The aggregation of molecular metal oxides into larger superstructures can bridge the gap between molecular compounds and solid-state materials. Here, we report that functionalization of polyoxotungstates with organo-boron substituents leads to giant polyoxometalate-based nanocapsules with dimensions of up to 4 nm. A "lock and key" mechanism enables the site-specific anchoring of aromatic organo-boronic acids to metal-functionalized Dawson anions [M 3 P 2 W 15 O 62 ] 9À (M = Ta V or Nb V ), resulting in unique nanocapsules containing up to twelve POM units. Experimental and theoretical studies provide initial insights into the role of the organo-boron moieties and the metal-functionalized POMs for the assembly of the giant aggregates. The study therefore lays the foundations for the design of organo-POM-based functional nanostructures.Supporting information and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

The influence of the pincer platform composition and substitution on the reactivity and physical properties of pincer complexes can be easily explored through different experimental techniques. However, the influence of these factors on the molecular structures and thermodynamic stability of pincer complexes is usually very subtle and cannot always be unambiguously established. To rationalize this subtle influence, a survey of crystallographic data from 130 group 10 metal pincer complexes supported by benzene-based PYCYP pincer ligands, [2,6-(R2PY)2C6H3–n R′ n ]­MX (Y = CH2, NH, O, S; M = Ni, Pd, Pt; R = tBu, iPr, Ph, Cy, Me; R′ = CO2Me, tBu, CF3, Ac; n = 0–2; X = F, Cl, Br, I, H, SH, SPh, SBn, Ph, Me, N3, NCS), was carried out. Theoretical calculations for some selected complexes were performed to evaluate the relative bond strength. It was found that the M–Cipso bond length decreases following the linker series of CH2 > NH > O and that the relative M–Cipso bond strength increases following the linker series of CH2 < NH < O. In most cases, the M–P bond length decreases following the linker series of NH > CH2 > O. The relative M–P bond strength increases following the linker series of CH2 < NH < O. A comparison of the thermochemical balance for the isodesmic displacement of the side-arm interactions with PH3 as a probe ligand indicated that the Ni–P bond in a PCCCP-type pincer complex is far less difficult to break compared with that in a POCOP-type complex. As a result, with the same donor substituents and the same auxiliary ligand, the POCOP-type pincer complexes are thermodynamically more stable than the PCCCP complexes. The influence of other backbone and donor substitutions as well as the pincer platform composition on the M–Cipso, M–P, and M–X bond lengths, relative bond strengths, and P–M–P bite angles was also discussed.

The structure, properties and catalytic activity of two series of Pd(ii) complexes supported by PBP and POCOP pincer ligands were investigated.

Cinnamaldehyde, of the genius Cinnamomum, is a major constituent of the bark of the cinnamon tree and possesses broad-spectrum antimicrobial activity. In this study, we used best multiple linear regression (BMLR) to develop quantitative structure activity relationship (QSAR) models for cinnamaldehyde derivatives against wood-decaying fungi Trametes versicolor and Gloeophyllun trabeum. Based on the two optimal QSAR models, we then designed and synthesized two novel cinnamaldehyde compounds. The QSAR models exhibited good correlation coefficients: R 2 Tv = 0.910 for Trametes versicolor and R 2 Gt = 0.926 for Gloeophyllun trabeum. Small errors between the experimental and calculated values of two designed compounds indicated that these two QSAR models have strong predictability and stability.

No abstract

Some synthetic sucrose esters (SE) are a relatively new class of insecticidal compounds produced by reacting sugars with fatty acids, which are safe for the environment. Especially, sucrose esters composed of C 6 -C 12 fatty acids have desirable insecticidal properties against many soft-bodied arthropod pests. In our study, sucrose octanoate which has the highest activity against a range of arthropod species was synthesized by a trans-esterification method and proved its insecticidal property. Under the condition of a homogeneous liquid, sucrose octanoate was prepared by reacting ethyl octanoate with sucrose at reduced pressure; the yield was 79.11%. Sucrose octanoate synthesized was identified and its property analyzed by IR, TLC and spectrophotometric analysis. It was shown that the ratio of monoester to polyester in sucrose octanoate was 1.48:1. The insecticidal activity of the synthetic sucrose octanoate was evaluated at a concentration of 4 and 8 mg·mL -1 . The mortality of first-instar larvae of Lymantria dispar from its contact toxicity was 72.5% after 36 hours, the revision insect reduced rate of Aphis glycines reached above 80% at 4 and 8 mg·mL -1 after being treated for 5 days. Since the SE products are nontoxic to humans and higher animals, fully biodegradable and hydrolyzed to readily metabolizable sucrose and fatty acid, they are not harmful to crops and appear to be good insecticide candidates.

Current antimold agents that capitalize on broad spectrum biocidal toxicity for their efficacy can create potential hazards in the environment, as in many cases these biocides are not chemically bonded to the wood. They can therefore leach into the ecosystem to jeopardize off-target organisms. In this study, "bio-catalysis" of potassium iodide (KI) was used to impart non-diffusible antimold properties to 4-year-old bamboo, and the mechanisms of how this system works against Aspergillus niger and Trichoderma viride fungi were also studied. In addition to the bamboo block material tested, powdered samples of lignin, cellulose and hemicellulose were studied to better understand binding of iodide to the chemical subcomponents of the bamboo cell walls. Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) analyses were used to investigate the sample chemistries and antimold mechanisms, respectively. The results revealed that a specific ratio of laccase enzyme with a laccase-mediator functioned best in binding KI to bamboo. Lignin samples showed the greatest changes in FTIR, especially relative to the methoxyl groups and aromatic skeleton. Additionally, enzyme activity on lignin moieties showed much more differences than on hemicellulose and cellulose after biocatalyzed KI modification. Moreover, the XPS binding energy readings of 621.1 and 632.7 eV (Aromatic region) for lignin were consistent with I-C binding associated with its phenolic structures. While the 620.7 eV (Aliphatic region) suggested

Enzymatic hydrolysis (EH) lignin was utilized to replace phenol partially for preparing phenol-formaldehyde (PF) resin adhesives. The influence of the degree of lignin substitution on the properties of the lignin phenol-formaldehyde (LPF) resin adhesive was investigated. The results demonstrated that up to 50% of phenol in the resin could be replaced by EH lignin without damaging the bonding strength of the adhesive, and a lower free phenol content was observed in LPF resin adhesives. Fourier transform infrared spectroscopy spectra of the resins revealed that the introduction of lignin did not appreciably change the final chemical structure of the adhesive, but did negatively impact the resin's thermal ultimate stability. Furthermore, compared to bio-ethanol production residue-modified phenol-formaldehyde (ERPF) resin, the LPF resin exhibited higher bonding strength at the same level of the phenol substitution. This result of the comparison indicated that the raw biomass extraction process improved the performance of the bio-based PF resin.