Enhanced electron transfer for the improvement of nitrogen removal efficiency and NO reduction at low temperatures.

Low temperature generally restricts biological activity, slowing down electron transfer in biogeochemical cycles and causing a series of environmental problems such as nitrogen pollution. We present a strategy to boost electron transfer in microbial cell at low temperatures via stimulation with low current. It is demonstrated by establishing a constructed wetland system coupled with solar powered microbial electrolysis cell, which enhances microbial activity through external micro currents (18.

Diverse metabolism drives comammox in continental-scale agricultural streams: Important ammonia oxidation but low NO production.

Agriculture receives approximately 25 % of the annual global nitrogen input, 37 % of which subsequently runs off into adjacent low-order streams and surface water, where it may contribute to high nitrification and nitrous oxide (NO). However, the mechanisms of nitrification and the pathways controlling NO production in agricultural streams remain unknown. Here, we report that the third microbial ammonia oxidation process, complete ammonia oxidation (comammox), is widespread and contributes to important ammonia oxidation with low ammonia-NO conversion in both basin- and continental-scale agricultural streams.

Crystalline nanosheets of three-dimensional supramolecular frameworks with uniform thickness and high stability.

Fabricating three dimensional (3D) supramolecular frameworks (SMFs) into stable crystalline nanosheets remains a great challenge due to the homogeneous and weak inter-building block interactions along 3D directions. Herein, crystalline nanosheets of a 3D SMF with a uniform thickness of 4.8 ± 0.

Ammonium-derived nitrous oxide is a global source in streams.

Global riverine nitrous oxide (NO) emissions have increased more than 4-fold in the last century. It has been estimated that the hyporheic zones in small streams alone may contribute approximately 85% of these NO emissions. However, the mechanisms and pathways controlling hyporheic NO production in stream ecosystems remain unknown.

Tailored Local Electronic Environment of Co-N Sites in Cobalt Phthalocyanines for Enhanced CO Reduction Reaction.

Atomically dispersed Co-N-based catalysts have been recently emerging as one of the most promising candidates for facilitating CO reduction reaction (CORR). The local electronic environment of Co-N sites in these catalysts is considered to play a critical role in adjusting the catalytic performance, the effort of which however is not yet clearly verified. Herein, a series of cobalt phthalocyanines with different peripheral substituents including unsubstituted phthalocyanine Co(II) (CoPc), 2,9,16,23-tetramethoxyphthalocyaninato Co(II) (CoPc-4OCH), and 2,9,16,23-tetranitrophthalocyaninato Co(II) (CoPc-4NO) are supported onto the surface of the multi-walled carbon nanotubes (CNTs), affording CoPc@CNTs, CoPc-4OCH@CNTs, and CoPc-4NO@CNTs.

12 Connecting Sites Linked Three-dimensional Covalent Organic Frameworks with Intrinsic Non-interpenetrated shp Topology for Photocatalytic HO Synthesis.

Developing high connectivity (>8) three-dimensional (3D) covalent organic frameworks (COFs) towards new topologies and functions remains a great challenge owing to the difficulty in getting high connectivity organic building blocks. This however represents the most important step towards promoting the diversity of COFs due to the still limited dynamic covalent bonds available for constructing COFs at this stage. Herein, highly connected phthalocyanine-based (Pc-based) 3D COFs MPc-THHI-COFs (M=H, Ni) were afforded from the reaction between 2,3,9,10,16,17,23,24-octacarboxyphthalocyanine M(TAPc) (M=H, Ni) and 5,5',5'',5''',5'''',5'''''-(triphenylene-2,3,6,7,10,11-hexayl)hexa(isophthalohydrazide) (THHI) with 12 connecting sites.

Dithiine-linked metalphthalocyanine framework with undulated layers for highly efficient and stable HO electroproduction.

Realization of stable and industrial-level HO electroproduction still faces great challenge due large partly to the easy decomposition of HO. Herein, a two-dimensional dithiine-linked phthalocyaninato cobalt (CoPc)-based covalent organic framework (COF), CoPc-S-COF, was afforded from the reaction of hexadecafluorophthalocyaninato cobalt (II) with 1,2,4,5-benzenetetrathiol. Introduction of the sulfur atoms with large atomic radius and two lone-pairs of electrons in the C-S-C linking unit leads to an undulated layered structure and an increased electron density of the Co center for CoPc-S-COF according to a series of experiments in combination with theoretical calculations.

Single Cobalt Ion-Immobilized Covalent Organic Framework for Lithium-Sulfur Batteries with Enhanced Rate Capabilities.

Covalent organic frameworks (COFs) are notable for their remarkable structure, function designability, and tailorability, as well as stability, and the introduction of "open metal sites" ensures the efficient binding of small molecules and activation of substrates for heterogeneous catalysis and energy storage. Herein, we use the postsynthetic metal sites to catalyze polysulfide conversion and to boost the binding affinity to active matter for lithium-sulfur batteries (LSBs). A dual-pore COF, USTB-27, with topology has been successfully assembled from the imine chemical reaction between 2,3,8,9,14,15-hexa(4-formylphenyl)diquinoxalino [2,3-:2',3'-c]phenazine and [2,2'-bipyridine]-5,5'-diamine.

Observation of Interpenetrated Topology Isomerism for Covalent Organic Frameworks with Atom-Resolution Single Crystal Structures.

Rational control and understanding of isomerism are of significance but still remain a great challenge in reticular frameworks, in particular, for covalent organic frameworks (COFs) due to the complicated synthesis and energy factors. Herein, reaction of 3,3',5,5'-tetra(4-formylphenyl)-2,2',6,6'-tetramethoxy-1,1'-biphenyl (TFTB) with 3,3',5,5'-tetrakis(4-aminophenyl)bimesityl (TAPB) under different reaction conditions affords single crystals of two 3D COF isomers, namely, USTB-20-dia and USTB-20-qtz. Their structures with resolutions up to 0.

Linkage conversions in single-crystalline covalent organic frameworks.

Single-crystal X-ray diffraction is a powerful characterization technique that enables the determination of atomic arrangements in crystalline materials. Growing or retaining large single crystals amenable to it has, however, remained challenging with covalent organic frameworks (COFs), especially suffering from post-synthetic modifications. Here we show the synthesis of a flexible COF with interpenetrated qtz topology by polymerization of tetra(phenyl)bimesityl-based tetraaldehyde and tetraamine building blocks.

Highly Connected Three-Dimensional Covalent Organic Framework with Flu Topology for High-Performance Li-S Batteries.

Lithium-sulfur batteries (LSBs) have been considered as a promising candidate for next-generation energy storage devices, which however still suffer from the shuttle effect of the intermediate lithium polysulfides (LiPSs). Covalent-organic frameworks (COFs) have exhibited great potential as sulfur hosts for LSBs to solve such a problem. Herein, a pentiptycene-based symmetrical octatopic polyaldehyde, 6,13-dimethoxy-2,3,9,10,18,19,24,25-octa(4'-formylphenyl)pentiptycene (DMOPTP), was prepared and utilized as a building block toward preparing COFs.

Post-Nickelation of a Crystalline Trinuclear Copper Organic Framework for Synergistic Photocatalytic Carbon Dioxide Conversion.

Rational regulation of electronic structures and functionalities of framework materials still remains challenging. Herein, reaction of 4,4',4''-nitrilo-tribenzhydrazide with tris(μ -4-carboxaldehyde-pyrazolato-N,N')-tricopper (Cu Py ) generates the crystalline copper organic framework USTB-11(Cu). Post-modification with divalent nickel ions affords the heterometallic framework USTB-11(Cu,Ni).

Learning from undercoded clinical records for automated International Classification of Diseases (ICD) coding.

Objectives: To develop an unbiased objective for learning automatic coding algorithms from clinical records annotated with only partial relevant International Classification of Diseases codes, as annotation noise in undercoded clinical records used as training data can mislead the learning process of deep neural networks.

Materials And Methods: We use Medical Information Mart for Intensive Care III as our dataset. We employ positive-unlabeled learning to achieve unbiased loss estimation, which is free of misleading training signal.

Conjugated Three-Dimensional High-Connected Covalent Organic Frameworks for Lithium-Sulfur Batteries.

Developing conjugated three-dimensional (3D) covalent organic frameworks (COFs) still remains an extremely difficult task due to the lack of enough conjugated 3D building blocks. Herein, condensation between an 8-connected pentiptycene-based building block (DMOPTP) and 4-connected square-planar linkers affords two 3D COFs (named 3D-scu-COF-1 and 3D-scu-COF-2). A combination of the 3D homoaromatic conjugated structure of the former building block with the 2D conjugated structure of the latter linking units enables the π-electron delocalization over the whole frameworks of both COFs, endowing them with excellent conductivities of 3.

Two-Dimensional Porphyrin-Based Covalent Organic Framework with Enlarged Inter-layer Spacing for Tunable Photocatalytic CO Reduction.

Two-dimensional (2D) porphyrin-based covalent organic frameworks (COFs) are one of the most promising candidates for photocatalytic carbon dioxide reduction reaction (CORR), which however still suffer from the hindered mass transfer during the catalysis procedure associated with the close packing of 2D COF layers due to the strong axial π-π stacking. Herein, condensation between the porphyrinic aldehydes -MPor-CHO (M = H, Co, and Ni) and 3,8-diamino-6-phenyl-phenanthridine (DPP) affords new porphyrin-based 2D COF architecture MPor-DPP-COFs (M = H, Co, and Ni). The bulky phenyl substituent at the phenanthridine periphery of the linking unit reduces the axial π-π stacking, providing an enlarged inter-layer spacing of 6.

In Situ Growth of Covalent Organic Framework Nanosheets on Graphene as the Cathode for Long-Life High-Capacity Lithium-Ion Batteries.

The poor electronic and ionic conductivities of covalent organic frameworks (COFs) severely restrict the development of COF-based electrodes for practical rechargeable batteries, therefore inspiring more research interest from the direction of both material synthesis and technology. Herein, a dual-porous COF, USTB-6, with good crystallinity and rich redox-active sites is conceived and fabricated by the polymerization of 2,3,8,9,14,15-hexa(4-formylphenyl)diquinoxalino [2,3-a:2',3'-c]phenazine and 2,7-diaminopyrene-4,5,9,10-tetraone. In particular, the heterogeneous polymerization of the same starting materials in the presence of graphene affords uniformly dispersed COF nanosheets with a thickness of 8.

Transformation of Porous Organic Cages and Covalent Organic Frameworks with Efficient Iodine Vapor Capture Performance.

The reaction of 5,5'-([2,2'-bipyridine]-5,5'-diyl)diisophthalaldehyde (BPDDP) with cyclohexanediamine and [benzidine (BZ)/[2,2'-bipyridine]-5,5'-diamine (BPDA)], respectively, affords a nitrogen-rich porous organic cage BPPOC and two two-dimensional (2D) covalent organic frameworks (COFs), USTB-1 and USTB-2 (USTB = University of Science and Technology Beijing), under suitable conditions. Interestingly, BPPOC with a single-crystal X-ray diffraction structure is able to successfully transform into USTB-1 and USTB-2 (newly converted COFs denoted as USTB-1c and USTB-2c, respectively) upon exchange of the imine unit of cyclohexanediamine in the cage by BZ and BPDA. Such a transformation also enables the isolation of analogous COFs (USTB-3c and USTB-4c) on the basis of an isostructural organic cage, BTPOC, which is derived from 5,5'-([2,2'-bithiophene]-4,4'-diyl)diisophthalaldehyde (BTDDP) and cyclohexanediamine.