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Writing is an essential part of a successful career in science. As such, many undergraduate science courses have begun to implement writing assignments that reflect "real-world" applications and focus on a critical analysis of current literature; these assignments are often in the form of a review or a research proposal. The semester-long project described herein is a unique marriage of these two ideas: students first select a topic and conduct a literature review, and then choose an area of that same topic to investigate further in a peer-reviewed grant proposal. A modified version of this project, which incorporates peer-reviewed oral presentations, is also discussed. This project is designed for an upper-level undergraduate course, typically having 15-20 students, and the approach (or parts of the approach) has been successfully incorporated in an advanced organic chemistry course, a biochemistry capstone course, and courses in endocrinology, as well as ecophysiology.

Abstract Hydrogen bonding, bond polarity, and charges in protein molecules play critical roles in the stabilization of protein structures, as well as affecting their functions such as enzymatic catalysis, electron transfer, and ligand binding. These effects can potentially be measured in Coulomb potentials using cryogenic electron microscopy (cryo-EM). We here present charges and bond properties of hydrogen in a sub-1.2 Å resolution structure of a protein complex, apoferritin, by single-particle cryo-EM. A weighted difference map reveals positive densities for most hydrogen atoms in the core region of the complex, while negative densities around acidic amino-acid side chains are likely related to negative charges. The former positive densities identify the amino- and oxo-termini of asparagine and glutamine side chains. The latter observations were verified by spatial-resolution selection and a dose-dependent frame series. The average position of the hydrogen densities depends on the parent bonded-atom type, and this is validated by the estimated level of the standard uncertainties in the bond lengths.

The addition of nanoparticles has been reported to be an effective strategy for enhancing seed germination, but the underlying mechanisms whereby this occurs are unclear. In the present study, we added silica nanoparticles (SiNPs) to an aqueous growth medium in which tomato seeds were germinated. We examined the effects of SiNPs on growth and possible mechanisms of action. SiNPs had a diameter of 10–17 nm and 110–120 nm. SiNPs shortened the mean germination time from 5.24 ± 0.29 days to 4.64 ± 0.29 days. Seedling vigor, measured by criteria including length and weight, was also improved compared to the control condition. The presence of SiNPs in the seedlings was assessed using an X-ray fluorescence spectrometer. The nanoparticles may have promoted germination by enhancing water imbibition by the seeds or altering the external microenvironment. Scanning electron microscopy revealed changes in the seed coat during germination, many of which were only observed in the presence of nanoparticles. Soil bacteria affect germination; specifically, Bacillus sp. may promote germination. The number of Bacillus sp. changed in the germination medium with SiNPs compared to the control. This suggested that these bacteria could interact with SiNPs to promote germination.

Microdevices have been actively implemented in chemical processes, such as in mixing and reactions. However, microseparation devices, excluding extraction devices, are still under development. In distillation, the use of microdevices has been expected to improve separation performance, as their large specific surface area enables a rapid vapor–liquid equilibrium and for large temperature gradients to be easily realized. In this study, improvements in throughput and product purities in microdistillation devices were achieved for ethyl acetate–toluene distillation. At low feedstock flow rates, ethyl acetate was successfully purified to 99.5 wt%. Although the performance decreased with increasing feedstock flow rate, by increasing the channel length, this performance decrease was suppressed even at high flow rates. The thickness of the channel was also important, and the highest performance was observed at the lowest thickness of 0.5 mm. A performance evaluation using the HETP showed that the efficiency was seven times higher than that of conventional packed column distillators.

Gel growth induced by contact of polymer solutions with crosslinker solutions yields an emerging class of anisotropic materials with many potential applications. Here, we report the case of a study on the dynamics in forming anisotropic gels using this approach with an enzyme as a trigger of gelation and gelatin as the polymer. Unlike the previously studied cases of gelation, the isotropic gelation was followed by gel polymer orientation after a lag time. The isotropic gelation dynamics did not depend on concentrations of the polymer turning into gel and of the enzyme inducing gelation, whereas, for the anisotropic gelation, the square of the gel thickness was a linear function of the elapsed time, and the slope increased with polymer concentration. The gelation dynamics of the present system was explained by a combination of diffusion-limited gelation followed by free-energy-limited orientation of polymer molecules.

A biologically-inspired method to access 2-formylpyrrole structures is reported using an Achmatowicz reaction and condensation sequence. This robust synthetic process has been used to access a variety of 2-formylpyrrole structures related to naturally isolated and bioactive compounds. Several families of pyrrole-based natural products have recently been isolated, and these structurally related compounds have been shown to demonstrate interesting bioactive properties. Synthesis targets include the natural products sinopyrine C and pyrrolezanthine.

In this paper, we report the synthesis, microstructure and some piezoelectric properties of (Bi0.5Na0.5)1−xBaxTi1−x(Fe0.5Nb0.5)xO3 (abbreviated as BNBTFN, x = 0.000, 0.025, 0.050, 0.065, 0.075 and 0.100). The BNBTFN powders were prepared by solid-state reaction method, and their green compacts were sintered at 1150 °C for 2 h. XRD study confirmed that there was no second phase for all the compositions. Morphotropic phase boundary (MPB) of rhombohedral and tetragonal phases existed at x ∼ 0.050, which was close to that of the BNT-BT system. With increasing x, diffuse phase transition, decrease in transition temperature (Tm), and increase in dielectric maximum at the transition temperature (εrm) were observed. The A and B sites simultaneous substitutions, i.e. Ba2+ into (Bi0.5Na0.5)2+ and (Fe0.5Nb0.5)4+ into Ti4+, have some positive effects on piezoelectric properties for x ⩽ 0.05 of (Bi0.5Na0.5)1−xBaxTi1−x(Fe0.5Nb0.5)xO3, despite the lowering of depolarization temperature. Keywords: Lead-free piezoelectric ceramics, Dielectric properties, BNT-BT, Solid-state reaction, Morphotropic phase boundary (MPB)

Graphene is a promising material for developing high-speed and wide-wavelength-range photodetectors. However, since the polarities of the photovoltages at each graphene/electrode interface of two electrodes on both ends of the graphene are opposite, they are canceled out under macroscopic light irradiation to the photodetectors. In this study, we propose two graphene-based photodetectors with different asymmetric device structures that can suppress the cancelation of photovoltage at the interfaces of two electrodes. One of the photodetectors has a local shadow mask, where only one side of the graphene/electrode interface is shadowed by a metal mask. The other has electrodes of different shapes, where the contact area of graphene/electrode interface is different by using a comb-shaped electrode. We measured the position dependence of light detection by scanning the focused light around the graphene photodetectors, and asymmetric photovoltage mapping can be obtained owing to the asymmetric structure of the two photodetectors. Furthermore, we also demonstrated macroscopic light detection by the photodetectors in the visible, near-infrared, and mid-infrared regions by suppressing the photovoltage cancelation. These graphene-based photodetectors with asymmetric structures are suitable for use as macroscopic photodetectors in the wide band of visible, near-infrared and mid-infrared regions.

We investigated the gelation of a hydrophilic polymer with metal-coordination units (HPMC) and metal ions (PdII or AuIII). Gelation proceeded by addition of an HPMC solution in N-methyl-2-pyrrolidone (NMP) to a metal ion aqueous solution. An increase in the composition ratio of the metal-coordination units from 10 mol% to 34 mol% (HPMC-34) increased the cross-linking rate with AuIII. Cross-linking immediately occurred after dropwise addition of an HPMC-34 solution to the AuIII solution, generating the separation between the phases of HPMC-34 and AuIII. The cross-linking of AuIII proceeded from the surface to the inside of the HPMC-34 droplets, affording spherical gels. In contrast, a decrease in the ratio of metal-coordination units from 10 mol% to 4 mol% (HPMC-4) decreased the PdII cross-linking rate. The cross-linking occurred gradually and the gels extended to the bottom of the vessel, forming fibrous gels. On the basis of the mechanism for the formation of gels with different morphologies, the gelation of HPMC-34 and AuIII provided nanosheets via gelation at the interface between the AuIII solution and the HPMC-34 solution. The gelation of HPMC-4 and PdII afforded nanofibers by a facile method, i.e., dropwise addition of the HPMC-4 solution to the PdII solution. These results demonstrated that changing the composition ratio of the metal-coordination units in HPMC can control the gelation behavior, resulting in different types of nanomaterials.

This study investigated the impact of a one-sided radial-landed cross-sectional design of a heat-treated nickel-titanium rotary instrument (JIZAI, MANI, Japan; JZ) on torque/force generation and canal-shaping ability, using an experimental non-landed instrument (non-landed JZ) for comparison. Both instruments had tip sizes of 25 and 0.04 or 0.06 taper and were similar in metallurgy and geometry, except for the presence/absence of a radial land. Twenty J-shaped simulated resin canals were instrumented in a two-instrument single-length sequence using an automated root canal instrumentation device with a torque/force analyzing unit. Pre- and post-instrumentation images of the resin canals were analyzed for canal-centering ability at 0–3 mm from the apex. The mean centering ratio was not significantly different between JZ and non-landed JZ (p > 0.05). In the 2nd instrumentation, JZ showed a significantly smaller torque compared with the non-landed JZ (p < 0.05). Regardless of instrumentation sequence, JZ showed a significantly smaller maximum upward force, representing screw-in force (p < 0.05), and a larger maximum downward force (p < 0.05) than the non-landed JZ. JZ generated smaller screw-in forces and had similar canal-centering ability compared with the non-landed JZ.

The steady rise in atmospheric long-lived greenhouse gas concentrations is the main driver of contemporary climate change. The Mauna Loa CO2 time series (1, 2), started by C. D. Keeling in 1958 and maintained today by the Scripps Institution of Oceanography and the Earth System Research Laboratory (ESRL) of NOAA, is iconic evidence of the effect of human-caused fossil fuel and land-use change emissions on the atmospheric increase of CO2. The continuity of such records depends critically on having stable funding, which is challenging to maintain in the context of 3- to 4-year research grant funding cycles (3), and is currently threatened by the financial crisis.The ESRL Global Monitoring Division maintains a network of about 100 surface and aircraft sites worldwide at which whole air samples are collected approximately every week for analysis of CO2, CH4, CO, halocarbons, and many other chemical species (4). This is complemented by high-frequency measurements at the Mauna Loa, Barrow, American Samoa, and South Pole observatories, and about 10 North American tall towers. The success of the NOAA program has inspired similar efforts in Europe (5), China (6), India (7), and Brazil (8), with the United Nations World Meteorological Organization providing guidance and precision requirements through the Global Atmosphere Watch program (9), but no funding.The data collected by NOAA and its worldwide partners have been used not only to demonstrate the unassailable rise of atmospheric greenhouse gas concentrations, but also to infer the magnitudes, locations, and times of surface-atmosphere exchange of those gases based on small concentration gradients between sites (10). Important findings from analysis of these records include the detection of a significant terrestrial carbon sink at northern mid-latitudes (11) and subsequent research aimed at identifying the mechanisms by which that sink must operate. Long-term, high-quality, atmospheric measurements are crucial for quantifying trends in greenhouse gas fluxes and attributing them to fossil fuel emissions, changes in land-use and management, or the response of natural land and ocean ecosystems to climate change and elevated CO2 concentrations.Greenhouse gas measurements along tall towers in the interior continents allow quantification of regional sources and sinks, which has a very high relevance for measuring the effectiveness of climate policy. NOAA ESRL provides measurements that are critical for the U.S. national security in that they provide independent verification and early warning of changing greenhouse gas emissions from countries involved in efforts to mitigate greenhouse gases.Dedicated carbon-observing satellites such as GOSAT and OCO-2 are needed to fill in the missing geographical information required for verification of carbon flux mitigation efforts. However, satellite retrievals do not yet provide sufficient information to deliver new constraints on surface fluxes, although quick progress is being made in this direction. In situ observations are crucial for anchoring space-borne measurements, for detecting potential biases of remote sensing techniques, and for providing continuity given the finite lifetime of satellites.Despite the growing importance of greenhouse gas observations to humanity, substantial budget cuts at NOAA have resulted in curtailment of our ability to observe and understand changes to the global carbon cycle. Already, a dozen surface flask-sampling sites have been removed from NOAA's operational network and aircraft profiling sites have been eliminated and reduced in frequency at the remaining NOAA sites. The planned growth in the tall tower program has stopped, and plans for closing some towers are being developed. The U.S. budget process in this election year, with the added risk of mandatory across-the-board cuts due to the 2011 Budget Control Act, foretells more bleak news for greenhouse gas monitoring at NOAA and could cause further retreat from the goal of recording ongoing changes in atmospheric composition. As scientists, we believe that preserving the continuity of these vital time series must remain a priority for U.S. carbon cycle research.

Urinary gamma-glutamyltransferase (u-γGT) concentration (U/L) and excretion (urinary creatinine-corrected u-γGT; u-γGT/u-Cre, U/g creatinine) are useful markers for kidney disease. However, there is limited information available on u-γGT and u-γGT/u-Cre distribution in the elderly Japanese population. In this study, we investigated the distribution of u-γGT and u-γGT/u-Cre in 113 Japanese women aged 40–74 years. The u-γGT was assessed from spot urine samples (collected from 09:00 to 14:00) spectrophotometrically according to the Japan Society of Clinical Chemistry reference measurement procedure using l-γ-glutamyl-3-carboxy-4-nitroanilide as the substrate. The u-Cre was measured enzymatically using creatininase, creatinase, sarcosine oxidase, and peroxidase. None of the participants was diagnosed with any kidney disease. Median u-γGT and u-γGT/u-Cre values (central 95% interval values) were 29.7 (5.3–144.0) U/L and 57.9 (32.9–122.7) U/g creatinine, respectively. The distribution of u-γGT tended to decline with age. There was a statistically significant difference in the u-γGT value between the 40-59- and 60-74-year-old groups. In contrast, there was no significant difference in the u-γGT/u-Cre between each age group. The u-Cre level also declined with age. It is suggested that the decline of u-γGT with aging would be masked by the u-Cre correction.

The westerly wind travelling at high altitudes over eastern Asia transports aerosols from the Asian deserts and urban areas to downwind areas such as Japan. These long-range-transported aerosols include not only mineral particles but also microbial particles (bioaerosols), that impact the ice-cloud formation processes as ice nuclei. However, the detailed relations of airborne bacterial dynamics to ice nucleation in high-elevation aerosols have not been investigated. Here, we used the aerosol particles captured in the snow cover at altitudes of 2450 m on Mt Tateyama to investigate sequential changes in the ice-nucleation activities and bacterial communities in aerosols and elucidate the relationships between the two processes. After stratification of the snow layers formed on the walls of a snow pit on Mt Tateyama, snow samples, including aerosol particles, were collected from 70 layers at the lower (winter accumulation) and upper (spring accumulation) parts of the snow wall. The aerosols recorded in the lower parts mainly came from Siberia (Russia), northern Asia and the Sea of Japan, whereas those in the upper parts showed an increase in Asian dust particles originating from the desert regions and industrial coasts of Asia. The snow samples exhibited high levels of ice nucleation corresponding to the increase in Asian dust particles. Amplicon sequencing analysis using 16S rRNA genes revealed that the bacterial communities in the snow samples predominately included plant associated and marine bacteria (phyla Proteobacteria) during winter, whereas during spring, when dust events arrived frequently, the majority were terrestrial bacteria of phyla Actinobacteria and Firmicutes. The relative abundances of Firmicutes (Bacilli) showed a significant positive relationship with the ice nucleation in snow samples. Presumably, Asian dust events change the airborne bacterial communities over Mt Tateyama and carry terrestrial bacterial populations, which possibly induce ice-nucleation activities, thereby indirectly impacting climate change.

Previous studies have shown that bioaerosols are injected into the atmosphere during dust events. These bioaerosols may affect leeward ecosystems, human health, and agricultural productivity and may even induce climate change. However, bioaerosol dynamics have rarely been investigated along the transport pathway of Asian dust, especially in China where dust events affect huge areas and massive numbers of people. Given this situation, the Dust-Bioaerosol (DuBi) Campaign was carried out over northern China, and the effects of dust events on the amount and diversity of bioaerosols were investigated. The results indicate that the number of bacteria showed remarkable increases during the dust events, and the diversity of the bacterial communities also increased significantly, as determined by means of microscopic observations with 4,6-diamidino-2-phenylindole (DAPI) staining and MiSeq sequencing analysis. These results indicate that dust clouds can carry many bacteria of various types into downwind regions and may have potentially important impacts on ecological environments and climate change. The abundances of DAPI-stained bacteria in the dust samples were 1 to 2 orders of magnitude greater than those in the non-dust samples and reached 105–106 particles m−3. Moreover, the concentration ratios of DAPI-stained bacteria to yellow fluorescent particles increased from 5.1 % ± 6.3 % (non-dust samples) to 9.8 % ± 6.3 % (dust samples). A beta diversity analysis of the bacterial communities demonstrated the distinct clustering of separate prokaryotic communities in the dust and non-dust samples. Actinobacteria, Bacteroidetes, and Proteobacteria remained the dominant phyla in all samples. As for Erenhot, the relative abundances of Acidobacteria and Chloroflexi had a remarkable rise in dust events. In contrast, the relative abundances of Acidobacteria and Chloroflexi in non-dust samples of R-DzToUb were greater than those in dust samples. Alphaproteobacteria made the major contribution to the increasing relative abundance of the phylum Proteobacteria in all dust samples. The relative abundance of Firmicutes did not exceed 5 % in all the air samples, even though it is the predominant phylum in the surface sand samples from the Gobi Desert. These results illustrate that the bacterial community contained in dust aerosol samples has a different pattern compared with non-dust aerosol samples, and the relative abundances of airborne bacteria are different from those in the surface sand or soil and differ by location and transmitting vector.

Aerosol particles, including airborne microorganisms, are transported through the free troposphere from the Asian continental area to the downwind area in East Asia and can influence climate changes, ecosystem dynamics, and human health. However, the variations present in airborne bacterial communities in the free troposphere over downwind areas are poorly understood, and there are few studies that provide an in-depth examination of the effects of long-range transport of aerosols (natural and anthropogenic particles) on bacterial variations. In this study, the vertical distributions of airborne bacterial communities at high altitudes were investigated and the bacterial variations were compared between dust events and non-dust events.Aerosols were collected at three altitudes from ground level to the free troposphere (upper level: 3000 or 2500 m; middle level: 1200 or 500 m; and low level: 10 m) during Asian dust events and non-dust events over the Noto Peninsula, Japan, where westerly winds carry aerosols from the Asian continental areas. During Asian dust events, air masses at high altitudes were transported from the Asian continental area by westerly winds, and laser imaging detection and ranging (lidar) data indicated high concentrations of non-spherical particles, suggesting that dust-sand particles were transported from the central desert regions of Asia. The air samples collected during the dust events contained 10–100 times higher concentrations of microscopic fluorescent particles and optical particle counter (OPC) measured particles than in non-dust events. The air masses of non-dust events contained lower amounts of dust-sand particles. Additionally, some air samples showed relatively high levels of black carbon, which were likely transported from the Asian continental coasts. Moreover, during the dust events, microbial particles at altitudes of > 1200 m increased to the concentrations ranging from 1. 2 × 106 to 6. 6 × 106 particles m−3. In contrast, when dust events disappeared, the microbial particles at > 1200 m decreased slightly to microbial-particle concentrations ranging from 6. 4 × 104 to 8. 9 × 105 particles m−3.High-throughput sequencing technology targeting 16S rRNA genes (16S rDNA) revealed that the bacterial communities collected at high altitudes (from 500 to 3000 m) during dust events exhibited higher diversities and were predominantly composed of natural-sand/terrestrial bacteria, such as Bacillus members. During non-dust periods, airborne bacteria at high altitudes were mainly composed of anthropogenic/terrestrial bacteria (Actinobacteria), marine bacteria (Cyanobacteria and Alphaproteobacteria), and plant-associated bacteria (Gammaproteobacteria), which shifted in composition in correspondence with the origins of the air masses and the meteorological conditions. The airborne bacterial structures at high altitudes suggested remarkable changes in response to air mass sources, which contributed to the increases in community richness and to the domination of a few bacterial taxa.

Background: Cyclosporine (CsA) and tacrolimus (TAC) are immunosuppressant drugs that are often used to treat autoimmune diseases and as transplantation therapy; therefore, their concentrations need to be monitored carefully. We herein evaluated the analytical performance of the Elecsys® Cyclosporine and Elecsys® Tacrolimus assay kits, which have been newly developed to measure CsA and TAC concentrations in the whole blood. Methods: We used residual whole blood samples from autoimmune disease and transplantation patients who were being treated with CsA or TAC. CsA concentrations were measured using an affinity chrome-mediated immunoassay (ACMIA) and an electrochemiluminescence immunoassay (ECLIA). TAC concentrations were measured using a chemiluminescence immunoassay (CLIA) and ECLIA. We investigated assay precision, linearity, lower limit of quantitation (LOQ), stability of calibration, influence of interference substances and the hematocrit, correlation of ACMIA with ECLIA, and correlation of CLIA with ECLIA. Results: Within-assay coefficients of variation were 1.8−3.6% (CsA: 94−1238 ng/mL) and 2.9−3.9% (TAC: 2.1−17.8 ng/mL), whereas day-to-day coefficients of variation ranged between 3.0−4.1% (CsA) and 2.8−3.9% (TAC). The limits of quantitation were defined as the concentration at which the CV was approximately 10%. Each lower LOQ obtained was 16 ng/mL (CsA), and 0.95 ng/mL (TAC). CsA and TAC calibrations were stable for at least 21 days. Neither the presence of conjugated bilirubin, unconjugated bilirubin, chyle, and rheumatoid factor nor the hematocrit affected these assays. A method comparison using a standardized major axis regression analysis of ACMIA and ECLIA was r=0.995, y=0.924x −1.175, n=200 (CsA), while that of CLIA and ECLIA was r=0.994, y=1.080x −0.197, n=200 (TAC). Conclusions: The analytical performances of the Elecsys® Cyclosporine and Elecsys®Tacrolimus assays were acceptable. Furthermore, CyA and TAC concentrations may be simultaneously measured using a single pretreatment which is of benefit if patients have to undertake conversion between these two drugs. Additionally, it benefits the workflow in the clinical laboratory. Thus, the Elecsys® Cyclosporine and Elecsys® Tacrolimus assays may be suitable for routine therapeutic drug monitoring.

To validate products of the Greenhouse gases Observing SATellite (GOSAT), we observed vertical profiles of aerosols, thin cirrus clouds, and tropospheric ozone with a mobile-lidar system that consisted of a two-wavelength (532 and 1064 nm) polarization lidar and a tropospheric ozone differential absorption lidar (DIAL). We used these lidars to make continuous measurements over Saga (33.24° N, 130.29° E) during 20–31 March 2015. High ozone and high aerosol concentrations were observed almost simultaneously in the altitude range 0.5–1.5 km from 03:00 to 20:00 Japan Standard Time (JST) on 22 March 2015. The maximum ozone volume mixing ratio was ∼ 110 ppbv. The maxima of the aerosol extinction coefficient and optical depth at 532 nm were 1.2 km−1 and 2.1, respectively. Backward trajectory analysis and the simulations by the Model of Aerosol Species IN the Global AtmospheRe (MASINGAR) mk-2 and the Meteorological Research Institute Chemistry-Climate Model, version 2 (MRI-CCM2), indicated that mineral dust particles from the Gobi Desert and an air mass with high ozone and aerosol (mainly sulfate) concentrations that originated from the North China Plain could have been transported over the measurement site within about 2 days. These high ozone and aerosol concentrations impacted surface air quality substantially in the afternoon of 22 March 2015. After some modifications of its physical and chemical parameters, MRI-CCM2 approximately reproduced the high ozone volume mixing ratio. MASINGAR mk-2 successfully predicted high aerosol concentrations, but the predicted peak aerosol optical thickness was about one-third of the observed value.

Graphene is promising for next-generation devices. However, one of the primary challenges in realizing these devices is the scalable growth of high-quality few-layer graphene (FLG) on device-type wafers; it is difficult to do so while balancing both quality and affordability. High-quality graphene is grown on expensive SiC bulk crystals, while graphene on SiC thin films grown on Si substrates (GOS) exhibits low quality but affordable cost. We propose a new method for the growth of high-quality FLG on a new template named “hybrid SiC”. The hybrid SiC is produced by bonding a SiC bulk crystal with an affordable device-type wafer and subsequently peeling off the SiC bulk crystal to obtain a single-crystalline SiC thin film on the wafer. The quality of FLG on this hybrid SiC is comparable to that of FLG on SiC bulk crystals and much higher than of GOS. FLG on the hybrid SiC exhibited high carrier mobilities, comparable to those on SiC bulk crystals, as anticipated from the linear band dispersions. Transistors using FLG on the hybrid SiC showed the potential to operate in terahertz frequencies. The proposed method is suited for growing high-quality FLG on desired substrates with the aim of realizing graphene-based high-speed devices.

Although anthropogenic mercury (Hg) releases to the environment have been substantially lowered in the United States and Canada since 1990, concerns remain for contamination in fish from remote lakes and rivers where atmospheric deposition is the predominant source of mercury. How have aquatic ecosystems responded? We report on one of the longest known multimedia data sets for mercury in atmospheric deposition: aqueous total mercury (THgaq), methylmercury (MeHgaq), and sulfate from epilimnetic lake-water samples from four lakes in Voyageurs National Park (VNP) in northern Minnesota; and total mercury (THg) in aquatic biota from the same lakes from 2001–2018. Wet Hg deposition at two regional Mercury Deposition Network sites (Fernberg and Marcell, Minnesota) decreased by an average of 22 percent from 1998–2018; much of the decreases occurred prior to 2009, with relatively flat trends since 2009. In the four VNP lakes, epilimnetic MeHgaq concentrations declined by an average of 44 percent and THgaq by an average of 27 percent. For the three lakes with long-term biomonitoring, temporal patterns in biotic THg concentrations were similar to patterns in MeHgaq concentrations; however, biotic THg concentrations declined significantly in only one lake. Epilimnetic MeHgaq may be responding both to a decline in atmospheric Hg deposition as well as a decline in sulfate deposition, which is an important driver of mercury methylation in the environment. Results from this case study suggest that regional- to continental-scale decreases in both mercury and sulfate emissions have benefitted aquatic resources, even in the face of global increases in mercury emissions.

The volume of a cylindrical polyacrylamide gel was measured when immersed in a binary mixture of isobutyric acid–water at different temperatures and weight fractions of isobutyric acid. Near the upper critical solution temperature of the binary mixture, the curve for gel volume vs. isobutyric acid weight fraction has a shoulder or a peak near the critical weight fraction. On the other hand, in a region away from the critical temperature, the gel volume decreased monotonically with increasing isobutyric acid weight fraction. The cloud point temperature of the binary mixture inside the gel was lower than that outside the gel. Thermodynamic description for the gel in the critical mixture is derived on the basis of the Ising model. By the description, the experimental results are explained consistently. The theoretical analysis shows that the shoulder and the peak appearing in the swelling behavior of the gel are respectively induced by the criticalities of the binary mixture outside and inside the gel. It also shows that the cloud point temperature lowering of the binary mixture inside the gel is attributed to the effective enhancement of the temperature of the binary mixture inside the gel induced by the presence of the gel polymer.

The biocompatibility and osteoconductivity of metallic biomaterials can be achieved by calcium phosphate (CaP) coating. We recently developed a laser-assisted biomimetic (LAB) process for rapid and area-specific CaP coating on several materials. In the present study, the LAB process was applied to cobalt–chromium (Co−Cr) alloy, a metallic biomaterial widely used in orthopedic and dental applications. The LAB process was conducted by irradiation of unfocused pulsed laser light onto the substrate immersed in supersaturated CaP solution. The LAB-processed substrate formed CaP on the irradiated surface within only 5 min and was coated with a micron-thick CaP layer within 30 min by the effects of laser-induced surface modification and heating. Ultrastructural analysis with transmission electron microscopy revealed that the resultant CaP layer was integrated with the underlying substrate through two intermediate layers, an upper chromium oxide layer and a lower Co-rich (Cr-deficient) alloy layer. The CaP layer was loaded with a large number of cobalt chromite (CoCr2O4) nanoparticles. The results obtained offer new insights into the mechanism of CaP coating in the LAB process and future applications of LAB-processed Co−Cr alloys.