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Raising insects in a laboratory for release into the wild is a common conservation practice, but maintaining breeding colonies year‐round can be limited by seasonal food availability. Food availability is particularly challenging for insects which depend on specific host plants. For example, our early efforts to rear the imperiled Atala hairstreak butterfly (Eumaeus atala Poey) resulted in colony failure during winter due to lack of food. To overcome this barrier, we developed a modified freeze‐dried host plant diet to support the colony. The diet consisted of reconstituted freeze‐dried leaves and stems from fresh‐growth coontie (Zamia integrifolia), the host plant for the Atala butterflies. We fed larvae less than 9 mm on this freeze‐dried diet and transferred them to live coontie plants after they were more than 9 mm. We reared a colony of Atala butterflies using these methods for 859 days, resulting in more than 3400 animals released into the wild. Comparing colony counts during that time period to the 548 days we reared them without modified freeze‐dried diet showed a clear benefit in using freeze‐dried diet. A growth trial (N = 40) of larvae fed on only freeze‐dried diet compared to larvae fed on fresh coontie cuttings found no significant difference in larval or pupal development between groups (p = 0.71 and p = 0.47, respectively). We, therefore, conclude that the freeze‐dried diet provided an appropriate alternative for Atala colonies when fresh growth from the host plant is unavailable, and we recommend use of this technique for raising other host plant‐dependent insect species of conservation concern., Graphical abstract Graphical abstract created by Jennifer Torchalski, Disney's Animals, Science and Environment, Lake Buena Vista, Florida, USA., RESEARCH HIGHLIGHTS When rearing butterflies ex situ for conservation, many species of butterflies are highly host‐plant specific, and it can be difficult to provide enough food for them during nongrowing seasonsAfter a colony failure due to food shortage, we created a modified freeze‐dried diet for the imperiled Atala hairstreak butterfly (Eumaus atala) using methods that could potentially be replicated for other butterfliesThe diet was highly successful, leading to the rearing and release of over 3800 adult butterflies back into the wildKey to the methods was using pure, new‐growth host plant, and switching larger larvae back to mature leaves

Decoherence arises from a fluctuating spin environment, captured by its noise spectrum S(ω). Dynamical decoupling (DD) with n π pulses extends the dephasing time if the associated filter function attenuates S(ω). Inversely, DD noise spectroscopy (DDNS) reconstructs S(ω) from DD data by approximating the filters pass band by a δ-function. This restricts application to qubit-like spin systems with inherently long dephasing times and/or many applicable pulses. We introduce regularized DDNS to lift this limitation and thereby infer S(ω) from DD traces of paramagnetic centers in glassy o-terphenyl and water–glycerol matrices recorded with n ≤ 5. For nitroxide radicals at low temperatures, we utilize deuteration to identify distinct matrix- and spin center-induced spectral features. The former extends up to a matrix-specific cut-off frequency and characterizes nuclear spin diffusion. We demonstrate that rotational tunneling of intramolecular methyl groups drives the latter process, whereas at elevated temperatures S(ω) reflects the classical methyl group reorientation. Ultimately, S(ω) visualizes and quantifies variations in the electron spins couplings and thus reports on the underlying spin dynamics as a powerful decoherence descriptor., A noise spectrum captures the decoherence-inducing spin environment fluctuations and thus provides a quantitative decoherence description.

Dissolution of mineral surfaces at asymmetric solid–liquid–solid interfaces in aqueous solutions occurs in technologically relevant processes, such as chemical/mechanical polishing (CMP) for semiconductor fabrication, formation and corrosion of structural materials, and crystallization of materials relevant to heterogeneous catalysis or drug delivery. In some such processes, materials at confined interfaces exhibit dissolution rates that are orders of magnitude larger than dissolution rates of isolated surfaces. Here, the dissolution of silica and alumina in close proximity to a charged gold surface or mica in alkaline solutions of pH 10–11 is shown to depend on the difference in electrostatic potentials of the surfaces, as determined from measurements conducted using a custom-built electrochemical pressure cell and a surface forces apparatus (SFA). The enhanced dissolution is proposed to result from overlap of the electrostatic double layers between the dissimilar charged surfaces at small intersurface separation distances (

The adsorption and reaction properties of heterogeneous zeolite catalysts (e.g. for catalytic cracking of petroleum, partial oxidation of natural gas) depend strongly on the types and distributions of Al heteroatoms in the aluminosilicate frameworks. The origins of these properties have been challenging to discern, owing in part to the structural complexity of aluminosilicate zeolites. Herein, combined solid-state NMR and synchrotron X-ray powder diffraction analyses show the Al atoms locate preferentially in certain framework sites in the zeolite catalyst Al-SSZ-70. Through-covalent-bond 2D 27 Al{29 Si} J-correlation NMR spectra allow distinct framework Al sites to be identified and their relative occupancies quantified. The analyses show that 94 % of the Al atoms are located at the surfaces of the large-pore interlayer channels of Al-SSZ-70, while only 6 % are in the sub-nm intralayer channels. The selective siting of Al atoms accounts for the reaction properties of catalysts derived from SSZ-70.

Cube-shaped nanocrystals (NCs) of conventional metals like gold and silver generally exhibit localized surface plasmon resonance (LSPR) in the visible region with spectral modes determined by their faceted shapes. However, faceted NCs exhibiting LSPR response in the infrared (IR) region are relatively rare. Here, we describe the colloidal synthesis of nanoscale fluorine-doped indium oxide (F:In2O3) cubes with LSPR response in the IR region, wherein fluorine was found to both direct the cubic morphology and act as an aliovalent dopant. Single-crystalline 160 nm F:In2O3 cubes terminated by (100) facets and concave cubes were synthesized using a colloidal heat-up method. The presence of fluorine was found to impart higher stabilization to the (100) facets through density functional theory calculations that evaluated the energetics of F-substitution at surface oxygen sites. These calculations suggest that the cubic morphology results from surface binding of F atoms. In addition, fluorine acts as an anionic al...

Tailorable sorption properties at the molecular level are key for efficient carbon capture and storage and a hallmark of covalent organic frameworks (COFs). Although amine functional groups are known to facilitate CO2 uptake, atomistic insights into CO2 sorption by COFs modified with amine-bearing functional groups are scarce. Herein, we present a detailed study of the interactions of carbon dioxide and water with two isostructural hydrazone-linked COFs with different polarities based on the 2,5-diethoxyterephthalohydrazide linker. Varying amounts of tertiary amines were introduced in the COF backbones by means of a copolymerization approach using 2,5-bis(2-(dimethylamino)ethoxy)terephthalohydrazide in different amounts ranging from 25 to 100% substitution of the original DETH linker. The interactions of the frameworks with CO2 and H2O were comprehensively studied by means of sorption analysis, solid-state NMR spectroscopy, and quantum-chemical calculations. We show that the addition of the tertiary amine linker increases the overall CO2 sorption capacity normalized by the surface area and of the heat of adsorption, whereas surface areas and pore size diameters decrease. The formation of ammonium bicarbonate species in the COF pores is shown to occur, revealing the contributing role of water for CO2 uptake by amine-modified porous frameworks.

Single-molecule magnets (SMMs) hold promise for unmatched information storage density as well as for applications in quantum computing and spintronics. To date, the most successful SMMs have been organometallic lanthanide complexes. However, their surface immobilization, one of the requirements for device fabrication and commercial application, remains challenging due to the sensitivity of the magnetic properties to small changes in the electronic structure of the parent SMM. Thus, finding controlled approaches to SMM surface deposition is a timely challenge. In this contribution we apply the concept of isolobality to identify siloxides present at the surface of partially dehydroxylated silica as a suitable replacement for archetypal ligand architectures in organometallic SMMs. We demonstrate theoretically and experimentally that isolated siloxide anchoring sites not only enable successful immobilization but also lead to a 2 orders of magnitude increase in magnetization relaxation times. ISSN:0002-7863 ISSN:1520-5126

Bromodomain and extra-terminal (BET) family proteins, BRD2-4 and T, are important drug targets; however, the biological functions of each bromodomain remain ill-defined. Chemical probes that selectively inhibit a single BET bromodomain are lacking, although pan inhibitors of the first (D1), and second (D2), bromodomain are known. Here, we develop selective BET D1 inhibitors with preferred binding to BRD4 D1. In competitive inhibition assays, we show that our lead compound is 9-33 fold selective for BRD4 D1 over the other BET bromodomains. X-ray crystallography supports a role for the selectivity based on reorganization of a non-conserved lysine and displacement of an additional structured water in the BRD4 D1 binding site relative to our prior lead. Whereas pan-D1 inhibitors displace BRD4 from MYC enhancers, BRD4 D1 inhibition in MM.1S cells is insufficient for stopping Myc expression and may lead to its upregulation. Future analysis of BRD4 D1 gene regulation may shed light on differential BET bromodomain functions.

Laurel wilt disease (LWD) is a highly virulent disease vectored by an invasive beetle. It was first observed in South Carolina in 2003, and it is now found in all Florida counties and nine southeastern US states. This disease causes extensive mortality of Lauraceae plants, an ecologically and economically important group. Many arthropods are associated with Lauraceae species, including palamedes (Papilio palamedes (Drury)) and spicebush (Papilio troilus (L.)) swallowtail butterflies, which host on swamp bay (Persea palustris) and redbay (Persea borbonia). It is thought that P. palamedes are at greatest risk from LWD. Limited information exists on the impacts on these butterflies after LWD becomes established. Therefore, we use a unique long-term tree and butterfly dataset in central Florida that spanned the introduction of LWD. We found that over two decades, swamp bay declined 90% in abundance. Interestingly, the majority (70%) of the swamp bays’ decline preceded the introduction of LWD. We suspect that a 5 year severe drought was the primary cause of mortality, since there was a 45% reduction in overall tree abundances. Despite these large reductions, a small number of swamp bay trees persisted, and others sprouted from basal roots. Butterfly monitoring began after 70% of the swamp bays had died. We found that, even though there was extensive loss of swamp bays, P. palamedes and P. troilus populations were relatively stable, and potentially were increasing. However, after LWD was confirmed in this area, these butterflies declined slightly. We also found that the reduction was slightly greater in P. palamedes than P. troilus. P. palamedes are more dependent on swamp bay whereas P. troilus are more adaptable at host-switching, perhaps to a Lauraceae tree Cinnamomum camphora (L.) J. Pesl. (Camphortree), which is common in our area and does not appear to be locally affected by LWD. Thus, while we found that swamp bay declined dramatically, dependent butterfly populations declined far less dramatically. Butterflies may be surviving because of host-switching, or because the remaining trees provide enough resources. Future research should focus on the persistence of these species, especially as this disease continues to spread throughout the southeastern US.

Climate change can influence consumer populations both directly, by affecting survival and reproduction, and indirectly, by altering resources. However, little is known about the relative importance of direct and indirect effects, particularly for species important to ecosystem functioning, like pollinators. We used structural equation modelling to test the importance of direct and indirect (via floral resources) climate effects on the interannual abundance of three subalpine bumble bee species. In addition, we used long-term data to examine how climate and floral resources have changed over time. Over 8 years, bee abundances were driven primarily by the indirect effects of climate on the temporal distribution of floral resources. Over 43 years, aspects of floral phenology changed in ways that indicate species-specific effects on bees. Our study suggests that climate-driven alterations in floral resource phenology can play a critical role in governing bee population responses to global change.

Orientation of the iliac blades is a key feature that appears to distinguish extant apes from monkeys. Iliac morphology is hypothesized to reflect variation in thoracic shape that, in turn, reflects adaptations for shoulder and forearm function in anthropoids. Iliac orientation is traditionally measured relative to the acetabulum, whereas functional explanations pertain to its orientation relative to the cardinal anatomical planes. We investigated iliac orientation relative to a median plane using digital models of hipbones registered to landmark data from articulated pelves. We fit planes to the iliac surfaces, midline, and acetabulum, and investigated linear metrics that characterize geometric relationships of the iliac margins. Our results demonstrate that extant hominoid ilia are not rotated into a coronal plane from a more sagittal position in basal apes and monkeys but that the apparent rotation is the result of geometric changes within the ilia. The whole ilium and its gluteal surface are more coronally oriented in apes, but apes and monkeys do not differ in orientation of the iliac fossa. The angular differences in the whole blade and gluteal surface primarily reflect a narrower iliac tuberosity set closer to the midline in extant apes, reflecting a decrease in erector spinae muscle mass associated with stiffening of the lumbar spine. Mediolateral breadth across the ventral dorsal iliac spines is only slightly greater in extant apes than in monkeys. These results demonstrate that spinal musculature and mobility have a more significant effect on pelvic morphology than does shoulder orientation, as had been previously hypothesized. Anat Rec, 300:810-827, 2017. © 2017 Wiley Periodicals, Inc.

Mesostructured MFI zeolite nanosheets are established to crystallize non-topotactically through a nanolayered silicate intermediate during hydrothermal synthesis. Solid-state 2D NMR analyses, with sensitivity enhanced by dynamic nuclear polarization (DNP), provide direct evidence of shared covalent 29 Si-O-29 Si bonds between intermediate nanolayered silicate moieties and the crystallizing MFI zeolite nanosheet framework.

Organic structure-directing agents (OSDAs) are exploited in the crystallization of microporous materials to tailor the physicochemical properties of the resulting zeolite for applications ranging from separations to catalysis. The rational design of these OSDAs often entails the identification of molecules with a geometry that is commensurate with the channels and cages of the target zeolite structure. Syntheses tend to employ only a single OSDA, but there are a few examples where two or more organics operate synergistically to yield a desired product. Using a combination of state-of-the-art characterization techniques and molecular modeling, we show that the coupling of N,N,N-trimethyl-1,1-adamantammonium and 1,2-hexanediol, each yielding distinct zeolites when used alone, results in the cooperative direction of a third structure, HOU-4, with the mordenite framework type (MOR). Rietveld refinement using synchrotron X-ray diffraction data reveals the spatial arrangement of the organics in the HOU-4 crystals, with amines located in the large channels and alcohols oriented in the side pockets lining the one-dimensional pores. These results are in excellent agreement with molecular dynamics calculations, which predict similar spatial distributions of organics with an energetically favorable packing density that agrees with experimental measurements of OSDA loading, as well as with solid-state two-dimensional 27Al{29Si}, 27Al{1H}, and 13C{1H} NMR correlation spectra, which establish the proximities and interactions of occluded OSDAs. A combination of high-resolution transmission electron microscopy and atomic force microscopy is used to quantify the size of the HOU-4 crystals, which exhibit a platelike morphology, and to index the crystal facets. Our findings reveal that the combined OSDAs work in tandem to produce ultrathin, nonfaulted HOU-4 crystals that exhibit improved catalytic activity for cumene cracking in comparison to mordenite crystals prepared via conventional syntheses. This novel demonstration of cooperativity highlights the potential possibilities for expanding the use of dual structure-directing agents in zeolite synthesis.

Advances in the research of intermolecular and surface interactions result from the development of new and improved measurement techniques and combinations of existing techniques. Here, we present a new miniature version of the surface forces apparatus-the μSFA-that has been designed for ease of use and multimodal capabilities with the retention of the capabilities of other SFA models including accurate measurements of the surface separation distance and physical characterization of dynamic and static physical forces (i.e., normal, shear, and friction) and interactions (e.g., van der Waals, electrostatic, hydrophobic, steric, and biospecific). The small physical size of the μSFA, compared to previous SFA models, makes it portable and suitable for integration into commercially available optical and fluorescence light microscopes, as demonstrated here. The large optical path entry and exit ports make it ideal for concurrent force measurements and spectroscopy studies. Examples of the use of the μSFA in combination with surface plasmon resonance (SPR) and Raman spectroscopy measurements are presented. Because of the short working distance constraints associated with Raman spectroscopy, an interferometric technique was developed and applied to calculate the intersurface separation distance based on Newton's rings. The introduction of the μSFA will mark a transition in SFA usage from primarily physical characterization to concurrent physical characterization with in situ chemical and biological characterization to study interfacial phenomena, including (but not limited to) molecular adsorption, fluid flow dynamics, the determination of surface species and morphology, and (bio)molecular binding kinetics.

As land use change drives global insect declines, the value of enhancing habitat in urban and suburban landscapes has become increasingly important for flower-visiting insects. In order to help identify best landscaping practices, we conducted plant surveys and insect bowl-trap surveys in 34 suburban yards for 21 months in Gainesville, FL, USA, which resulted in 274 paired days of plant and insect survey data. We assessed the impact of nearest greenspace size, distance to greenspace, yard area, plant richness, plant type, bloom abundance, bloom richness and bloom evenness on insect abundance and richness. Our samples include 34,972 insects captured, 485,827 blooms counted and 774 species of plants recorded. We found that bloom evenness had a modulating effect on bloom abundance—a more even sample of the same number of blooms would have a disproportionately greater positive impact on flower visitor richness, insect richness and insect abundance. Bloom abundance was also highly significant and positively associated with flower visitor abundance, but nearest greenspace size, distance to greenspace, plant type (native vs. non-native vs. Florida Friendly), and yard area were not found to be important factors. Plant richness was a highly significant factor, but its effect size was very small.

Climate change has had numerous ecological effects, including species range shifts and altered phenology. Altering flowering phenology often affects plant reproduction, but the mechanisms behind these changes are not well-understood. To investigate why altering flowering phenology affects plant reproduction, we manipulated flowering phenology of the spring herb Claytonia lanceolata (Portulacaceae) using two methods: in 2011-2013 by altering snow pack (snow-removal vs. control treatments), and in 2013 by inducing flowering in a greenhouse before placing plants in experimental outdoor arrays (early, control, and late treatments). We measured flowering phenology, pollinator visitation, plant reproduction (fruit and seed set), and pollen limitation. Flowering occurred approx. 10 days earlier in snow-removal than control plots during all years of snow manipulation. Pollinator visitation patterns and strength of pollen limitation varied with snow treatments, and among years. Plants in the snow removal treatment were more likely to experience frost damage, and frost-damaged plants suffered low reproduction despite lack of pollen limitation. Plants in the snow removal treatment that escaped frost damage had higher pollinator visitation rates and reproduction than controls. The results of the array experiment supported the results of the snow manipulations. Plants in the early and late treatments suffered very low reproduction due either to severe frost damage (early treatment) or low pollinator visitation (late treatment) relative to control plants. Thus, plants face tradeoffs with advanced flowering time. While early-flowering plants can reap the benefits of enhanced pollination services, they do so at the cost of increased susceptibility to frost damage that can overwhelm any benefit of flowering early. In contrast, delayed flowering results in dramatic reductions in plant reproduction through reduced pollination. Our results suggest that climate change may constrain the success of early-flowering plants not through plant-pollinator mismatch but through the direct impacts of extreme environmental conditions.

We compare local electronic structure at different atom types of a metallic semiconductor in bulk and nanocrystalline form. Multinuclear magic-angle-spinning nuclear magnetic resonance (MAS NMR) establishes that GaN synthesized as an intentionally doped bulk powder or as annealed nanocrystalline particles exhibits metallic behavior and a wide distribution of differing electronic environments in both forms. Bulk polycrystalline wurtzite GaN doped with 0.13% Ge as a shallow donor exhibits a temperature-independent distribution of $^{71}\mathrm{Ga}$ Knight shifts over the temperature range 123--473 K. Each Knight shift frequency in the inhomogeneously broadened spectrum is characterized by a $^{71}\mathrm{Ga}$ spin-lattice relaxation time ${T}_{1}$ that is in good agreement with the value predicted by the Knight-Korringa relation across the broad range of temperatures. The $^{14}\mathrm{N}$ spectrum shows a slightly smaller Knight shift distribution with spin-lattice relaxation time ${T}_{1}$ values at 295 K across the distribution also in good agreement with the Knight-Korringa relation. Similarly, annealed nanocrystalline wurtzite GaN (50--100 nm, and without Ge) exhibits a $^{71}\mathrm{Ga}$ Knight shift distribution and ${T}_{1}$ values (at 295 K) that follow the same Knight-Korringa behavior. Thus, both bulk and nanocrystalline forms of GaN are n type and well above the metal-insulator transition (MIT), the nanocrystals most likely as a result of incorporation of shallow donor oxygen atoms during synthesis. Carriers in both forms of samples exhibit the near-ideal characteristics of a degenerate Fermi gas of noninteracting spins. The observation of NMR signals from both atom types, Ga and N, allows for the direct spatial correlation of the local electronic structure at the two sites in the lattice, specifically the $s$-orbital character of the electronic wave function of conduction band electrons at the Fermi edge. The relative values of these carrier wave-function probabilities (nearly twice as great for the N atom as for the Ga) are in line with theoretical predictions. Analyses of $^{71}\mathrm{Ga}, ^{14}\mathrm{N}$, and $^{15}\mathrm{N}$ NMR results, including double-resonance 2D $^{15}\mathrm{N}{^{71}\mathrm{Ga}}$ measurements, reveal electronic disorder in the form of broad distributions of local metallic properties (Knight shifts) that are shown to be spatially correlated on a subnanometer scale.

There is significant interest in the development of methods to create hybrid materials that transform capabilities, in particular for Earth-abundant metal oxides, such as TiO2, to give improved or new properties relevant to a broad spectrum of applications. Here we introduce an approach we refer to as ‘molecular cross-linking’, whereby a hybrid molecular boron oxide material is formed from polyhedral boron-cluster precursors of the type [B12(OH)12]2–. This new approach is enabled by the inherent robustness of the boron-cluster molecular building block, which is compatible with the harsh thermal and oxidizing conditions that are necessary for the synthesis of many metal oxides. In this work, using a battery of experimental techniques and materials simulation, we show how this material can be interfaced successfully with TiO2 and other metal oxides to give boron-rich hybrid materials with intriguing photophysical and electrochemical properties.

In the version of this Article originally published, Liban M. A. Saleh was incorrectly listed as Liban A. M. Saleh due to a technical error. This has now been amended in all online versions of the Article.