Defect-Induced All-Solid-State Frustrated Lewis Pair on Metal-Organic Monolayer Accelerating Photocatalytic CO2 Reduction with H2O Vapor.

Understanding the structure-performance relationships of a frustrated Lewis pair (FLP) at the atomic level is key to yielding high efficiency in activating chemically "inert" molecules into value-added products. A sound strategy was developed herein through incorporating oxygen defects into a Zr-based metal-organic layer (Zr-MOL-D) and employing Lewis basic proximal surface hydroxyls for the in situ formation of solid heterogeneous FLP (Zr4-δ-VO-Zr-OH). Zr-MOL-D exhibits a superior CO2 to CO conversion rate of 49.4 µmol g-1 h-1 in water vapor without any sacrificing agent or photosensitizer, which is about 12 times higher than that of pure MOL (Zr-MOL-P), with extreme stability even after being placed for half a year. Theoretical and experimental results reveal that the introduction of FLP converts the process of the crucial intermediate COOH* from an endothermic reaction to an exothermic spontaneous reaction. This work is expected to provide new prospects for developing efficient MOL-based photocatalysts in FLP chemistry through a sound defect-engineering strategy.

Phosphate Coordination to Metal-Organic Layer Secondary Building Units Prolongs Drug Retention for Synergistic Chemoradiotherapy.

Chemoradiotherapy combines radiotherapy with concurrent chemotherapy to potentiate antitumor activity but exacerbates toxicities and causes debilitating side effects in cancer patients. Herein, we report the use of a nanoscale metal-organic layer (MOL) as a 2D nanoradiosensitizer and a reservoir for the slow release of chemotherapeutics to amplify the antitumor effects of radiotherapy. Coordination of phosphate-containing drugs to MOL secondary building units prolongs their intratumoral retention, allowing for continuous release of gemcitabine monophosphate (GMP) for effective localized chemotherapy. In the meantime, the MOL sensitizes cancer cells to X-ray irradiation and provides potent radiotherapeutic effects. GMP-loaded MOL (GMP/MOL) enhances cytotoxicity by 2-fold and improves radiotherapeutic effects over free GMP in vitro. In a colon cancer model, GMP/MOL retains GMP in tumors for more than four days and, when combined with low-dose radiotherapy, inhibits tumor growth by 98 %. The synergistic chemoradiotherapy enabled by GMP/MOL shows a cure rate of 50 %, improves survival, and ameliorates cancer-proliferation histological biomarkers.

π-Sticked Metal-Organic Monolayers for Single-Metal-Site Dependent CO2 Photoreduction and Hydrogen Evolution Reaction.

Hierarchical self-assembly of 2D metal-organic layers (MOLs) for the construction of advanced functional materials have witnessed considerable interest, due to the increasing atomic utilizations and well-defined atom-property relationship. However, the construction of atomically precise MOLs with mono-/few-layered thickness through hierarchical self-assembly process remains a challenge, mostly because the elaborate long-range order is difficult to control via conventional noncovalent interaction. Herein, a quadruple π-sticked metal-organic layer (πMOL) is reported with checkerboard-like lattice in ≈1.0 nanometre thickness, on which the catalytic selectivity can be manipulated for highly efficient CO2 reduction reaction (CO2 RR) and hydrogen evolution reaction (HER) over a single metal site. In saturated CO2 aqueous acetonitrile, Fe-πMOL achieves a highly effective CO2 RR with the yield of ≈3.98 mmol g-1  h-1 and 91.7% selectivity. In contrast, the isostructural Co-πMOL as well as mixed metallic FeCo-πMOL exhibits a high activity toward HER under similar conditions. DFT calculations reveal that single metal site exhibits the significant difference in CO2 adsorption energy and activation barrier, which triggers highly selective CO2 RR for Fe site and HER for Co site, respectively. This work highlights the potential of supramolecular π… π interaction for constructing monolayer MOL materials to uniformly distribute the single metal sites for artificial photosynthesis.

Spin Manipulation in a Metal-Organic Layer through Mechanical Exfoliation for Highly Selective CO2 Photoreduction.

Spin manipulation of transition-metal catalysts has great potential in mimicking enzyme electronic structures to improve activity and/or selectivity. However, it remains a great challenge to manipulate room-temperature spin state of catalytic centers. Herein, we report a mechanical exfoliation strategy to in situ induce partial spin crossover from high-spin (s=5/2) to low-spin (s=1/2) of the ferric center. Due to spin transition of catalytic center, mixed-spin catalyst exhibits a high CO yield of 19.7 mmol g-1 with selectivity of 91.6 %, much superior to that of high-spin bulk counterpart (50 % selectivity). Density functional theory calculations reveal that low-spin 3d-orbital electronic configuration performs a key function in promoting CO2 adsorption and reducing activation barrier. Hence, the spin manipulation highlights a new insight into designing highly efficient biomimetic catalysts via optimizing spin state.

Metal-Organic Layer Delivers 5-Aminolevulinic Acid and Porphyrin for Dual-Organelle-Targeted Photodynamic Therapy.

The efficacy of photodynamic therapy (PDT) depends on the subcellular localization of photosensitizers. Herein, we report a dual-organelle-targeted nanoparticle platform for enhanced PDT of cancer. By grafting 5-aminolevulinic acid (ALA) to a Hf12 -based nanoscale metal-organic layer (Hf-MOL) via carboxylate coordination, ALA/Hf-MOL enhanced ALA delivery and protoporphyrin IX (PpIX) synthesis in mitochondria, and trapped the Hf-MOL comprising 5,15-di-p-benzoatoporphyrin (DBP) photosensitizers in lysosomes. Light irradiation at 630 nm simultaneously excited PpIX and DBP to generate singlet oxygen and rapidly damage both mitochondria and lysosomes, leading to synergistic enhancement of the PDT efficacy. The dual-organelle-targeted ALA/Hf-MOL outperformed Hf-MOL in preclinical PDT studies, with a 2.7-fold lower half maximal inhibitory concentration in cytotoxicity assays in vitro and a 3-fold higher cure rate in a colon cancer model in vivo.

Organic layer characteristics and microbial utilization of the biosulfur globules produced by haloalkaliphilic Thioalkalivibrio versutus D301 during biological desulfurization.

The haloalkaliphilic genus Thioalkalivibrio, widely used in bio-desulfurization, can oxidize H2S to So, which is excreted outside cells in the form of biosulfur globules. As by-product of bio-desulfurization, information on biosulfur globules is still very scant, which limits its high-value utilization. In this paper, the characteristics of biosulfur globules produced by Thioalkalivibrio versutus D301 and the possibility of cultivating sulfur-oxidizing bacteria as a high biological-activity sulfur source were studied. The sulfur element in the biosulfur globules existed in the form α-S8, which was similar to chemical sulfur. The biosulfur globule was wrapped with an organic layer composed of polysaccharides and proteins. The composition of this organic layer could change. In the formation stage of biosulfur globules, the organic layer was dominated by polysaccharides, and in later stage, proteins became the main component. We speculated that the organic layer was mainly formed by the passive adsorption of organic matter secreted by cells. The existence of organic layer endowed biosulfur with better bioavailability. Compared with those found using chemical sulfur, the growth rates of Acidithiobacillus thiooxidans ATCC 19377T, Thiomicrospira microaerophila BDL05 and Thioalkalibacter halophilus BDH06 using biosulfur increased several folds to an order of magnitude, indicating that biosulfur was a good sulfur source for cultivating sulfur-oxidizing bacteria.

Changes in soil fungal community composition depend on functional group and forest disturbance type.

Disturbances have altered community dynamics in boreal forests with unknown consequences for belowground ecological processes. Soil fungi are particularly sensitive to such disturbances; however, the individual response of fungal guilds to different disturbance types is poorly understood. Here, we profiled soil fungal communities in lodgepole pine forests following a bark beetle outbreak, wildfire, clear-cut logging, and salvage-logging. Using Illumina MiSeq to sequence ITS1 and SSU rDNA, we characterized communities of ectomycorrhizal, arbuscular mycorrhizal, saprotrophic, and pathogenic fungi in sites representing each disturbance type paired with intact forests. We also quantified soil fungal biomass by measuring ergosterol. Abiotic disturbances changed the community composition of ectomycorrhizal fungi and shifted the dominance from ectomycorrhizal to saprotrophic fungi compared to intact forests. The disruption of the soil organic layer with disturbances correlated with the decline of ectomycorrhizal and the increase of arbuscular mycorrhizal fungi. Wildfire changed the community composition of pathogenic fungi but did not affect their proportion and diversity. Fungal biomass declined with disturbances that disrupted the forest floor. Our results suggest that the disruption of the forest floor with disturbances, and the changes in C and nutrient dynamics it may promote, structure the fungal community with implications for fungal biomass-C.

Metal-Organic Layers Catalyze Photoreactions without Pore Size and Diffusion Limitations.

Metal-organic frameworks (MOFs) have emerged as promising single-site solid catalysts for organic reactions. However, MOF catalysts suffer from pore size limitation and slow diffusion, which are detrimental for photoreactions. Metal-organic layers (MOLs) have unique ultrathin 2D monolayer structures and overcome pore size and diffusion limitations. Here, the synthesis of photoactive Zr-RuBPY MOL based on Zr-oxo clusters and [Ru(bpy)3 ]2+ -containing linkers is reported as well as its application in photocatalytic [2+2] cyclizations of enones and Meerwein addition reactions between aryl diazonium salts, styrenes, and nitriles.

Organic carbon stocks and sequestration rates of forest soils in Germany.

The National Forest Soil Inventory (NFSI) provides the Greenhouse Gas Reporting in Germany with a quantitative assessment of organic carbon (C) stocks and changes in forest soils. Carbon stocks of the organic layer and the mineral topsoil (30 cm) were estimated on the basis of ca. 1.800 plots sampled from 1987 to 1992 and resampled from 2006 to 2008 on a nationwide grid of 8 × 8 km. Organic layer C stock estimates were attributed to surveyed forest stands and CORINE land cover data. Mineral soil C stock estimates were linked with the distribution of dominant soil types according to the Soil Map of Germany (1 : 1 000 000) and subsequently related to the forest area. It appears that the C pool of the organic layer was largely depending on tree species and parent material, whereas the C pool of the mineral soil varied among soil groups. We identified the organic layer C pool as stable although C was significantly sequestered under coniferous forest at lowland sites. The mineral soils, however, sequestered 0.41 Mg C ha(-1) yr(-1) . Carbon pool changes were supposed to depend on stand age and forest transformation as well as an enhanced biomass input. Carbon stock changes were clearly attributed to parent material and soil groups as sandy soils sequestered higher amounts of C, whereas clayey and calcareous soils showed small gains and in some cases even losses of soil C. We further showed that the largest part of the overall sample variance was not explained by fine-earth stock variances, rather by the C concentrations variance. The applied uncertainty analyses in this study link the variability of strata with measurement errors. In accordance to other studies for Central Europe, the results showed that the applied method enabled a reliable nationwide quantification of the soil C pool development for a certain period.

Rapid and large-capacity adsorption of heterocyclic aromatic amines on heat resistant two-dimensional metal organic layer/cellulose nanofiber aerogels constructed by a thawing cross-linking strategy.

Composite aerogels, formed by the combination of nanoscale polymers and highly efficient adsorbents, offer the potential to deploy adsorbent distinct separation properties into a processable matrix. This paper presents a method for the fabrication of low energy bio-aerogels with high ductility, excellent wet strength and favorable heat resistance, based on cellulose nanofibers (CNFs) bound by calcium carbonate particles (CaCO3) via a simple process of ice induction, cross-linking during freezing and freeze-drying. Due to induced defects, two-dimensional metal-organic layers (MOLs) were rich in mesoporous structure and embedded in the aerogel (AGCa-MOL), which exhibited a powerful adsorption capacity. AGCa-MOL could take full advantage of their hierarchical pores and available surface area to obtain high adsorption capacity (0.694-5.470 µmol/g) and rapid adsorption kinetics (5 min) for 14 heterocyclic aromatic amines (HAAs). Moreover, the CaCO3 particles and MOLs gave the AGCa-MOL excellent thermal stability, so that it could maintain excellent adsorption capacity at a high temperature (100 °C) and be applied as an adsorbent to remove HAAs in the boiling marinade. The intrinsic potential of composite aerogels was revealed due to the synergistic properties of the various components in the composite aerogel.

Dye Doped Metal-Organic Frameworks for Enhanced Phototherapy.

Phototherapy is a noninvasive cancer treatment that relies on the interaction between light and photoactive agents. These photoactive agents are typically organic dyes, but their hydrophobic nature and self-aggregation tendency in biological media greatly restricts the development of highly effective phototherapeutic systems. In the past decade, functional dye-doped metal-organic framework (MOF)-based phototherapy has attracted enormous interest because organic dyes can be encapsulated and isolated within the MOF structure to show superior treatment efficacy. In addition to incorporating the reported phototherapeutic dyes into MOF as the ligand or the guest in the pores, the construction of an MOF-based phototherapy agent can also be extended to these dye units that are previously inactive for phototherapy. Thus, this review focuses on the emerging development of phototherapeutic MOFs that exhibited better performance than the involving dye units due to the controlled dye aggregation within the MOF. The related mechanisms and some emerging future directions of dye-doped MOF-based phototherapy are also discussed and summarized.

Fabrication of organic-inorganic hybrid materials on metal surface for optimizing electrochemical performance.

Surface chemistry is a significant field of research, especially for the preparation of organic-inorganic hybrid materials in which nearly every atom is anchored at the interface. Herein we report on the functional binding agents (FBAs), Mg(OH)2 or Co(OH)2-Mg(OH)2-Co(OH)(NO3), as efficient tools for functionalising surfaces, whereby the morphology and growth of the organic-inorganic coating can be varied by varying the interfacial composition to achieve improved functionality. To demonstrate the potential of this strategy, we combine plasma electrolytic oxidation (PEO) and a two-step dip chemical coating (DCC) technique to deliver multi-layered constructions of several chemical compositions comprising inorganic and organic components. A novel single layer of FBAs is fabricated on the rough inorganic coating through chemical treatment via DCC, transforming it into a binding site for primary clusters of 2-mercaptobenzimidazole (MBI) molecules. Thus, FBAs form coordination complexes with organic molecules, which grow on FBA surfaces. Finally, electrochemical measurements reveal that the self-assembly of organic-inorganic hybrid heterostructures appreciably suppresses metal oxidation and oxygen reduction, due to a synergistic effect arising from the combination of FBAs with organic and inorganic coatings.

Freestanding anticorrosion hybrid materials based on coordination interaction between metal-quinoline compounds and TiO2-MgO film.

Flower-like organic materials have been used for applications in supercapacitors, catalysis, corrosion science, but no report of "flower" from metal-organic compounds on porous inorganic surface has been available. Here, we report the successful fabrication of flowerlike organic-inorganic materials via the combination of TiO2-MgO film prepared on magnesium alloy through plasma electrolytic oxidation (PEO) as inorganic components and metal-quinoline, Na-8-hydroxyquinoline-5-sulfonic acid (NaHQS) and Co(II)-8-hydroxyquinoline-5-sulfonic acid (CoHQS), as the organic component. Interaction between the CoHQS complex and the porous inorganic materials then leads to the formation of flowerlike organic-inorganic coating on the magnesium surface. Furthermore, a detailed analysis of surface morphologies indicates that MHQS molecules are linked together via kinds of intermolecular hydrogen bonds and non-covalent π-π bonds between heterocyclic molecules. PEO-TiO2-CoHQS and PEO-TiO2-NaHQS exhibit enhanced electrochemical performance and chemical stability compared with the free MHQS, which was discussed based on polarization and impedance interpretation. This is attributed to the physical and chemical adsorption on the coating surface as well as the high surface area of the CoHQS in the nanoflowers.

Vertical distributions of radiocesium in Japanese forest soils following the Fukushima Daiichi Nuclear Power Plant accident: A meta-analysis.

This study investigated the temporal change in vertical distributions of radiocesium inventories in Japanese forest soils during the early phase (from 2011 to 2017) following the Fukushima Daiichi Nuclear Power Plant (FDNPP) accident, using three simple parameters. We calculated the fraction in the organic layer (Fl/t), the migration center (Xc) and the relaxation depth (α) using 99 soil inventory data sets. Fl/t decreased significantly from 2011 to 2017 (logistic analysis, p < 0.001). In addition, Fl/t in the FDNPP zone rapidly decreased compared to that in the Chernobyl Nuclear Power Plant (ChNPP) zone from the first year to the second year. Different migration rates from organic to mineral soil layers between previous studies in the ChNPP and this study have several possible causes such as organic litter features, climate and physico-chemical forms of initial deposition. In mineral soil layers in the FDNPP zone, only Xc increased significantly with time according to generalized mixed model analysis (p < 0.01). However, Xc and α in the ChNPP zone decreased from two to five years after the accident in 1986, which shows a high 137Cs retention in the organic layer even in the fifth year after the accident. The vertical migration of 137Cs in the mineral soil layer in the FDNPP zone appears to be due to low input of 137Cs from organic to surface mineral soil layer after the second year. These results indicate that 137Cs retention capacity of the organic layer can affect the apparent vertical migration of 137Cs in the underlying mineral soil layer.

Temporal changes in the spatial patterns of air dose rate from 2012 to 2016 at forest floors in Fukushima, Japan.

This study investigates temporal changes in the distribution of air dose rates at forest floors from 2012 to 2016 by measuring air dose rates at a height of 10 cm. The study was conducted at four different topography forest sites in Fukushima Prefecture, Japan. At each forest site, the air dose rate was found to have decreased by 7%-22% over time from 2012 to 2016 owing to the movement of radiocesium from organic layers to mineral soil layers in the forest site. However, the spatial distribution patterns of air dose rates did not change at these forest sites over five years. Besides, high correlations between air dose rates and organic plus surface mineral soil inventories were found at these forest sites during most of study years. Therefore, little changes in the spatial distribution of air dose rates could be caused by radiocesium retention at the same location in these forest sites. No statistical correlation between air dose rates and slope gradients was found in the two hilly forest sites with steep slopes above 35°. Accordingly, this study shows that the distribution patterns of air dose rates in the forest floors remained stable depending on the spatial distribution of radiocesium, which formed in the early phase after the Fukushima Daiichi Nuclear Power Plant accident.

Characterizing vertical migration of 137Cs in organic layer and mineral soil in Japanese forests: Four-year observation and model analysis.

Because of the Fukushima Dai-ichi Nuclear Power Plant accident, forest ecosystems in wide areas were contaminated with 137Cs. It is important to characterize the behavior of 137Cs after its deposition onto forest surface environments for evaluating and preventing long-term radiation risks. In the present study, 137Cs vertical distributions in the soil profile were observed repeatedly at five forest sites with different vegetation types for 4.4 years after the accident in 2011, and 137Cs migration in the organic layer and mineral soil was analyzed based on a comparison of models and observations. Cesium-137 migration from the organic layer to the underlying mineral soil was represented by a two-component exponential model. Cesium-137 migration from the organic layer was faster than that observed in European forests, suggesting that the mobility and bioavailability of 137Cs could be suppressed rapidly in Japanese forests. At all sites, 137Cs transfer in mineral soil could be reproduced by a simple diffusion equation model with continuous 137Cs supply from the organic layer. The diffusion coefficients of 137Cs in the mineral soil were estimated to be 0.042-0.55 cm2 y-1, which were roughly comparable with those of European forest soils affected by the Chernobyl Nuclear Power Plant accident. Model predictions using the determined model parameters indicated that 10 years after the accident, more than 70% of the deposited 137Cs will migrate to the mineral soil but only less than 10% of the total 137Cs inventory will penetrate deeper than 10 cm in the mineral soil across all sites. The results of the present study suggest that the 137Cs deposited onto Japanese forest ecosystems will be retained in the surface layers of mineral soil for a long time.

Click Chemistry: A Versatile Method for Tuning the Composition of Mixed Organic Layers Obtained by Reduction of Diazonium Cations.

Postfunctionalization of glassy carbon electrodes previously modified by reduction of 4-azidobenzenediazonium was exploited to conveniently synthesize controlled mixed organic layers. Huisgen 1,3-dipolar cycloaddition was used to anchor functional entities to azide platform. By this way, ((4-ethynylphenyl)carbamoyl)ferrocene (ϕ-Fc) was coimmobilized with a set of acetylene derivatives: 1-ethynyl-4-nitrobenzene (ϕ-NO2), 4-ethynylaniline (ϕ-NH2) or ethylnylbenzene (ϕ). The composition of the resulting organic layers was tuned by adjusting the acetylene derivatives ratio in the postfunctionalization binary solution. Electronic properties of the substituents beared by the aromatic rings were found to have a strong impact on the cycloaddition kinetics toward the confined azide moieties. From this study, rules to prepare finely tuned bifunctional organic layers can be anticipated.

Increased Electromer Formation and Charge Trapping in Solution-Processed versus Vacuum-Deposited Small Molecule Host Materials of Organic Light-Emitting Devices.

We investigate and compare between organic light-emitting devices (OLEDs) fabricated by solution-coating versus vacuum-deposition. Electroluminescence, photoluminescence, and chromatographic measurements on typical OLED host materials reveal significant electromer formation in layers fabricated by solution-processing, pointing to stronger intermolecular interactions in these systems. Delayed electroluminescence measurements reveal that solution-processed layers also have increased charge traps. The findings provide insights on the morphological differences between solution-processed and vacuum-deposited materials and shed light on the root causes behind the lower electroluminescence stability of solution-processed OLEDs.

Designing a high performance, stable spectroscopic biosensor for the binding of large and small molecules.

In the context of FTIR ATR-based sensors, the organic layer covering the ATR element has to be as stable as possible for optimal spectroscopic measurements. Previously, this self-assembled covering was considered stable after several hours under a PBS flux, probably due to a hydrophobic barrier, which prevents water penetration into the grafted network. Stability and reactivity, measured simultaneously using FTIR ATR, identify the limits of the previously used molecular construction. For the first time, surface etching of the previous functionalised Ge devices (Ge-PEG-NHS), a few minutes after BSA injection, was observed. It was concluded that the molecular chain deformation of Ge-PEG-NHS likely occurred when large molecules were bound. BSA loaded onto a Ge-PEG-NHS surface led to network deprotection, with the probable disruption of hydrogen bonds for single barrier-based networks. This, in turn, was presumably influenced by the random deposition of the NHS moiety on the PEG chain. A new functionalised germanium device, using a rapid three-step in situ procedure, provides an efficient robust network composed of two protective barriers, ideal for the binding of various sized molecules. The Ge-APS-PEG-NHS device has shown exceptional sensitivity with regards to BSA and ethanolamine target molecules while offering homogeneous NHS distribution.

Modeling dynamics of (137)Cs in forest surface environments: Application to a contaminated forest site near Fukushima and assessment of potential impacts of soil organic matter interactions.

A process-based model for (137)Cs transfer in forest surface environments was developed to assess the dynamic behavior of Fukushima-derived (137)Cs in a Japanese forest. The model simulation successfully reproduced the observed data from 3year migration of (137)Cs in the organic and mineral soil layers at a contaminated forest near Fukushima. The migration of (137)Cs from the organic layer to the mineral soil was explained by the direct deposition pattern on the forest floor and the turnover of litter materials in the organic layer under certain ecological conditions. Long-term predictions indicated that more than 90% of the deposited (137)Cs would remain within the top 5cm of the soil for up to 30years after the accident, suggesting that the forest acts as an effective long-term reservoir of (137)Cs with limited transfer via the groundwater pathway. The model was also used to explore the potential impacts of soil organic matter (SOM) interactions on the mobility and bioavailability of (137)Cs in the soil-plant system. The simulation results for hypothetical organic soils with modified parameters of (137)Cs turnover revealed that the SOM-induced reduction of (137)Cs adsorption elevates the fraction of dissolved (137)Cs in the soil solution, thereby increasing the soil-to-plant transfer of (137)Cs without substantially altering the fractional distribution of (137)Cs in the soil. Slower fixation of (137)Cs on the flayed edge site of clay minerals and enhanced mobilization of the clay-fixed (137)Cs in organic-rich soils also appeared to elevate the soil-to-plant transfer of (137)Cs by increasing the fraction of the soil-adsorbed (exchangeable) (137)Cs. A substantial proportion (approximate 30%-60%) of (137)Cs in these organic-rich soils was transferred to layers deeper than 5cm decades later. These results suggested that SOM influences the behavior of (137)Cs in forests over a prolonged period through alterations of adsorption and fixation in the soil.