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Preparation, characterization, and surface modification of silver nanoparticles in formamide.

The reduction of silver ions in formamide is shown to take place spontaneously at room temperature without addition of any reductant. The growth of Ag particles was found to be dependent on Ag+ ion concentration. In the absence of any stabilizer, deposition of silver film on the glass walls of the container takes place. However, in the presence of poly(N-vinyl-2-pyrrolidone) (PVP) or colloidal silica (SiO2), which are capable of stabilizing silver nanoparticles by complexing and providing support, a clear dispersion was obtained. The formation of the silver nanoparticles under different conditions was investigated through UV-visible absorption spectrophotometry, gas chromatography, and also electron and atomic force microscopic techniques. Atomic force microscopy results for silver films prepared in the absence of any stabilizer showed the formation of polygonal particles with sizes around 100 nm. Transmission electron microscopy results showed that the prepared silver particles in the presence of PVP were around 20 nm. The Ag nanoparticles get oxidized in the presence of chloroform and toluene. Surface modification of silver film was done in the presence of the tetrasodium salt of ethylenediaminetetraaceticacid (Na4EDTA). It was shown that the reactivity of the silver film increased in its presence. The Fermi potential of silver particles in the presence of Na4EDTA seems to lie between -0.33 and -0.446 V vs NHE.

Journal Article↗

Real structure of formamide entrapped by AOT nonaqueous reverse micelles: FT-IR and 1H NMR studies.

Noninvasive techniques such as FT-IR and (1)H NMR spectroscopy have been employed to investigate the solubilization of formamide, FA, and its aqueous solution, FA-water, by sodium 1,4-bis(2-ethylhexyl)sulfosuccinate, AOT, in heptane or isooctane reverse micelles, respectively. Partially deuterated FA (FADH) was used in the FT-IR experiments and nu(OD), n(ND) were analyzed. Also, the nu(C=O) band of FA was investigated. For AOT, the changes of the SO(3)(-) group's symmetric, nu(s), and asymmetric, nu(a), bands were also studied. The results are showing that FA is interacting strongly with the Na+ counterions of the surfactant through electrostatic interactions maintaining their hydrogen bond network present in the FA bulk. Accordingly, partially deuterated FA is "frozen" inside the aggregates and it is possible to detect, by FT-IR technique, the cis and trans isomers. Curve fitting of the nu(OD) (in the FA-water mixture) band requires use of two peaks because the band is asymmetric, not because the solubilizate molecules are present in layers of different structure. The chemical shifts of the (1)H bound to N and C of FA were studied by (1)H NMR. The comparison of the chemical shift of AOT in reverse micelles with FA and the FA-water mixture in the polar core of the aggregate shows that there is a strong preferential solvation of Na+ by FA (through electrostatic interaction) and the AOT's sulfonate group by water (through hydrogen bond interaction).

Journal Article↗

The possible covalent nature of N-H...O hydrogen bonds in formamide dimer and related systems: an ab initio study.

The N-H...O hydrogen bonds are analyzed for formamide dimer and its simple fluorine derivatives representing a wide spectrum of more or less covalent interactions. The calculations were performed at the MP2/6-311++G(d,p) level of approximation. To explain the nature of such interactions, the Bader theory was also applied, and the characteristics of the bond critical points (BCPs) were analyzed: the electron density at BCP and its Laplacian, the electron energy density at BCP and its components, the potential electron energy density, and the kinetic electron energy density. These parameters are used to justify the statement that some of the interactions analyzed are partly covalent in nature. An analysis of the interaction energy components for the systems considered indicates that the covalent character of the hydrogen bond is manifested by a markedly increased contribution of the delocalization term relative to the electrostatic interaction energy. Moreover, the ratio of stabilizing the delocalization/electrostatic contributions grows linearly with the decreasing lengths of the hydrogen bond.

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l-Piperazine-2-carboxylic acid derived N-formamide as a highly enantioselective Lewis basic catalyst for hydrosilylation of N-aryl imines with an unprecedented substrate profile.

[reaction: see text] l-Piperazine-2-carboxylic acid derived N-formamides have been developed as highly enantioselective Lewis basic catalysts for the hydrosilylation of N-aryl imines with trichlorosilane. The arene sulfonyl group on N4 was found to be critical for the high enantioselectivity of the catalyst. High isolated yields (up to 99%) and enantioselectivities (up to 97%) were obtained for a broad range of substrates, including aromatic and aliphatic ketimines, particularly those with R(2) as relatively bulky alkyl groups.

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Electron localization in negatively charged formamide clusters studied by photodetachment spectroscopy.

Size-dependent features of the electron localization in negatively charged formamide clusters (FAn-, n = 5-21) have been studied by photodetachment spectroscopy. In the photoelectron spectra for all the sizes studied, two types of bands due to different isomers of anions were found. The low binding energy band peaking around 1 eV is assigned to the solvated electron state by relative photodetachment cross-section measurements in the near-infrared region. It is suggested that nascent electron trapping is dominated by formation of the solvated electron. The higher energy band originates from the covalent anion state generated after a significant relaxation process, which exhibits a rapid increase of electron binding energy as a function of the cluster size. A unique behavior showing a remarkable band intensity of the higher energy band was found only for n = 9.

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Ab initio molecular-dynamics study of liquid formamide.

Properties of neat liquid formamide (HCONH2) have been studied by the combination of gradient-corrected density-functional theory, norm-conserving pseudopotentials, and the adaptive finite-element method. The structural and dynamical quantities have been calculated through molecular dynamics simulations under the Born-Oppenheimer approximation. Satisfactory agreement with experimental data was obtained for both intramolecular and intermolecular properties. Our results are also compared with those of the empirical potential functions to clarify their accuracies.

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Hydrogen-bond vibrations in the S(1)<-->S(0) spectra of a nucleobase pair analog: a mixed dimer between 2-pyridone and formamide.

The vibronically resolved electronic spectra for S(1)<-->S(0) transitions of a mixed dimer between 2-pyridone (2PY) and formamide have been measured in a supersonic free jet expansion using laser-induced fluorescence spectroscopy. Quantum chemistry method at different levels of theory has been used to optimize the geometries of the dimer for the S(0) and S(1) electronic states and also to calculate the normal vibrational modes. Assignments for the vibronic bands observed in the dispersed fluorescence spectrum of the 0(0) (0) band have been suggested with the aid of the ground state frequencies calculated by density functional theoretical method. Spectral analysis reveals that electronic excitation causes extensive mixing of the low-frequency intermolecular vibrational modes of the dimer with some of the intramolecular modes of the 2PY moiety. This spectral behavior is consistent with the complete active space self-consistent field theoretical prediction that with respect to a number of geometrical parameters the dimer geometry in S(1) is significantly distorted from the geometry of the S(0) state.

Journal Article↗

Direct DNA sequencing of the rat neu oncogene transmembrane domain reveals no mutation in urinary bladder carcinomas induced by N-butyl-N-(4-hydroxybutyl)nitrosamine, N-[4-(5-nitro-2-furyl)-2-thiazolyl]formamide or N-methyl-N-nitrosourea.

Epidermal growth factor (EGF) and EGF-related growth factors are present in the urine, and EGF has been identified as a urinary component that enhances urinary bladder tumor formation in rats. Neu oncogene encodes a cell surface receptor similar to the EGF receptor and is known to be activated by a point mutation of DNA that encodes the transmembrane domain of the neu protein (p185). In this study, we examined the possible mutational activation of neu oncogene in 50 urinary bladder transitional cell carcinomas (TCC) induced in F344 rats by the following carcinogenesis models: (i) 0.05% N-butyl-N-(4-hydroxybutyl)nitrosamine (BBN) (4 weeks)----3% uracil (20 weeks); (ii) 0.2% N-[4-(5-nitro-2-furyl)-2-thiazolyl]formamide (FANFT) (6 weeks)----5% sodium saccharin (72 weeks); and (iii) N-methyl-N-nitrosourea (MNU) 20 mg/kg body wt, i.p. twice per week for 4 weeks----3% uracil (20 weeks). The DNA sequence around the transmembrane domain of neu gene was amplified by PCR and sequenced. The results showed no mutation within the examined DNA sequences, indicating that neu oncogene is not activated by a point mutation in the transmembrane domain in urinary bladder carcinomas induced by BBN, FANFT or MNU.

Amino Acid Sequence↗

Ras involvement in cells transformed with 2-amino-4-(5-nitro-2-furyl)thiazole (ANFT) in vitro and with N-[4-(5-nitro-2-furyl)-2-thiazoyl]formamide in vivo.

N-[4-(5-nitro-2-furyl)-2-thiazolyl]formamide (FANFT) administration to rats followed by sodium saccharin results in transitional cell carcinomas of the bladder, of which 24% harbor an activated H-ras gene. Since 2-amino-4-(5-nitro-2-furyl)thiazole (ANFT) is the mutagenic and carcinogenic metabolite of FANFT in vivo, we wished to examine ras activation in in vitro ANFT-transformed rat bladder epithelial cells as well as four cell lines established in culture from in vivo FANFT-induced rat bladder tumors. Screening by Western blotting revealed no enhanced levels of p21ras in ANFT-transformed cells nor in cells established in culture from FANFT-induced rat bladder carcinomas. Further investigations using immunohistochemical staining with a different pan-reactive p21 monoclonal antibody (Cetus Corporation) specific for this method, however, showed two groups of cells from FANFT-induced rat bladder tumors had enhanced immunoreactivity. Apart from this, p21ras expression of most of the cells groups varied little from the controls. We examined the reported hot spots (exons 1 and 2) of each of the ras genes (H-, K- and N-ras) by direct sequencing of amplified DNA. No mutations were present. We conclude, therefore, that ANFT transformation of primary rat bladder epithelial cells in vitro may not in this case be mediated by ras activation, although this is difficult to determine since others have observed that optimal culture conditions can select for certain populations of cells without ras activation.

Animals↗

Effect of indomethacin on N-[4-(5-nitro-2-furyl)-2-thiazolyl]formamide-induced urinary tract carcinogenesis.

The effects of indomethacin on the urinary bladder and renal pelvis in rats treated with N-[4-(5-nitro-2-furyl)-2-thiazolyl]formamide (FANFT) were studied. Two hundred female Sprague-Dawley rats were divided into four groups. Group 1 received control diet without added chemicals. Group 2 was treated with indomethacin (1 mg/kg per day) in the drinking water throughout the experiment. Groups 3 and 4 received 0.2% FANFT in the diet for seven weeks followed by control diet. In addition to FANFT, Group 4 received indomethacin, 1 mg/kg per day, for the entire experiment. The rats were sacrificed after 92 weeks. There were no urothelial tumors in the control group, one renal pelvic tumor in the indomethacin group, 4 tumors in the FANFT group and 10 urothelial tumors in the FANFT + indomethacin group. The difference between Groups 3 and 4 was statistically significant (P < 0.05). Moderate and severe hyperplasia of the renal pelvic and papillary epithelium was found in 15 of 48 rats in Group 2 (indomethacin only) as compared with 6 of 49 control rats (P < 0.05). Moderate and severe hyperplasia was equally frequent in Groups 3 and 4 (14 and 17 animals in each group, respectively). Twenty-four rats in Group 2 had mammary tumors as compared to 12 animals in Group 1 (P < 0.01). Five of the tumors in Group 2 were adenocarcinomas. There was no difference between the number of mammary tumors in Groups 3 and 4 (36 and 32 animals in each group, respectively). The results suggest that indomethacin enhances FANFT-induced urinary tract carcinogenesis. Indomethacin also seems to exert some tumorigenic activity in the mammary gland.

Animals↗

Co-carcinogenicity of sodium saccharin and N-[4-(5-nitro-2-furyl)-2-thiazolyl]formamide for the urinary bladder.

The co-carcinogenic activity of sodium saccharin and N-[4-(5-nitro-2-furyl)-2-thiazolyl]formamide (FANFT) was evaluated in male Fischer rats by co-administering them as 5% and 0.005% of the diet, respectively, for 2 years. The effect of simultaneous administration of two urinary bladder promoting substances, sodium saccharin and L-tryptophan as 5% and 2% of the diet, respectively, was also evaluated. Five of 16 rats administered sodium saccharin plus FANFT developed bladder tumors whereas none of the rats administered FANFT, sodium saccharin, or L-tryptophan alone, sodium saccharin plus L-tryptophan, or the control diet developed bladder tumors. Possible mechanisms for the co-carcinogenic activity of sodium saccharin and FANFT are discussed.

Animals↗

Inhibition by aspirin of N-[4-(5-nitro-2-furyl)-2-thiazolyl] formamide-induced bladder carcinogenesis and enhancement of forestomach carcinogenesis.

N-[4-(5-Nitro-2-furyl)-2-thiazolyl]formamide (FANFT) is a potent urinary bladder carcinogen in the rat, and it can be metabolically activated in vitro by a variety of enzyme systems including aerobic cooxidation by prostaglandin H synthase. The latter enzyme is present in the rat bladder mucosa and can be inhibited by the oral administration of aspirin (ASA). To determine if ASA could inhibit the bladder carcinogenicity of FANFT, FANFT (0.2%) was co-administered in the diet with ASA (0.5%) for 12 weeks followed by 1 week of ASA only and then 56 weeks on control diet. 0.2% FANFT followed by control diet induced bladder carcinomas in 18 of 21 (87%) rats, but when ASA was co-administered, only 10 of 27 (37%) rats developed bladder carcinoma (p less than 0.001). However, forestomach tumors, not seen in rats fed only FANFT, developed in 7 rats fed FANFT plus ASA. No tumors occurred in control rats or those fed only ASA. Possible mechanisms, including the role of prostaglandin H synthase in FANFT metabolism, are discussed.

Animals↗

Immunohistochemical study of keratin in proliferative bladder epithelium induced by freezing, cyclophosphamide or N-[4-(5-nitro-2-furyl)-2-thiazolyl]formamide in the rat.

The distribution of intracellular keratin proteins was examined in a variety of urinary bladder lesions of the rat using the immunoperoxidase staining technique. In ethanol-fixed sections, the normal epithelium was strongly positive for keratin staining. Focal regenerative hyperplasia of the bladder epithelium induced by freezing exhibited relatively weak staining. However, diffuse regenerative hyperplasia induced by a single intraperitoneal injection of cyclophosphamide (CP) showed an intensely positive reaction throughout the epithelium. Of the sections fixed with Bouin's solution, the staining reaction was drastically reduced in the normal bladder and the staining was totally negative in the regenerative hyperplasia caused by freezing. Simple hyperplasia induced by a 4-week feeding of N-[4-(5-nitro-2-furyl)-2-thiazolyl]formamide (FANFT) as 0.2% of the diet exhibited strong reactivity, and nodular and papillarly hyperplasia induced by a 10-week feeding of FANFT was also positive for keratin throughout the lesions. In contrast to the preneoplastic lesions, FANFT-induced transitional cell carcinoma showed differential staining within the tumors. These results suggest that different keratin expression is involved in the proliferative bladder lesions induced mechanically by freezing and chemically by CP or by the carcinogen FANFT.

Animals↗

Effect of dose on the induction of urothelial proliferation by N-[4-(5-nitro-2-furyl)-2-thiazolyl]formamide and its relationship to bladder carcinogenesis in the rat.

The effect on urothelial proliferation of a urinary bladder carcinogen, N-[4-(5-nitro-2-furyl)-2-thiazolyl]formamide (FANFT), fed to male F344 rats at doses of 0.2, 0.1, 0.05, 0.01, 0.005 and 0.001% of diet for 4 or 10 weeks was evaluated by autoradiography, using [3H-methyl]thymidine, and by histopathology. At week 4, hyperplasia was induced in 10/11 and 6/11 rats given 0.2% and 0.1% FANFT, respectively. The dose-related increase of labeling index in the bladder epithelium was significant for the groups given 0.01% or higher doses of FANFT. At week 10, histopathologic lesions were observed in groups given 0.05% or higher doses of FANFT. This was accompanied by a significant increase in labeling index for these groups. The results are consistent with the long-term carcinogenicity studies conducted with the same dose levels of FANFT. The interrelationships between numbers of cells (hyperplasia), cell proliferation (labeling index) and cancer induction are discussed utilizing a computerized model of bladder carcinogenesis.

Animals↗

The influence of antipyrene on N-[4-(5-nitro-2-furyl)-2-thiazolyl]-formamide-induced urinary tract carcinogenesis.

Human over-use of analgesics containing phenacetin, antipyrene (phenazone) and caffeine has been associated with the development of both renal pelvic and bladder tumors. In Sprague-Dawley rats antipyrene has been shown to be a weak complete urinary tract carcinogen. The present study was designed to evaluate the promoting capacity of antipyrene in N-[4-(5-nitro-2-furyl)-2-thiazolyl]formamide (FANFT)-induced urinary tract carcinogenesis. One hundred and eighty male Sprague-Dawley rats were divided into groups of 30 and were treated with the following chemicals in the diet: group 1 received a control diet without chemicals; group 2 was treated with 0.2% FANFT in the diet for five weeks followed by control diet; group 3 received 0.2% FANFT for five weeks followed by 0.535% antipyrene in the diet; group 4 was treated with 0.535% antipyrene; group 5 was treated with 0.102% caffeine; and group 6 was treated with 0.535% antipyrene and 0.102% caffeine in the diet. Ten of 27 rats in group 3 (37%) developed urinary tract tumors (P greater than 0.001, five of which were renal pelvic tumors and five were bladder tumors. The majority of the tumors were well differentiated non-invasive urothelial carcinomas. None of the rats in other groups developed urinary tract tumors. In addition, renal papillary necrosis (RPN) was found in 33% of the rats in group 3, 50% in group 4, and 10% in group 6. The present study clearly shows that antipyrene acts as a promoter of FANFT-induced urinary tract carcinogenesis and that it is nephrotoxic to the renal papilla resulting in renal papillary necrosis.

Animals↗

Light and scanning electron microscopy of exfoliated bladder epithelial cells in rats fed N-(4-(5-nitro-2-furyl)-2-thiazolyl)formamide.

Urine specimens obtained periodically from weanling male F344 rats fed 0.2% N-[4-(5-nitro-2-furyl)-2-thiazolyl]formamide (FANFT) for 25 weeks followed by control diet for an additional 35 weeks, were examined by light microscopy (LM) and scanning electron microscopy (SEM). LM revealed red blood cells and atypical transitional cells in the urine at 25 and 43 weeks, when microinvasive transitional cell carcinoma was present. Malignant transitional cells were seen in the urine by LM at 60 weeks, when muscle invasion was present in histologic sections. However, SEM showed pleomorphic microvilli on exfoliated urothelial cells as early as 10 weeks after the beginning of FANFT administration, and the microvilli became increasingly pleomorphic as the bladder lesions progressed to muscle invasion at 60 weeks. Noninvasive tumors were present in histologic sections of rat bladders examined at the end of 10 weeks of FANFT administration. The numerous microvilli on exfoliated bladder tumor cells were in sharp contrast to the peaked microridges of normal exfoliated superficial cells.

Animals↗