. The manatee's transverse septum is a separate structure that lies at a right angle to the diaphragm and separates the heart from the liver and other viscera. The extreme muscularity of the diaphragm and the ability of manatees to adjust their position in the water column with minimal external movement suggest that diaphragmatic contractions may change the volume of each pleural cavity to affect buoyancy, roll, and pitch. We also hypothesize that such contractions, in concert with contractions of powerful abdominal muscles, may compress gas in the massive large intestine, and thereby also contribute to buoyancy control., (Copyright 2000 Wiley-Liss, Inc.)

We assess population trends of the Atlantic coast population of Florida manatee, Trichechus manatus latirostris, by reanalyzing aerial survey data collected between 1982 and 1992. To do so, we develop an explicit biological model that accounts for the method by which the manatees are counted, the mammals' movement between surveys, and the behavior of the population total over time. Bayesian inference, enabled by Markov chain Monte Carlo, is used to combine the survey data with the biological model. We compute marginal posterior distributions for all model parameters and predictive distributions for future counts. Several conclusions, such as a decreasing population growth rate and low sighting probabilities, are consistent across different prior specifications.

Background: The Florida manatee, Trichechus manatus latirostris (Sirenia: Trichechidae), is the largest herbivorous marine mammal. Previously, components of the gastrointestinal (GI) tract of the species have been described, but no comprehensive descriptions of the gross and microscopic anatomy existed. This study integrates function and structure of the entire Florida manatee GI tract., Methods: The GI tracts of several recently dead Florida manatees were examined from the following viewpoints: gross anatomical studies of preserved and unpreserved specimens, histology and histochemistry, and ultrastructure., Results: The manatee GI tract has an enlarged hindgut, as do other nonruminant herbivores (i.e., hindgut digesters such as horses), but it also has important adaptations not seen in most other mammals. These structural adaptations include a discrete accessory digestive gland (the cardiac gland), submucosal mucous glands along the greater curvature of the stomach, and unkeratinized, stratified squamous epithelial cells overlying the glandular mucosae of the pyloric antrum, midgut cecum, colon, and rectum., Conclusions: The adaptations described above may relate to osmoregulation as well as to herbivory. The Florida manatee GI tract is most similar to those of other members of the Order Sirenia and to that of the herbivorous green sea turtle (Chelonia mydas), but it also shows superficial similarities to those of phylogenetically close Orders, the Proboscidea and Hyracoidea. The immense size of both the manatee and its large intestine suggests that, relative to smaller hindgut digesters, manatees have a slow rate of passage of digesta and efficient breakdown of fibrous plant material.

The anatomy of the duodenum of the West Indian manatee has both macroscopic and microscopic features that are unusual when compared to other mammalian forms. Macroscopically, the voluminous duodenal ampulla and the paired duodenal diverticula are distinctive. The general microscopic structure of the manatee duodenum is not unusual, but the duodenal glands secrete an acid mucin (sialomucin). The cells of these glands appear to be intermediate between classical serous and mucous cell types. These cells also contain granules with regions of high peripheral electron density. The overall structure of the manatee duodenum most strongly resembles that of the dugong, another member of the order Sirenia.

Examination of the gross and microscopic anatomy of the kidney of the West Indian manatee, Trichechus manatus, revealed that: (1) the medulla is about 6 times thicker than the cortex; (2) juxtamedullary glomeruli have a mean diameter 1.3 times greater than that of cortical glomeruli; (3) juxtamedullary glomeruli have 1.7 times as much volume as cortical glomeruli; (4) there are about twice as many cortical glomeruli as juxtamedullary glomeruli per square millimeter of cortical tissue, and (5) the vasa recta are closely juxtaposed to the thin loops of Henle in the outer medulla. Many of these results suggest an enhanced urine-concentrating ability in this species.

The West Indian manatee, Trichechus manatus, has amedullary, pachyostotic long bones. Since marrow cavities of the long bones typically are the locations of hemopoiesis in adult mammals, the manatee has evolved an alternative primary site of hemopoiesis. Histological examinations of spleens, livers, kidneys, and vertebral bodies indicate that the last-named location is the main site of erythropoiesis and granulopoiesis in T. manatus. This conclusion is based on the presence in the vertebrae of bone-marrow-containing diagnostic cell types including erythroblasts, megakaryocytes, and myelocytes, which are the precursor cells of erythrocytes, platelets, and granular leukocytes, respectively. No developing lymphocytes were found, so that the location of lymphopoiesis remains unknown.