Bifunctional fluorescent molecularly imprinted resin based on carbon dot for selective detection and enrichment of 2,4-dichlorophenoxyacetic acid in lettuce.

The work provided a method for synthesizing a simple fluorescent molecularly imprinted polymer by surface-initiated atom transfer radical polymerization (SI-ATRP) and its application in real sample. Poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) microspheres were selected as a matrix, 4-vinylpyridine, ethylene glycol dimethacrylate, 2,4-dichlorophenoxyacetic acid (2,4-D) as functional monomer, cross-linker and template molecule, respectively, to fabricate MAR@MIP with core-shell structure. For comparison, carbon dot (CD) as a fluorescence source was synthesized with o-phenylenediamine and tryptophan as precursors via hydrothermal method and integrated into MIP to acquire MAR@CD-MIP. MAR@CD-NIP was also prepared without adding the template molecule. The adsorption capacity of MAR@CD-MIP reached 104 mg g-1 for 2,4-D, which was higher than that of MAR@MIP (60 mg g-1). However, the adsorption capacity of MAR@CD-NIP was only 13.2 mg g-1. The linear range of fluorescence detection for 2,4-D was 18-72 µmol/L, and the limit of detection (LOD) was 0.35 µmol/L. The fluorescent MAR@CD-MIP was successfully applied in enrichment of lettuce samples. The recoveries of the three spiked concentrations of 2,4-D in lettuce were tested by fluorescence spectrophotometry and ranged in 97.3-101.7 %. Meanwhile, the results were also verified by HPLC. As a result, bi-functional molecularly imprinted resin was successfully fabricated to detect and enrich 2,4-D in real samples, and exhibited good selectivity, sensitivity and great application prospect in food detection.

Dual-functional molecularly imprinted doped carbon dot based on metal-organic frameworks for tetracycline adsorption and determination.

A carbon dot (CD) was prepared by using tryptophan as a single carbon source and demonstrated its good selective fluorescence quenching effect on tetracycline (TC). The modified metal-organic frameworks (MOF) NH2-MIL-101 was chosen as matrix, doped with CD, molecularly imprinted polymer (MIP) prepared with TC as the template, and finally CD-MOF-MIP complexes (CD@MIP) was synthesized. For comparison, MIP were also prepared without CD as well as non-imprinted polymers and their ability was tested, respectively. CD@MIP is a nanomaterial with bright fluorescence under the irradiation of ordinary UV equipment (λ = 360 nm), which has a fast and stable fluorescence quenching for TC and a good linear relationship for TC in the concentration range 0-400 µmol L-1. The quantum yield of CD@MIP was 12.75% and the 3σ limit of detection (LOD) for CD@MIP was 0.59 µmol L-1. The maximum adsorption capacity of CD@MIP reached 304.6 mg g-1 and the adsorption equilibrium was reached after about 75 min. The adsorption of CD@MIP to tetracycline spiked in milk samples reached 90.0 mg g-1 within 2 h, which was much higher than that of NIP (48.4 mg g-1) under the same conditions, as demonstrated by high performance liquid chromatography (HPLC). The results obtained showed that CD@MIP combined the high adsorption capacity of MOF, the specific adsorption of molecular imprinting and the fluorescence properties of CD, can determine and rapidly removeTC in the environment.

Simple fabrication of carbon quantum dots and activated carbon from waste wolfberry stems for detection and adsorption of copper ion.

Removal of heavy metal pollution is an endless topic, because heavy metals can cause irreversible damage to the human body and environment. It is urgent to develop novel materials for detection and adsorption of heavy metal ions. In this paper, waste wolfberry straw was utilized as a carbon source, and two simple methods were developed to successfully prepare activated carbon (AC) and carbon quantum dots (CQDs). The fabrication conditions were optimized by adjusting the mass ratio of precursor to activator, type of activator and activation times. When sodium hydroxide (NaOH) was selected as an activator (6 : 1, mass ratio of NaOH to AC-precursor), and the activation was performed at 600 °C for 1 h, the highest specific surface area of the obtained AC-NaOH-3 reached 3016 m2 g-1. The adsorption capacity for copper ions (Cu2+) reached 68.06 mg g-1. The preparation conditions for CQDs were also optimized by adjusting the concentration of wolfberry stem, reaction time and temperature. When the wolfberry stem concentration was 7.5 g L-1, and the activation was performed at 200 °C for 24 h, the obtained CQDs exhibited strong fluorescence emission in the blank and 12 kinds of metal ion solutions, respectively, however, the fluorescence intensity was remarkably decreased after adding Cu2+. In the range of 10-80 nM, the linear correlation coefficient between the concentration of Cu2+ and fluorescence intensity of CQDs was 0.992, and the limit of detection was 2.83 nmol L-1. Thus, these two kinds of materials were prepared from wolfberry stem, which opened up a new way for the application in adsorption and detection of copper ions.

Fabrication of molecularly imprinted resin via controlled polymerization applied in the enrichment of bisphenol A for plastic products.

The addition of bisphenol A has been frequently used in industrial manufacturing because it imparts plastic products with characteristics such as transparency, durability, and excellent impact resistance. However, its widespread use raises concerns about potential leakage into the surrounding environment, which poses a significant risk to human health. In this study, molecularly imprinted polymers with specific recognition of bisphenol A were synthesized through surface-initiated atom transfer radical polymerization using poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) as the substrate, bisphenol A as the template molecule, 4-vinylpyridine as the monomer, and ethylene glycol dimethacrylate as the cross-linker. The bisphenol A adsorption capacity was experimentally investigated, and the kinetic analysis of the molecularly imprinted polymers produced an adsorption equilibrium time of 25 min, which is consistent with the pseudo-second-order kinetic model. The results of the static adsorption experiments exhibited consistency with the Langmuir adsorption model, revealing a maximum adsorption capacity of 387.2 µmol/g. The analysis of molecularly imprinted polymers-enriched actual samples using high-performance liquid chromatography demonstrated excellent selectivity for bisphenol A, with a linear range showing 93.4%-99.7% recovery and 1.1%-6.4% relative standard deviation, demonstrating its high potential for practical bisphenol A detection and enrichment applications.

Membrane separation of antibiotics predicted with the back propagation neural network.

Antibiotics and antibiotic resistance genes (ARGs) have been frequently detected in the aquatic environment and are regarded as emerging pollutants. The prediction models for the removal effect of four target antibiotics by membrane separation technology were constructed based on back propagation neural network (BPNN) through training the input and output. The membrane separation tests of antibiotics showed that the removal effect of microfiltration on azithromycin and ciprofloxacin was better, basically above 80%. For sulfamethoxazole (SMZ) and tetracycline (TC), ultrafiltration and nanofiltration had better removal effects. There was a strong correlation between the concentrations of SMZ and TC in the permeate, and the R2 of the training and validation processes exceeded 0.9. The stronger the correlation between the input layer variables and the prediction target was, the better the prediction performances of the BPNN model than the nonlinear model and the unscented Kalman filter model were. These results showed that the established BPNN prediction model could better simulate the removal of target antibiotics by membrane separation technology. The model could be used to predict and explore the influence of external conditions on membrane separation technology and provide a certain basis for the application of the BPNN model in environmental protection.

Carbon dot-functionalized macroporous adsorption resin for bifunctional ultra-sensitive detection and fast removal of iron(III) ions.

Heavy metal pollution has spread around the world with the development of industry, posing a major threat to human health. It is urgent to design and fabricate bifunctional materials for detection and adsorption of heavy metal ions. Herein, poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) microspheres, a kind of common macroporous adsorption resin (MAR), were employed as the matrix, and carbon dots (CDs) with excellent optical properties were grafted onto the surface of MAR by surface-initiated atom transfer radical polymerization (SI-ATRP) and photo-initiated "thiol-yne" click chemistry. The synthesized MAR@poly(PA)@CD could produce fluorescence quenching with Fe3+. A simple fluorescence spectrometric method for detection of Fe3+ was established. The fluorescence intensity of MAR@poly(PA)@CD decreased linearly with the concentration of Fe3+ in the range of 0-70 nmol L-1, with a limit of detection (LOD) of 6.6 nmol L-1, which had the potential for trace detection. In addition, after SI-ATRP modification, many adsorption sites were generated on the surface of MAR, and the adsorption capacity for Fe3+ was 23.8 mg g-1. Isothermal and kinetic adsorption experiments were more consistent with the Langmuir model (r = 0.9992) and pseudo-second-order model (r = 0.9902), indicating that the adsorption was monolayer adsorption and chemical adsorption, respectively. MAR@poly(PA)@CD with dual functions of detecting and adsorbing Fe3+ was successfully prepared, showing great application prospects in the environmental field.

Comparison of chilling and heat requirements for leaf unfolding in deciduous woody species in temperate and subtropical China.

Climate warming has advanced the spring phenology of many plant species by accelerating heat accumulation. However, delayed phenophases due to insufficient chilling have also been reported. Based on phenological observation data (1963-2010), we compared the effects of preseason chill and heat accumulation on leaf unfolding dates of four deciduous woody species (Lagerstroemia indica, Robinia pseudoacacia, Sophora japonica, and Ulmus pumila) in temperate and subtropical regions of China. Daily chill and heat accumulation were calculated by two chilling models (the Positive Utah Model and the Dynamic Model) and the Growing Degree Hour (GDH) Model. We determined the temporal trends in chill and heat accumulations for leaf unfolding of the four species. The results showed that there were shorter chilling periods in the subtropics than in temperate sites because the chilling period typically started later and ended earlier. There was no significant difference in the length of the forcing period in the different regions. The chilling requirements for leaf unfolding were higher in temperate regions (1344.9-1798.9 chilling units (CU) or 64.7-79.4 chilling portions (CP)) than in the subtropics (1145.9-1828.1 CU or 47.9-75.2 CP). Plants in the subtropics needed higher forcing temperatures (4135.8-10084.8 GDH) than those in temperate regions (3292.0-8383.6 GDH). The earlier-leafing species (e.g., U. pumila) had a lower heat requirement for leaf unfolding than the later-leafing species (e.g., L. indica). A significant increase in heat accumulation was found at all sites except Guiyang, while chill accumulation only increased in Beijing.

Molecular Mechanism of HSF1-Upregulated ALDH2 by PKC in Ameliorating Pressure Overload-Induced Heart Failure in Mice.

Evidences abound that HSF1 and ALDH2 are of cardioprotective effect, yet there is still no report on whether HSF1 can regulate ALDH2 to delay the occurrence of heart failure. We first established the pressure overload-induced heart failure model of mice by transverse aortic constriction (TAC) and discovered that, in the forming period of heart failure, changes of HSF1 and ALDH2 expression recorded the consistent trend. When HSF1 was upregulated/downregulated to delay/promote the occurrence of heart failure, PKC and ALDH2 also showed increased/decreased expression. And when ALDH2 was upregulated/downregulated, the role of HSF1 in delaying the occurrence of heart failure strengthened/weakened. Next, we used mechanical stretch to establish a pressure-stimulated myocardial hypertrophy model and discovered an increased expression of both HSF1 and ALDH2. When HSF1 was upregulated/downregulated to increase/decrease the expression of myocardial hypertrophy gene beta-MHC, PKC and ALDH2 recorded an increased/decreased expression. When an inhibitor was used to downregulate the expression of PKC in cardiomyocytes, we found that the role of HSF1 in upregulating ALDH2 beta-MHC weakened. These findings suggest that HSF1 can upregulate the expression of ALDH2 via PKC to promote pressure-stimulated myocardial compensatory hypertrophy, which is an important molecular pathway for HSF1 to ameliorate heart failure.

Variations in the temperature sensitivity of spring leaf phenology from 1978 to 2014 in Mudanjiang, China.

Continuous long-term temperature sensitivity (ST) of leaf unfolding date (LUD) and main impacting factors in spring in the period 1978-2014 for 40 plant species in Mudanjiang, Heilongjiang Province, Northeast China, were analyzed by using observation data from the China Phenological Observation Network (CPON), together with the corresponding meteorological data from the China Meteorological Data Service Center. Temperature sensitivities, slopes of the regression between LUD and mean temperature during the optimum preseason (OP), were analyzed using 15-year moving window to determine their temporal trends. Major factors impacting ST were then chosen and evaluated by applying a random sampling method. The results showed that LUD was sensitive to mean temperature in a defined period before phenophase onset for all plant species analyzed. Over the period 1978-2014, the mean ST of LUD for all plant species was - 3.2 ± 0.49 days °C-1. The moving window analysis revealed that 75% of species displayed increasing ST of LUD, with 55% showing significant increases (P < 0.05). ST for the other 25% exhibited a decreasing trend, with 17% showing significant decreases (P < 0.05). On average, ST increased by 16%, from - 2.8 ± 0.83 days °C-1 during 1980-1994 to - 3.30 ± 0.65 days °C-1 during 2000-2014. For species with later LUD and longer OP, ST tended to increase more, while species with earlier LUD and shorter OP tended to display a decreasing ST. The standard deviation of preseason temperature impacted the temporal variation in ST. Chilling conditions influenced ST for some species, but photoperiod limitation did not have significant or coherent effects on changes in ST.

Downregulation of MiR-199b-5p Inducing Differentiation of Bone-Marrow Mesenchymal Stem Cells (BMSCs) Toward Cardiomyocyte-Like Cells via HSF1/HSP70 Pathway.

BACKGROUND Bone-marrow mesenchymal stem cells (BMSCs) are pluripotent stem cells with potent self-renewal and differentiation ability that are widely used in transplantation of cell therapy. But the mechanism on microRNA (miRNA) regulating stem cell differentiation is complicated and unclear. The aim of this study was to investigate whether miR-199b-5p is involved in differentiation of cardiomyocyte-like cells and identify potential signal pathways in BMSCs. MATERIAL AND METHODS Mouse BMSCs were treated with 5-azacytidine and transfected by miR-199b-5p mimic and inhibitor, respectively. qRT-PCR was used to detect the expression of miR-199b-5p in BMSCs, 5-azacytidine treated BMSCs, and neonatal murine cardiomyocytes. The expression of cardiac specific genes and the HSF1/HSP70 signal pathway were examined by qRT-PCR or western blotting. The proliferation and migration of BMSCs were evaluated by CCK-8 assay and wound-healing assay. RESULTS The expression of miR-199b-5p decreased gradually in the process of differentiation of BMSCs toward cardiomyocyte-like cells. The expression of cardiac specific genes and HSF1/HSP70 were increased in the miR-199b-5p inhibitor group; however, the miR-199b-5p mimic group presented an opposite result. Both the miR-199b-5p inhibitor group and the miR-199b-5p mimic group had no influence on BMSCs proliferation and migration. Using lentivirus vectors bearing HSF1 shRNA to silence HSF1 and HSP70, the anticipated elevated expression effect of cardiac specific genes induced by miR-199b-5p inhibitor was suppressed. CONCLUSIONS Downregulation of miR-199b-5p induced differentiation of BMSCs toward cardiomyocyte-like cells partly via the HSF1/HSP70 signaling pathway, and had no influence on BMSCs proliferation and migration.