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Utilizing a deep ultraviolet light assisted anneal and a “flat” Al13 hydroxo cluster precursor generates scalable, hydrophobic cotton textiles.

The short C–H(…)S contacts found in available structural data for both small molecules and larger biomolecular systems suggest that such contacts are an often overlooked yet important stabilizing interaction. Moreover, many of these short C–H(…)S contacts meet the definition of a hydrogen bonding interaction. Using available structural data from the Cambridge Structural Database (CSD), as well as selected examples from the literature in which important C–H(…)S contacts may have been overlooked, we highlight the generality of C–H(…)S hydrogen bonding as an important stabilizing interaction. To uncover and establish the generality of these interactions, we compare C–H(…)S contacts with other traditional hydrogen bond donors and acceptors as well as investigate how oxidation state, coordination number, and metal bonding affect the preferred geometry of interactions in the solid state. This work establishes that the C–H(…)S bond meets the definition of a hydrogen bond and serves as a guide to identify C–H(…)S hydrogen bonds in diverse systems.

Background Obesity is a barrier to kidney transplantation for patients with kidney failure. Consequently, bariatric surgery is often considered as a bridge to transplantation, even though its risks and benefits are poorly characterised in the dialysis population. Methods Systematic searches of observational studies indexed in Embase, MEDLINE and CENTRAL till April 2020 were performed to identify relevant studies. Risk of bias was assessed by the Newcastle Ottawa Scale and quality of evidence was summarised in accordance with GRADE methodology. Random effects meta-analyses were performed to obtain summary odds ratios for postoperative outcomes. Results Four cohort studies involving 4196 chronic dialysis and 732,204 non-dialysis patients undergoing bariatric surgery were included. Sleeve gastrectomy (61%), and Roux-en-Y gastric bypass (29%) were the most common procedures performed. Absolute rates of adverse events were low, but the odds of postoperative mortality (0.4–0.5% vs. 0.1%; odds ratio [OR] 4.7, 95%CI 2.2–9.9), and myocardial infarction (0.0–0.5% vs. 0.1%, OR 3.4, 95% CI 2.0–5.9) were higher in dialysis compared to non-dialysis patients. Patients on dialysis also had more than 2-fold increased odds of returning to theatre and having a readmission. Rates of kidney transplant wait-listing among dialysis patients was 59%, with 28% of all patients eventually receiving a kidney transplant. Conclusion Patients receiving chronic dialysis have substantially increased odds of postoperative mortality and myocardial infarction following bariatric surgery compared with patient who do not have kidney failure. It is uncertain whether bariatric surgery improves the likelihood of kidney transplantation, with mid- to long-term outcomes being poorly described.

Cyclophanes are an admirable class of macrocyclic and cage compounds that often display unusual properties due to their high strain and unusual conformations. However, the exploration of new, complex cyclophanes has been encumbered by syntheses that can be low yielding, require harsh reaction conditions, and arduous purification steps. Herein, we discuss our work using metalloid-directed self-assembly and dynamic covalent chemistry to form cryptands. These were then subjected to mild conditions to produce discrete disulfide, thioether and hydrocarbon macrocycles in high yields. ‘Design of Experiments’ was then used to selectively synthesize targeted macrocycles from complex mixtures.1 Introduction2 Cryptands to Cyclophanes3 Functionalizable Macrocycles4 ‘Design of Experiments’ Targeted Synthesis5 Conclusions and Outlook

Tagging studies are often used to measure survival and growth in wild populations. However, issues such as low returns of tagged animals, tag loss, and handling mortality can affect the precision and accuracy of demographic estimates if not accounted for. We conducted a mark-recapture study to measure the survival and growth of juvenile and adult wavy turban snails Megastraea undosa. Our study highlights several methodological advances, including a method for estimating a single growth function by analyzing the joint changes in length and weight of tagged animals; a simple method for estimating rates of tag loss when some animals are double tagged; and a way to estimate handling mortality by comparing encounter histories of animals immediately after tagging and after several weeks in the field. Tag loss was moderate (≈15% over a 100 d period) and handling mortality was substantial during the fall (≈55%), but negligible during the spring. If we did not account for tag loss and handling mortality, our estimate of survival would have been severely underestimated (≈46% lower over a 100 d period). After accounting for such effects, our study revealed that survival probably increased sharply with body size, but survival did not differ among seasons. These snails are slow-growing, mature after approximately 6 yr, and can routinely grow to >10 yr old. There is an emerging fishery for this species, and because our results suggest that the oldest snails have a very high reproductive value, measures that protect these large individuals are likely to be beneficial for the resilience of these populations.

The use of a novel inorganic nanoscale cluster (Al[(μ-OH)2Co(NH3)4]3(NO3)6) was investigated for its utility as a precursor for AlCoOx films. Mixed-metal aluminum and cobalt oxide thin films were solution deposited from the novel cluster solution via the spin-coating method on Si (100) and quartz substrates. The films were annealed at increasing temperatures up to 800 °C, and characterization of these films via TEM and XRD confirms binary Co3O4 crystalline phase present in an amorphous Al2O3 network. Films are relatively smooth (Rrms < 4 nm), polycrystalline, and demonstrate a tunable optical response dominated by Co3O4 with two electronic transitions.

Inclusion of a second nitrogen atom in the aromatic core of phosphorus-nitrogen (PN) heterocycles results in unexpected tautomerization to a nonaromatic form. This tautomerization, initially observed in the solid state through X-ray crystallography, is also explained by computational analysis. We prepared an electron deficient analogue (2 e) with a fluorine on the pyridine ring and showed that the weakly basic pyridine resisted tautomerization, providing key insights to why the transformation occurs. To study the difference in solution vs. solid-state heterocycles, alkylated analogues that lock in the quinoidal tautomer were synthesized and their different

Examining vital rates helps clarify how environmental characteristics, biological resources and human activities affect population growth. Carapace lengths were gathered for 241 Kemp’s ridley Lepidochelys kempii sea turtles that were marked and recaptured (n = 23) between 2011 and 2019 at a foraging location in northwest Florida, USA. There was a strong correlation between length, width and weight of captured turtles. Mean ± SD size of all captured turtles was 36.6 ± 7.6 cm. Mean recapture interval was 499 ± 475.4 d. Straight-line carapace lengths at initial capture ranged from 20.6 to 53.3 cm. Growth rates from 0.21 to 12.44 cm yr-1 (mean 3.15 ± 2.64 cm) were documented and were greatest for turtles in the 20.0-29.9 cm size class. Growth rates from northwest Florida were slower than those reported from other sites in the Gulf of Mexico. These results indicate that Kemp’s ridleys recruit from oceanic habitat into coastal bays in northwest Florida, where they remain until they reach adulthood. However, some adult-sized turtles may continue to use the nearshore habitat. A gradient in growth rates in the Gulf of Mexico may occur from faster growth in the south to slower growth in the north. Fine-scale variations in resources and environmental conditions may drive regional differences in growth rates, and research on what drives these differences is needed.

Hydrogen sulfide (H2S) is an important biological signaling molecule and one of three established gasotransmitters. Upon oxidation, H2S can form reactive sulfur species (RSS) that play a central role in protein persulfidation. Here we report that a molybdenum tetrasulfide can react directly with hydrosulfide to form polysulfides and oxidize the Mo center. Specifically, [NBu4][TpMoS(S4)] reacts with 2 equiv of [NBu4][SH] to form [NBu4][TpMoS3]. Trapping experiments with BnBr confirm the formation of polysulfides, as evidenced by the direct trapping of Bn2S2. This work demonstrates new reaction pathways for H2S oxidation and RSS generation from metal-bound polysulfides that will increase our understanding of the potential roles that metals play in signaling processes.

The temperament of animals can vary among individuals and among populations, but it is often unclear whether spatial variation in temperament is the result of acclimation to local environmental conditions or genetic adaptation to spatial differences in natural selection. This study tested whether populations of a marine fish that experience different levels of mortality and fishing exhibited local adaptation in behaviors related to predator avoidance and evasion. First, we measured variation in reactivity to perceived risk in wild populations of black surfperch (Embiotoca jacksoni). We compared flight initiation distances (FID) between populations with significantly different mortality rates. After finding that FID values were substantially lower in the low-risk locations, we tested for local adaptation by rearing lab-born offspring from both high- and low-risk populations in a common environment before measuring their behavior. Lab-reared offspring from high- and low-risk populations exhibited significant differences in several behaviors related to reactivity. Between 23 and 43% of the total variation in behaviors we measured could be attributed to source population. These results thus suggest that a substantial amount of spatial variation in behaviors related to predator evasion may represent local adaptation. In addition, behaviors we measured had an average, broad-sense heritability of 0.24, suggesting that the behavioral tendencies of these populations have some capacity to evolve further in response to any changes in selection.

Supramolecular chemistry provides an effective strategy for the molecular recognition of diverse molecules. Significant efforts to design synthetic hosts have enabled the successful binding of many types of guests; however, less is known about how host-guest environments influence binding. Herein, we present a comprehensive study in which we measure the host-guest binding of a bis(arylethynyl phenylurea) host with a chloride guest in eight solvents spanning

The Haley and Johnson labs at the University of Oregon have been collaborating since 2006, combining skillsets in synthetic organic, physical organic, and supramolecular chemistries. This joint project has produced many examples of host molecules that bind anionic guests and give chemical, photophysical, and/or electrical responses. Many of these receptors utilize two-armed arylethynyl backbones that have a variety of hydrogen- or halogen-bonding functional groups appended. However, in attempts to produce a bisamide-containing host using a peptide-coupling protocol with P(OPh)3 present, we isolated something unexpected – a heterocycle containing neighboring P and N atoms. This ‘failed’ reaction turned into a surprisingly robust synthesis of phosphaquinolinones, an unusual class of PN-heterocycles. This Account article tells the rollercoaster story of these heterocycles in our lab. It will highlight our key works to this field, including a suite of fundamental studies of both the original PN-naphthalene moiety, as well as a variety of structural modifications to the arene backbone. It will also discuss the major step forward the project took when we developed a phosphaquinolinone-containing receptor molecule capable of binding HSO4 – selectively, reversibly, and with recyclability. With these findings, the project has gone from hospice care to making a full, robust recovery.1 Introduction2 Initial Discovery3 Setbacks Breathe New Life4 A New Dynamic Duo Develops Dozens of Derivatives5 Physicochemical Characterization5.1 Fluorescence5.2 Molecular Structures5.3 Solution Dimerization Studies6 Applying What We Have Learned6.1 Development of Supramolecular Host6.2 Use of PN Moiety as an Impressive Fluorophore7 Conclusions and Outlook

Microplastics are now found throughout the world’s oceans, and although many organisms ingest microplastics, less is known about how plastics in seawater may affect key processes such as feeding rate, growth, and survival. We used a series of laboratory experiments to test whether microplastics in seawater affected the feeding rates of larvae of the California Grunion, Leuresthes tenuis. In addition, we tested whether trophic transfer of microplastics from zooplankton to larval fish can occur and affect growth and survival of fish. We measured feeding rates of grunion larvae at various concentrations of 75–90 µm and 125–250 µm polyethylene microplastics and under both still water and turbulent conditions. In these experiments, exposure to microplastics had modest effects on feeding rates, though responses may be somewhat complex. Low concentrations of microplastics increased feeding rates compared to the control, but at higher concentrations, feeding rates were indistinguishable from those in the control group, though effects were small compared to natural variation in feeding rates among individual fish. Experiments to test for trophic transfer of microplastics revealed that grunion larvae that were fed brine shrimp exposed to high concentrations of microplastics had lower growth rates and elevated mortality rates. Overall, our results suggest that the direct effects of microplastics on feeding rates of California Grunion during the early larval phase are minor, while the trophic transfer of microplastics from zooplankton to larval fish may have significant effects on their growth and survival. Supplementary Information The online version contains supplementary material available at 10.1007/s00227-021-04010-x.

Cyclophanes are a venerable class of macrocyclic and cage compounds that often contain unusual conformations, high strain, and unusual properties. However, synthesis of complex, functional derivatives remains difficult due to low functional group tolerance, high dilution, extreme reaction conditions, and sometimes low yields using traditional stepwise synthetic methods. "Design of experiments" (DOE) is a method employed for the optimization of reaction conditions, and we showcase this approach to generate a dramatic increase in the yield of specific targets from two different self-assembling systems. These examples demonstrate that DOE provides an additional tool in tuning self-assembling, dynamic covalent systems.

We highlight a convenient synthesis to selectively deuterate an aryl C–H hydrogen bond donor in an arylethynyl bisurea supramolecular anion receptor and use the Perrin method of competitive titrations to study the deuterium equilibrium isotope effects (DEIE) of anion binding for HS−, Cl−, and Br−. This work highlights the utility and also challenges in using this method to determine EIE with highly reactive and/or weakly binding anions.

We report the synthesis and characterization of P-phenyl modified phosphorus- and nitrogen-containing phosphaquinolinone heterocycles. The change from -OPh to -Ph results in a marked increase in the quantum yield of the scaffold as well as a moderate red-shifting of the emission. While calculations suggest that π to π* transitions are dominant, intramolecular charge transfer (ICT) also contributes in the excited state. Solution- and solid-state studies of the dimerization of this new congener to the P-phenoxy variant are also reported, showing retention of the dimerization behavior in this scaffold.

A straightforward method for the preparation of non-K region fused phosphorus- and nitrogen-containing (PN)-heterocyclic pyrenes has been accomplished. Their structural, photophysical, and electrochemical properties have been fully investigated. The described compounds exhibit intriguing redox properties and show strong photoluminescence with a wide range of tunable emission colors, with λem ranging from blue at 459 nm to red at 622 nm in CH2Cl2 solution.

It is well known that demographic rates such as growth and mortality may vary among populations, but the degree of variation in demography is often unknown, especially when considering multiple populations at large spatial scales (e.g., across hundreds of kilometers). Likewise, of the many factors that may affect demography, it is often unknown which are the major factors responsible for spatial variation in demographic rates. In this study, we estimated rates of growth and examined age distributions within nine populations of black perch (Embiotoca jacksoni) distributed across ~350 km of coastline. We tested whether spatial variation in demography was associated with several explanatory variables including population density, predator density, food availability, and fishing activity. Our study revealed a substantial amount of spatial variation in demographic rates. Among-population variation in growth accounted for 55% of the total variation, and the coefficient of variation for mean age within a population was 27%, suggesting substantial variation in mortality. Spatial variation in growth was most sensitive to variation in food availability and mean age was lowest at locations with high levels of spearfishing activity. Although the fishery for black perch is not a major one, fishing mortality rates may be very high in some areas. Overall, our results shed light on the ecological forces that shape demographic variation of this species, and suggest that fishing mortality may have a major influence on the dynamics of perch populations.

Three organotin carboxylate species stabilized by the same ligands, but varying in size and structure, were studied to elucidate the effects of the structure on reactivity in the context of direct-...

Thin films made from transparent conducting oxide (TCO) nanocrystals are promising alternatives to traditional vacuum-sputtered films. However, the material properties of nanocrystal-derived thin f...

We describe two novel hybrid receptors combining a phosphorus-/nitrogen-containing (PN) phosphonamidate heterocycle with urea recognition units in an arylethynyl backbone. Structural, spectroscopic and computational studies reveal that the origin of superior binding for hydrogen sulfate (HSO4- ) anion is correlated with the formation of strong hetero-complementary hydrogen bonds with the phosphonamidate motif. We further demonstrate that the hybrid host system is capable of capturing/transporting the HSO4- anion from an aqueous, biphasic system.

Variation in water temperature can have important effects on the energetics underlying metabolism, growth, and reproduction of many organisms. In order to anticipate how a species' allocation of energy may change in a warming ocean, we need to know the degree to which processes such as metabolic rate change with temperature (i.e., the thermal sensitivity of metabolism, Q10 ). In the context of long-term climate change, it will also be helpful to know whether local populations that experience different thermal regimes exhibit differences in thermal sensitivity. If so, it would indicate that thermal sensitivities of populations may adjust via acclimation or adaptation. We measured metabolic rates of Woolly Sculpin collected from two distant populations (Santa Cruz (SC) and Los Angeles (LA) counties, California, USA) and housed in a common environment. Using respirometry, we estimated resting mass-specific oxygen consumption ( MO2) and calculated metabolic rates (MR) at temperatures of 12 °C, 16 °C, and 20 °C for 59 fish. The Q10 value across this range of temperatures was 2.92. Populations did not differ with respect to overall MO2, nor did they vary in their degree of thermal sensitivity. However, the LA population had greater variation in MO2 among individuals when compared to the SC population. Larger variation in overall MO2 among individuals within specific populations may reflect greater genetic diversity , and this may buffer some populations against the effect of future increases in water temperature.

A supramolecular approach to catalyzing the Ritter reaction by utilizing enhanced anion-binding affinity in the presence of alkali metal cations was developed with ditopic hydrogen-bonded amide macrocycles. With prebound cations in the macrocycle, particularly Li(+) ion, their metal complexes exhibit greatly enhanced catalytic activities. The catalysis is switchable by removal or addition of the bound cation. The method described in this work may be generalized for use in other anion-triggered organic reactions involving heteroditopic receptors capable of ion pairing.

We have rationally designed and synthesized a library of phosphaquinolinone derivatives containing various electron-donating and -withdrawing groups on two positions of the scaffold. Distinct trends are observed between the substituents on R1 and R2 with both the photophysical properties of the molecules and their dimerization strengths. With withdrawing groups upon the scaffold, dimerization constants surpass 500 M−1 in H2O-saturated CDCl3. Computational studies on the dimeric structures corroborate the experimental findings.

Metal-oxide thin films are used extensively in electronic and energy applications. Solution processing offers a potentially scalable and inexpensive deposition method to expand the applications of metal-oxide films and to complement vacuum-deposition techniques. Among precursors for solution deposition, metal nitrates stand out for their ability to form high-quality metal-oxide thin films. This review focuses on unique aspects of metal-nitrate chemistry that have been exploited to advance the development of solution-processed thin films. We discuss the solid-state bulk, solution, and thin-film chemical reactions involving metal nitrates and illustrate how the resulting metal-oxide thin-film properties depend on the entire reaction pathway. To conclude, we offer perspective as to how understanding the chemistry of film formation from metal-nitrate precursors is useful for addressing the primary drivers for industrial manufacturing of solution-processed metal-oxide thin films.

We expand on our approach combining dynamic covalent self-assembly and sulfur extrusion to synthesize new biphenyl-linked disulfide and thioether macrocycles, which are variants of the venerable phenyl-bridged paracyclophanes. We then advance this strategy further to use two different thiols in tandem to provide new, elusive unsymmetrical disulfides which can also be trapped as unsymmetrical thioether "nanohoops". This approach enables substantial amplification of two unsymmetrical trimers out of a library of at least 21 possible macrocycles of various sizes.

A 3,5-bis((2-iodophenyl)ethynyl)pyridinium scaffold was synthesized which introduces the use of methanesulfonyl withdrawing groups to polarize iodine halogen bonding units for anion binding. We investigate the capability of this receptor to bind halides in polar media, while further probing the structure-property relationship of this well-polarized yet under-explored halogen bonding system.

Ocean acidification can reduce the growth and survival of marine species during their larval stages. However, if populations have the genetic capacity to adapt and increase their tolerance of low pH and high pCO2 levels, this may offset the harmful effects of ocean acidification. By combining controlled breeding experiments with laboratory manipulations of seawater chemistry, we evaluated genetic variation in tolerance of ocean acidification conditions for a nearshore marine fish, the California Grunion (Leuresthes tenuis). Our results indicated that acidification conditions increased overall mortality rates of grunion larvae, but did not have a significant effect on growth. Groups of larvae varied widely with respect to mortality and growth rates in both ambient and acidified conditions. We demonstrate that the potential to evolve in response to ocean acidification is best described by considering additive genetic variation in fitness‐related traits under both ambient and acidified conditions and by evaluating the genetic correlation between traits expressed in these environments. We used a multivariate animal model to estimate additive genetic (co)variance in larval growth and mortality rates under both ambient and acidified conditions (low pH/high pCO2). Our results suggest appreciable genetic variation in larval mortality rates (h 2 Ambient = 0.120; h 2 Acidified = 0.183; rG = 0.460), but less genetic variation in growth (h 2 Ambient = 0.092; h 2 Acidified = 0.101; rG = 0.135). Maternal effects on larval mortality rates accounted for 26%–36% of the variation in phenotypes, but maternal effects accounted for only 8% of the variation in growth. Collectively, our estimates of genetic variation and covariation suggest that populations of California Grunion have the capacity to adapt relatively quickly to long‐term changes in ocean chemistry.

Multilevel selection on offspring size occurs when offspring fitness depends on both absolute size (hard selection) and size relative to neighbors (soft selection). We examined multilevel selection on egg size at two biological scales-within clutches and among clutches from different females-using an external fertilizing tube worm. We exposed clutches of eggs to two sperm environments (limiting and saturating) and measured their fertilization success. We then modeled environmental (sperm-dependent) differences in hard and soft selection on individual eggs as well as selection on clutch-level traits (means and variances). Hard and soft selection differed in strength and form depending on sperm availability-hard selection was consistently stabilizing; soft selection was directional and favored eggs relatively larger (sperm limitation) or smaller (sperm saturation) than the clutch mean. At the clutch level, selection on mean egg size was largely concave, while selection on within-clutch variance was weak but generally negative-although some correlational selection occurred between these two traits. Importantly, we found that the optimal clutch mean egg size differed for mothers and offspring, suggesting some antagonism between the levels of selection. We thus identify several pathways that may maintain offspring size variation: environmentally (sperm-) dependent soft selection, antagonistic multilevel selection, and correlational selection on clutch means and variances. Multilevel approaches are powerful but seldom-used tools for studies of offspring size, and we encourage their future use.

We have prepared and characterized hydrosulfide-selective ChemFET devices based on a nitrile butadiene rubber membrane containing tetraoctylammonium nitrate as a chemical recognition element that is applied to commercially available field-effect transistors. The sensors have fast (120 s) reversible responses, selectivity over other biologically relevant thiol-containing species, detection limits of 8 mM, and a detection range from approximately 5 to 500 mM. Sensitivities are shown to be 53 mV per decade at pH 8. Use of this compact, benchtop sensor platform requires little training - only the ability to measure DC voltage, which can be accomplished with a conventional multimeter or a simple analog data acquisition device paired with a personal computer. To the best of our knowledge, this report describes the first example of direct potentiometric measurement of the hydrosulfide ion in water.

Spinel iron oxide nanocrystals (NCs) have been reported to have atomic-level core and surface structural features that differ from those of the bulk material. Recent advances in a continuous growth synthesis of metal oxide NCs make it possible to prepare a series of NCs with subnanometer control of size with diameters below 10 nm that are well-suited for investigating size-dependent structure and reactivity. Here, we study the evolution of size-dependent structure in spinel iron oxide and determine how nanoscale structure influences the growth of NCs. We synthesized spinel iron oxide NCs via a continuous growth method that permits layer-by-layer control of size in order to monitor nanoscale structure over 16 core sizes between 3 and 10 nm. X-ray total scattering data were collected and analyzed with pair distribution function (PDF) analysis in order to refine quantitative structural features including cation occupancies that could be used to detect changes both in the oxidation state and the presence of tetrahedrally coordinated cation vacancies in the NCs. We find that the average iron oxidation state increases as core diameters decrease from 8 down to 3 nm. The trend in iron oxidation state can be explained by the oxidation of surface layers in the NCs. For samples exposed to air for several weeks, oxidation appears to cease when a volume equivalent to that of an ∼1.3 nm shell is converted to the more oxidized maghemite. The number of tetrahedrally coordinated cation vacancies also increases as the NC core size decreases. The correlation between the number of these vacancies and the faster growth for smaller NCs suggests that these reactive vacancies may be responsible for the rapid growth observed for nanocrystals with diameters smaller than 8 nm.

Supramolecular anion receptors can be used to study the molecular recognition properties of the reactive yet biologically-critical hydrochalcogenide anions (HCh(–)). Achieving selectivity for HCh(–) over the halides is challenging but is necessary for not only developing future supramolecular probes for HCh(–) binding and detection, but also for understanding the fundamental properties that govern these binding and recognition events. Here we demonstrate that linear free energy relationships (LFERs)—including Hammett and Swain-Lupton plots—reveal a clear difference in sensitivity to the polarity of an aryl C–H hydrogen bond (HB) donor for HS(–) over other HCh(–) and halides. Analysis using electrostatic potential maps highlights that this difference in sensitivity results from a preference of the aryl C–H HB donor for HS(–) in this host scaffold. From this study, we demonstrate that LFERs are a powerful tool to gain interpretative insight into motif design for future anion-selective supramolecular receptors and highlight the importance of C–H HB donors for HS(–) recognition. From our results, we suggest that aryl C–H HB donors should be investigated in the next generation of HS(–) selective receptors based on the enhanced HS(–) selectivity over other competing anions in this system.

Dynamic Covalent Chemistry (DCC) - combining the robustness of covalent bonds with the self-correcting nature of supramolecular chemistry - facilitates the modular synthesis of complex molecular assemblies in high yields. Although numerous reactions form covalent bonds, only a small set of chemical transformations affect covalent bond formation reversibly under suitable conditions for DCC. Further progress in this area still requires the identification of dynamic motifs and greater insights into their reversibility. We have fruitfully employed DCC of both thiolate coordination to main-group elements and disulfide formation for the facile self-assembly of: (1) metal/metalloid-thiolate assemblies, and (2) purely organic cyclic and caged disulfides, thioethers, and even hydrocarbons, many of which have remained elusive by traditional stepwise synthesis yet form readily through our methods. In this Minireview, we highlight the approaches to prepare these unusual compounds and the factors inducing structural transformations or favoring the formation of certain products over others, given a set of external stimuli or reaction conditions.

Thin films formed by the condensation of metal oxo–hydroxo clusters offer a promising approach to ultrahigh-resolution patterning including next-generation photolithography using extreme ultraviolet (EUV) radiation and electron-beam lithography. In this work, we elucidate the thermal and radiative mechanisms that drive the chemical transformations in these materials and therefore control the patterning performance. Beginning from aqueous hafnium clusters, peroxide and sulfate additions serve to modify the clusters and, upon spin coating to form a thin film, provide the chemical contrast necessary to create resist. The coordination and functionality of peroxide and sulfate in hafnium-based metal oxo–hydroxo clusters were monitored at various stages of the patterning process which provided insight into the chemical and structural evolution of the material. Peroxide serves as the radiation sensitive species while sulfate enhances solubility and controls the concentration of hydroxide in the films. Peroxide a...

As climate continues to change, many marine species will experience both an increase in average temperature and more extreme diel and seasonal fluctuations. Understanding how these variations in ocean temperature affect processes such as metabolism and energy consumption is important for many species, and may be particularly important for sedentary species that cannot make large-scale movements in response to changes in environmental conditions. We examined how metabolic rates and energetic demands responded to temperature in a temperate reef fish, the bluebanded goby ( Lythrypnus dalli ). Using respirometry, we estimated resting oxygen consumption (VO2) for 42 L. dalli individuals of varying sizes and calculated metabolic rates (MR) at three different temperatures (13 °C, 16 °C, and 20 °C). As predicted, VO2 and MR increased significantly with temperature and mass, but the rate of temperature-dependent increase in metabolism indicated a very high degree of thermal sensitivity for L. dalli (Q10 value for VO2 was 5.21 across the range of experimental temperatures). The mass-scaling exponent (b ) was estimated to be 0.95 and aligned closely with other benthic species. Our results suggest that changes in temperature – especially those that occur over weeks and seasons – likely play a significant role in the ecology of these gobies. Long-term increases in seawater temperature will either necessitate an increase in foraging and consumption, or drive costly trade-offs between metabolism and processes such as growth and reproduction.