Computational design and synthesis of molecular imprinted polymers for selective solid phase extraction of sulfonylurea herbicides.

A high-efficiency approach for the synthesis of molecularly imprinted polymers has been developed and further for the solid-phase extraction of sulfonylurea herbicides in food samples. Molecular simulation approach combined chemometric selected metsulfuron-methyl (MSM) and 2-trifluoromethyl acrylic acid (TFMAA) as the template and the monomer to synthesize the molecularly imprinted polymers (MIPs). Experimental validation confirmed that the MSM-imprinted polymers showed a higher selectivity and affinity to sulfonylurea herbicides. The optimized molecularly imprinted solid-phase extraction (MISPE) conditions, including loading, washing, and eluting conditions, were established. The developed MISPE technology combined HPLC-MSMS was successfully used for the determination of sulfonylurea herbicides in foods. Compared with commercial SPE columns, MISPE showed high affinity, excellent selectivity and low matrix effect. The recoveries of sulfonylurea herbicides spiked in four matrices were between 86.4% and 100.2%, with the relative standard deviations (RSD) in the range of 0.9%-10.5%.

Aminolactonization of Unactivated Alkenes Catalyzed by Aryl Iodine.

A one-step protocol of the aryl iodine-catalyzed aminolactonization of unactivated alkenes under oxidation conditions was first reported to efficiently construct diverse amino lactones in a short time using HNTs2 as the compatible nitrogen source. In addition, we investigated the influence of the reaction rate based on the structure of the iodoarene precatalyst, which revealed the selective adjustment effect on aminolactonization and oxylactonization. Finally, preliminary experiments verified the feasibility of asymmetric aminolactonization catalyzed by a chiral iodoarene precatalyst.

Iodoarene-Catalyzed Oxyamination of Unactivated Alkenes to Synthesize 5-Imino-2-Tetrahydrofuranyl Methanamine Derivatives.

Reported here is the room-temperature metal-free iodoarene-catalyzed oxyamination of unactivated alkenes. In this process, the alkenes are difunctionalized by the oxygen atom of the amide group and the nitrogen in an exogenous HNTs2 molecule. This mild and open-air reaction provided an efficient synthesis to N-bistosyl-substituted 5-imino-2-tetrahydrofuranyl methanamine derivatives, which are important motifs in drug development and biological studies. Mechanistic study based on experiments and density functional theory calculations showed that this transformation proceeds via activation of the substrate alkene by an in situ generated cationic iodonium(III) intermediate, which is subsequently attacked by an oxygen atom (instead of nitrogen) of amides to form a five-membered ring intermediate. Finally, this intermediate undergoes an SN2 reaction by NTs2 as the nucleophile to give the oxygen and nitrogen difunctionalized 5-imino-2-tetrahydrofuranyl methanamine product. An asymmetric variant of the present alkene oxyamination using chiral iodoarenes as catalysts also gave promising results for some of the substrates.

The effect of blood lactate and NT-proBNP predict the survival in patients with invasive mechanical ventilation.

BACKGROUND: Respiratory failure is one of the most common critical diseases. It has already been reported that invasive mechanical ventilation (IMV) should be used to treat respiratory failure. The present study aims to evaluate the prognostic value of blood lactate and NT-proBNP in patients with IMV. METHODS: We retrospectively included 353 patients who were hospitalized in the emergency department of Shanghai Sixth People's Hospital from 2016 to 2019. All patients had IMV. R&D Human Premixed Multi-Analyte Kit detected the expression of various inflammatory factors in serum. Receiver operating characteristic (ROC) curve analysis, survival analysis, and multivariate cox proportional hazards analysis were implemented as statistical analysis methods. RESULTS: The mean duration of hospitalization was 25.5±20.6 days. Twenty-four men and 41 women died. Compared with the survivors, the nonsurvivors were older, had different types of diagnosis, longer ventilation time, and shorter survival time (P<0.05). Also, the expression levels of PCT, NT-proBNP, lactate in 12 h and lactate in 24 h in the nonsurvivors were significantly higher than those in the survivor group (P<0.05). There was a significant correlation between these parameters and ventilation times (P<0.001). The results showed that age, NT-proBNP, and lactate were independent predictors of survival rate. ROC analysis showed that the cut-off values of age, NT-proBNP and lactate were 61.5 years, 230.5 pg/mL and 3.7 mmol/L, respectively. Patients aged ≥61.5 years or NT-proBNP ≥230.5 pg/mL or lactate ≥3.7 mmol/L had a worse prognosis. Therefore, patients with three parameters higher than cut-off value had the lowest survival rate, while patients with three parameters lower than cut-off value had the best survival rate. CONCLUSIONS: Blood lactate and NT-proBNP may be used as biomarkers to predict the prognosis of patients undergoing IMV.

Non-invasive Fecal Steroid Measurements for Monitoring the Reproductive Status of a Critically Endangered Yangtze Finless Porpoises (Neophocaena asiaeorientalis asiaeorientalis).

Yangtze finless porpoise (Neophocaena asiaeorientalis asiaeorientalis) is a critically endangered freshwater cetacean dwelling in the Yangtze River and its adjoining lakes. Affected mainly by the various anthropogenic activities in this region, its population decreased dramatically in the past two decades. To protect this animal from extinction, captive breeding program is an important way to provide basic knowledge for wild population conservation. Non-invasive fecal steroid radioimmunoassay technique was validated in three captive Yangtze finless porpoises for the first time in this study. The seasonality of one captive male and the reproductive status of two females were investigated by longitudinal monitoring their fecal reproductive steroid hormone metabolites. Pregnancy could be diagnosed by an abrupt increase in fecal progesterone metabolites. In late pregnancy (4 months before birth), a significant decrease of fecal progesterone metabolites was observed, which might be referenced for the expectation of parturition date. Seven estrous cycles were recognized in one breeding season of a non-pregnant female judged by the variation of fecal progesterone metabolite levels. The fecal progesterone metabolite level was proved a reliable and precise indicator for estrus and pregnancy diagnosis.

Effects of stand type of artificial forests on soil microbial functional diversity.

We explored the changes of soil microbial biodiversity in response to forest ecological restoration. Soil samples were collected from the close-to nature managed Chinese fir plantation (CF), Moso bamboo plantation (MB), and natural secondary forest (NF). Soil microbial community diversity was analyzed by Biolog-Eco micro-plate technique. The results showed that plant diversity was significantly different among the three stands. Plant diversity of NF was significantly higher than MB and CF, and MB was higher than CF. Soil pH and bulk density showed a great difference, while there was no difference of other soil physiochemical properties among the three stands. Avera-ge well color development (AWCD) of soil in various stands followed the order of NF＞MB＞CF, consistent with the changes of utilization of six types of carbon sources. Shannon index of NF was the highest, and the index of MB was significantly higher than that of CF. Soil physical and chemical properties in different stands were not significantly different, except soil pH and bulk density. The Shannon diversity index (H), Shannon species richness index (S), Simpson dominance index (D) and McIntosh index (U) were the highest in NF, second in MB, and the lowest in CF. Results from principal component analysis (PCA) showed that two factors from 31 carbon sources could explain 60.0% and 12.4% of the variation and that carboxylic acids, carbohydrates and its derivatives, amino acids were the main carbon sources of the two principal component factors. Correlation analysis indicated that plant species richness and Shannon diversity indexes, soil bulk density were significantly correlated to soil microbial community diversity. The microbial community of NF was more efficient in carbon utilization than that in MB and CF, while that in MB was more efficient than that of CF. Based on plant diversity and soil microbial carbon utilization, MB is much better than CF in the artificial forest restoration and improvement in South China.

Perivascular adipose tissue dysfunction aggravates adventitial remodeling in obese mini pigs via NLRP3 inflammasome/IL-1 signaling pathway.

Perivascular adipose tissue (PVAT), a special type of adipose tissue, closely surrounds vascular adventitia and produces numerous bioactive substances to maintain vascular homeostasis. PVAT dysfunction has a crucial role in regulating vascular remodeling, but the exact mechanisms remain unclear. In this study, we investigated whether and how obesity-induced PVAT dysfunction affected adventitia remodeling in early vascular injury stages. Mini pigs were fed a high sugar and fat diet for 6 months to induce metabolic syndrome and obesity. In the mini pigs, left carotid vascular injury was then generated using balloon dilation. Compared with normal mini pigs, obese mini pigs displayed significantly enhanced vascular injury-induced adventitial responses, evidenced by adventitia fibroblast (AF) proliferation and differentiation, and adventitia fibrosis, as well as exacerbated PVAT dysfunction characterized by increased accumulation of resident macrophages, particularly the M1 pro-inflammatory phenotype, increased expression of leptin and decreased expression of adiponectin, and production of pro-inflammatory cytokines interleukin (IL)-1ß and IL-18. Primary AFs cultured in PVAT-conditioned medium from obese mini pigs also showed significantly increased proliferation and differentiation. We further revealed that activated nod-like receptor protein 3 (NLRP3) inflammasome and its downstream products, i.e., IL-1 family members such as IL-1ß and IL-18 were upregulated in the PVAT of obese mini pigs; PVAT dysfunction was also demonstrated in preadipocytes treated with palmitic acid. Finally, we showed that pretreatment with IL-1 receptor (IL-1R) antagonist or IL-1R knockdown blocked AF proliferation and differentiation in AFs cultured in PVAT-conditioned medium. These results demonstrate that obesity-induced PVAT dysfunction aggravates adventitial remodeling after early vascular injury with elevated AF proliferation and differentiation via activating the NLRP3/IL-1 signaling pathway.

Comparison of the effects of albumin and crystalloid on mortality among patients with septic shock: systematic review with meta-analysis and trial sequential analysis.

BACKGROUND: This study aimed to compare the effects on mortality of albumin and crystalloid, used for fluid resuscitation among adult patients with septic shock, through conducting a meta-analysis and trial sequential analysis (TSA). DESIGN AND SETTING: Meta-analysis and TSA conducted at Shanghai Jiao Tong University Affiliated Sixth People's Hospital, Shanghai, China. METHODS: Data were collected from several major databases including MEDLINE, EMBASE, Clinical Trials.gov and Cochrane Central Register of Controlled Trials. Studies that compared the effects of albumin therapy versus crystalloid therapy on mortality among adult septic shock patients were eligible for inclusion in the analyses. The study name, year of publication, country of the trial, albumin concentration, type of crystalloid and all reported mortalities at different follow-up endpoints were extracted. RESULTS: Compared with crystalloid, albumin did not decrease all-cause mortality at the final follow-up. However, in TSA, the required information size was not achieved in all groups, which means that the effect size was not definitive and further RCTs are needed to confirm or deny these findings. CONCLUSIONS: Compared with crystalloid solutions, albumin was unable to decrease all-cause mortality. However, TSA indicated that these results could be false-negative. Additional randomized controlled trials are needed to clarify this discrepancy.

Comparison of the effects of albumin and crystalloid on mortality among patients with septic shock: systematic review with meta-analysis and trial sequential analysis

ABSTRACT BACKGROUND: This study aimed to compare the effects on mortality of albumin and crystalloid, used for fluid resuscitation among adult patients with septic shock, through conducting a meta-analysis and trial sequential analysis (TSA). DESIGN AND SETTING: Meta-analysis and TSA conducted at Shanghai Jiao Tong University Affiliated Sixth People's Hospital, Shanghai, China. METHODS: Data were collected from several major databases including MEDLINE, EMBASE, Clinical Trials.gov and Cochrane Central Register of Controlled Trials. Studies that compared the effects of albumin therapy versus crystalloid therapy on mortality among adult septic shock patients were eligible for inclusion in the analyses. The study name, year of publication, country of the trial, albumin concentration, type of crystalloid and all reported mortalities at different follow-up endpoints were extracted. RESULTS: Compared with crystalloid, albumin did not decrease all-cause mortality at the final follow-up. However, in TSA, the required information size was not achieved in all groups, which means that the effect size was not definitive and further RCTs are needed to confirm or deny these findings CONCLUSIONS: Compared with crystalloid solutions, albumin was unable to decrease all-cause mortality. However, TSA indicated that these results could be false-negative. Additional randomized controlled trials are needed to clarify this discrepancy.

A novel fusarivirus isolated from the phytopathogenic fungus Nigrospora oryzae.

In this study, we report the discovery and molecular characterization of a novel mycovirus, Nigrospora oryzae fusarivirus 1 (NoFV1) isolated from the rice-infecting fungus Nigrospora oryzae. Excluding a poly (A) tail, the genome of the virus is 7004 nucleotide (nt) long containing three putative nonoverlapping open reading frames (ORF1, ORF2, and ORF3). The large ORF1 encodes a polypeptide with a conserved RNA-dependent RNA polymerase (RdRp) domain and a helicase domain that functions for RNA replication. Each of the smaller ORF2 and the smallest ORF3 encodes a putative protein with an unknown function. Amino acid (aa) sequence similarities between the NoFV1-ORF1- and ORF2-encoded proteins and the homologous sequences from other mycoviruses were found. Phylogenetic analysis on the basis of the RdRp and helicase domains showed that NoFV1 is phylogenetically related to viruses in the newly proposed family Fusariviridae. Thus, we suggest that NoFV1 might be a novel member of family Fusariviridae.

[Stable Isotope Characteristics in Different Water Bodies in Changsha and Implications for the Water Cycle].

Analysis of the variation characteristics of different water bodies is the basis of applying isotopic tracer technique in regional water cycle research. Based on the samples of atmospheric precipitation, surface water (river water) and groundwater (spring water and well water) in Changsha from January 2012 to December 2013, the study analyzed the variation characteristics of δD and δ(18)O in different water bodies. The results showed that the values of D and 18O in precipitation of Changsha showed obvious seasonal variation because of the seasonal difference of the water vapor source, and it showed significant negative correlation between δ(18)O in precipitation and some meteorological factors such as the temperature and the amount, the local meteoric water line revealed the climatic characteristic of humid and rainy in Changsha; the fluctuation of 8D and 80 in surface water was more moderate than those in precipitation, and the seasonal variation of stable isotope value showed lagging characteristic compared with that in precipitation, the difference of river water line (RWL) indicated that the main supply sources of surface water were changing in different seasons; the fluctuation of δD and δ(18)O in groundwater was the least, the variation ranges and mean values of δD and δ(18)O in spring water and well water were very close, it showed that there were some hydraulic connections in the two water bodies, the values of δD and δ(18)O in groundwater were constantly lower during drought months, this phenomenon might have a certain relationship with the increasing absorbency of tree roots from groundwater. The results of the study have certain guiding significance for rational utilization of water resources in the region.

Simultaneous determination of thirty non-steroidal anti-inflammatory drug residues in swine muscle by ultra-high-performance liquid chromatography with tandem mass spectrometry.

An ultra-high-performance liquid chromatography with tandem mass spectrometric detection (UHPLC-MS/MS) method was established for the simultaneous determination of residues of thirty non-steroidal anti-inflammatory drugs (NSAIDs) in swine muscle. The samples were extracted with acetonitrile and phosphoric acid. The extracts were defatted with n-hexane, and then purified by HLB solid-phase extraction cartridge. Analysis was carried out on UHPLC-ESI-MS/MS working with multiple reaction monitoring mode with polarity switching. Limits of detection were between 0.4 µg/kg and 2.0 µg/kg, and limits of quantification were between 1.0 µg/kg and 5.0 µg/kg. The recoveries of NSAIDs were between 61.7% and 125.7% at spiked levels of 1.0-500 µg/kg. The repeatability was less than 8% and the within-laboratory reproducibility was not more than 12.3%. The method was reliable, convenient and sensitive.

[The evaluation of four-year highly active antiretroviral therapy in HIV-1 infected patients].

OBJECTIVE: To observe that antiretroviral efficacy, immune reconstitution of four-year highly active antiretroviral therapy (HAART), and evaluate its side effect in Chinese HIV-1-infected patients. METHODS: A total of 258 HIV-1 infected patients, given HAART regimens composed of two nucleoside reverse transcriptase inhibitor (NRTI) and one non-nucleoside reverse transcriptase inhibitor (NNRTI) for mean 51.5 months, measured HIV RNA viral load (VL) and the counts of CD(4)(+) T cell, CD(8)(+) T cell at the baseline and 6, 12, 24, 36 and 48 months after HAART initiation, respectively, monitoring side effect, blood routine, main biochemical parameters, and other disadvantageous accidents during the 51.5-month treatment. RESULTS: Plasma HIV-1 RNA level was determined by fluorescent quantitative polymerase chain reactions (FQ-PCR) at the baseline and 6, 12, 24, 36 and 48 months after starting HAART, and showed 5.27, 2.97, 2.74, 2.62, 2.67 and 2.75 lg (copies/ml), respectively. The counts of CD(4)(+) T cell from (127 ± 63) cells/µl at the baseline increased to (190 ± 115), (248 ± 93), (269 ± 127), (296 ± 156) and (317 ± 195) cells/µl at 6, 12, 24, 36 and 48 months after starting HAART. A total of 149 treated patients (57.8%)had gastrointestinal side effects, peripheral polyneuropathy, various rashes, central nervous system disorders, fever or baldness. Twenty-two patients changed one of three medicines to another because toxicity. Sixteen changed the regimen to the second line HAART for lactic acidosis or other serious toxicities. CONCLUSIONS: A total of 258 HIV-1 infected Chinese patients treated with two NRTI and one NNRTI as first line HAART regimen during mean 51.5 months, showed a good antiretroviral efficacy and immune reconstitution, but a few side-effects at the parts of patients. It is necessary to treat adverse effect and change HAART regimen for severe toxicity in time.

A novel mixed-mode solid phase extraction for simultaneous determination of melamine and cyanuric acid in food by hydrophilic interaction chromatography coupled to tandem mass chromatography.

Utilizing a solid phase extraction column (MCT) containing mixed hydrophilic functional gel and cation exchange sorbent, a sensitive and rapid HPLC-MS/MS method for simultaneously determining the residues of melamine (MEL) and cyanuric acid (CYA) in human foodstuffs was developed. MEL and CYA in egg, pork, liver, kidney and pork, shrimp, sausage casing, honey, soybean milk, soybean powder and dairy product were extracted using acetonitrile/water, defatted with hexane and isolated using MCT solid phase extraction column. The residues were separated upon a hydrophilic interaction liquid chromatography (HILIC) column and analyzed by electrospray ionization under negative-positive switched mode on a triplequadrupole mass spectrometry. The selected reaction monitoring was performed on [M+H](+) of m/z 127.9 to provide the transition of 127>85 and 127>68 (MEL) while the [M-H](-) of m/z 127.1 was selected as the precursor ion for CYA resulting in product ions m/z 85 and 42. Isotope labeled internal standard ((15)N(3)-MEL and (13)C(3)-CYA) and matrix-matched calibration were both used to observe the recovery to be 70.0-129.6% and 70.0-128.9% with RSD of 1.4-23.3% and 1.5-21.7% for MEL and CYA, respectively (n=6). All the LODs and LOQs of MEL and CYA were less than 39.4 and 99.1µgkg(-1), respectively, in 18 matrices, which were sensitive enough for quantitative analysis. This method has been proven effective in simultaneous determination of melamine and cyanuric acid when inspecting unknown and positive samples.

[Molecular diagnosis of spinal muscular atrophy by multiplex ligation-dependent probe amplification].

OBJECTIVE: To investigate the effect of multiplex ligation-dependent probe amplification (MLPA) in molecular diagnosis of spinal muscular atrophy (SMA). METHODS: Peripheral blood samples were collected from 13 SMA patients, 31 parents of SMA patients, 50 healthy individuals without family history of SMA, and 10 specimens of amniotic fluid from these families were collected too. Genomic DNA was analyzed by MLPA, conventional PCR-RFLP, and allele-specific PCR. RESULTS: In complete agreement with the results of conventional PCR-RFLP and allele-specific PCR, MLPA analysis showed that all of the 13 patients had homozygous deletion of the survival of motor neuron 1 (SMN1) gene, and there was significant difference between the SMA severity (type I to type III) and SMN2 copy number (P < 0.05). Of the 31 parents 29 (93.5%) had 1 copy of SMN1, 2 (6.5%) had 2 copies of SMN1. Of the 50 healthy individuals, 1 (2.0%) had 1 copy of SMN1, 48 (96.0%) had 2 copies of SMN1, and 1 (2.0%) had 3 copies. The SMN1 copy number of the parents was significantly higher than that of the healthy individuals (P < 0.01). Two of the 10 fetuses had homozygous deletion of SMN1. CONCLUSION: The MLPA technique has proved to be an accurate and reliable tool for the molecular diagnosis of SMA, both in patients and in healthy carriers.

Increased expression of hLRH-1 in human gastric cancer and its implication in tumorigenesis.

Altered signaling pathways or deregulated transcription factors represent an important category of molecular events leading to aberrant gene regulation in gastric cancer, among which the role of WNT/beta-catenin pathway remains unclear. LRH-1 is a critical transcription factor in controlling cell proliferation via crosstalk with the beta-catenin signaling pathway. In order to gain a knowledge of the expression of hLRH-1v1 and hLRH-1 in gastric cancer, a Q-PCR analysis was carried out. Our results showed that in about 50 and 47.6% of 42 tested patients with gastric cancer, the mRNA expression of hLRH-1v1 and hLRH-1 was significantly upregulated, as compared with self-paired normal control, respectively. Besides, overexpression of hLRH-1 was shown to promote the proliferation of gastric adenocarcinoma cell SGC-7901 via induction of cyclin E1. Taken together, our present study demonstrated for the first time the increased expression of hLRH-1v1 and hLRH-1 in human gastric cancer, an alteration which may implicate in tumorigenesis.

[Plant volatiles and their metabolic engineering].

Plant volatiles mainly include terpenoid, benzenoid/phenylpropanoid and fatty-acid derivatives, and they play diverse roles in plant-plant and plant-insect communications. In recent years, great progress has been made in biochemical and molecular characterization of the formation and release of these volatiles, and this make it possible to dissect their biological functions. More than 30 kinds of genes related with biosynthesis of these volatiles have been cloned. The pathways leading to synthesis of these metabolites can be controlled by enzyme activity and the substrates available as well as gene architecture. Plant volatiles can serve as attractants for specific pollinators, important cellular regulators in developmental processes and protection against environmental stress, whereas those released after herbivory or pathogen attacks can induce the expression a set of defensive genes or attraction of predators of the herbivores. An attractive prospect in this area is to design scent spectrum of plant with genetic and molecular technology. Two alternative approaches are used to genetically engineer these plant volatiles. One is based on the introduction of foreign genes encoding enzymes with activities that are missing in target plant, while the other is focused on modulating the expression of native genes.

[Study on preparation of lanthanum-doped TiO2 nanometer thin film materials and its photocatalytic activity].

In this paper, lanthanum-doped TiO2 nanometer film materials coated on glass were prepared in Ti(OBu)4 precursor solutions by sol-gel processing. Transmittance and photocatalytic activity were respectively investigated and tested for these nanometer thin films prepared with different amount of lanthanum (La), different amount of polyethylene glycol (PEG), and different coating layer times. Some reactive mechanisms were also discussed. For one layer La-addition had little effect on the film transmissivity; but the photocatalytic activity was significantly improved due to La-addition. With increasing PEG, the transmittance of the film decreased for one layer film; but its photocatalytic activity did not rise. Increasing layer number did not affect the transmissivity of multilayer film. After coating two times, increasing layer number did not significantly improve the photocatalytic activity. The highest photocatalytic activity and best transmissivity were obtained for two layer TiO2 film when the dosage of lanthanum was 0.5 g and the dosage of polyethylene was 0.2 g in the precursor solutions. These materials will probably be used in the protection of environment, waste water treatment, and air purification.