Advanced Characterization Methodology to Unravel the Biodegradability of Metal-Organic Framework Nanoparticles in Extremely Diluted Conditions.

Porous iron(III) carboxylate metal-organic frameworks (MIL-100; MIL stands for Material of Institute Lavoisier) of submicronic size (nanoMOFs) have attracted a growing interest in the field of drug delivery due to their high drug payloads, excellent entrapment efficiencies, biodegradable character, and poor toxicity. However, only a few studies have dealt with the nanoMOF degradation mechanism, which is key to their biological applications. Complementary methods have been used here to investigate the degradation mechanism of Fe-based nanoMOFs under neutral or acidic conditions and in the presence of albumin. High-resolution STEM-HAADF coupled with energy-dispersive X-ray spectroscopy enabled the monitoring of the crystalline organization and elemental distribution during degradation. NanoMOFs were also deposited onto silicon substrates by dip-coating, forming stable thin films of high optical quality. The mean film thickness and structural changes were further monitored by IR ellipsometry, approaching the "sink conditions" occurring in vivo. This approach is essential for the successful design of biocompatible nano-vectors under extreme diluted conditions. It was revealed that while the presence of a protein coating layer did not impede the degradation process, the pH of the medium in contact with the nanoMOFs played a major role. The degradation of nanoMOFs occurred to a larger extent under neutral conditions, rapidly and homogeneously within the crystalline matrices, and was associated with the departure of their constitutive organic ligand. Remarkably, the nanoMOFs' particles maintained their global morphology during degradation.

Spatial distribution characteristics and degradation mechanism of microorganisms in n-hexadecane contaminated vadose zone.

The damage caused by petroleum hydrocarbon pollution to soil and groundwater environment is becoming increasingly significant. The vadose zone is the only way for petroleum hydrocarbon pollutants to leak from surface into groundwater. The spatial distribution characteristics of indigenous microorganisms in vadose zone, considering presence of capillary zones, have rarely been reported. To explore the spatial distribution characteristics of indigenous microorganisms in vadose zone contaminated by petroleum hydrocarbons, a one-dimensional column migration experiment was conducted using n-hexadecane as characteristic pollutant. Soil samples were collected periodically from different heights during experiment. Corresponding environmental factors were monitored online. The microbial community structure and spatial distribution characteristics of the cumulative relative abundance were systematically analyzed using 16S rRNA sequencing. In addition, the microbial degradation mechanism of n-hexadecane was analyzed using metabolomics. The results showed that presence of capillary zone had a strong retarding effect on n-hexadecane infiltration. Leaked pollutants were mainly concentrated in areas with strong capillary action. Infiltration and displacement of NAPL-phase pollutants were major driving force for change in moisture content (θ) and electric conductivity (EC) in vadose zone. The degradation by microorganisms results in a downward trend in potential of hydrogen (pH) and oxidation-reduction potential (ORP). Five petroleum hydrocarbon-degrading bacterial phyla and 11 degradable straight-chain alkane bacterial genera were detected. Microbial degradation was strong in the area near edge of capillary zone and locations of pollutant accumulation. Mainly Sphingomonas and Nocardioides bacteria were involved in microbial degradation of n-hexadecane. Single-end oxidation involved microbial degradation of n-hexadecane (C16H34). The oxygen consumed, hexadecanoic acid (C16H32O2) produced during this process, and release of hydrogen ions (H+) were the driving factors for reduction of ORP and pH. The vadose zone in this study considered presence of capillary zone, which was more in line with actual contaminated site conditions compared with previous studies. This study systematically elucidated vertical distribution characteristics of petroleum hydrocarbon pollutants and spatiotemporal variation characteristics of indigenous microorganisms in vadose zone considered presence of capillary zone. In addition, the n-hexadecane degradation mechanism was elucidated using metabolomics. This study provides theoretical support for development of natural attenuation remediation measures for petroleum-hydrocarbon-contaminated soil and groundwater.

Lignin bioconversion based on genome mining for ligninolytic genes in Erwinia billingiae QL-Z3.

BACKGROUND: Bioconversion of plant biomass into biofuels and bio-products produces large amounts of lignin. The aromatic biopolymers need to be degraded before being converted into value-added bio-products. Microbes can be environment-friendly and efficiently degrade lignin. Compared to fungi, bacteria have some advantages in lignin degradation, including broad tolerance to pH, temperature, and oxygen and the toolkit for genetic manipulation. RESULTS: Our previous study isolated a novel ligninolytic bacterial strain Erwinia billingiae QL-Z3. Under optimized conditions, its rate of lignin degradation was 25.24% at 1.5 g/L lignin as the sole carbon source. Whole genome sequencing revealed 4556 genes in the genome of QL-Z3. Among 4428 protein-coding genes are 139 CAZyme genes, including 54 glycoside hydrolase (GH) and 16 auxiliary activity (AA) genes. In addition, 74 genes encoding extracellular enzymes are potentially involved in lignin degradation. Real-time PCR quantification demonstrated that the expression of potential ligninolytic genes were significantly induced by lignin. 8 knock-out mutants and complementary strains were constructed. Disruption of the gene for ELAC_205 (laccase) as well as EDYP_48 (Dyp-type peroxidase), ESOD_1236 (superoxide dismutase), EDIO_858 (dioxygenase), EMON_3330 (monooxygenase), or EMCAT_3587 (manganese catalase) significantly reduced the lignin-degrading activity of QL-Z3 by 47-69%. Heterologously expressed and purified enzymes further confirmed their role in lignin degradation. Fourier transform infrared spectroscopy (FTIR) results indicated that the lignin structure was damaged, the benzene ring structure and groups of macromolecules were opened, and the chemical bond was broken under the action of six enzymes encoded by genes. The abundant enzymatic metabolic products by EDYP_48, ELAC_205 and ESOD_1236 were systematically analyzed via liquid chromatography-mass spectrometry (LC-MS) analysis, and then provide a speculative pathway for lignin biodegradation. Finally, The activities of ligninolytic enzymes from fermentation supernatant, namely, LiP, MnP and Lac were 367.50 U/L, 839.50 U/L, and 219.00 U/L by orthogonal optimization. CONCLUSIONS: Our findings provide that QL-Z3 and its enzymes have the potential for industrial application and hold great promise for the bioconversion of lignin into bioproducts in lignin valorization.

[Biodegradation of polyethylene terephthalate: a review].

Plastics are widely used in human daily life, which bring great convenience. Nevertheless, the disposal of a large amount of plastic wastes also brings great pressure to the environment. Polyethylene terephthalate (PET) is a polymer thermoplastic material produced from petroleum. It has become one of the most commonly used plastics in the world due to its durability, high transparency, light weight and other characteristics. PET can exist in nature for a long time due to its complex structure and the difficulty in degradation, which causes serious pollution to the global ecological environment, and threatens human health. The degradation of PET wastes has since become one of the global challenges. Compared with physical and chemical methods, biodegradation is the greenest way for treating PET wastes. This review summarizes the recent advances on PET biodegradation including microbial and enzymatic degradation of PET, biodegradation pathway, biodegradation mechanisms, and molecular modification of PET-degrading enzymes. In addition, the prospect for achieveing efficient degradation of PET, searching and improving microorganisms or enzymes that can degrade PET of high crystallinity are presented, with the aimto facilitate the development, application and molecular modification of PET biodegradation microorganisms or enzymes.

Sonochemical synthesis of amphoteric Cu0-Nanoparticles using Hibiscus rosa-sinensis extract and their applications for degradation of 5-fluorouracil and lovastatin drugs.

Recent studies reported the detection of numerous emerging and active pharmaceutical constituents in the ground and surface water. To address these issues, the present study reported the ultrasound-assisted synthesis of zero-valent copper (Cu0) nanoparticles using Hibiscus rosa-sinensis extract as reducing and stabilizing agent. The catalyst was characterized using XRD, SEM, EDX, PSA, BET, etc., and the results revealed that sonochemical synthesis technique influenced the crystallinity with controlled growth of Cu0. While the hard ligand hydroxyl group (-OH) reduces the Cu2+ to Cu0 and soft ligand carbonyl group (CO) present in the oxidized polyphenols helps in capping and stabilizing the Cu0-nanoparticles. During the ultrasound application, continuous release of Cu+ from Cu0 promoted the degradation by producing OH and O2•- radicals. Approx. 91.3 % and 93.2 % degradation efficiencies were achieved for 5-fluorouracil and lovastatin. The results showed that Cu0 nanoparticles were amphoteric in nature and the synergy calculation revealed that ultrasound has a direct influence on degradation of drugs which are difficult to degrade/mineralize using conventional techniques. Based on the results, a possible degradation mechanism of drug molecules in the presence of oxidants, zero-valent copper and ultrasound has been proposed.

Study on Stability of Salvianolate Lyophilized Injection and Establishment of Stability-Indicating Analysis Method / 中国实验方剂学杂志

Objective::To study the degradation of salvianolate lyophilized injection (SLI) and establish a stability-indicating analysis method. Method::UPLC-Q-TOF-MS/MS was used to conduct a qualitative study on the main components of SLI, and a stability-indicating analysis method was established for simultaneous determination of the original components of SLI and its degradation products. The stability of SLI were systematically assessed under physicochemical conditions of high temperature, oxidation, metal ions. Result::Totally 13 main active ingredients in SLI were identified, and a semi-quantitative analysis was performed. Under the conditions of high temperature, oxidation, light, trivalent ion and divalent ion, 6, 4, 3, 4 and 1 new degradation products were added respectively. The established stability-indicating analysis method can simultaneously determine the degradation products of the main components and their active components in SLI, with a good separation effect. Conclusion::According to the degradation mechanism of the main ingredients in SLI, macromolecular polyphenol acid compounds are degraded into small molecular compounds, such as tanshinol and protocatechu aldehyde by a series of reactions, like benzofuran open-loop, hydrolysis of ester bond and removal of DSS. The stability-indicating analysis method can be used for the stability quality control of traditional Chinese medicine Salvianolate Lyophilized Injection (SLI).

Characteristics and mechanism of toluene removal from gas by novelty array double dielectric barrier discharge combined with TiO2/Al2O3 catalyst.

A new reactor of array double dielectric barrier discharge (DDBD) combined with catalysis was prepared, and the effect of different factors on removal efficiency of toluene at pilot scale were investigated. The possible degradation mechanism was explored. The results indicate that the removal efficiency of toluene in the exhaust gas decreases with the increasing of the toluene initial concentration and the gas flow rate, but increases with the increasing of the specific energy density. When the air relative humidity is 55%, the removal efficiency of toluene is higher than that of the relative humidity by 85%. The results of XPS, FT-IR and GC-MS analysis show that the main intermediate products of removing toluene by DDBD combined with TiO2/Al2O3 catalyst are phenol, benzaldehyde, benzyl alcohol, benzoic acid, N-benzyl formamide, dimethyl terephthalate, dimethyl isophthalate and other substances. There are five possible pathways to degrade toluene by DDBD combined with TiO2/Al2O3.

Thermal and Photochemical Stability of Anthocyanins from Black Carrot, Grape Juice, and Purple Sweet Potato in Model Beverages in the Presence of Ascorbic Acid.

Anthocyanins are natural dyes widely used in the food industry, but their chemical stability in beverages can be affected by the presence of additives. In the present paper, the interaction between anthocyanins and ascorbic acid (AA) is more particularly investigated. Ascorbic acid is an ubiquitous component in food products. In this study, the thermal stability at 43 °C and the photolysis stability in air and in an inert atmosphere (N2) of anthocyanins extracted from black carrot (BC), grape juice (GJ), and purple sweet potato (SP) were studied in the presence and absence of ascorbic acid (in citrate buffer at pH 3). Discriminating the main environmental factors (i.e., heat and light) affecting anthocyanin stability is a key point for better understanding the degradation pathways. The stability of the anthocyanins was followed by UV-vis spectrometry. Moreover, to understand the degradation mechanisms in both the presence and absence of ascorbic acid, various techniques such as fluorescence quenching, cyclic voltammetry, and electron-spin-resonance (ESR) spectroscopy were also used to furnish a full coherent picture of the chemical mechanisms associated with the anthocyanin degradation. In addition, molecular orbitals and bond-dissociation energies (BDE) were calculated to extend the investigation. Moreover, the effects of some supplementary stabilizers (chlorogenic acid, sinapic acid, tannic acid, fumaric acid, ß-carotene, isoquercitrin, myricitrin, green coffee bean extract, and rosemary extract) and sugars (sucrose, fructose, and glucose) on anthocyanins stability in the presence of ascorbic acid were examined.

Degradation of atenolol via heterogeneous activation of persulfate by using BiOCl@Fe3O4 catalyst under simulated solar light irradiation.

Efficient oxidative degradation of pharmaceutical pollutants in aquatic environments is of great importance. This study used magnetic BiOCl@Fe3O4 catalyst to activate persulfate (PS) under simulated solar light irradiation. This degradation system was evaluated using atenolol (ATL) as target pollutant. Four reactive species were identified in the sunlight/BiOCl@Fe3O4/PS system. The decreasing order of the contribution of each reactive species on ATL degradation was as follows: h+ ≈ HO· > O2·- > SO4·-. pH significantly influenced ATL degradation, and an acidic condition favored the reaction. High degradation efficiencies were obtained at pH 2.3-5.5. ATL degradation rate increased with increased catalyst and PS contents. Moreover, ATL mineralization was higher in the sunlight/BiOCl@Fe3O4/PS system than in the sunlight/BiOCl@Fe3O4 or sunlight/PS system. Nine possible intermediate products were identified through LC-MS analysis, and a degradation pathway for ATL was proposed. The BiOCl@Fe3O4 nanomagnetic composite catalyst was synthesized in this work. This catalyst was easily separated and recovered from a treated solution by using a magnet, and it demonstrated a high catalytic activity. Increased amount of the BiOCl@Fe3O4 catalyst obviously accelerated the efficiency of ATL degradation, and the reusability of the catalyst allowed the addition of a large dosage of BiOCl@Fe3O4 to improve the degradation efficiency.

Machine learning for the prediction of L. chinensis carbon, nitrogen and phosphorus contents and understanding of mechanisms underlying grassland degradation.

The grasslands of Western Jilin Province in China have experienced severe degradation during the last 50 years. Radial basis function neural networks (RBFNN) and support vector machines (SVM) were used to predict the carbon, nitrogen, and phosphorus contents of Leymus chinensis (L. chinensis) and explore the degree of grassland degradation using the matter-element extension model. Both RBFNN and SVM demonstrated good prediction accuracy. The results indicated that there was severe degradation, as samples were mainly concentrated in the 3rd and 4th levels. The growth of L. chinensis was shown to be limited by either nitrogen, phosphorus, or both during different stages of degradation. The soil chemistry changed noticeably as degradation aggravated, which represents a destabilization of L. chinensis community homeostasis. Soil salinization aggravates soil nutrient loss and decreases the bioavailability of soil nutrients. This, along with the destabilization of C/N, C/P and N/P ratios, weakens the photosynthetic ability and productivity of L. chinensis. This conclusion was supported by observations that L. chinensis is gradually being replaced by a Chloris virgata, Puccinellia tenuiflora and Suaeda acuminate mixed community.

Effects of copper on biodegradation mechanism of trichloroethylene by mixed microorganisms / 生物工程学报

We isolated and enriched mixed microorganisms SWA1 from landfill cover soils supplemented with trichloroethylene (TCE). The microbial mixture could degrade TCE effectively under aerobic conditions. Then, we investigated the effect of copper ion (0 to 15 μmol/L) on TCE biodegradation. Results show that the maximum TCE degradation speed was 29.60 nmol/min with 95.75% degradation when copper ion was at 0.03 μmol/L. In addition, genes encoding key enzymes during biodegradation were analyzed by Real-time quantitative reverse transcription PCR (RT-qPCR). The relative expression abundance of pmoA gene (4.22E-03) and mmoX gene (9.30E-06) was the highest when copper ion was at 0.03 μmol/L. Finally, we also used MiSeq pyrosequencing to investigate the diversity of microbial community. Methylocystaceae that can co-metabolic degrade TCE were the dominant microorganisms; other microorganisms with the function of direct oxidation of TCE were also included in SWA1 and the microbial diversity decreased significantly along with increasing of copper ion concentration. Based on the above results, variation of copper ion concentration affected the composition of SWA1 and degradation mechanism of TCE. The degradation mechanism of TCE included co-metabolism degradation of methanotrophs and oxidation metabolism directly at copper ion of 0.03 μmol/L. When copper ion at 5 μmol/L (biodegradation was 84.75%), the degradation mechanism of TCE included direct-degradation and co-metabolism degradation of methanotrophs and microorganisms containing phenol hydroxylase. Therefore, biodegradation of TCE by microorganisms was a complicated process, the degradation mechanism included co-metabolism degradation of methanotrophs and bio-oxidation of non-methanotrophs.

[Effects of copper on biodegradation mechanism of trichloroethylene by mixed microorganisms].

We isolated and enriched mixed microorganisms SWA1 from landfill cover soils supplemented with trichloroethylene (TCE). The microbial mixture could degrade TCE effectively under aerobic conditions. Then, we investigated the effect of copper ion (0 to 15 µmol/L) on TCE biodegradation. Results show that the maximum TCE degradation speed was 29.60 nmol/min with 95.75% degradation when copper ion was at 0.03 µmol/L. In addition, genes encoding key enzymes during biodegradation were analyzed by Real-time quantitative reverse transcription PCR (RT-qPCR). The relative expression abundance of pmoA gene (4.22E-03) and mmoX gene (9.30E-06) was the highest when copper ion was at 0.03 µmol/L. Finally, we also used MiSeq pyrosequencing to investigate the diversity of microbial community. Methylocystaceae that can co-metabolic degrade TCE were the dominant microorganisms; other microorganisms with the function of direct oxidation of TCE were also included in SWA1 and the microbial diversity decreased significantly along with increasing of copper ion concentration. Based on the above results, variation of copper ion concentration affected the composition of SWA1 and degradation mechanism of TCE. The degradation mechanism of TCE included co-metabolism degradation of methanotrophs and oxidation metabolism directly at copper ion of 0.03 µmol/L. When copper ion at 5 µmol/L (biodegradation was 84.75%), the degradation mechanism of TCE included direct-degradation and co-metabolism degradation of methanotrophs and microorganisms containing phenol hydroxylase. Therefore, biodegradation of TCE by microorganisms was a complicated process, the degradation mechanism included co-metabolism degradation of methanotrophs and bio-oxidation of non-methanotrophs.