Porous monolith-based magnetism-reinforced in-tube solid phase microextraction of sulfonylurea herbicides in water and soil samples.

In the present study, porous monolith-based magnetism-reinforced in-tube solid phase microextraction (MB-MR/IT-SPME) was first introduced to concentrate sulfonylurea herbicides (SUHs). To realize the effective capture of SUHs, a monolithic capillary microextraction column (MCMC) based on poly (vinylimidazole-co-ethylene dimethacrylate) polymer doped with Fe3O4 magnetic nanoparticles was in-situ synthesized in the first step. After that, the MCMC was twined with a magnetic coil which was employed to carry out variable magnetic field during adsorption and desorption procedure. Various important parameters that affecting the extraction performance were inspected in detailed. Results well indicated that exertion of magnetic field in the whole extraction procedure was in favor of the capture and release of the studied SUHs, with the extraction efficiencies increased from 36.8-58.1% to 82.6-94.5%. At the same time, the proposed MB-MR/IT-SPME was online combined to HPLC with diode array detection (HPLC/DAD) to quantify trace levels of SUHs in water and soil samples. The limits of detection (S/N = 3) for water and soil samples were in the ranges of 0.030-0.15 μg/L and 0.30-1.5 μg/kg, respectively. The relative standard deviations (RSDs) for intra- and inter-day variability were both less than 10%. Finally, the introduced approach was successfully applied to monitor the low contents of studied SUHs in environmental water and soil samples. Satisfying fortified recovery and precision were achieved

Sensitive determination of organic acid preservatives in juices and soft drinks treated by monolith-based stir cake sorptive extraction and liquid chromatography analysis

A simple, efficient, and sensitive method for simultaneous determination of sorbic acid (SA), benzoic acid (BA), and cinnamic acid (CA) in juices and soft drinks was developed by stir cake sorptive extraction (SCSE) coupling to high-performance liquid chromatography with diode array detection. The SCSE based on polymeric ionic liquid-based monolith (PILM) as extractive medium was used to concentrate these three organic acid preservatives. Because hydrophobic and ion-exchange interactions co-contributed to the extraction, the PILM-SCSE exhibited a high extractive capability towards analytes. To obtain optimum extraction performance, several SCSE parameters were investigated and discussed, including desorption solvent, pH value, ionic strength in the sample matrix, and the extraction and desorption time. Under the optimized extraction conditions, limits of detection of 0.16, 1.08, and 0.18 μg/L (S/N = 3) and quantification limits of 0.52, 3.42, and 0.61 (S/N = 10) were obtained for SA, BA, and CA, respectively. The method also showed good linearity and reproducibility, as well as advantages such as simplicity, low cost, and high feasibility. Finally, the proposed method was successfully applied to the determination of SA, BA, and CA in real juices and soft drinks, and the recoveries ranged from 63.0 to 107 %.The work described in this article was supported by the National Natural Science Foundation of China (grant 21077085); Scientific Research Foundation for the Returned Overseas Chinese Scholars, State Education Ministry; New Century Excellent Talents in Fujian Province University and Fundamental Research Funds for the Central Universities (no. CXB2011037)

Preparation of cation-exchange stir bar sorptive extraction based on monolithic material and its application to the analysis of soluble cations in milk by ion chromatography

In this study, a new cation-exchange coating for stir bar sorptive extraction (SBSE) based on poly (acrylic acid-ethylene dimethacrylate) monolithic material was synthesized. The effect of polymerization conditions such as the ratio of functional monomer to cross-linker and the content of porogenic solvent on the extraction efficiencies were investigated in detail. The monolithic material was characterized by elemental analysis, scanning electron microscopy and infrared spectroscopy. In order to evaluate the usability of the new coating for the extraction of inorganic cations, the analysis of soluble K(+), Mg(2+) and Ca(2+) in milk by ion chromatography with conductivity detection was selected as a paradigm. Several extractive parameters, including pH value in sample matrix, desorption solvent, extraction and desorption time were optimized. Under the optimum conditions, low detection limits (S/N = 3) and quantification limits (S/N = 10) of the proposed method for the target cations were achieved within the range of 0.12-0.28 and 0.4-0.92 mu g L(-1), respectively. The method also showed good linearity, simplicity, practicality and low cost for the extraction of inorganic cations. Finally, the proposed method was successfully used to analyse three different trademarks of commercial milk samples with satisfactory recoveries in the range of 71.1% to 102.8%.National Nature Science Foundation of China[21077085]; Nature Science Foundation of Fujian Province of China[2010J01047

Solid-phase extraction of polar organophosphorous pesticides from aqueous samples with oxidized carbon nanotubes

The development of new sorbents, which are able to trap polar compounds, is a growing research field in solid-phase extraction (SPE). In this study, multi-walled carbon nanotubes (MWCNTs) and single-walled carbon nanotubes (SWCNTs) were oxidized in air at 600 degrees C and 500 degrees C, respectively, for 2 h. MWCNTs, SWCNTs, air oxidized MWCNTs (OMWCNTs) and SWCNTs (OSWCNTs) (200 mg of each) were packed in SPE cartridges. The four cartridges obtained, together with a commercial Oasis HLB cartridge, were used to extract six polar organophosphorous pesticides (OPPs), i. e., dichlorvos, methamidophos, acephate, omethoate, monocrotophos and dimethoate, from an aqueous sample. The results showed that the oxidation process significantly enhanced the adsorption abilities of both SWCNTs and MWCNTs for polar OPPs. A comparative study indicated that OSWCNTs were more effective than Oasis HLB for the extraction of methamidophos and acephate and as effective as Oasis HLB for the other four OPPs from aqueous samples. When 100 mL of a natural sample was spiked with OPPs and extracted with OSWCNTs, the recoveries of five of the six polar OPPs ( methamidophos excepted) ranged from 79.1 to 101.9%. The detection limits of the method based on OSWCNTs was found to be 0.07-0.12 mu g L-1.National Natural Science Foundation of China [20607017]; Natural Science Foundation of Fujian Province of China [D0610018

A new anionic exchange stir bar sorptive extraction coating based on monolithic material for the extraction of inorganic anion

A novel anionic exchange stir bar sorptive extraction (SBSE) coating based on poly(2(methacryloyloxy)ethyltrimethylammonium chloride-co-divinylbenzene) monolithic material for the extraction of inorganic anion was prepared. The effect of preparation conditions such as ratio of functional monomer to cross-linker, content of porogenic solvent on the extraction efficiencies were investigated in detailed. The monolithic material was characterized by elemental analysis, scanning electron microscopy and infrared spectroscopy. In order to investigate the extraction capacity of the new coating for inorganic anion, the new SBSE was combined with ionic chromatography with conductivity detection, Br-, NO3-, PO43- and SO42- were selected as detected solutes. Several extractive parameters, including pH value and ionic strength in sample matrix, desorption solvent, extraction and desorption time were optimized. The results showed that strongly ionic strength did not favor the extraction of anlaytes. Under the optimum experimental conditions, low detection limits (S/N = 3) and quantification limits (S/N = 10) of the proposed method for the target anions were achieved within the range of 0.92-2.62 and 3.03-9.25 mu g/L, respectively. The method also showed good linearity, simplicity, practicality and low cost for the extraction inorganic anions. Finally, the proposed method was successfully used to detect the two different trademarks of commercial purified water with satisfactory recovery in the range of 70.0-92.6%. To the best of our knowledge, this is the first to use SBSE to enrich inorganic anions. (C) 2010 Elsevier By. All rights reserved.National Nature Science Foundation of China [20805039]; Youth Talent Foundation of Fujian Province [2006F3117]; Start-up foundation of Xiamen University ; Innovation Foundation of Xiamen University [XDKJCX20063007

Preparation of sorbent based on porous monolith incorporated with graphene oxide nanosheets for stir cake sorptive extraction of strongly polar aromatic amines

National Natural Science Foundation of China [21377105, 21077085]; Scientific Research Foundation for the Returned Overseas Chinese Scholars, State Education Ministry; New Century Excellent Talents in Fujian Province UniversityIn this study, poly(ethylene glycol dimethacrylate/graphene oxide) (EDMA/GO) monolith was prepared by one-step in situ polymerization. The porous monolith was used for the first time as the sorbent of stir cake sorptive extraction (SCSE) for the preconcentration of strongly polar aromatic amines (AAs) from water samples. The effect of the content of EDMA and GO in the monolith on the extraction efficiencies was investigated in detail. The sorbent was characterized by elemental analysis, transmission electron microscopy, scanning electron microscopy and infrared spectroscopy. Analysis of polar AAs in environmental water samples by a combination of poly(EDMA/GO)-SCSE and HPLC with diode-array detection was selected as a paradigm for the practical application of the new sorbent. Under the optimal conditions, the limits of detection (S/N = 3.0) of the developed method for AAs ranged from 0.04 to 0.19 mu g L-1. Good reproducibility of the method was obtained as intra-and inter-day precisions, the relative standard deviations (RSDs) were less than 4.0%. Finally, the proposed method was successfully applied to the determination of trace AAs in environmental water samples. The recoveries of AAs spiked in different matrices ranged from 74.2% to 105%, and RSDs of repeatability ranged from 1.6% to 9.6%

Short-term dynamics of nutrients influenced by upwelling in a small oligotrophic coastal ecosystem, Gan Bay, in the northwest Philippines

We present a time-series analysis of nutrient and pCO(2) (partial pressure of CO2) levels in an oligotrophic coastal ecosystem (Gan Bay), which was likely to be influenced by upwelled subsurface water. Gan Bay is off Currimao Harbor, in the northwest Philippines and is located at the boundary of the South China Sea (SCS). This 42-h time-series observation was conducted in December 2006. In addition to continuous observations of dissolved oxygen (DO) and pCO(2), discrete samples were collected at a depth of 5 m every 3 h for measurements of nutrients, including soluble reactive phosphorus (SRP) and inorganic nitrogen (NO3- + NO2-) in order to examine their dynamics and possible physical and biological controls. We observed remarkably large short-term variations in the surface water, spanning a 10-fold change for SRP (32-330 nM) and from <0.3 mu M to 4.3 mu M for (NO3- + NO2-. DO also varied substantially from a lower end of 171 to 205 mu M O-2. Surface water pCO(2) changed from an equilibrium stage with the atmosphere (similar to 386 mu atm) to a stage where it was a significant source for the atmospheric CO2 (seawater pCO(2) similar to 469 mu atm). We found that the variation of nutrients was driven neither by tidal mixing nor by biological activities, as was suggested by the variations in the total bacterial abundance and chlorophyll a. Instead, our inverse T-S relationship suggested a two end-member mixing process during the observation period. The N:P ratio throughout the observation period was similar to 13.2, which is characteristic of SCS subsurface and deep waters. Moreover, pCO(2) was correlated inversely with the sea surface temperature. It is likely, therefore, that an upwelled subsurface cold water with high nutrients, low-temperature and high-pCO(2) existed. It should be noted that this upwelled cold water did not appear to impact the entire observation period (approximately 35 h of 42 h), which might suggest an extremely dynamic nature for this upwelled cold water mass. (C) 2009 National Natural Science Foundation of China and Chinese Academy of Sciences. Published by Elsevier Limited and Science in China Press. All rights reserved

Sirt7 protects against vascular calcification via modulation of reactive oxygen species and senescence of vascular smooth muscle cells

Vascular calcification is frequently seen in patients with chronic kidney disease (CKD), and significantly increases cardiovascular mortality and morbidity. Sirt7, a NAD+-dependent histone deacetylases, plays a crucial role in cardiovascular disease. However, the role of Sirt7 in vascular calcification remains largely unknown. Using in vitro and in vivo models of vascular calcification, this study showed that Sirt7 expression was significantly reduced in calcified arteries from mice administered with high dose of vitamin D3 (vD3). We found that knockdown or inhibition of Sirt7 promoted vascular smooth muscle cell (VSMC), aortic ring and vascular calcification in mice, whereas overexpression of Sirt7 had opposite effects. Intriguingly, this protective effect of Sirt7 on vascular calcification is dependent on its deacetylase activity. Unexpectedly, Sirt7 did not alter the osteogenic transition of VSMCs. However, our RNA-seq and subsequent studies demonstrated that knockdown of Sirt7 in VSMCs resulted in increased intracellular reactive oxygen species (ROS) accumulation, and induced an Nrf-2 mediated oxidative stress response. Treatment with the ROS inhibitor N-acetylcysteine (NAC) significantly attenuated the inhibitory effect of Sirt7 on VSMC calcification. Furthermore, we found that knockdown of Sirt7 delayed cell cycle progression and accelerated cellular senescence of VSMCs. Taken together, our results indicate that Sirt7 regulates vascular calcification at least in part through modulation of ROS and cellular senescence of VSMCs. Sirt7 may be a potential therapeutic target for vascular calcification.</p

Identifying a Heart Rate Recovery Criterion After a 6-Minute Walk Test in COPD

Background: Slow heart rate recovery (HRR) after exercise is associated with autonomic dysfunction and increased mortality. What HRR criterion at 1-minute after a 6-minute walk test (6MWT) best defines pulmonary impairment?. Study Design and Methods: A total of 5008 phase 2 COPDGene (NCT00608764) participants with smoking history were included. A total of 2127 had COPD and, of these, 385 were followed-up 5-years later. Lung surgery, transplant, bronchiectasis, atrial fibrillation, heart failure and pacemakers were exclusionary. HR was measured from pulse oximetry at end-walk and after 1-min seated recovery. A receiver operator characteristic (ROC) identified optimal HRR cut-off. Generalized linear regression determined HRR association with spirometry, chest CT, symptoms and exacerbations. Results: HRR after 6MWT (bt/min) was categorized in quintiles: ≤ 5 (23.0% of participants), 6– 10 (20.7%), 11– 15 (18.9%), 16– 22 (18.5%) and ≥ 23 (18.9%). Compared to HRR≤ 5, HRR≥ 11 was associated with (p\u3c 0.001): lower pre-walk HR and 1-min post HR; greater end-walk HR; greater 6MWD; greater FEV1%pred; lower airway wall area and wall thickness. HRR was positively associated with FEV1%pred and negatively associated with airway wall thickness. An optimal HRR ≤ 10 bt/min yielded an area under the ROC curve of 0.62 (95% CI 0.58– 0.66) for identifying FEV1\u3c 30%pred. HRR≥ 11 bt/min was the lowest HRR associated with consistently less impairment in 6MWT, spirometry and CT variables. In COPD, HRR≤ 10 bt/min was associated with (p\u3c 0.001): ≥ 2 exacerbations in the previous year (OR=1.76[1.33– 2.34]); CAT≥ 10 (OR=1.42[1.18– 1.71]); mMRC≥ 2 (OR=1.42[1.19– 1.69]); GOLD 4 (OR=1.98[1.44– 2.73]) and GOLD D (OR=1.51[1.18– 1.95]). HRR≤ 10 bt/min was predicted COPD exacerbations at 5-year follow-up (RR=1.83[1.07– 3.12], P=0.027). Conclusion: HRR≤ 10 bt/min after 6MWT in COPD is associated with more severe expiratory flow limitation, airway wall thickening, worse dyspnoea and quality of life, and future exacerbations, suggesting that an abnormal HRR≤ 10 bt/min after a 6MWT may be used in a comprehensive assessment in COPD for risk of severity, symptoms and future exacerbations

Recent Developments of Extraction and Micro-extraction Technologies with Porous Monoliths

National Nature Science Foundation of China [21077085]; Nature Science Foundation of Fujian Province of China [2010J01047]Porous monoliths are widely used as stationary phase in high-performance liquid chromatography and capillary electrochromatography due to their simple preparation, versatile surface chemistries, high reproducibility, and fast mass transport. In recent years, porous monoliths were also used as sorbents in sample preparation and impressive achievements have been obtained. This review focuses on all facets of extraction technologies based on porous monoliths. Cartridge-based solid-phase extraction (SPE), CIM-based SPE, in-tube solid-phase micro extraction (SPME), fiber-based SPME, chip-based micro extraction, tip-based micro extraction, stir bar sorptive extraction, and monolithic spin column micro-extraction are presented and discussed with regards to these emerging roles