Vacuum-assisted headspace thin-film microextraction: Theoretical formulation and method optimization for the extraction of polycyclic aromatic hydrocarbons from water samples.

The thin films used in headspace thin-film microextraction (HS-TFME) enable higher sensitivity and superior extraction rates compared to other microextraction approaches, largely due to their greater surface area-to-volume ratio and extraction-phase volume. Nonetheless, analytes exhibiting a low affinity for the headspace and/or large partitioning between the extraction phase and headspace will still require more time to reach equilibrium. In this paper, we detail the development of a new method, termed as vacuum-assisted HS-TFME (Vac-HS-TFME), and we demonstrate how its use of vacuum conditions can accelerate the extraction kinetics of analytes with long equilibration times. The pressure-dependence of the extraction process was formulated and related to improvements in gas-phase diffusivity when lowering the total pressure. Four low-molecular-weight polycyclic aromatic hydrocarbons (PAHs) were used to experimentally verify the improvements in extraction efficiencies enabled by Vac-HS-TFME (vs. HS-TFME). To this end, the effects of temperature and extraction time on Vac-HS-TFME were investigated, with the results being compared to those obtained via regular HS-TFME. Furthermore, the use of a high-capacity sorbent in TFME allowed the positive effects of temperature and vacuum conditions to be combined successfully. Extraction-time profiles constructed at 30 and 50 °C revealed substantial acceleration in the overall extraction kinetics when sampling under vacuum conditions. At 50 °C, all of the analytes extracted via Vac-HS-TFME reached equilibrium within 45 min, whereas only two reached this state under atmospheric pressure. Vac-HS-TFME's analytical performance was evaluated under optimized conditions, and the results were compared to those obtained with regular HS-TFME. The findings revealed that for the two lighter PAHs, the performance of the two methods was similar since they were extracted close or at equilibrium. However, the calibration models for the two heavier PAHs tested here were linear over a wider concentration range (50-10000 ng L-1) when using Vac-HS-TFME, had superior intra-day repeatability (7.4% and 6.7% vs. 11% and 9.3% with regular HS-TFME), and the limits of detection were lower compared to regular HS-TFME (15 and 11 ng L-1 compared to 136 to 100 ng L-1 with regular HS-TFME). Finally, the analysis of spiked wastewater effluent samples showed that the matrix did not affect extraction. The proposed Vac-HS-TFME approach combines the advantages of low-pressure sampling and high-capacity sorbent, and has a great potential for future applications in food, flavour, environmental, and biological analyses.

The effect of obesity and dietary habits on oxidative stress in Hashimoto's thyroiditis

Objective: Increased oxidative stress has been described in patients with Hashimoto's thyroiditis (HT). The aim of the present study was to investigate whether high oxidative stress is further influenced by obesity and dietary habits in euthyroid women with HT. Methods: Two hundred eighteen consecutive euthyroid women with HT were studied and separated in two groups; 102 with thyroxine replacement and 114 without. For the evaluation of oxidative stress, total lipid peroxide levels in serum (TOS) were measured and recoded as 'high TOS' vs 'medium/low TOS'. The type of food and consumption frequency were recorded. Two binary variables were considered; normal vs low fruit consumption and daily vs sporadic vegetable consumption. Results: 'High TOS' was more frequent in women under thyroxine replacement (31.4% vs 14.7%, OR = 2.7, 95% CI: 1.4­5.2). The prevalence of 'high TOS' was higher among overweight/obese women compared to women with normal BMI (30.4% vs 12.5%, OR = 3.1, 95% CI: 1.5­6.4). Low fruit consumption was associated with increased 'high TOS' prevalence (30.6% vs 12.9%, OR = 3.0, 95% CI: 1.4­6.2). Sporadic vegetable consumption was associated with increased 'high TOS' prevalence compared to daily consumption (29.9% vs 13.5%, OR = 2.7, 95% CI: 1.3­5.7). The examined risk factors were independent and additive in their effect on TOS. At least three risk factors had to be concomitantly present for the likelihood of 'high TOS' to be significantly elevated. Conclusions: Oxidative stress is increased in women with HT under thyroxine replacement. Nevertheless, normal BMI, daily fruit and vegetable consumption, all contribute in maintaining oxidative stress at low levels.

RAGE polymorphisms and oxidative stress levels in Hashimoto's thyroiditis.

BACKGROUND: Polymorphisms of the receptor for advanced glycation end products (RAGE) gene have been studied in various autoimmune disorders, but not in Hashimoto's thyroiditis. Also, increased oxidative stress has been described in patients with Hashimoto's thyroiditis. The aim of this study was to investigate the possible role of two common RAGE polymorphisms (-429T>C, -374T>A) in Hashimoto's thyroiditis; in parallel, we studied oxidative stress levels. MATERIALS AND METHODS: A total of 300 consecutive euthyroid women were examined and classified into three groups: Hashimoto's thyroiditis with treatment (n = 96), Hashimoto's thyroiditis without treatment (n = 109) and controls (n = 95). For a rough evaluation of oxidative stress, total lipid peroxide levels in serum were measured. The -429T>C AluI and -374T>A MfeI polymorphisms of RAGE were studied in genomic DNA. RESULTS: Significant association of the RAGE system with Hashimoto's thyroiditis was found only with regard to the prevalence of the -429T>C, but not with -374T>A polymorphism. The levels of oxidative stress were significantly elevated in Hashimoto's thyroiditis patients under treatment. Further analysis demonstrated that an oxidative stress cut-off value of 590 µmol/L is associated with an increased risk of progression of Hashimoto's thyroiditis from euthyroidism to hypothyroidism; this risk is further increased in carriers of the RAGE -429T>C polymorphism. CONCLUSIONS: Our findings indicate that both examined risk factors may be implicated in the occurrence of Hashimoto's thyroiditis, but this covers only a fraction of the pathophysiology of the disease.

Dysfunction of the hypothalamic-pituitary-adrenal axis in HIV infection and disease.

Abnormalities of the hypothalamic-pituitary-adrenal (HPA) axis have been documented in HIV patients in the early as well as late stages of the infection and range from subtle subclinical disturbances to frank adrenal insufficiency. Potential etiologies of these disorders include opportunistic infections, neoplasms, drugs administered to treat infections, cytokine abnormalities associated with the HIV disease process and acquired alterations in tissue sensitivity to glucocorticoids. In this article, we present a concise review of HPA abnormalities in HIV infection and disease with regard to their etiology with emphasis on syndromes of hypersensitivity/resistance to glucocorticoids associated with antiviral medications and/or the HIV infection itself.

Thyroid tuberculosis.

Although the association of thyroid disorders with tuberculosis has been known for a long time, the diagnosis of thyroid tuberculosis is rare. Differential diagnosis can be very difficult without fine needle aspiration. The clinical course of the disease may resemble toxic goiter or acute thyroiditis or may follow a subacute or chronic pattern without specific symptomatology. We describe a 49-year old male patient with thyroid tuberculosis presenting as thyroid enlargement, fever, increased erythrocyte sedimentation rate, normal thyroid function tests, and a chest x-ray indicating the presence of a lesion with distinct calcification in the lower lobe of the right lung. Tuberculosis of the thyroid gland, although very rare, should be considered as a possible diagnosis when localized swelling, cold abscess or thyroid nodule with or without a cystic component are present.