Protein Corona-Mediated Inhibition of Nanozyme Activity: Impact of Protein Shape.

During biomedical applications, nanozymes, exhibiting enzyme-like characteristics, inevitably come into contact with biological fluids in living systems, leading to the formation of a protein corona on their surface. Although it is acknowledged that molecular adsorption can influence the catalytic activity of nanozymes, there is a dearth of understanding regarding the impact of the protein corona on nanozyme activity and its determinant factors. In order to address this gap, we employed the AuNR@Pt@PDDAC [PDDAC, poly(diallyldimethylammonium chloride)] nanorod (NR) as a model nanozyme with multiple activities, including peroxidase, oxidase, and catalase-mimetic activities, to investigate the inhibitory effects of the protein corona on the catalytic activity. After the identification of major components in the plasma protein corona on the NR, we observed that spherical proteins and fibrous proteins induced distinct inhibitory effects on the catalytic activity of nanozymes. To elucidate the underlying mechanism, we uncovered that the adsorbed proteins assembled on the surface of the nanozymes, forming protein networks (PNs). Notably, the PNs derived from fibrous proteins exhibited a screen mesh-like structure with smaller pore sizes compared to those formed by spherical proteins. This structural disparity resulted in a reduced efficiency for the permeation of substrate molecules, leading to a more robust inhibition in activity. These findings underscore the significance of the protein shape as a crucial factor influencing nanozyme activity. This revelation provides valuable insights for the rational design and application of nanozymes in the biomedical fields.

Nontargeted Analysis of Coumarins in Source Water and Their Formation of Chlorinated Coumarins as DBPs in Drinking Water.

Coumarin was detected as one of the most abundant compounds by nontargeted analysis of natural product components in actual water samples prior to disinfection. More importantly, prechlorination of humic acid generated 3-hydroxycoumarin and monohydroxy-monomethyl-substituted coumarin with a total yield of ≤10.1%, which suggested the humic substance in raw water is an important source of coumarins. 7-Hydroxycoumarin, 6-hydroxy-4-methylcoumarin, 6,7-dihydroxycoumarin, and 7-methoxy-4-methylcoumarin were identified in raw water by high-performance liquid chromatography-tandem high-resolution mass spectrometry because only some coumarin standards were commercially available. Their chlorination generated monochlorinated and polychlorinated coumarins, and their structures were confirmed by the synthesized standards. These products could form at various dosages of chlorine and pH levels, and some with a concentration of 600 ng/L can be stable in tap water for days. 3,6,8-Trichloro-7-hydroxycoumarin, 3-chloro-7-methoxy-4-methylcoumarin, and 3,6-dichloro-7-methoxy-4-methylcoumarin were first identified in finished water with concentrations of 0.0670, 78.1, and 14.7 ng/L, respectively, but not in source water, suggesting that they are new DBPs formed during disinfection. The cytotoxicity of 3-chloro-7-methoxy-4-methylcoumarin in CHO-K1 cells was comparable to those of 2,6-dibromo-1,4-benzoquinone and 2,6-dichloro-1,4-benzoquinone in TIC-Tox analyses, suggesting that further investigation of their occurrence and control in drinking water systems is warranted.

Spatial Scale Effects of the Relationship between Fractional Vegetation Coverage and Land Surface Temperature in Horqin Sandy Land, North China.

Sandy range land refers to a major component of grassland area types in the semi-arid area of northern China. Monitoring of vegetation and land surface temperature (LST) using remote sensing technology can help determine the degree of desertification in a regional and/or sub regional scale, as in the Horqin Sandy Land selected in this study. Correlation analysis was performed to examine the relationship between the fractional vegetation coverage (FVC) and the LST within one growing season (from May to August 2017), at different spatial scales. The results showed that the FVC increased from 0.12 in May to 0.29 in August, and the LST increased first and then declined. The highest LST was 41.68 °C in July, while the lowest was 28.62 °C in August. At the grid scale, the LST increased first and then declined with the increase of the FVC on 25 May, 10 June, and 29 August; the FVC ranged from 0.29-0.38, 0.27-0.32, and 0.29-0.38 with the preference of the 'turning point', respectively. A negative correlation was identified between the FVC and the LST and without any 'turning point' in the fitting curve on 28 July. The correlation between FVC and LST complied with the grid scale at the sample area scale. The coupling analysis of landscape pattern expressed by FVC and LST showed that, the landscape evenness, Euclidean nearest neighbor distance, and landscape splitting degree all showed strong coupling correlation in any study period (P). The landscape aggregation of FVC and LST showed a good coupling at the relatively high and low air temperature conditions of P1 and P3. Landscape contagion showed a good coupling between FVC and LST at relatively moderate air temperature condition of P1 and P4. Air temperature conditions and characteristics of vegetation coverage should be considered for a more targeted analysis when analyzing the relationship between FVC and LST and attention should be paid to the timing and type of study area in practical application.

Effects of aspect on phenology of Larix gmelinii forest in Northeast China.

The response of vegetation phenology to global climate change is one of the main forms in terrestrial ecosystem change, the study of vegetation phenology is an important complement to the understanding of how global climate change affects ecosystems in multiple dimensions. We selected the distribution area of Larix gmelinii in The Greater Khingan Mountains as a case area by eliminating the heterogeneity of vegetation types, with the support of Google Earth Engine platform, we studied the effects of different aspects and land surface temperature (LST) on remote sensing phenology (RSP) that is defined as start of growing season (SOS), end of growing season (EOS) and length of growing season (LOS) respectively in the study area through Normalized Difference Vegetation Index (NDVI) changes. The results showed that SOS advanced in different aspects during the study period, and the advance amplitude of SOS on the east and west aspect was greater than that on the south and north. Except for the east aspect, EOS showed a slight postponed, and LOS was prolonged on all aspects. The latitude difference between 51° and 53° N had no significant effect on L. gmelinii in different aspects. LST had an obviously direct effect on the RSP of L. gmelinii in different aspects, and the effect of LST on SOS and LOS was significantly greater than that on EOS. The effect of LST on SOS and LOS was significant in April and spring. The main contributor to the increase of LOS was the advance of SOS, while the postponed of EOS has a relatively small contribution to LOS. Due to the redistribution of meteorological factor by aspect, the spatial and temporal heterogeneity of RSP tends to be complex, so determining the same aspect is one of the main ways to reduce the phenological heterogeneity in the study of vegetation RSP.

2,6-Dichloro-1,4-benzoquinone formation from chlorination of substituted aromatic antioxidants and its control by pre-ozonation in drinking water treatment plant.

Halobenzoquinones are frequently detected as disinfection by-products in drinking water. Among identified halobenzoquinones, 2,6-dichloro-1,4-benzoquinone (2,6-DCBQ) is particularly toxic and is frequently detected in drinking water. Synthetic aromatic antioxidants discharged to source water may increase the risk of 2,6-DCBQ formation, as many studies suggest that aromatic compounds are the most likely precursors to 2,6-DCBQ. Herein, we investigated the formation of 2,6-DCBQ from chlorination of three model aromatic antioxidants, including 3-tert-butyl-4-hydroxyanisole (BHA), 2,6-di-tert-butyl-4-methylphenol (BHT) and bis(4-tert-butylphenyl)amine (BBPA). Only BBPA produced 2,6-DCBQ under chlorination, while chlorination of BHA and BHT formed α, ß-unsaturated C4-dicarbonyl ring-opening products and phenolic compounds. Based on mass balance and intermediate transformation analysis, mechanisms for the formation of 2,6-DCBQ from BBPA chlorination involved hydrolysis, tert-butyl group cleavage, chlorine substitution, desamination and oxidation. Mitigating aromatic compounds will be an efficient method for 2,6-DCBQ control, such as pre-ozonation, because the intermediates involved in 2,6-DCBQ formation were aromatic compounds. Real water samples from two drinking water treatment plants (DWTPs), one with pre-ozonation (DWTP 2) and the other without pre-ozonation (DWTP1), were analyzed. The two DWTPs were built along the Yangtse river in Nanjing city. Raw water parameters from the two DWTPs, including dissolved organic carbon (DOC), UV absorbance at 254 nm (UV254) and NH3-N, indicated the water quality between these sources was similar. Pre-ozonation in DWTP 2 vanished 2,6-DCBQ in raw water. Concentrations of 2,6-DCBQ in finished water from DWTP 1 (5.69 ng/L) was higher than concentrations generated from DWTP 2 (1.31 ng/L). These results demonstrate that pre-ozonation, granular activated carbon (GAC) and quartz sand treatments at DWTP 2 remove more 2,6-DCBQ precursors than the conventional quartz sand and GAC treatments in DWTP 1. These results suggest the pre-ozonation, GAC and quartz sand treatments can help minimize concentrations of 2,6-DCBQ generated in DWTPs.

In situ analysis of nanoparticle soft corona and dynamic evolution.

How soft corona, the protein corona's outer layer, contributes to biological identity of nanomaterials is largely because capturing protein composition of the soft corona in situ remains challenging. We herein develop an in situ Fishing method that can monitor the dynamic formation of protein corona on ultra-small chiral Cu2S nanoparticles (NPs) allowing us to directly separate and identify the corona protein composition. Our method detects spatiotemporal processes in the evolution of hard and soft coronas on chiral NPs, revealing subtle differences in NP - protein interactions even within several minutes. This study highlights the importance of in situ and dynamic analysis of soft/hard corona, provides insights into the role of soft corona in mediating biological responses of NPs, and offers a universal strategy to characterize soft corona to guide the rational design of biomedical nanomaterials.

Width identification of transition zone between desert and oasis based on NDVI and TCI.

The oasis-desert transition zone, the boundary between the desert and oasis, has special significance in maintaining oasis stability and indicating ecosystem health. The width of the boundary is one of the critical indicators to determine the sampling design and restrict findings scaling in the study of the desert oasis transition zone. Buffer analyze and focal analyze were conducted to determine the width among oasis-desert transition zone and oasis artificial sand fixation zone in Hexi corridor China. Focal analyses indicate that TCImax and TCImin can constrain NDVI of trend variation, and the effect increases with the analysis scale. On the same spatial scale, NDVI and TCI have opposite trends and have intersections. The intersection of the sandy desert transition zone is between 30-90 m, and the oasis artificial sand-fixaion zone is between 90-150 m. The width of the sandy desert transition zone is between 220-300 m, and the width increases with the increase of analysis scale. The oasis artificial sand-fixation zone is between 420 and 540 m, which decreases with the increase of the analysis scale. NDVI shows a trend of decreasing from the oasis boundary to the desert, the trend of TCI is different from that of NDVI, showing an increase from the edge of oasis to the interior of desert. The differences in the spatial distribution of NDVI and TCI can be clearly expressed, and different types of transition zones and analysis scales have their own characteristics.