The chemistry of 5-oxodihydroisoxazoles .16. A new synthesis of pyrroles, furans, thiophens and their benzo analogues

Ethyl 5-oxo-2-phenyl-2,5-dihydroisoxazole-4-carboxylate (2) was photolysed at 300 mn in the presence of phenols, enols, anilines, enamines, aryl thiols and thioenols affording enamines. Treatment of these enamines with Lewis or protic acids gives the respective benzo and five-membered ring systems.

Comprehensive study of surface chemistry of MCM-41 using Si-29 CP/MAS NMR, FTIR, pyridine-TPD, and TGA

A comprehensive study was conducted on mesoporous MCM-41. Spectroscopic examinations demonstrated that three types of silanol groups, i.e., single, (SiO)(3)Si-OH, hydrogen-bonded, (SiO)(3)Si-OH-OH-Si(SiO)(3), and geminal, (SiO)(2)Si(OH)(2), can be observed. The number of silanol groups/nm(2), alpha(OH), as determined by NMR, varies between 2.5 and 3.0 depending on the template-removal methods. All these silanol groups were found to be the active sites for adsorption of pyridine with desorption energies of 91.4 and 52.2 kJ mol(-1), respectively. However, only free silanol groups (involving single and geminal silanols) are highly accessible to the silylating agent, chlorotrimethylsilane. Silylation can modify both the physical and chemical properties of MCM-41.

Chemistry of 5-oxodihydroisoxazoles .17. Acylation of 5-oxodihydroisoxazoles

2-Unsubstituted isoxazol-5(4H)-ones and -5(2N)-ones may be acylated by acid chlorides, anhydrides or carboxylic acids in the presence of carbodiimides, to give O- and N-acylated products, The solvent, the presence of base and the temperature are found to alter the product ratios dramatically, but the substituents present at C-3 have the greatest effect, Aliphatic acid anhydrides and chlorides generally react at nitrogen, but aroyl halides give significant proportions of O-acylated products, Limited success in converting O-aroyl to N-aroyl isoxazolones is reported.

Chemistry of 5-oxodihydroisoxazoles .18. Synthesis of oxazoles by the photolysis and pyrolysis of 2-acyl-5-oxo-2,5-dihydroisoxazoles

N-Acylisoxazol-5-ones lose carbon dioxide under photochemical and thermal conditions affording iminocarbenes which undergo intramolecular cyclisation through the oxygen of the acyl group to give oxazoles. Under photochemical conditions those acylisoxazolones with electron withdrawing groups at C-4 usually give high yields of oxazoles, while those with electron donating groups at C-4 give only poor yields: the reverse is observed under thermal conditions.

The chemistry of 5-oxodihydroisoxazoles .19. The synthesis and photolysis of N-thioacylisoxazol-5(2H)-ones

5-Oxodihydroisoxazoles react with thiocarbonyl chlorides to afford N-thioacylisoxazol-5(2H)-ones which lose carbon dioxide under photochemical conditions and undergo intramolecular cyclisation of the iminocarbene to afford thiazoles, However, in some cases loss of carbon dioxide is accompanied by loss of sulfur, giving 1,3-oxazin-6-ones.

The chemistry of novolac resins .3. C-13 and N-15 nmr studies of curing with hexamethylenetetramine

The reactions between novolac resins and hexamethylenetetramine (HMTA) which occur on curing have been studied by C-13 and N-15 high-resolution n.m.r. in both solution and the solid state. Strong evidence for the existence of many curing intermediates is obtained. New curing intermediates are reported along with experimental data to support previously postulated intermediates. The initial curing reactions between novolac and HMTA produce various substituted benzoxazines and benzylamines. Thermal decomposition/oxidation and further reactions of these initial intermediates generate methylene linkages between phenolic rings for chain extension and cross-linking. Among the three kinds of methylene linkages, the para-para methylene linkages are formed at relatively lower temperatures. Various imine, amide and imide side-products also concurrently appear during the process. The initial amount of HMTA plays a critical role in the curing reactivity and chemical structures of the cured resins. The lower the amount of HMTA, the lower the temperature at which curing occurs, and the lower the amount of the nitrogen-containing side-products in the finally cured resins. The ortho-linked intermediates are relatively stable, and can remain in the cured resins up to higher temperatures. The study provides an extensive description of the curing reactions of novolac resins. (C) 1997 Elsevier Science Ltd.

Chronic exposure to fine particulate matter emitted by traffic affects reproductive and fetal outcomes in mice

Air pollution is an important environmental health risk factor that can result in many different gestational and reproductive negative outcomes. In this study, we have investigated the effects of two different times of exposure (before conception and during pregnancy) to urban ambient particulate matter on reproductive and pregnancy outcomes in mice. Using exposure chambers receiving filtered (F) and non-filtered (NF) air, we observed that exposed females exhibited changes in the length of estrus cycle and extended estrus and, therefore, a reduction in the number of cycles during the studied period (F2.6 +/- 0.22 and NF 1.2 +/- 0.29, p = 0.03). The mean number of antral follicles declined by 36% (p = 0.04) in NF mice (75 +/- 35.2) compared to F mice (118.6 +/- 18.4). our results further indicate a significant increase in time necessary for mating and decreased fertility and pregnancy indices (p = 0.003) in NF couples. Mean post-implantation loss rates were increased by 70% (p <= 0.005) in the NF2 group (exposed before and during pregnancy to NF air) compared to the F1 group (exposed before and during pregnancy to F air) and were influenced by both pre-gestational (p < 0.004) and gestational (p < 0.01) period exposure. Fetal weight was significantly higher in the F1 group when compared with the other groups (p < 0.001), at a 20% higher weight in the F1 group (0.86 +/- 0.18 g) than in the NF2 group (0.68 +/- 0.10g). Furthermore, fetal weight was influenced by both pre-gestational and gestational period exposure, and a significant interaction between these two factors was found (p < 0.001). This study demonstrated that exposure to ambient levels of urban traffic-generated particulate matter negatively affects different functions and stages of the reproductive process. Our results also reinforce the idea that maternal exposure to air pollution is linked to negative pregnancy outcomes, even if the exposure occurs only before conception. (C) 2009 Elsevier Inc. All rights reserved.

Low dose of fine particulate matter (PM2.5) can induce acute oxidative stress, inflammation and pulmonary impairment in healthy mice

Air pollution is associated with morbidity and mortality induced by respiratory diseases. However, the mechanisms therein involved are not yet fully clarified. Thus, we tested the hypothesis that a single acute exposure to low doses of fine particulate matter (PM2.5) may induce functional and histological lung changes and unchain inflammatory and oxidative stress processes. PM2.5 was collected from the urban area of Sao Paulo city during 24 h and underwent analysis for elements and polycyclic aromatic hydrocarbon contents. Forty-six male BALB/c mice received intranasal instillation of 30 mu L of saline (CTRL) or PM2.5 at 5 or 15 mu g in 30 mu L of saline (P5 and P15, respectively). Twenty-four hours later, lung mechanics were determined. Lungs were then prepared for histological and biochemical analysis. P15 group showed significantly increased lung impedance and alveolar collapse, as well as lung tissue inflammation, oxidative stress and damage. P5 presented values between CTRL and P15: higher mechanical impedance and inflammation than CTRL, but lower inflammation and oxidative stress than P15. In conclusion, acute exposure to low doses of fine PM induced lung inflammation, oxidative stress and worsened lung impedance and histology in a dose-dependent pattern in mice.

In vitro fertilization, embryo development, and cell lineage segregation after pre- and/or postnatal exposure of female mice to ambient fine particulate matter

Objective: To evaluate effects of pre- and/or postnatal exposure to ambient fine particulate matter on fertilization, embryo development, and cell lineage segregation in preimplantation blastocysts using the IVF mouse model. Design: Animal model. Setting: Academic institution. Animal(S): Six-week-old, superovulated mice. Intervention(s): Pre- and postnatal exposure to filtered air (FA-FA), filtered-ambient air (FA-AA), or ambient air (AA-AA) in exposure chambers 24 hours a day for 9 weeks. Main Outcome Measure(S): Gestation length, litter size, sex ratio, ovarian response to superovulation, fertilization rate, embryo development, blastocyst and hatching rates, total cell count, and proportion of cell allocation to inner-cell mass (ICM) and trophectoderm (TE). Result(S): Gestation length, litter size and birth weight, live-birth index, and sex ratio were similar among exposure groups. Ovarian response was not affected by the exposure protocol. A multivariate effect for pre- and/or postnatal exposure to ambient fine particulate matter on IVF, embryo development, and blastocyst differential staining was found. Cell counts in ICM and ICM/TE ratios in blastocysts produced in the FA-FA protocol were significantly higher than in blastocysts produced in the FA-AA and AA-AA protocols. No difference in total cell count was observed among groups. Conclusion(S): Our study suggests that exposure to ambient fine particulate matter may negatively affect female reproductive health by disrupting the lineage specification at the blastocyst stage without interfering in early development of the mouse embryo. (Fertil Steril (R) 2009;92:1725-35. (C) 2009 by American Society for Reproductive Medicine.)

Isolated lymphadenitis due to Histoplasma capsulatum diagnosed by fine-needle aspiration biopsy and immunohistochemistry

In the disseminated form of histoplasmosis, isolation and further identification of Histoplasma capsulatum can be performed by several methods, namely, bone marrow aspiration, blood culture, and liver biopsy. Lymph node disease usually is diagnosed by excisional biopsy. Although fungal stains can identify this fungus, detection of specific antigens by immunohistochemistry shows a higher specificity and sensitivity. This approach can use the cell block method when the material is not sent to fungal cultures or fresh staining.

Fine-needle aspiration biopsy of disseminated sporotrichosis: A case report

In this report, we describe a case of disseminated sporotrichosis that was diagnosed by fine-needle aspiration biopsy (FNAB). The cytologic smears exhibited a large number of macrophages, few polymorphonuclear neutrophils and numerous round or oval, sometimes elongated, isolated and scattered yeast-like structures localized extracellularly or inside macrophages. These structures were clearly visualized by Giemsa and Papanicolaou methods. Cultures from skin biopsy material revealed,fungal colonies which were subsequently identified as Sporothrix schenckii. The cytologic aspects, the correlation with histologic findings and the differential cytologic diagnosis were reviewed.