[Chemical structure characteristics of organic carbon in saline soil aggregates under straw returning condition]. / 秸秆还田条件下盐渍土团聚体中有机碳化学结构特征.

We examined the regularity of distribution and chemical structure characteristics of organic carbon in soda alkaline fluvo-aquic soil aggregates after straw returning. We set up six different straw returning treatments in 2020, including 0 (CK), 2100 (ST1), 4200 (ST2), 6300 (ST3), 8400 (ST4) and 10500 kg·hm-2(full straw returning, ST5). We measured organic carbon (OC) content and infrared spectroscopy characteristics of aggregates and internal different components through physical fractionation method and infrared spectroscopy technology. The results showed that: 1) the OC content of soil and all aggregates increased with the increasing amount of returned straw; 2) different straw returning treatments significantly increased the content of light organic carbon (LOC) in 53-250 µm aggregates. Compared with CK, ST3 and ST4 treatments significantly increased the content of mineral-bound organic carbon (MOC) in 250-2000 µm aggregates and the content of fine particulate organic carbon (fPOC) in 53-250 µm aggregates. The OC content of different components in aggregates followed the order of LOC>MOC>POC. The fPOC content in 250-2000 µm aggregates was higher than that of coarse particulate organic carbon (cPOC); 3) the results of principal component analysis showed that OC chemical structure of different components in aggregates was seldom affected by the straw returning, but was mainly affected by particle size; 4) the OCs in >250 µm aggregates were mainly derived from aromatic carbon and polysaccharides. The OCs in 53-250 µm aggregates were mainly derived from carbohydrates, such as monosaccharides and polysaccharides, while the OC in <53 µm aggregates was mainly derived from aliphatic carbon, alkyl carbon, aromatic carbon and phenolic alcohols. Within different aggregates, LOC was mainly derived from aliphatic carbon, aromatic carbon and phenolic alcohols. Particulate organic carbon (POC) was mainly derived from carbohydrates. MOC was mainly derived from alkyl carbon. In summary, straw returning increased organic carbon content in soil aggregates in short term, but did not alter organic carbon chemical structure. The organic carbon chemical structures of the same particle size fractions in different aggregates were similar. The organic carbon content increased with the decreases of particle size, and the chemical structure tended to be stable. Therefore, straw returning promoted the fixation of organic carbon by saline soil aggregates in short term, but did not change their chemistry structural characteristics, indicating that the location and protection degree of soil organic carbon in aggregates were the main factors affecting the chemical structure of organic carbon.

A POM-based copper-coordination polymer crystal material for phenolic compound degradation by immobilizing horseradish peroxidase.

A new polyoxometalate (POM)-based organic-inorganic hybrid Cu-coordination polymer, namely {((Cu(bipy))2(µ-PhPO3)2Cu(bipy))2H(PCuW11O39)·3H2O}n (denoted as compound 1, bipy = 2,2'-bipyridine, PhPO3 = phenylphosphonate), was self-assembled hydrothermally. Single-crystal X-ray diffraction (SC-XRD) analysis shows that two unique types of 1D chains are present in compound 1, i.e. Cu(II)-organophosphine and organonitrogen complex cation ([((Cu(bipy))2(µ-PhPO3)2Cu(bipy))2]4+) chains and Cu-monosubstituted Keggin-type polyoxoanion ([PCuW11O39]5-) chains, forming a hetero-POM. Crystalline compound 1 as a new enzyme immobilization support exhibited a high horseradish peroxidase (HRP) loading capacity (268 mg g-1). The powder X-ray diffraction (PXRD), FTIR, zeta potential, confocal laser scanning microscopy (CLSM) and circular dichroism (CD) results show that HRP is only immobilized on the surface of compound 1 through simple physical adsorption without a secondary structure change. This POM-immobilized enzyme (HRP/1) was first used for degradation of pollutants in wastewater, and it showed a high degradation efficiency and TOC removal efficiency for phenol, 4-chlorophenol (4-CP) and 2,4-dichlorophenol (2,4-DCP) within 30 min reaction time. Moreover, HRP/1 exhibited better operational and storage stabilities and reusability compared with free HRP. This work suggests that POMs can be used as new supports for enzyme immobilization and POM-immobilized enzymes may be used as a new kind of biocatalyst for degradation of phenolic pollutants.

A new hexamolybdate-based copper-2,2'-biimidazole coordination polymer serving as an acid catalyst and support for enzyme immobilization.

The hydrothermal reaction of (NH4)3[CoMo6O24H6]·7H2O (CoMo6), CuCl2·2H2O and 2,2'-biimidazole (H2biim) led to the formation of a new coordination polymer, namely poly[diaquabis(2,2'-biimidazole)hexa-µ3-oxo-octa-µ2-oxo-hexaoxodicopper(II)hexamolybdate(VI)], [Cu2Mo6O20(C6H6N4)2(H2O)2]n (Cu-Mo6O20), at pH 2-3. It is obvious that in the formation of crystalline Cu-Mo6O20, the original Anderson-type skeleton of heteropolymolybdate CoMo6 was broken and the new isopolyhexamolybdate Mo6O20 unit was assembled. In Cu-Mo6O20, one Mo6O20 unit connects four [Cu(H2biim)(H2O)]2+ ions in a pentacoordinate mode via four terminal O atoms, resulting in a tetra-supported structure, and each CuII ion is shared by two adjacent Mo6O20 units. Infinite one-dimensional chains are established by linkage between two adjacent Mo6O20 units and two CuII ions, and these chains are further packed into a three-dimensional framework by hydrogen bonds, π-π interactions and electrostatic attractions. The catalytic performance of this crystalline material used as an efficient and reusable heterogeneous acid catalyst for carbonyl-group protection is discussed. In addition, Cu-Mo6O20 was applied as a new support for enzyme (horseradish peroxidase, HRP) immobilization, forming immobilized enzyme HRP/Cu-Mo6O20. HRP/Cu-Mo6O20 showed good catalytic activity and could be reused.

Three new Strandberg-type phenylphosphomolybdate supports for immobilizing horseradish peroxidase and their catalytic oxidation performances.

Three organic-inorganic hybrids containing Strandberg-type phenylphosphomolybdate anion [(C6H5PO3)2Mo5O15]4- with phenylphosphonate (PhP) centers, transition metal (TM) ions and 2,2'-biimidazole (H2biim) ligand, formulated as [(TM(H2biim)2)2(C6H5PO3)2Mo5O15]·H2O (TM = Co and Cu, abbreviated as Co-(PhP)2Mo5 and Cu-(PhP)2Mo5, respectively) and ([Ni(H2biim)3])2[(C6H5PO3)2Mo5O15]·2H2O (abbreviated as Ni-(PhP)2Mo5), were self-assembled by simple hydrothermal methods and were systematically characterized through single-crystal X-ray diffraction and other physicochemical and spectroscopic methods, which demonstrated that TM-H2biim complexes were firstly introduced into Strandberg-type organophosphomolybdate skeletons. Selecting the oxidation of cyclohexanol to cyclohexanone as a model reaction, using H2O2 as an oxidant, the catalytic oxidation activities of the Strandberg-type compounds were firstly evaluated. More importantly, these TM-(PhP)2Mo5 (TM = Co, Cu, Ni) compounds were employed to immobilize horseradish peroxidase (HRP), and showed high adsorption capacities for HRP. Laser scanning confocal microscope images showed that HRP adsorbed on the surfaces of the TM-(PhP)2Mo5 supports. Application of immobilized enzyme HRP/TM-(PhP)2Mo5 for the detection of H2O2 is also discussed.