N-Heterocyclic Carbene-Palladium Polymers Network: Recyclable Pre-catalyst for Effective Suzuki–Miyaura Coupling Reaction in Water

Rational design of high-efficiency N-heterocyclic carbene (NHC) palladium catalyst is of great importance to modern organic synthesis, especially in chemical and pharmaceutical industries. Herein, we fabricate a polymer network containing N-heterocyclic carbene palladium (PNNHC-Pd) catalytic active sites via an immobilization process. The N-heterocyclic carbene palladium can serve as a promising linkage of polymer network as well as an effective catalytic active site owing to its structural preference and strong σ-donating ability with palladium species. The results display that N-heterocyclic carbene palladium disperses homogeneously in polymer network, thus rendering PNNHC-Pd excellent catalytic activity, high stability and superior reusability in palladium-catalyzed Suzuki–Miyaura coupling reaction in aqueous medium. This work provides a new insight into the development of heterogenization of homogeneous catalysts based on polymer network.     

Steel Anti-Corrosion Strategy Enables Long-Cycle Zn Anode

The progress of aqueous zinc batteries (AZBs) is limited by the poor cycling life due to Zn anode instability, including dendrite growth, surface corrosion, and passivation. Inspired by the anti-corrosion strategy of steel industry, a compounding corrosion inhibitor (CCI) is employed as the electrolyte additive for Zn metal anode protection. It is shown that CCI can spontaneously generate a uniform and ≈30 nm thick solid-electrolyte interphase (SEI) layer on Zn anode with a strong adhesion via Zn O bonding. This SEI layer efficiently prohibits water corrosion and guides homogeneous Zn deposition without obvious dendrite formation. This enables reversible Zn deposition and dissolution for over 1100 h under the condition of 1 mA cm⁻² and 1 mAh cm⁻² in symmetric cells. The Zn-MnO₂ full cells with CCI-modified electrolyte deliver an ultralow capacity decay rate (0.013% per cycle) at 0.5 A g⁻¹ over 1000 cycles. Such an innovative strategy paves a low-cost way to achieve AZBs with long lifespan.     

Soil amendment with biochar and manure alters wood stake decomposition and fungal community composition

Biochar and manure can be used for sustainable land management. However, little is known about how soil amendments might affect surface and belowground microbial processes and subsequent wood decomposition. In a split-split-split plot design, we amended soil with two rates of manure (whole plot; 0 and 9 Mg ha⁻¹) and biochar (split plot; 0 and 10 Mg ha⁻¹). Wood stakes of three species (hybrid poplar, triploid Populus tomentosa Carr.; aspen, Populus tremuloides Michx.; and pine, Pinus taeda L.) were placed in two positions (horizontally on the soil surface, and inserted vertically in the mineral soil), which served as a substrate for fungal growth. In 3 years, the decomposition rate (density loss), moisture content, and fungal community (via high-throughput sequencing methods) of stakes were evaluated. Results indicated that biochar and/or manure increased the wood stake decomposition rates, moisture content, and operational taxonomic unit abundance. However, the richness and diversity of fungi were dependent on wood stake position (surface > mineral), species (pine > the two Populus), and sample dates. This study highlights that soil amendment with biochar and/or manure can alter the fungal community, which in turn can enhance an important soil process (i.e., decomposition).     

EVIDENCE OF AN ORGANIC MATRIX FROM DIATOM BIOSILICA1

Most biominerals appear to be composites of organic material and mineral. Whether biosilica is such a composite is unresolved because of a lack of evidence for such organic components. We present evidence that organic material exists within diatom biosilica and can be extracted using HF/NH₄F solutions from frustules isolated from Cyclotella meneghiniana Kütz and diatomaceous earth. To eliminate organic casing on the silicified frustules as a source of organic materials, the casing was removed by oxidation of frustules with NaOCl before extraction. The removal of the casing was confirmed in that oxidized frustules no longer displayed the ability to be stained with ruthenium red and fluorescamine. Frustules examined with EDXA showed an emission peak from sulfur before treatment but no peak following treatment, indicating that oxidation removed organic sulfur. The organic material obtained from extracts of fresh frustules contained both soluble and insoluble components. Only soluble material was evident in extracts from diatomaceous earth. The soluble material appears to contain glycoproteins with relatively high levels of serine and glycine. The soluble proteins from fresh frustules also appear to be phosphorylated. Indirect evidence is presented that suggests the soluble proteins may contain regions of primary structure enriched in anionic amino acids. The soluble extracts differ from general cell contents when the two fractions are compared, suggesting that frustules contain specialized organic material. The identification of silica-specific organic material suggests that mineralization in diatoms may be in part matrix-mediated.     

Effects of organic amines on α-aminoisobutyric acid uptake into the vacuole and on ethylene production by tomato pericarp slices

Experiments were conducted to test the possibility that organic amines inhibit ethylene production by inhibiting transport of the ethylene precursor, 1-aminocyclopro-pane-1-carboxylic acid (ACC), into the vacuole. α-Aminoisobutyric acid (αAIB) was used as a model substrate to study ACC uptake into the vacuole in relationship to ethylene production in pericarp slices of Lycopersicon esculentum Mill. cv. Liberty treated with and without organic amines and related substances. Organic amines (polyamines and other basic amines) inhibited αAIB uptake into the vacuole. These amines also enhanced ACC accumulation in the tissue and reduced the passive efflux of αAIB from the vacuole. Overall, ethylene production was inhibited. The inhibition of αAIB transport and of ethylene production followed a polyvalent cationic progression in the order polyamines > diamines> basic 1-amino acids. Ca²⁺, but not Mg²⁺, strongly stimulated αAIB uptake into the vacuole and ethylene production. At equal concentrations, Ca²⁺ counteracted the inhibitory effects of polyamines on both αAIB uptake and ethylene production. Competitive and irreversible inhibitors of polyamine biosynthesis stimulated αAIB uptake into the vacuole and ethylene production. The results indicate an apparent relationship between polyamines, ACC uptake into the vacuole and ethylene production.     

Summer Epidemics of Apple Scab: The Relationship between Measurements and their Implications for the Development of Predictive Models and Threshold Levels under Different Disease Control Regimes

A 2‐year study on epidemic progress of apple scab was conducted at Randwijk, the Netherlands, in 1998 and 1999. The summer epidemic caused by conidia was studied instead of the well‐described spring season epidemic originating from ascospores. The aim was to investigate relationships between disease measurements, i.e. disease incidence and severity measures of apple scab, and their implications for the development of predictive models and threshold levels. The study characterized good relationships between the measurements on cultivar Jonagold using regression analyses in three disease control regimes (untreated, organic and integrated). For fruit quality prediction, the relationship between fruit incidence (I_f) and leaf incidence (I_l) in the organic control regime was given by I_f = 1.966 + 0.402 × (I_l) (R² = 0.92). As a result of low level of disease in the integrated control regime, shoot incidence (I_s), with higher values than leaf incidence, was better suited for prediction. The relationship was given by I_f = ?0.162 + 0.028 × (I_s) (R² = 0.91). For the integrated control regime, disease threshold levels were constructed for timing of the final fungicide application. If an apple grower wants to keep fruit infection under 1% incidence (harvest scab threshold), the timing of the final fungicide application (action threshold) should correspond to 4% shoot scab incidence at the beginning of August. The results are compared with similar studies and their biological interpretation is discussed.     

Soil 13C–15N dynamics in an N2-fixing clover system under long-term exposure to elevated atmospheric CO2

Reduced soil N availability under elevated CO₂ may limit the plant's capacity to increase photosynthesis and thus the potential for increased soil C input. Plant productivity and soil C input should be less constrained by available soil N in an N₂‐fixing system. We studied the effects of Trifolium repens (an N₂‐fixing legume) and Lolium perenne on soil N and C sequestration in response to 9 years of elevated CO₂ under FACE conditions. ¹⁵N‐labeled fertilizer was applied at a rate of 140 and 560 kg N ha^?1 yr^?1 and the CO₂ concentration was increased to 60 Pa pCO₂ using ¹³C‐depleted CO₂. The total soil C content was unaffected by elevated CO₂, species and rate of ¹⁵N fertilization. However, under elevated CO₂, the total amount of newly sequestered soil C was significantly higher under T. repens than under L. perenne. The fraction of fertilizer‐N (f_N) of the total soil N pool was significantly lower under T. repens than under L. perenne. The rate of N fertilization, but not elevated CO₂, had a significant effect on f_N values of the total soil N pool. The fractions of newly sequestered C (f_C) differed strongly among intra‐aggregate soil organic matter fractions, but were unaffected by plant species and the rate of N fertilization. Under elevated CO₂, the ratio of fertilizer‐N per unit of new C decreased under T. repens compared with L. perenne. The L. perenne system sequestered more ¹⁵N fertilizer than T. repens: 179 vs. 101 kg N ha^?1 for the low rate of N fertilization and 393 vs. 319 kg N ha^?1 for the high N‐fertilization rate. As the loss of fertilizer‐¹⁵N contributed to the ¹⁵N‐isotope dilution under T. repens, the input of fixed N into the soil could not be estimated. Although N₂ fixation was an important source of N in the T. repens system, there was no significant increase in total soil C compared with a non‐N₂‐fixing L. perenne system. This suggests that N₂ fixation and the availability of N are not the main factors controlling soil C sequestration in a T. repens system.     

Land use induced changes of organic carbon storage in soils of China

Using the data compiled from China's second national soil survey and an improved method of soil carbon bulk density, we have estimated the changes of soil organic carbon due to land use, and compared the spatial distribution and storage of soil organic carbon (SOC) in cultivated soils and noncultivated soils in China. The results reveal that ～ 57% of the cultivated soil subgroups ( ～ 31% of the total soil surface) have experienced a significant carbon loss, ranging from 40% to 10% relative to their noncultivated counterparts. The most significant carbon loss is observed for the non‐irrigated soils (dry farmland) within a semiarid/semihumid belt from northeastern to southwestern China, with the maximum loss occurring in northeast China. On the contrary, SOC has increased in the paddy and irrigated soils in northwest China. No significant change is observed for forest soils in southern China, grassland and desert soils in northwest China, as well as irrigated soils in eastern China. The SOC storage and density under noncultivated conditions in China are estimated to ～ 77.4 Pg (10¹⁵ g) and ～ 8.8 kg C m^?2, respectively, compared to a SOC storage of ～ 70.3 Pg and an average SOC density of ～ 8.0 kg C m^?2 under the present‐day conditions. This suggests a loss of ～ 7.1 Pg SOC and a decrease of ～ 0.8 kg C m^?2 SOC density due to increasing human activities, in which the loss in organic horizons has contributed to ～ 77%. This total loss of SOC in China induced by land use represents ～ 9.5% of the world's SOC decrease. This amount is equivalent to ～ 3.5 ppmv of the atmospheric CO₂ increase. Since ～ 78% of the currently cultivated soils in China have been degraded to a low/medium productivities and are responsible for most of the SOC loss, an improved land management, such as the development of irrigated and paddy land uses, would have a considerable potential in restoring the SOC storage. Assuming a restoration of ～ 50% of the lost SOC during the next 20–50 years, the soils in China would absorb ～ 3.5 Pg of carbon from the atmosphere.     

The catchment and climate regulation of pCO2 in boreal lakes

The regulation of surface water pCO₂ was studied in a set of 33 unproductive boreal lakes of different humic content, situated along a latitudinal gradient (57°N to 64°N) in Sweden. The lakes were sampled four times during one year, and analyzed on a wide variety of water chemistry parameters. With only one exception, all lakes were supersaturated with CO₂ with respect to the atmosphere at all sampling occasions. pCO₂ was closely related to the DOC concentration in lakes, which in turn was mainly regulated by catchment characteristics. This pattern was similar along the latitudinal gradient and at different seasons of the year, indicating that it is valid for a variety of climatic conditions within the boreal forest zone. We suggest that landscape characteristics determine the accumulation and subsequent supply of allochthonous organic matter from boreal catchments to lakes, which in turn results in boreal lakes becoming net sources of atmospheric CO₂.