超临界二氧化碳介质中的有机反应*

本文主要介绍了超临界近5年来超临界二氧化碳中的有机反应研究的最新进展,包括加氢反应、氧化反应、羰基化反应、碳碳键形成反应、酯化反应和酶催化反应的研究现状;同时,还介绍了超临界二氧化碳作为反应底物用于合成碳酸酯和氨基甲酸酯的研究进展;并对未来的发展进行了展望。     

Photolysis of glyoxal in air

The photolysis of glyoxal in synthetic air was investigated in a quartz cell at 298 K using three types of UV sources (TL/12 lamps (275–380 nm), TL/03 lamps (390–470 nm) and mercury lamps (254 nm)) and products were identified and quantitatively analyzed using long-path FTIR spectroscopy. For all light sources, the observed products were CO, HCHO and HCOOH. Absolute quantum yields were determined using Cl₂ and Br₂ as actinometers. Photolysis in the first absorption band of glyoxal, using TL/12 lamps, provided an overall quantum yield of Φ_T = 0.97 ± 0.05, independent of total pressure ranging from 100 to 700 Torr air. The absolute quantum yields obtained with the TL/03 lamps, covering the second absorption band of glyoxal, showed dependency on total pressure, ranging from Φ_T = 0.12 at 100 Torr to Φ_T = 0.042 at 700 Torr, which can be expressed as a Stern–Volmer-type equation 1/Φ_T = (6.80 + 251.8) × 10⁻⁴ × P (Torr).By combining the product yields with literature data, we deduced the detailed picture of glyoxal photolysis, including the dependency of the quantum yield of each particular channel: CHOCHO + hν → 2HCO (Φ₁); CHOCHO + hν → H₂ + 2CO (Φ₂); CHOCHO + hν → H₂CO + CO (Φ₃) on the applied wavelength. The product quantum yields indicate that dissociation into two HCO radicals is the most important pathway under atmospheric conditions. The mean photolysis rate was measured under solar radiation in the EUPHORE outdoor chamber to be J_obs = 1.04 ± 0.10 × 10⁻⁴ s⁻¹, corresponding to a mean effective quantum yield ϕ_eff = 0.035 ± 0.007. Although glyoxal has a very low effective quantum yield, photolysis remains an important removal path in the atmosphere.     

Study of natural radionuclides in Karun river region

In this study the concentration of natural radionuclides has been investigated in soil and water of Karun river by using a high resolution (HPGe detector, n-type) γ-spectrometry. The concentrations range in water sample was 47.6 ± 5.6–130.8 ± 6.3, 0.0–23.4 ± 0.5 and 0–6.4 ± 2.0 Bq L⁻¹ for ⁴⁰K, ²³²Th and ²²⁶Ra respectively. For soil samples the concentration range of 275.7 ± 8.6–458.6 ± 6.8, 19.2 ± 5.35–41.1 ± 3.95 and 29.9 ± 1.53–50 ± 1.54 Bq kg⁻¹ was obtained respectively for ⁴⁰K, ²³²Th and ²³⁸U. ¹³⁷Cs was also detected in some part of the region in soil samples. The mean concentration of ¹³⁷Cs was 5.5 ± 0.6 Bq kg⁻¹. The origin of this activity is unknown. The average absorbed dose rate in outdoor air at a height of 1 m above the ground was found to be 54.3 ± 3.7 nGy h⁻¹. The results of this study indicate that the area has standard background radiation level.     

Limitations of the scalp-hair biologic monitor in assessing selenium status in epidemiological investigations

Scalp hair is routinely used to assess exposure to toxic trace elements and nutritional status of some required trace elements. The advantages and disadvantages of hair as a biologic monitor have been comprehensively discussed in the literature for many years. Among the concerns is distinguishing between exogenous and endogenous contributions. Nested in this issue is the longitudinal distribution of a trace element along the hair strand. The typical observation for many elements of interest is that the element concentration increases from the root end to the distal end; and this is attributed to continuing contamination from exogenous sources. In this study we used neutron activation analysis to measure 14 trace elements in 6 mm segments of full-length scalp hair from three healthy members of the same household having light-urban environmental exposure. To extend the data set for selenium, we included three adult female subjects with longer than average scalp hair. From these trace-element concentrations we calculated the root-to-distal end ratios as a profile diagnostic of trace-element distributions. Ratios fall into three diagnostic categories, >1, ≈1, and <1 corresponding to profiles having decreasing root-to-distal concentrations, unchanging concentrations, and increasing concentrations, respectively. Of the 14 elements measured, only Se has R > 1, Zn and S have R ≈ 1, and the remaining 11 elements all have R < 1 in the order: As > I > Hg ≈ Au ≈ Mg ≈ Mn ≈ Sb ≈ Ca > Cu > Al ≈ Ag. R _Se is greater than 1 and increases with hair length (P = 0.02) corresponding to a continuous longitudinal loss of Se in stark and puzzling contrast to the other elements measured. An analogous loss of Se in the nail monitor was not observed leading us to conclude that the nail is less prone to misclassification of selenium status in epidemiological studies.     

Determination of uranium,thorium and potassium contents of rock samples in Yemen

Uranium, thorium and potassium contents in 16 different rock samples from various sites in Republic of Yemen were determined using three different techniques of analysis: γ-spectrometry, Instrumental neutron activation analyses (INAA) and X-ray fluorescence (XRF). The concentration range for thorium, uranium and potassium were found to be from 9,810 ± 272 to 3.6 ± 1.3 ppm, 1,072 ± 40 to 1.2 ± 0.7 ppm and 11 ± 1 to 0.26 ± 0.05%, respectively.     

Radiolysis of 1-naphthol in aqueous solutions

The effects of absorbed doses, initial pH and 1-naphthol concentration onto its radiolysis in aqueous sulphuric and hydrochloric acids by gamma rays from ⁶⁰Co were investigated. Under the experimental conditions, 1-naphthol degradation yields increased with increasing the absorbed doses (0.3–3.0 kGy) and with decreasing the initial 1-naphthol concentration (20–1 ppm). It was found out that the hydrated electrons did not play any significant roles in 1-naphthol radiolysis, as the degradation yields were higher at pH₀ ~ 0.46 compared to those at pH₀ ~ 2.0–5.0. The corresponding radiolytic yields G(−1-naphthol) were (6.13 ± 1.00)) × 10⁻² and (5.11 ± 0.22) × 10⁻² μmol/J in sulphuric acids, (15.61 ± 3.85) × 10⁻² and (4.76 ± 0.48) × 10⁻² μmol/J in hydrochloric acids. 1-Naphthol degradation rates could be described by the kinetic equations of pseudo-first-order reactions. An empirical relation between the observed reaction constants k _D and the initial 1-naphthol concentrations was established, enabling to predict the absorbed doses required for a given treatment efficiency. Three products of 1-naphthol degradation were revealed using an HPLC/UV procedure.     

Natural radioactivity in cultivated land in the vicinity of a phosphate fertilizer plant in Nigeria

Natural radioactivity in soil and vegetable samples in cultivated land in the vicinity of an active phosphate fertilizer plant in Kaduna, Nigeria was carried out to assess the potential radiological impact of the plant on its immediate environment. The activity counting was carried out using sodium iodide gamma spectrometry. The annual committed effective dose for two vegetables in the farmlands due to uranium (²³⁸U) and thorium (²³²Th) was assessed. The mean activity concentration of radionuclides in the soil samples ranges from 20.5±7.3 to 31.6±4.1 Bq kg^?1 for ²²⁶Ra, 19.6±1.6 to 53.2±3.7 Bq kg^?1 for ²³²Th and 203.9±6.3 to 253.6±9.5 Bq kg^?1 for ⁴⁰K. The annual intake of ²³⁸U and ²³²Th from consumption of okra were 1.9 Bq kg^?1 and 5.22 Bq kg^?1 and for tomatoes 2.66 Bq kg^?1 and 5.1 Bq kg^?1 respectively. The committed effective doses from consumption of okra and tomatoes were 0.1 μSv y^?1 and 0.12 μSv y^?1 respectively.     

Trans fatty acid accumulation in the human placenta

Trans fatty acid may impair fetal growth and infant neurodevelopment, but the quantity in a placenta and human tissues remains unknown. To address the issue, a simple and reliable method of quantification is needed. We established a method of quantifying trans‐octadecenoic acids (trans‐6,8,9,11 18:1 fatty acids, TOAs), a major component of trans fatty acid, in human tissue samples, and then determined the TOAs level in the placenta. Oleic acid (OA) (C18:1(9c)) was measured by isotope dilution gas chromatography–mass spectrometry, and the TOAs level was subsequently calculated based on the ratio of the peak areas for TOAs and OA (TOAs/OA) in the mass chromatogram. Lipids were extracted from 28 human placentas at different gestational ages from 28 to 41 weeks, and the TOAs and OA levels were measured. In method validation, the limit of detection for elaidic acid (trans‐9,18:1 fatty acid), a major component of TOAs, was 0.57 ng, and linearity of calibration ranging from 7.7 to 68.0 μg/g placenta for TOAs. In human placenta analysis, the TOAs level was significantly higher in term (n  = 15, 40.2 ± 9.7 μg/g placenta) than in preterm placentas (n  = 13, 18.9 ± 7.4 μg/g placenta) (p  < 0.001), while OA levels were similar in term (n  = 15, 863 ± 132 μg/g placenta) and preterm (n  = 13, 743 ± 283 μg/g placenta) placentas (p  = 0.15). TOAs accumulate in the placenta as pregnancy progresses and have a fate different from that of OA in vivo. To our knowledge, this is the first report of TOA quantification in human tissue samples. Copyright © 2017 John Wiley & Sons, Ltd.     

Determination of total As in onion plants growing in contaminated substrates by total reflection X-ray fluorescence

The onion (Allium cepa L.) is one of the most important cultivars in the world and its production level occupies the second place in Venezuela. It becomes important to develop analytical procedures for arsenic determination and to study the effect of this element on the cultures, as well the absorption, transport and translocation processes. A TXRF method for As determination in onions was developed. Two treatments were applied to the onion plants, As contaminated and control. The contaminant was added to the plants to an amount of 100 μg, in a single time 3 weeks after the transplant of plantlets. The green leaves bulbs, and roots together with the stems were separated 45 days after transplant and analyzed by TXRF and HG-AAS for total Arsenic determination. A good agreement was found between these two techniques, demonstrating the accuracy of the TXRF procedure. It was found that the highest concentration corresponded to the root and stems (37 ± 31 μg g⁻¹), followed by the bulbs (11 ± 7 μg g⁻¹), being the smallest level found in the green leaves (4 ± 3 μg g⁻¹). At low As contamination levels of 0.25 μg g⁻¹, a risk for translocation of the toxic element to the edible parts of the onion plants exists. At this level the normal development of the plant is not affected, being the only exception the root length, which is significantly higher in the contaminated treatment.     

Measurement uncertainty of shikimic acid in red wines produced in Chile

High-performance liquid chromatography (HPLC) to determine shikimic acid is used as a complementary tool to differentiate wine varieties. In order to correctly classify, measurement uncertainty of shikimic acid by HPLC in red wine was estimated considering the following components: uncertainty associated with the preparation of shikimic acid stock solution, uncertainty associated with quantification using a calibration curve, and uncertainty associated with precision. The most important contribution to total uncertainty was the method precision. The expanded uncertainty (U) for different wine varieties was between 2.6 and 8.5%. The method was applied to determine the concentration of shikimic acid in different emerging wine varieties cultivated in Chile, such as Carmenère, Shiraz, and Pinot Noir, comparing them with classical varieties, such as Cabernet Sauvignon and Merlot. Shiraz wines presented lower shikimic acid concentrations (between 27 and 86 mg L⁻¹ with U _(k=2) = 2.6%) than Cabernet Sauvignon wines (between 41 and 142 mg L⁻¹ with U _(k=2) = 8.1%), but their concentrations were higher than found in Merlot (from 9 to 41 mg L⁻¹ with U _(k=2) = 4.3%) and Carmenère wines (between 7 and 49 mg L⁻¹ with U _(k=2) = 5.8%). Pinot Noir was the variety with the lowest concentration of this acid (7–14 mg L⁻¹ with U _(k=2) = 8.5%). Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Description of intra-diffusion in liquid mixtures

Employing a previously derived model to describe intra-diffusion coefficients in liquid mixtures based on molecular simulations of spherical Lennard–Jones particles [T. Merzliak, A. Pfennig, Mol. Simul. 30 (7) (2004) 459–468], an improved set of coefficients was obtained from optimized molecular dynamics simulations. In these simulations, the thermodynamic states were planned with the help of optimal experimental design, which allows to reduce the number of simulations necessary for significant determination of the coefficients by roughly a decade. The model was then applied to the real liquid mixtures toluene + cyclohexane, toluene + 1,4-dioxane, n-hexane + toluene, 1,4-dioxane + cyclohexane and cyclohexane + n-hexane, which have molecular properties that correspond to the model assumptions. Experimental intra-diffusion coefficients for the mixtures toluene + cyclohexane, toluene + 1,4-dioxane, n-hexane + toluene and 1,4-dioxane + cyclohexane were determined with nuclear magnetic resonance (NMR) techniques in this work. Even without additional parameters for the mixture the proposed model can describe the diffusion coefficients with an average accuracy of 5%. Allowing a deviation from Lorentz–Berthelot mixing rules leads generally only to slight improvement.     

Lithological and seasonal variations in radon concentrations in Cypriot groundwaters

The paper presents and discusses radon activity concentrations in Cypriot groundwater systems as a function of the background lithology and seasonal/meteorological conditions using an airborne radon monitoring system (ARM) after separation of radon by out-gassing. Radiometric analysis of groundwater samples obtained from non-contaminated systems showed that radon concentration in groundwaters varies strongly (0.1–10 Bq L⁻¹) depending mainly on the hosting geological matrix but also to lesser degree on atmospheric/meteorological conditions. The associated excess annual dose has been estimated to range between 10⁻⁶ and 10⁻⁴ mSv y⁻¹, which is an insignificant contribution to the radiation exposure of the Cypriot population caused by airborne radon (0.5 ± 0.4 mSv y⁻¹).     

INAA application in the age dynamics assessment of Br,Ca, Cl,K, Mg,Mn, and Na content in the normal human prostate

The effect of age on chemical element contents in intact prostate of 64 apparently healthy 13–60 years old men was investigated by neutron activation analysis with high resolution spectrometry of short-lived radionuclides. Mean values (M ± SΕΜ) for content (mg/kg, dry weight basis) of chemical elements were: Br–31.6 ± 3.2, Ca–2150 ± 160, Cl–12670 ± 675, K–12010 ± 400, Mg–1150 ± 75, Mn–1.56 ± 0.09, and Na–10520 ± 340, respectively. A tendency of age-related increase in Ca content and decrease in Mn content was observed.     

Identification of novel diclofenac acid and naproxen bearing hydrazones as 15-LOX inhibitors: Design,synthesis, in vitro evaluation,cytotoxicity, and in silico studies

Inflammation is the immune system's adaptive response to tissue dysfunction or homeostatic imbalance, inducing fever, pain, physiological and biochemical changes via the cyclooxygenase (COX) and lipoxygenase (LOX) pathways. NSAIDs (non-steroidal anti-inflammatory drugs), such as diclofenac acid and naproxen, are the most common inhibitors of the COX pathway. These drugs, however, are currently being studied as LOX inhibitors as well. Therefore, in the present study, a novel series of diclofenac acid and naproxen-bearing hydrazones 7(a-r) were designed, synthesized, and characterized by different spectroscopic methods like ¹H NMR, ¹³C NMR, IR and HRMS (EI) analysis. All these synthesized compounds were evaluated for their in vitro inhibitory potential against the Soybean 15-lipoxygenase (15-LOX) enzyme. These compounds exhibited varying degrees of inhibitory potential ranging from IC₅₀ 4.61 ± 3.21 μM to 193.62 ± 4.68 μM in comparison to standard inhibitors quercetin (IC₅₀ 4.84 ± 6.43 μM) and baicalein (IC₅₀ 22.46 ± 1.32 μM). The most potent compounds in the series were compounds 7c (IC₅₀ 4.61 ± 3.21 μM), and 7f (IC₅₀ 6.64 ± 4.31 μM). These compounds were found least cytotoxic and showed 96.42 ± 1.3 % and 94.87 ± 1.6 % viability to cells at 0.25 mM concentration respectively. ADME and in silico studies supported the drug-likeness and binding studies of the molecules with the target enzyme.     

Mechanistic studies on the intramolecular electron transfer in an adduct species of the oxo-centred trinuclear iron(III) cation and <Emphasis Type="SmallCaps">l</Emphasis>-ascorbic acid in aqueous solution

The kinetics of the intra-molecular electron transfer of an adduct of l-ascorbic acid and the [Fe₃^IIIO(CH₃COO)₆(H₂O)₃]⁺ cation in aqueous acetate buffer was studied spectrophotometrically, over the ranges 2.55 ≤ pH ≤ 3.74, 20.0 ≤ θ ≤ 35.0 °C, at an ionic strength of 0.50 and 1.0 mol dm⁻³ (NaClO₄). The reaction of l-ascorbic acid and the complex cation involves the rapid formation of an adduct species followed by a slower reduction in the iron centres through consecutive one-electron transfer processes. The final product of the reaction is aqueous iron(II) in acetate buffer. The proposed mechanism involves the triaqua and diaqua-hydroxo species of the complex cation, both of which form adducts with l-ascorbic acid. At 25 °C, the equilibrium constant for the adduct formation was found to be 86 ± 15 and 5.8 ± 0.2 dm³ mol⁻¹ for the triaqua and diaqua-hydroxo species, respectively. The kinetic parameters derived from the rate expression have been found to be: k ₀ = (1.12 ± 0.02) × 10⁻² s⁻¹ for the combined spontaneous decomposition and k ₁ = (4.47 ± 0.06) × 10⁻² s⁻¹ (ΔH ₁^‡ = 51.0 ± 2.3 kJ mol⁻¹, ΔS ₁^‡ = −100 ± 8 J K⁻¹ mol⁻¹), k ₂ = (4.79 ± 0.38) × 10⁻¹ s⁻¹ (ΔH ₂^‡ = 76.5 ± 0.8 kJ mol⁻¹, ΔS ₂^‡ = 6 ± 3 J K⁻¹ mol⁻¹) for the triaqua and diaqua-hydoxo species, respectively.     

Effect of gambogenic acid in attenuating diethylnitrosamine (DEN)-induced hepatocellular carcinoma in rat model

Liver cancer, specifically hepatocellular carcinoma has been a widespread problem among general population. This study aims to investigate the modulating mechanism of gambogenic acid, a phenolic xanthonoid, in diethylnitrosamine (DEN)-induced liver cancer in rats. Male Wistar albino rats were clustered into four groups (n = 6). Group I served as control treated with normal saline. Hepatocellular carcinogenesis was induced in rats by single intraperitoneal (i.p.) administration of DEN in saline (200 mg/kg b.w.) for groups II and III. Group III received oral administration of gambogenic acid (20 mg/kg b.w.) one hour post DEN administration, whereas group IV received oral administration of gambogenic acid (20 mg/kg b.w.) alone. Rats were sacrificed after 16 weeks to determine the levels of hepatic biomarkers, oxidative stress markers, hematological profile and histopathological changes. Gambogenic acid significantly ameliorated the expressions of oxidative stress markers TBARS, GSH (P < 0.05), enzymatic antioxidants GPx, CAT, SOD, GST (P < 0.05), apoptosis mediators (P < 0.05), and serum biomarkers for liver damage and tumor formation (P < 0.05) compared with DEN-induced model group. Hepatocellular levels of 8-OHdG were significantly diminished (P < 0.05) by gambogenic acid against the damage incurred by DEN. Liver histopathological derangements caused by DEN were reversed by gambogenic acid. The results clearly impacted the effect of gambogenic acid in attenuating DEN-induced hepatocellular carcinoma in rats mediated through NF-kβ pathway and hepatocellular oxidative damage.     

Quantitative leak test for microholes and microtears in whole gloves and glove pieces

The current leak tests for gloves are qualitative. The developed quantitative leak test uses vacuum pressure to draw measured volumes of water to detect microholes/tears in whole gloves and glove pieces. A modified plastic vacuum desiccator interfaced with a Frazier air permeability tester allowed exposure of disposable unsupported/unlined/powderless Kimtech Blue nitrile to 50 mL of water for glove pieces or to 600 mL within a whole glove at vacua of 8–9 in. (20–23 cm) and 11–12 in. (28–30 cm) water gauge, respectively. Punctures of known dimensions were made before testing in specific glove areas using 21-, 22-, 26-, 30-, and 33-gauge needles (outer/inner diameters in micrometres of 873/514, 794/413, 635/311, 476/127, 318/159 and 238/133, respectively). The length of the punctures varied from 0.13 ± 0.01 to 0.80 ± 0.11 mm. Flow rates of water through the holes/tears ranged from 2.5 ± 0.4 to 106 ± 7 mL/min for glove pieces. For whole gloves, the ranges were from 31 ± 9 to 543 ± 110 mL/min in the palm area; and 0.23 ± 0.06 to 82 ± 18 mL/min in the finger/fingertip area. The method quantified tear lengths as short as 0.13 ± 0.01 mm.     

Differential scanning calorimetric examination of ruptured lower limb tendons in human

The tendon ruptures are serious injuries of the lover limb in middle age and physically active population. While the Achilles tendon rupture is common, the patellar ligament and quadriceps ligament ruptures are an absolutely rare injury. Usually there is no correlation between the velocity of the trauma and the supervening of the rupture. The aetiology of the degenerative changes in the collagen structures of the tendons and ligaments which could be disposed for the rupture are still not clear. Our hypothesis was that before the injury there are clear pathological abnormalities in the tissues of the tendons, which are predisposed for the rupture, and could be monitored besides the classical histological methods by differential scanning calorimetry. The thermal denaturation of human samples was monitored by a SETARAM Micro DSC-II calorimeter. All the experiments were performed between 0 and 100 °C. The heating rate was 0.3 K/min. DSC scans clearly demonstrated significant differences between the control and ruptured samples (control: T _m = 59.7 °C, T _1/2 = 1.4 °C and ΔH _cal = 8.54 J/g; ruptured Achilles tendon: T _m = 62.75 °C, T _1/2 = 2.6 °C and ΔH _cal = 1.54 J/g, ruptured Quadriceps tendon: T _m = 64.8 °C, T _1/2 = 1.6 °C and ΔH _cal = 1.53 J/g, ruptured Patellar tendon: T _m = 63.9 °C, T _1/2 = 1.41 °C and ΔH _cal = 0.97 J/g). These observations could be explained with the structural alterations caused by the biochemical processes. With our investigations we could demonstrate that DSC is a useful and well applicable method for the investigation of collagen tissue of the degenerated human tendons and ligaments. We can prove with this method that the degenerative changes of the tissue elements increase the thermal stability of collagen tissues of the tendons which could be disposed for the rupture.     

Exposure to underground radon in and around Kolkata Municipal Corporation area: an exhaustive study

Air radon survey was carried out at different underground locations at Kolkata using radon monitor. Average radon concentration for basements was found to be 22.70 ± 1.12 Bq/m³ with maximum 59.00 ± 7.18 Bq/m³ and minimum 8.50 ± 3.14 Bq/m³. Average level for sub-ways was 23.05 ± 2.59 Bq/m³ fluctuating between maximum 39.00 ± 1.24 Bq/m³ and minimum 13.50 ± 1.78 Bq/m³. In comparison, open air background at basement entrance was 19.44 ± 1.06 Bq/m³ and subway entrance was 18.58 ± 1.14 Bq/m³. Annual effective dose was calculated to assess probable health risk. Radon concentration level and annual effective dose were found well below safe levels recommended by International Agencies WHO and UNSCEAR.

     

Tritium in water bodies around the Kaiga generating station

Tritium concentration was monitored in different water sources collected around Kaiga Nuclear Power plant, India. The concentration was in the ranges?<?1.9–27.4 Bq L^?1 (GM?=?4.0 Bq L^?1) for groundwater,?<?1.9–42.1 Bq L^?1 (GM?=?3.5 Bq L^?1) for surface water and in 12.4–42.0 Bq L^?1 (GM?=?24.07 Bq L^?1) for reservoir water. The concentration values observed in this study are similar to those reported for other PHWR stations of the world. The radiation dose to the public due to ingestion of Tritium through groundwater was computed to be 0.08 μSvy^?1.