A global analysis of avian island diversity-area relationships in the Anthropocene.

Research on island species-area relationships (ISAR) has expanded to incorporate functional (IFDAR) and phylogenetic (IPDAR) diversity. However, relative to the ISAR, we know little about IFDARs and IPDARs, and lack synthetic global analyses of variation in form of these three categories of island diversity-area relationship (IDAR). Here, we undertake the first comparative evaluation of IDARs at the global scale using 51 avian archipelagic data sets representing true and habitat islands. Using null models, we explore how richness-corrected functional and phylogenetic diversity scale with island area. We also provide the largest global assessment of the impacts of species introductions and extinctions on the IDAR. Results show that increasing richness with area is the primary driver of the (non-richness corrected) IPDAR and IFDAR for many data sets. However, for several archipelagos, richness-corrected functional and phylogenetic diversity changes linearly with island area, suggesting that the dominant community assembly processes shift along the island area gradient. We also find that archipelagos with the steepest ISARs exhibit the biggest differences in slope between IDARs, indicating increased functional and phylogenetic redundancy on larger islands in these archipelagos. In several cases introduced species seem to have 're-calibrated' the IDARs such that they resemble the historic period prior to recent extinctions.

Soil Micro-eukaryotic Diversity Patterns Along Elevation Gradient Are Best Estimated by Increasing the Number of Elevation Steps Rather than Within Elevation Band Replication.

The development of high-throughput sequencing (HTS) of environmental DNA (eDNA) has stimulated the study of soil microbial diversity patterns and drivers at all scales. However, given the heterogeneity of soils, a challenge is to define effective and efficient sampling protocols that allow sound comparison with other records, especially vegetation. In studies of elevational diversity pattern, a trade-off is choosing between replication within elevation bands vs. sampling more elevation bands. We addressed this question for soil protists along an elevation gradient on Mt. Asahi, Hokkaido, Japan. We compared two sampling approaches: (1) the replicate strategy (five replicates at six elevational bands, total = 30) and (2) the transect strategy (one sample in each of 16 different elevational bands). Despite a nearly twofold lower sampling effort, the transect strategy yielded congruent results compared to the replicate strategy for the estimation of elevational alpha diversity pattern: the regression coefficients between diversity indices and elevation did not differ between the two options. Furthermore, for a given total number of samples, gamma diversity estimated across the entire transect was higher when sampling more elevational bands as compared to replication from fewer elevational bands. Beta diversity (community composition turnover) was lower within a given elevational band than between adjacent bands and increased with elevation distance. In redundancy analyses, soil organic matter-related variable (the first principal component of soil organic matter, water content, total organic carbon, and nitrogen by whom were highly correlated) and elevation best explained elevational beta diversity pattern for both sampling approaches. Taken together, our results suggest that sampling a single plot per elevation band will be sufficient to obtain a good estimate of soil micro-eukaryotic diversity patterns along elevation gradients. This study demonstrated the effectiveness of the transect strategy in estimating diversity patterns along elevation gradients which is instructive for future environmental or even experimental studies. While not advocating for completely replacing replication-based sampling practices, it is important to note that both replicate and transect strategies have their merits and can be employed based on specific research goals and resource limitations.

Past and future decline of tropical pelagic biodiversity.

A major research question concerning global pelagic biodiversity remains unanswered: when did the apparent tropical biodiversity depression (i.e., bimodality of latitudinal diversity gradient [LDG]) begin? The bimodal LDG may be a consequence of recent ocean warming or of deep-time evolutionary speciation and extinction processes. Using rich fossil datasets of planktonic foraminifers, we show here that a unimodal (or only weakly bimodal) diversity gradient, with a plateau in the tropics, occurred during the last ice age and has since then developed into a bimodal gradient through species distribution shifts driven by postglacial ocean warming. The bimodal LDG likely emerged before the Anthropocene and industrialization, and perhaps ∼15,000 y ago, indicating a strong environmental control of tropical diversity even before the start of anthropogenic warming. However, our model projections suggest that future anthropogenic warming further diminishes tropical pelagic diversity to a level not seen in millions of years.

Synthesis of Near-Infrared-Absorbing Anionic Heptamethine Cyanine Dyes with Trifluoromethyl Groups.

A novel anionic heptamethine cyanine (HMC) dye with two trifluoromethyl groups that selectively absorb near-infrared light is synthesized. When contrasted with previously studied anionic HMC dyes with substituents such as methyl, phenyl, and pentafluorophenyl groups, the trifluoromethylated dye displays a red-shifted maximum absorption wavelength (for instance, 948 nm in CH2Cl2) along with enhanced photostability. Furthermore, HMC dyes with broad absorption in the near-infrared region are synthesized by combining a trifluoromethylated anionic HMC dye with a cationic HMC dye as a counterion.

Global raster dataset on historical coastline positions and shelf sea extents since the Last Glacial Maximum.

Motivation: Historical changes in sea level caused shifting coastlines that affected the distribution and evolution of marine and terrestrial biota. At the onset of the Last Glacial Maximum (LGM) 26 ka, sea levels were >130 m lower than at present, resulting in seaward-shifted coastlines and shallow shelf seas, with emerging land bridges leading to the isolation of marine biota and the connection of land-bridge islands to the continents. At the end of the last ice age, sea levels started to rise at unprecedented rates, leading to coastal retreat, drowning of land bridges and contraction of island areas. Although a growing number of studies take historical coastline dynamics into consideration, they are mostly based on past global sea-level stands and present-day water depths and neglect the influence of global geophysical changes on historical coastline positions. Here, we present a novel geophysically corrected global historical coastline position raster for the period from 26 ka to the present. This coastline raster allows, for the first time, calculation of global and regional coastline retreat rates and land loss rates. Additionally, we produced, per time step, 53 shelf sea rasters to present shelf sea positions and to calculate the shelf sea expansion rates. These metrics are essential to assess the role of isolation and connectivity in shaping marine and insular biodiversity patterns and evolutionary signatures within species and species assemblages. Main types of variables contained: The coastline age raster contains cells with ages in thousands of years before present (bp), representing the time since the coastline was positioned in the raster cells, for the period between 26 ka and the present. A total of 53 shelf sea rasters (sea levels <140 m) are presented, showing the extent of land (1), shelf sea (0) and deep sea (NULL) per time step of 0.5 kyr from 26 ka to the present. Spatial location and grain: The coastline age raster and shelf sea rasters have a global representation. The spatial resolution is scaled to 120 arcsec (0.333° × 0.333°), implying cells of c. 3,704 m around the equator, 3,207 m around the tropics (±30°) and 1,853 m in the temperate zone (±60°). Time period and temporal resolution: The coastline age raster shows the age of coastline positions since the onset of the LGM 26 ka, with time steps of 0.5 kyr. The 53 shelf sea rasters show, for each time step of 0.5 kyr, the position of the shelf seas (seas shallower than 140 m) and the extent of land. Level of measurement: Both the coastline age raster and the 53 shelf sea rasters are provided as TIFF files with spatial reference system WGS84 (SRID 4326). The values of the coastline age raster per grid cell correspond to the most recent coastline position (in steps of 0.5 kyr). Values range from 0 (0 ka, i.e., present day) to 260 (26 ka) in bins of 5 (0.5 kyr). A value of "no data" is ascribed to pixels that have remained below sea level since 26 ka. Software format: All data processing was done using the R programming language.

Design, Regioselective Synthesis, and Photophysical Properties of Perfluoronaphthalene-Based Donor-Acceptor-Donor Fluorescent Dyes.

A one-step route to a series of perfluoronaphthalene-based donor (D)-acceptor (A)-D fluorescent dyes with various electron-donating groups was developed. The perfluoronaphthalene moiety in the D-A-D dyes served as a good electron-accepting aromatic ring with excellent intramolecular charge transfer properties, as determined by density functional theory calculations and measurements of the fluorescence properties in solution, in poly(methyl methacrylate) (PMMA) films, and in crystal form. Notably, replacing the naphthalene ring with perfluoronaphthalene in the D-A-D dyes carrying the phenothiazine moiety not only stabilized the highest occupied molecular orbital and lowest unoccupied molecular orbital energy levels but also reduced the energy band gap to change the emission color from blue to yellow. Among the four synthesized perfluoronaphthalene D-A-D dyes, those bearing diphenylamino groups afforded the best fluorescence quantum yields in Et2O solution (0.60) and in PMMA film (0.65) because the propeller structure of the diphenylamino group that acts as a donor substituent effectively suppresses radiation-free deactivation. In contrast, in the crystalline state, the carbazoyl-bearing D-A-D dye provided the best fluorescence quantum yield (0.35) because the radiation-free inactivation was suppressed by π-πF stacking at the donor site, which was confirmed by single-crystal X-ray analysis.

Highly diastereo- and enantioselective organocatalytic synthesis of trifluoromethylated erythritols based on the in situ generation of unstable trifluoroacetaldehyde.

Thus far, only a few methods for the asymmetric synthesis of erythritols bearing a trifluoromethyl group have been developed, and these methods present serious disadvantages such as the requirement of multiple steps for the preparation of their starting materials, low stereoselectivity, and the use of highly toxic reagents. Herein, we have developed a highly diastereo- and enantioselective organocatalytic method to synthesise erythritols bearing a trifluoromethyl group using (1) a commercially available organocatalyst to produce unstable trifluoroacetaldehyde in situ from its corresponding hemiacetal, followed by the simultaneous asymmetric carbon-carbon bond-forming reaction of the organocatalyst with an in situ-generated chiral enamine derived from 2,2-dimethyl-1,3-dioxane-5-one to obtain the corresponding aldol product in good yield (65-80%) with high diastereoselectivity (up to 94% de) and excellent enantioselectivity (up to >98% ee), (2) the highly diastereoselective reduction of the ketone moiety in the aldol product (up to 98% de), and (3) the deprotection of the acetal moiety.

Interfacial Modeling of Fibrinogen Adsorption onto LiNbO3 Single Crystal-Single Domain Surfaces.

For the development of next-generation protein-based biosensor surfaces, it is important to understand how functional proteins, such as fibrinogen (FBG), interact with polar substrate surfaces in order to prepare highly sensitive points of medical care diagnostics. FBG, which is a fibrous protein with an extracellular matrix, has both positively and negatively charged regions on its 3-dimensional surface, which makes interpreting how it effectively binds to polarized surfaces challenging. In this study, single-crystal LiNbO3 (LNO) substrates that have surface charges were used to investigate the adsorption of FBG protruding polar fragments on the positively and negatively charged LNO surfaces. We performed a combination of experiments and multi-scale molecular modeling to understand the binding of FBG in vacuum and water-solvated surfaces of LNO. XPS measurements showed that the FBG adsorption on LNO increased with increment in solution concentration on surfaces independent of charges. Multi-scale molecular modeling employing Quantum Mechanics, Monte Carlo, and Molecular Mechanics addressed the phenomenon of FBG fragment bonding on LNO surfaces. The binding simulation validated the experimental observation using zeta potential measurements which showed presence of solvated medium influenced the adsorption phenomenon due to the negative surface potential.

A geometric approach to scaling individual distributions to macroecological patterns.

Understanding macroecological patterns across scales is a central goal of ecology and a key need for conservation biology. Much research has focused on quantifying and understanding macroecological patterns such as the species-area relationship (SAR), the endemic-area relationship (EAR) and relative species abundance curve (RSA). Understanding how these aggregate patterns emerge from underlying spatial pattern at individual level, and how they relate to each other, has both basic and applied relevance. To address this challenge, we develop a novel spatially explicit geometric framework to understand multiple macroecological patterns, including the SAR, EAR, RSA, and their relationships. First, we provide a general theory that can be used to derive the asymptotic slopes of the SAR and EAR, and demonstrates the dependency of RSAs on the shape of the sampling region. Second, assuming specific shapes of the sampling region, species geographic ranges, and individual distribution patterns therein based on theory of stochastic point processes, we demonstrate various well-documented macroecological patterns can be recovered, including the tri-phasic SAR and various RSAs (e.g., Fisher's logseries and the Poisson lognormal distribution). We also demonstrate that a single equation unifies RSAs across scales, and provide a new prediction of the EAR. Finally, to demonstrate the applicability of the proposed model to ecological questions, we provide how beta diversity changes with spatial extent and its grain over multiple scales. Emergent macroecological patterns are often attributed to ecological and evolutionary mechanisms, but our geometric approach still can recover many previously observed patterns based on simple assumptions about species geographic ranges and the spatial distribution of individuals, emphasizing the importance of geometric considerations in macroecological studies.

Iron-Promoted Intramolecular Cascade Cyclization for the Synthesis of Selenophene-Fused, Quinoline-Based Heteroacenes.

Herein, we report the Fe(III)-promoted linear intramolecular cascade cyclization of 1,3-diyne and 1,3,5-triyne for the construction of selenophene-fused, quinoline-based heteroacene scaffolds. In one step, 1,3-diyne and 1,3,5-triyne were cyclized via diversified internal nucleophiles by using diorganyl diselenides. The diorganyl diselenide plays dual role, one as a cyclizing agent and second as insertion of one and/or two selenium atom and one R'-Se group in the final product. This is highly important in terms of atom economy. Diversified internal nucleophiles were used to afford quinoline- and acridine-based cores. The synthesized selenophene-fused derivatives showed λmax, Fmax, and Φf values in the range from 370-411 nm, 427-472 nm, and 0.003-0.059, respectively, in dichloromethane solvent.

Aromatic Fluorine-Induced One-Pot Synthesis of Ring-Perfluorinated Trimethine Cyanine Dye and Its Remarkable Fluorescence Properties.

We have developed a novel aromatic fluorine-induced one-pot synthesis of ring-perfluorinated trimethine cyanine dye without the use of a pyridine by reacting hexafluorobenzoindolenine with 5 equiv of methyl trifluoromethanesulfonate in mixed solvents of dimethylformamide and toluene. The thus-obtained ring-perfluorinated trimethine cyanine dye shows much better fluorescence properties, including intensity, quantum yield, and lifetime, than the nonfluorinated dye, not only in CH2Cl2 solution and the poly(methyl methacrylate) film but also in the powder state. Furthermore, ring-perfluorinated trimethine cyanine dye 2a shows better photostability toward white light-emitting diode irradiation than nonfluorinated dye trimethine cyanine dye 2b.

Wide-Range Near-Infrared Sensitizing 1 H-Benzo[ c, d]indol-2-ylidene-Based Squaraine Dyes for Dye-Sensitized Solar Cells.

NIR absorbing squaraine dyes SQ1-SQ7 having 1 H-benzo[ c, d]indol-2-ylidene as a donor moiety were designed for application in DSSCs. Annulation of the benzene ring to an 3 H-indolium-based anchor moiety led to a red-shifted and broadened absorption band on TiO2 film, which were reflected in the improved short-circuit current density of SQ2 (6.22 mA cm-2) compared to the nonbenzene fused derivative SQ1 (4.39 mA cm-2). Although the introduction of a butoxy (SQ4: 806 nm) or dialkylamino group (SQ5-SQ7: 815-820 nm) to the 1 H-benzo[ c, d]indol-2-ylidene-based donor moiety resulted in red-shifted absorption maxima in ethanol compared to the nonsubstituted derivative SQ2 (784 nm), the HOMO energy level of SQ4-SQ7 gave rise to an undesirable approximation to the redox potential of I-/I3-. Thus, the butoxy (SQ4: 0.56) and dialkylamino (SQ5-SQ7: 0.25-0.30) derivatives had relatively lower conversion efficiencies. Since the 2-ethylhexyl derivative SQ3 exhibited red-shifted absorption (λmax: 796 nm), suitable HOMO and LUMO energy levels, and relatively efficient restriction of charge recombination, this dye achieved the highest conversion efficiency (1.31%), along with a high IPCE response of over 20% over a wide range from 640 to 860 nm and an onset of IPCE at 1000 nm.

Rational Molecular Design and Synthesis of Highly Thermo- and Photostable Near-Infrared-Absorbing Heptamethine Cyanine Dyes with the Use of Fluorine Atoms.

Highly thermo- and photostable, near-infrared-absorbing heptamethine cyanine dyes were achieved with the use of fluorine-containing components. In particular, one prepared heptamethine cyanine dye, bearing a tetrakis(pentafluorophenyl)borate as a counter anion and an N-ethyl-2,2,2-trifluoroacetamido group at the meso position, showed not only a high decomposition temperature (Tdt ), but also very high photostability toward white LED irradiation.

Synthesis and Fluorescence Properties of Pyrimidine-Based Diboron Complexes with Donor-π-Acceptor Structures.

Pyrimidine-based diboron complexes bearing ß-iminoenolate ligands and phenyl groups as bulky substituents on the boron atoms were synthesized as novel fluorescent dyes, and their fluorescence properties were investigated in solution and in the solid state. The diboron complexes with donor-π-acceptor structures showed positive solvatochromism in the fluorescence spectra. The cyano derivative exhibited the most dramatic redshift of the fluorescence maximum Fmax with increasing solvent polarity (from 551 nm in n-hexane to 710 nm in acetonitrile). The diboron complexes showed solid-state fluorescence in the range of 578-706 nm with fluorescence quantum yields of 0.06-0.28. Additionally, the trifluoromethyl derivative exhibited solvent-inclusion solid-state fluorescence. The trifluoromethyl derivative formed toluene-inclusion and ethyl acetate-inclusion crystals. The toluene-inclusion crystal (Fmax = 668 nm, Φf = 0.16) showed a blueshifted Fmax and higher Φf value compared to the original trifluoromethyl derivative (Fmax = 694 nm, Φf = 0.08) in the solid state. On the other hand, the Fmax (709 nm) and Φf (0.04) values of the ethyl acetate-inclusion crystal were redshifted and lower, respectively.

Solvatochromic fluorescence properties of pyrazine-boron complex bearing a ß-iminoenolate ligand.

Pyrazine-based monoboron complexes bearing two fluorine atoms (BF2 complex) or two phenyl groups (BPh2 complex) on the boron atom were synthesized, and the fluorescence properties were investigated. The BPh2 complexes exhibited red-shifted maximum absorption and maximum fluorescence wavelengths and lower molar absorption coefficients than the corresponding BF2 complexes in n-hexane. The fluorescence quantum yields of the BPh2 complexes were higher than or comparable to the corresponding BF2 complexes owing to the relatively low nonradiative rate constants. Although the nonsubstituted and trifluoromethyl-substituted derivatives did not show solvatochromism, the dimethylamino-substituted BF2 and BPh2 complexes exhibited pronounced solvatochromism in the fluorescence spectra. Dual fluorescence was observed for the dimethylamino-substituted BF2 complex in toluene, 1,4-dioxane, and chloroform, corresponding to locally excited (LE) and twisted intramolecular charge-transfer (TICT) states.

Synthesis and fluorescence properties of pyrimidine mono- and bisboron complexes.

Novel fluorescent mono- and bisboron complexes based on pyrimidine bearing ß-iminoenolate ligands were synthesized, and their fluorescence properties were investigated. The nonsubstituted and trifluoromethyl-substituted monoboron complexes showed higher fluorescence quantum yield in solid state than in solution. The dimethylamino derivative of the monoboron complex exhibited positive solvatochromism in the fluorescence spectra. The bisboron complex showed significantly higher molar absorption coefficient and red-shifted maximum absorption and maximum fluorescence wavelengths than the corresponding monoboron complex.

[The impact of guidelines for the management of acute cholecystitis in a rural area of Japan].

We monitored the management of acute cholecystitis in a rural area of Japan to determine the effectiveness of new guidelines for the management of acute cholecystitis and cholangitis. Between January 2000 and September 2011, 366 patients were treated for acute cholecystitis. Of these, 59 had common bile duct stones (CBDS) and 307 did not. Patients in both groups were further subdivided into two groups: a before guidelines group (BGG; n=153) and an after guideline group (AGG; n=154). Among the patients without CBDS, early cholecystectomy was more common in the AGG group (n=53) than in the BGG group. Furthermore, the length of hospital stay was four days shorter in the AGG group than in the BGG group (n=23). Among the patients with CBDS, the timing of cholecystectomy after endoscopic retrograde cholangiography was seven days earlier in the AGG group than in the BGG group. Even in a rural area of Japan, early cholecystectomy appears safe and can decrease the length of hospital stay.

A Rapid and Dual Optical CO2 -responsive Polydimethylsiloxane Elastomer with a Fluorinated Cyanine Dye.

We found that our optically CO2 -responsive polydimethylsiloxane (PDMS) elastomer rapidly and reversibly underwent both visible and fluorescent color changes in the presence of CO2 gas. Unlike conventional optically CO2 -responsive polymeric materials, it functions in totally dry gaseous conditions. The visible color and fluorescence of the elastomer sheet change after only 1 min of exposure to CO2 , and the sheet exhibits excellent repeatability in terms of color switching that persists for at least 20 times.

Occurrence-based diversity estimation reveals macroecological and conservation knowledge gaps for global woody plants.

Incomplete sampling of species' geographic distributions has challenged biogeographers for many years to precisely quantify global-scale biodiversity patterns. After correcting for the spatial inequality of sample completeness, we generated a global species diversity map for woody angiosperms (82,974 species, 13,959,780 occurrence records). The standardized diversity estimated more pronounced latitudinal and longitudinal diversity gradients than the raw data and improved the spatial prediction of diversity based on environmental factors. We identified areas with potentially high species richness and rarity that are poorly explored, unprotected, and threatened by increasing human pressure: They are distributed mostly at low latitudes across central South America, Central Africa, subtropical China, and Indomalayan islands. These priority areas for botanical exploration can help to efficiently fill spatial knowledge gaps for better describing the status of biodiversity and improve the effectiveness of the protected area network for global woody plant conservation.

Soil filtration-sedimentation improves shelled protist recovery in eukaryotic eDNA surveys.

A large part of the soil protist diversity is missed in metabarcoding studies based on 0.25 g of soil environmental DNA (eDNA) and universal primers due to ca. 80% co-amplification of non-target plants, animals and fungi. To overcome this problem, enrichment of the substrate used for eDNA extraction is an easily implemented option but its effect has not yet been tested. In this study, we evaluated the effect of a 150 µm mesh size filtration and sedimentation method to improve the recovery of protist eDNA, while reducing the co-extraction of plant, animal and fungal eDNA, using a set of contrasted forest and alpine soils from La Réunion, Japan, Spain and Switzerland. Total eukaryotic diversity was estimated by V4 18S rRNA metabarcoding and classical amplicon sequence variant calling. A 2- to 3-fold enrichment in shelled protists (Euglyphida, Arcellinida and Chrysophyceae) was observed at the sample level with the proposed method, with, at the same time, a 2-fold depletion of Fungi and a 3-fold depletion of Embryophyceae. Protist alpha diversity was slightly lower in filtered samples due to reduced coverage in Variosea and Sarcomonadea, but significant differences were observed in only one region. Beta diversity varied mostly between regions and habitats, which explained the same proportion of variance in bulk soil and filtered samples. The increased resolution in soil protist diversity estimates provided by the filtration-sedimentation method is a strong argument in favour of including it in the standard protocol for soil protist eDNA metabarcoding studies.