Monitoring the adsorption of per- and polyfluoroalkyl substances on carbon black by LDI-MS capable of simultaneous analysis of elemental and organic carbon.

Elemental carbon (EC) and organic carbon (OC) exist ubiquitously and interact mutually in the environment. Simultaneous analysis of EC and OC will greatly advance our understanding of the behavior and fate of EC and OC, but is however still a great challenge due to the lack of suitable analytical tools. Here, we report a matrix-free laser desorption/ionization mass spectrometry (LDI-MS) method capable of simultaneous analysis of EC and OC by monitoring two independent groups of specific MS fingerprint peaks. We found that EC itself can generate carbon cluster peaks in the low mass range under laser excitation, and meanwhile it can also serve as a matrix to assist the ionization of OC in LDI-MS. By using per- and polyfluoroalkyl substances (PFASs) as a typical set of OC and carbon black (CB) as a model EC, we successfully monitored the adsorption process of PFASs on CB enabled by LDI-MS. We show that hydrophobic interaction dominates the sorption of PFASs to CB, which was affected by the functional groups and carbon chain length of PFASs. Furthermore, environmental substances in water such as humic acid (HA) and surfactants can significantly affect the adsorption of PFASs on CB probably by changing the adsorption sites of CB. Overall, we demonstrate that LDI-MS offers a versatile and high-throughput tool for simultaneous analysis of EC and OC species in real environmental samples, which makes it promising for investigating the environmental behaviors and ecological risks of pollutants.

[Drugs malabsorption after bariatric surgery]. / Zaburzenia wchlaniania leków u chorych po operacjach bariatrycznych.

Along with the increasing prevalence of obesity surgical methods of treatment are becoming more accessible. The success of bariatric surgery results from the failure of conservative treatment of obesity through diet, exercises and behavioral changes. Such behaviors, including less effective drug therapy, are responsible for rather small and unstable weight reduction. In contrast, surgical treatment restrictions limiting the amount of food intake, excluding treatments and mixed treatments usually give a spectacular effect, though it is not always consistent with the previous assumptions. Most of us, however, do not realize the risk of the consequences that these treatments bring. The change of the absorption of oral medications, vitamins, microelements, often change the way they are metabolized and it forces ones to change the form of the drug, the way they are taken, which undoubtedly is associated with higher costs of later treatment. Many clinicians are unaware of the need for lifelong supplementation of some vitamins and microelements, as well as the need to modify pharmacotherapy in patients who have undergone this type of operations. This article presents examples of the best known and described changes in the absorption of drugs and micronutrients and explains how well oriented the internist ought to be when qualifying a patient to undergo this type of treatment. The described topic is interesting, but also controversial due to the fact that it corresponds closely with the surgical specialties, quite spectacular in their effects and behavioral specializations, that in many years time will be looking after the patient who underwent the surgery, but is still sick.

Large reverse saturable absorption under weak continuous incoherent light.

In materials showing reverse saturable absorption (RSA), the optical absorbance increases as the power of the light incident on them increases. To date, RSA has only been observed when very intense light sources, such as short-pulse lasers, are used. Here, we show that hydroxyl steroidal matrices embedding properly designed aromatic molecules as acceptors and transition-metal complexes as donors exhibit high RSA on exposure to weak incoherent light at room temperature and in air. Accumulation by photosensitization of long-lived room-temperature triplet excitons in acceptors with a large triplet-triplet absorption coefficient allows a nonlinear increase in absorbance also under low-power irradiation conditions. As a consequence, continuous exposure to weak light significantly decreases the transmittance of thin films fabricated with these compounds. These optical limiting properties may be used to protect eyes and light sensors from exposure to intense radiation generated by incoherent sources and for other light-absorption applications that have not been realized with conventional RSA materials.

Urban impacts on regional carbonaceous aerosols: case study in central Texas.

Rural and background sites provide valuable information on the concentration and optical properties of organic, elemental, and water-soluble organic carbon (OC, EC, and WSOC), which are relevant for understanding the climate forcing potential of regional atmospheric aerosols. To quantify climate- and air quality-relevant characteristics of carbonaceous aerosol in the central United States, a regional background site in central Texas was chosen for long-term measurement. Back trajectory (BT) analysis, ambient OC, EC, and WSOC concentrations and absorption parameters are reported for the first 15 months of a long-term campaign (May 2011-August 2012). BT analysis indicates consistent north-south airflow connecting central Texas to the Central Plains. Central Texas aerosols exhibited seasonal trends with increased fine particulate matter (< 2.5 microm aerodynamic diameter, PM2.5) and OC during the summer (PM2.5 = 10.9 microg m(-3) and OC = 3.0 microg m(-3)) and elevated EC during the winter (0.22 microg m(-3)). When compared to measurements in Dallas and Houston, TX, central Texas OC appears to have mixed urban and rural sources. However central Texas EC appears to be dominated by transport of urban emissions. WSOC averaged 63% of the annual OC, with little seasonal variability in this ratio. To monitor brown carbon (BrC), absorption was measured for the aqueous WSOC extracts. Light absorption coefficients for EC and BrC were highest during summer (EC MAC = 11 m2 g(-1) and BRC MAE365 = 0.15 m2 g(-1)). Results from optical analysis indicate that regional aerosol absorption is mostly due to EC with summertime peaks in BrC attenuation. This study represents the first reported values of WSOC absorption, MAE365, for the central United States. Implications: Background concentration and absorption measurements are essential in determining regional potential radiative forcing due to atmospheric aerosols. Back trajectory, chemical, and optical analysis of PM2.5 was used to determine climatic and air quality implications of urban outflow to a regional receptor site, representative of the central United States. Results indicate that central Texas organic carbon has mixed urban and rural sources, while elemental carbon is controlled by the transport of urban emissions. Analysis of aerosol absorption showed black carbon as the dominant absorber, with less brown carbon absorption than regional studies in California and the southeastern United States.

Effect of solar radiation on the optical properties and molecular composition of laboratory proxies of atmospheric brown carbon.

Sources, optical properties, and chemical composition of atmospheric brown carbon (BrC) aerosol are uncertain, making it challenging to estimate its contribution to radiative forcing. Furthermore, optical properties of BrC may change significantly during its atmospheric aging. We examined the effect of photolysis on the molecular composition, mass absorption coefficient, and fluorescence of secondary organic aerosol (SOA) prepared by high-NOx photooxidation of naphthalene (NAP SOA). Our experiments were designed to model photolysis processes of NAP SOA compounds dissolved in cloud or fog droplets. Aqueous solutions of NAP SOA were observed to photobleach (i.e., lose their ability to absorb visible radiation) with an effective half-life of ∼15 h (with sun in its zenith) for the loss of near-UV (300-400 nm) absorbance. The molecular composition of NAP SOA was significantly modified by photolysis, with the average SOA formula changing from C14.1H14.5O5.1N0.085 to C11.8H14.9O4.5N0.023 after 4 h of irradiation. However, the average O/C ratio did not change significantly, suggesting that it is not a good metric for assessing the extent of photolysis-driven aging in NAP SOA (and in BrC in general). In contrast to NAP SOA, the photobleaching of BrC material produced by the reaction of limonene + ozone SOA with ammonia vapor (aged LIM/O3 SOA) was much faster, but it did not result in a significant change in average molecular composition. The characteristic absorbance of the aged LIM/O3 SOA in the 450-600 nm range decayed with an effective half-life of <0.5 h. These results emphasize the highly variable and dynamic nature of different types of atmospheric BrC.

Effects of cadmium and copper biosorption on Chlorella vulgaris.

Changes in protein levels and lipid compositions in algal cells indicate the severity of stress related to toxic concentrations of heavy metals. In this study, the effects of exposure to cadmium and copper on Chlorella vulgaris and its capacity to remove metals were evaluated. The data revealed ion removal activity by microalgae under all treatments and different levels of protein expression after 48 h of exposure. Furthermore, we analyzed lipids contents to characterize them.

[Absorption and transportation of calycosin in Astragali Radix by using Caco-2 monolayer model].

Flavonoids are a class of important active ingredients in traditional Chinese medicine, pharmacological activity and in vivo process is the focus of research in recent years. Calycosin is the main active ingredients of flavonoids in Astragali Radix, recent studies indicate that it has many kinds of pharmacological activity, but the absorption and transport characteristics in vivo is unclear. The experiment using Caco-2 cell model, with apigenin as internal standard substance, using the method for the determination of drug concentration by HPLC, were studied at different concentrations and absorption transport characteristics of respectively adding different types of protein inhibitors. Data were analyzed by Q test, the results show that low, middle, high concentration of P(app)(BL-AP)/ P(app)(AP-BL) = 1.38 < 1.5, respectively adding different types of protein inhibitors, compared with the control group of P(app)(BL-AP)/ P(app)(AP-BL), there were no significant differences. Calycosin absorption may mainly passive transport, also involved in active transport mechanism, the transport may not be affected by the P-protein, MRP2 protein, SGLT protein.

Influence of heavy metal rich tannery sludge on soil enzymes vis-à-vis growth of Tagetes minuta, an essential oil bearing crop.

Tannery sludge is available in plenty and is hazardous to environment as well as plant and animal life. It is very important to manage the tannery sludge in an environmentally sound manner. The aim of this study was to assess the physico-chemical, microbial and biochemical properties of soil treated with different levels of sludge. In this study, Tagetes minuta an essential oil bearing crop was grown in two different textured soils treated with different levels of tannery sludge. Application of tannery sludge (TS) increased the growth and oil yield of plant and also the activity of urease and soil microbial biomass nitrogen (SMBN) when applied in 50:50 combinations of soil:sludge. The crop performed well in coarse soil with a soil:sludge ratio of 50:50. High concentration of tannery sludge exhibited inhibitory effect on SMBN and urease activity. Acid/alkaline phosphatase, dehydrogenase and soil microbial biomass carbon (SMBC) increased as the sludge concentration increased in soil. This may be due to high organic matter present in tannery sludge. Roots accumulated more metal than the shoot. No detectable amount of metal was found in oil of T.minuta. To test the relation between 20 characters principal component analysis (PCA) was performed. PCA analysis indicates that cation exchange capacity (CEC), SMBC, dehydrogenase, acid and alkaline phosphatases were grouped in group 1. SMBN, urease and cis-ocimene content in oil were in group 2 whereas biomasss, chlorophyll a, limonene, Z and E-tagetone were in group 3. PC-I contributes 54% of total variance and PC-II contributes 38% of the total variance. The results concluded that T.minuta can mitigate metal toxicity by root absorption. Microbial activity and biomass of plant was higher in coarse soil with TS than fine soil with TS.

Elucidating differences in metal absorption efficiencies between terrestrial soft-bodied and aquatic species.

It is unknown whether metal absorption efficiencies in terrestrial soft-bodied species can be predicted with the same metal properties as for aquatic species. Here, we developed models for metal absorption efficiency from the dissolved phase for terrestrial worms and several aquatic species, based on 23 metal physicochemical properties. For the worms, the absorption efficiency was successfully related to 7 properties, and is best predicted with the ionic potential. Different properties (8 in total) were found to be statistically significant in regressions predicting metal absorption in aquatic species, with the covalent index being the best predictor. It is hypothesized that metal absorption by soft-bodied species in soil systems is influenced by the rate of metal supply to the membrane, while in aquatic systems accumulation is solely determined by metal affinity to membrane bound transport proteins. Our results imply that developing predictive terrestrial bioaccumulation and toxicity models for metals must consider metal interactions with soil solids. This may include desorption of a cation bound to soil solids through ion exchange, or metal release from soil surfaces involving breaking of metal-oxygen bonds.

[Study on oral absorption enhancers of astragalus polysaccharides].

Astragalus polysaccharides was lounded to 4-(2-aminoethylphenol), followed by labeling the APS-Tyr with fluorescein-5-isothiocyanate (FITC) at the secondary amino group. The absorption enhancement effects of low molecular weight chitosan and protamine on astragalus polysaccharides were evaluated via Caco-2 cell culture model. The results show that the fluorecent labeling compound has good stability and high sensitivity. On the other hand low molecular weight chitosan and protamine also can promoted absorption of the astragalus polysaccharides without any cytotoxity, and the absorption increase was more significant with increasing the amount of low molecular weight chitosan and protamine. At the same time, the low molecular weight chitosan has slightly better effect. The transepithelial electric resistance (TEER) of Caco-2 cells show that absorption enhancers could improve its membrane transport permeability by opening tight junctions between cells and increasing the cell membrane fluidity.

Phosphorus leaching from a sandy soil in the presence of modified and un-modified adsorbents.

Phosphorus (P) leaching from a sandy soil was investigated in the presence of modified and unmodified clay minerals and nanoparticles (NPs). Compared with control soil, amended soil with NPs had the highest percentage of P retention than amended soil with clay minerals. Among the adsorbents used, the highest percentage of P retention was produced by Al2O3-chitosan while the lowest percentage of P retention was by zeolite. Data measured for P leaching after using adsorbents were used to predict P leaching using transport model. PHREEQC model was able to model P leaching from control and amended soil. After leaching, P values in control and amended soil were fractionated by a sequential extraction procedure. Concentration of P in Ca-bound fraction (HCl-P) after application of modified and unmodified clay minerals and NPs (except TiO2 and Al2O3) increased and decreased, respectively. Saturation indices (SIs) and P speciation were assessed using the Visual MINTEQ version 2.3 program. According to the SIs, leaching P from control and amended soil with different adsorbent was controlled by dissolution of hydroxyapatite. The results indicated that used adsorbents can reduce P leaching from the sandy soil. Thus, retention of P by amended soil reduced a risk in terms of groundwater contamination with P.

In vivo measurement of the absorption of strontium in the rumen and small intestine of sheep as an index of calcium absorption capacity.

In the present study, a method was developed for determining the alimentary tract Ca absorption capacity of ruminant animals by measuring the absorption rate of Sr after the administration of an oral dose of strontium chloride acting as a tracer analogue of Ca. A close correlation between the absorption rates of the two tracers was observed upon simultaneous administration of an oral dose of stable Sr and radioactive calcium (r 0·98). The Ca absorption capacity of the rumen and small intestine was determined separately by either directing the solution into the rumen or by diverting it into the post-ruminal tract by vasopressin-induced closure of the ruminoreticular groove. The animals were treated with 1α-hydroxyvitamin D3 administered via subcutaneously implanted mini-osmotic pumps. The effect of elevated plasma 1,25-dihydroxycholecalciferol concentrations on the Ca absorption capacity of the alimentary tract was then determined. An increased rate of Sr absorption was observed in both the rumen and small intestine of sheep after treatment, although it is unclear whether the rumen possesses the same vitamin D-dependent Ca absorption pathway as the small intestine.

Biosorption of hexavalent chromium from aqueous medium with Opuntia biomass.

The biosorption of hexavalent chromium from aqueous solutions by Opuntia cladodes and ectodermis from cactus fruits was investigated. Both types of biomass are considered low-cost, natural, and ecofriendly biosorbents. Batch experiments were carried out to determine Cr(VI) biosorption capacity and the efficiency of the biosorption process under different pH, initial Cr(VI) concentration, and sorbent dosage. The biosorption of Cr(VI) by Opuntia biomass was highly pH dependent, favoring higher metal uptake at low pH. The higher biosorption capacity was exhibited at pH 2. The optimal conditions were obtained at a sorbent dosage of 1 g L(-1) and initial metal concentration of 10 mg L(-1). Biosorption kinetic data were properly fitted with the pseudo-second-order kinetic model. The rate constant, the initial biosorption rate, and the equilibrium biosorption capacity were determined. The experimental equilibrium data obtained were analyzed using two-parameter isotherm models (Langmuir, Freundlich, and Temkin). The Langmuir maximum monolayer biosorption capacity (q max) was 18.5 mg g(-1) for cladodes and 16.4 mg g(-1) for ectodermis. The results suggest that Opuntia biomass could be considered a promising low-cost biosorbent for the ecofriendly removal of Cr(VI) from aqueous systems.

In vitro assessment of commercial sunscreens available in Latin America.

In Latin America, people have largely abandoned the practice of wearing hats and traditional clothing that provided skin protection. Sunscreen application has therefore become essential to protect against the increased sun exposure. The physician-prescribed medical-grade sunscreens provide sufficient sun protection but the requirement for regular use puts a financial burden on the patient that is often not sustainable. An appropriate sunscreen should provide a high and broad ultraviolet (UV) protection against UVB and UVA. Several over-the-counter (OTC) sunscreens have been developed for sale at affordable prices and are available for purchase in convenient locations, such as local grocery stores. The aim of this study was to assess the in vitro UV protection of 34 popular OTC sunscreens found in the Latin American market. UV absorbance/transmittance was quantified by diffusion transmission spectroscopy using coarse silica plaques. Photostability was tested by irradiating them with simulated solar light and calculating the sun protection factor (SPF), critical length of absorption (C lambda ), UVA/UVB ratio, and the spectral uniformity index (SUI). The results indicated that the in vitro SPFs were significantly lower than the value declared on the labels, particularly for those claiming high SPF values; however, the majority of these sunscreens offered high levels of UV protection. Considering the advantages of low cost and ample accessibility, we concluded that this sample of OTC sunscreens can be beneficial to the general public by providing some level of skin protection from solar radiation, and may be promoted to improve compliance with recommended photoprotection behavior.

Optimization of UV absorptivity of layered double hydroxide by intercalating organic UV-absorbent molecules.

Intercalation of Zn/Al layered double hydroxide (LDH) with benzophenone 9 (B9), a strong ultraviolet (UV) absorber, had been carried out by two different routes; co-precipitation and ion exchange method. Powder X-ray diffraction (PXRD) patterns of co-precipitated (ZB9C) and ion exchanged product (ZB91) showed basal spacing of 15.9 angstrom and 16.6 angstrom, respectively, as a result of the intercalation of B9 anions into the lamellae spaces of LDH. Intercalation was further confirmed by Fourier transform infrared spectra (FTIR), carbon, hydrogen, nitrogen and sulfur (CHNS) and thermogravimetric and differential thermogravimetric (TGA/DTG) studies. UV-vis absorption properties of the nanocomposite was investigated with diffuse reflectance UV-visible spectrometer and showed broader UV absorption range. Furthermore, stability of sunscreen molecules in LDH interlayer space was tested in deionized water, artificial sea water and skin pH condition to show slow deintercalation and high retention in host. Cytotoxicity study of the synthesized nanocomposites on human dermal fibroblast (HDF) cells shows no significant cytotoxicity after 24 h exposure for test concentrations up to 25 microg/mL.

Phosphate absorption across multiple epithelia in the Pacific hagfish (Eptatretus stoutii).

Inorganic phosphate (Pi) is an essential nutrient for all organisms, but in seawater, Pi is a limiting nutrient. This study investigated the primary mechanisms of Pi uptake in Pacific hagfish (Eptatretus stoutii) using ex vivo physiological and molecular techniques. Hagfish were observed to have the capacity to absorb Pi from the environment into at least three epithelial surfaces: the intestine, skin, and gill. Pi uptake in all tissues was concentration dependent, and saturable Pi transport was observed in the skin and gill at <2.0 mmol/l Pi. Gill and intestinal Pi uptake was sodium dependent, but Pi uptake into the skin increased under low sodium conditions. Gill Pi transport exhibited an apparent affinity constant ~0.23-0.6 mmol/l Pi. A complete sequence of a type II sodium phosphate cotransporter (Slc34a) was obtained from the hagfish gill. Phylogenetic analysis of the hagfish Slc34a transporter indicates that it is earlier diverging than, and/or ancestral to, the other identified vertebrate Slc34a transporters (Slc34a1, Slc34a2, and Slc34a3). With the use of RT-PCR, the hagfish Slc34a transcript was detected in the intestine, skin, gill, and kidney, suggesting that this may be the transporter involved in Pi uptake into multiple epithelia in the hagfish. This is the first measurement of Pi uptake across the gill or skin of any vertebrate animal and first sodium phosphate cotransporter identified in hagfish.

Drug release from matrix tablets: physiological parameters and the effect of food.

INTRODUCTION: As dissolution plays an important and vital role in the drug-delivery process of oral solid dosage forms, it is, therefore, essential to critically evaluate the parameters that can affect this process. AREAS COVERED: The consumption of food as well as the physiological environment and properties of the gastrointestinal tract, such as its volume and composition of fluid, the fluid hydrodynamics, properties of the intestinal membrane, drug dose and solubility, pKa, diffusion coefficient, permeability and particle size, all affect drug dissolution and absorption rate. There are several dissolution approaches that have been developed to address the conditions as experienced in the in vivo environment, as the traditional dissolution being a quality control method is not biorelevant and as such do not always produce meaningful data. This review also describes the development of a systematic way that differentiates between robust and non-robust formulations by varying the effects of agitation and ionic strength through the use of the automated United States Pharmacopeia type III Bio-Dis apparatus. EXPERT OPINION: With the improved understanding of the physiological parameters that can affect the oral bioperformance of dosage forms, strides have, therefore, been made in making dissolution testing methods more biologically based with the view of obtaining more in vitro-in vivo correlations.

Application of gas chromatography-mass spectrometry in analyzing pharmacokinetics and distribution of deltamethrin in miniature pig tissues.

OBJECTIVE: To characterize the pharmacokinetics and distribution profiles of deltamethrin in miniature pig tissues by gas chromatography-mass spectrometry (GC-MS). METHODS: Pharmacokinetics and distribution of deltamethrin in blood and tissues of 30 miniature pigs were studied by GC-MS after oral administration of deltamethrin (5 mg/kg bw). Data were processed by 3P97 software. RESULTS: The serum deltamethrin level was significantly lower in tissues than in blood of miniature pigs. The AUC0-72 h, Cmax, of deltamethrin were 555.330 ± 316.987 ng h/mL and 17.861 ± 11.129 ng/mL, respectively. The Tmax, of deltamethrin was 6.004 ± 3.131 h. CONCLUSION: The metabolism of deltamethrin in miniature pigs is fit for a one-compartment model with a weighting function of 1/C2. Deltamethrin is rapidly hydrolyzed and accumulated in miniature pig tissues.

Characterization of primary and permanent teeth using terahertz spectroscopy.

OBJECTIVES: To analyse teeth samples by using terahertz time-domain spectroscopy (THz-TDS) system that was developed in the laboratory to measure the properties of sliced teeth sections in transmission mode. METHODS: Using home-built THz-TDS system, we analysed a total of 25 teeth samples (9 primary and 16 permanent teeth). For transmission measurements, the refractive index and absorptive properties of the teeth sections were calculated. Difference between groups was tested using Mann-Whitney U-test statistics at the specific frequency of 0.5 THz, which was at the midpoint of the bandwidth. Median and minimum-maximum values were given as descriptive statistics. Type-I error rate was taken as α = 0.05. RESULTS: Median refractive index values for permanent and primary teeth were found to be 2.53 and 2.54, respectively. Median absorption coefficient values for permanent and primary teeth were found to be 26.29 and 29.67, respectively. Median refractive index values for both healthy and carious teeth were found to be 2.54. Median absorption coefficient values for healthy and carious teeth were found to be 26.52 and 27.13, respectively. Although higher median absorption coefficient values were found for primary and carious teeth than those of permanent and healthy teeth, the differences were insignificant (p > 0.05). In addition, no statistical differences were found for refractive index values among different groups (p > 0.05). CONCLUSIONS: THz imaging has the potential to be used in assessing dental structures.