Functional changes in rat liver mitochondria on administration of 2-methyl-4-dimethylaminoazobenzene

Administration of 2-methyl-4-dimethylaminobenzene in the diet (0.1%, w/w) for 85-90 days doubled the content of mitochondria in the livers of rats. The azodye was covalently bound to liver proteins, and about 15% of the amount found in liver was associated with the mitochondrial fraction. Mitochondria isolated from the livers of azodye-fed animals showed drastically lowered ability to oxidize NAD+-linked substrates. The inhibited electron-transfer step was the reduction of ubiquinone. The organelles showed a large increase in succinate oxidase activity. The activity of cytochrome oxidase and the content of cytochrome aa3 were substantially higher in these organelles. Azodye-fed animals showed depressed serum cholesterol concentrations. The content of ubiquinone in liver also registered a small increase.

Self-Assembly of Molecular Prisms via Pt-3 Organometallic Acceptors and a Pt-2 Organometallic Clip

The design and two-component [2 + 3] self-assembly of a series of new organometallic molecular prisms (3a-d) are described. Assemblies 3a,b incorporate 4,4',4'-tris[ethynyl-trans-Pt(PEt3)(2)]triphenylamine (1a) containing a Pt-ethynyl functionality as tritopic planar acceptor and organic ``clips'' 2a and 2b, respectively [where 2a = 1,3-bis(3-pyridyl)isophthalic amide; 2b= 1,3-bis(ethynyl-3-pyridyl)benzene]. In a complementary approach all organic tritopic planar donor ligand 2c [2c 4,4',4'-tris(4-pyridylethynyl)triphenylamine] was assembled with all organometallic ``clip'', 1,8-bis[{trans-Pt(PEt3) (2)(NO3)}ethynyl]anthracene (1b), to obtain prism 3c. A organometallic carbon-centered acceptor, 1,1,1- tris[4-{trans-Pt(PEt3)(2)(NO3)}ethynylphenyl]ethane (1c), has been prepared, and its prism derivative (3d) using an organic `clip'' is prepared. Assemblies (3a-d) were characterized by multinuclear NMR spectroscopy, electrospray ionization mass spectroscopy, and elemental analysis. 3a-d showed fluorescence behavior in solution, and quenching of fluorescence intensity (3a,3c-d) was noticed upon addition of TNT (2,4,6-trinitrotoluene), a common constituent of many commercial explosives. A thin film of the assembly 3d made by spin coating of a solution of 3 x 10(-5) M in DMF on it 1 cm(2) quartz plate showed fluorescence response to the vapor of TNT.

Quasi-2D XY Magnetic Properties and Slow Relaxation in a Body Centered Metal Organic Network of [Co-4] Clusters

Octahedral Co2+ centers have been connected by mu(3)-OH and mu(2)-OH2 units forming [Co-4] clusters which are linked by pyrazine forming a two-dimensional network. The two-dimensional layers are bridged by oxybisbenzoate (OBA) ligands giving rise to a three-dimensional structure. The [Co-4] clusters bond with the pyrazine and the OBA results in a body-centered arrangement of the clusters, which has been observed for the first time. Magnetic studies reveal a noncollinear frustrated spin structure of the bitriangular cluster, resulting in a net magnetic moment of 1.4 mu B per cluster. For T > 32 K, the correlation length of the cluster moments shows a stretched-exponential temperature dependence typical of a Berezinskii-Kosterlitz-Thouless model, which points to a quasi-2D XY behavior. At lower temperature and down to 14 K, the compound behaves as a soft ferromagnet and a slow relaxation is observed, with an energy barrier of ca. 500 K. Then, on further cooling, a hysteretic behavior takes place with a coercive field that reaches 5 Tat 4 K. The slow relaxation is assigned to the creation/annihilation of vortex-antivortex pairs, which are the elementary excitations of a 2D XY spin system.

Methyl 2-methyl-2H-1,2,3-triazole-4-carboxylate

In the title compound, C5H7N3O2, all non-H atoms lie in a common plane, with a maximum deviation of 0.061 (2)° for the ester methyl C atom. The structure is stabilized by intermolecular C-H O hydrogen bonds.

3-Acetyl-6-chloro-1-ethyl-4-phenylquinolin-2(1H)-one

In the title compound, C19H16ClNO2, the dihedral angle between the plane of the phenyl substituent and 3-acetylquinoline unit is 75.44 (5)degrees. The crystal structure is stabilized by intermolecular C-H center dot center dot center dot O hydrogen bonds.

Antizyme Inhibitor 2 : A Novel Regulator of Cellular Polyamine Homeostasis

Polyamines are organic polycations that participate in various physiological functions, including cell proliferation, differentiation and apoptosis. Cellular polyamines originate from endogenous biosynthesis and exogenous sources. Their subcellular pool is under strict control, achieved by regulating their uptake and metabolism. Polyamine-induced proteins called antizymes (AZ) act as key regulators of intracellular polyamine concentration. They regulate both the transport of polyamines and the activity and degradation of ornithine decarboxylase (ODC), the rate-limiting enzyme in polyamine biosynthesis. AZs themselves are negatively regulated by antizyme inhibitor (AZIN). AZIN functions as a positive regulator of cellular polyamine homeostasis, which by binding to AZs reactivates ODC and induces the uptake of polyamines. In various pathological conditions, including cancer, polyamine levels are misregulated. Polyamine homeostasis has therefore become an attractive target for therapeutic interventions and it is thus crucial to characterize the molecular basis underlying the homeostatic regulation. A novel human AZIN-resembling protein was previously identified in our group. The purpose of this study was to elucidate the function and distribution of this protein, termed as an antizyme inhibitor 2 (AZIN2). According to my results, AZIN2 functions as a novel regulator of polyamine homeostasis. It shows no enzymatic activity, but instead it binds AZs and negates their activity, which subsequently leads to reactivation of ODC and inhibition of its degradation. Expression of AZIN2 is restricted to terminally differentiated cells, such as mast cells (MC) and neurosecretory cells. In these actively secreting cell types, AZIN2 localizes to subcellular vesicles or granules where its function is important for the vesicle-mediated secretion. In MCs, AZIN2 localizes to the serotonin-containing subset of MC granules, and its expression is coupled to MC activation. The functional role of polyamines as potential mediators of MC activity was also investigated, and it was observed that the secretion of serotonin is selectively dependent on activation of ODC. In neurosecretory cells, AZIN2-positive vesicles localize mainly to the trans-Golgi network (TGN). Depletion of AZIN2 or cellular polyamines causes selective fragmentation of the TGN and retards secretion of proteins. Since addition of exogenous polyamines reverses these effects, the data indicate that AZIN2 and its downstream effectors, polyamines, are functionally implicated in the regulation of secretory vesicle transport. My studies therefore reveal a novel function for polyamines as modulators of both constitutive and regulated secretion. Based on the results, I propose that the role of AZIN2 is to act as a local in situ activator of polyamine biosynthesis.

Lanthanide perchlorate complexes of 4-cyano pyridine-N-oxide, 4-chloro 2-picoline-N-oxide and 4-dimethyl amino-2-picoline-N-oxide

Complexes of lanthanide perchlorates with 4-cyano pyridine-1-oxide, 4-chloro 2-picoline-1-oxide and 4-dimethyl-amino 2-picoline-1-oxide have been isolated for the first time and characterized by analysis, conductance, infrared, NMR and electronic spectra. The complexes of 4-cyano pyridine-1-oxides have the composition Ln(CyPO)6(ClO4)3. 2H2O (Ln=La, Sm, Dy and Ho); Ln(CyPO)7 (ClO4)3. 2H2O (Ln=Pr, Nd, Er and Yb); and Ln(CyPO)5 (ClO4)3. 2H2O (Ln=Gd and Tb). The complexes of 4-chloro 2-picoline-1-oxide analyse for the formulae Ln(CpicO)6 (ClO4)3 (Ln=La, Pr, Nd and Ho); and Ln (CpicO)5 (ClO4)3 (Ln=Er and Yb), and those of 4-dimethylamino 2-picoline-1-oxide for Ln(DMPicO)6 (ClO4)3 (Ln=La and Nd); Ln(DMPicO)7 (ClO4)3 (Ln=Gd, Er and Yb); and Ln(DMPicO)8 (ClO4)3 (Ln=Dy and Ho).

Optical and surface characterization of radio frequency plasma polymerized 1-isopropyl-4-methyl-1,4-cyclohexadiene thin films

Low pressure radio frequency plasma-assisted deposition of 1-isopropyl-4-methyl-1,4-cyclohexadiene thin films was investigated for different polymerization conditions. Transparent, environmentally stable and flexible, these organic films are promising candidates for organic photovoltaics (OPV) and flexible electronics applications, where they can be used as encapsulating coatings and insulating interlayers. The effect of deposition RF power on optical properties of the films was limited, with all films being optically transparent, with refractive indices in a range of 1.57–1.58 at 500 nm. The optical band gap (Eg) of ~3 eV fell into the insulating Eg region, decreasing for films fabricated at higher RF power. Independent of deposition conditions, the surfaces were smooth and defect-free, with uniformly distributed morphological features and average roughness between 0.30 nm (at 10 W) and 0.21 nm (at 75 W). Films fabricated at higher deposition power displayed enhanced resistance to delamination and wear, and improved hardness, from 0.40 GPa for 10 W to 0.58 GPa for 75 W at a load of 700 μN. From an application perspective, it is therefore possible to tune the mechanical and morphological properties of these films without compromising their optical transparency or insulating property.

Wetting, solubility and chemical characteristics of plasma-polymerized 1-isopropyl-4-methyl-1,4-cyclohexadiene thin films

Investigations on the wetting, solubility and chemical composition of plasma polymer thin films provide an insight into the feasibility of implementing these polymeric materials in organic electronics, particularly where wet solution processing is involved. In this study, thin films were prepared from 1-isopropyl-4-methyl-1,4-cyclohexadiene (γ-Terpinene) using radio frequency (RF) plasma polymerization. FTIR showed the polymers to be structurally dissimilar to the original monomer and highly cross-linked, where the loss of original functional groups and the degree of cross-linking increased with deposition power. The polymer surfaces were hydrocarbon-rich, with oxygen present in the form of O–H and C=O functional groups. The oxygen content decreased with deposition power, with films becoming more hydrophobic and, thus, less wettable. The advancing and receding contact angles were investigated, and the water advancing contact angle was found to increase from 63.14° to 73.53° for thin films prepared with an RF power of 10 W to 75 W. The wetting envelopes for the surfaces were constructed to enable the prediction of the surfaces’ wettability for other solvents. The effect of roughness on the wetting behaviour of the films was insignificant. The polymers were determined to resist solubilization in solvents commonly used in the deposition of organic semiconducting layers, including chloroform and chlorobenzene, with higher stability observed in films fabricated at higher RF power.

Plasma polymerisation and retention of antibacterial properties of terpinen-4-ol

Plasma polymerisation was used to deposit thin oligomeric films of terpinen-4-ol on a range of substrates. The coatings were examined in terms of their chemical properties and surface architecture to ascertain the changes in chemical composition as a result of exposure to the plasma field. The antifouling and antimicrobial activity of oligomeric terpinen-4-ol coatings were then examined against such human pathogens as Staphylococcus aureus, Pseudomonas aeruginosa and Staphylococcus epidermis. The bacterial adhesion patterns were investigated using scanning electron microscopy (SEM), atomic force microscopy (AFM) and confocal scanning laser microscopy (CSLM).

Synthesis of radio frequency plasma polymerized non-synthetic Terpinen-4-ol thin films

Recent advancements in the area of organic polymer applications demand novel and advanced materials with desirable surface, optical and electrical properties to employ in emerging technologies. This study examines the fabrication and characterization of polymer thin films from non-synthetic Terpinen-4-ol monomer using radio frequency plasma polymerization. The optical properties, thickness and roughness of the thin films were studied in the wavelength range 200–1000 nm using ellipsometry. The polymer thin films of thickness from 100 nm to 1000 nm were fabricated and the films exhibited smooth and defect-free surfaces. At 500 nm wavelength, the refractive index and extinction coefficient were found to be 1.55 and 0.0007 respectively. The energy gap was estimated to be 2.67 eV, the value falling into the semiconducting Eg region. The obtained optical and surface properties of Terpinen-4-ol based films substantiate their candidacy as a promising low-cost material with potential applications in electronics, optics, and biomedical industries.

Structure of (6S,13bR)-1,2,3,5,6,13b-hexahydro-6-isopropyl-8H-pyrrolo[1',2':1,2]pyrazino[3,4,-b]quinazoline-5,8-dione

C17H19N302, monoclinic, P21, a = 5.382 (1), b = 17.534(4), c = 8.198(1)/L ,8 = 100.46(1) °, Z= 2, d,, = 1.323, dc= 1.299 Mg m-3, F(000) = 316, /~(Cu .Ka) = 0.618 mm -1. R = 0.052 for 1284 significant reflections. The proline-containing cispeptide unit which forms part of a six-membered ring deviates from perfect planarity. The torsion angle about the peptide bond is 3.0 (5) ° and the peptide bond length is 1.313 (5)A. The conformation of the proline ring is Cs-Cf~-endo. The crystal structure is stabilized by C-H... O interactions.

Follicle stimulating hormone secretion and dominant follicle growth during treatment of Bos indicus heifers with intra-vaginal progesterone releasing devices, oestradiol benzoate, equine chorionic gonadotrophin and prostaglandin F-2 alpha

The aim of this study was to investigate the effects on follicle stimulating hormone (FSH) secretion and dominant follicle (OF) growth, of treatment of Bos indicus heifers with different combinations of intra-vaginal progesterone releasing devices (IPRD), oestradiol benzoate (ODB), PGF(2 alpha), and eCG. Two-year-old Brahman (BN; n=30) and Brahman-cross (BNX; n=34) heifers were randomly allocated to three IPRD-treatments: (i) standard-dose IPRD [CM 1.56 g; 1.56 g progesterone (P-4); n = 17]; (ii) half-dose IPRD (CM 0.78 g; 0.78 g p(4); n=15); (iii) half-dose IPRD + 300 IU eCG at IPRD removal (CM 0.78 g+G; n=14); and, (iv) non-IPRD control (2 x PGF(2 alpha); n=18) 500 mu g cloprostenol on Days -16 and -2. IPRD-treated heifers received 250 mu g PGF(2 alpha) at IPRD insertion (Day 10) and IPRD removal (Day -2) and 1 mg ODB on Day -10 and Day -1. Follicular dynamics were monitored daily by trans-rectal ultrasonography from Day -10 to Day 1. Blood samples for determination of P-4 were collected daily and samples for FSH determination were collected at 12 h intervals from Day -9 to Day -2. A significant surge in concentrations of FSH was observed in the 2 x PGF(2 alpha), treatment 12 h prior and 48 h after follicular wave emergence, but not in the IPRD-treated heifers. Estimated mean concentrations of total plasma P-4 during the 8 days of IPRD insertion was greater (P<0.001) in the CM 1.56 g P-4 treated heifers compared to the CM 0.78 g P-4 treated heifers (18.38 ng/ml compared with 11.09 ng/ml, respectively). A treatment by genotype interaction (P=0.036) was observed in the mean plasma P4 concentration in heifers with no CL during IPRD insertion, whereby BN heifers in the CM 1.56 g treatment had greater plasma P-4 than the BNX heifers on Days-9, -7, -6, -5, and -4. However, there was no genotype effect in the CM 0.78 g +/- G or the 2 x PGF(2 alpha) treatment. Treatment had no effect on the DF growth from either day of wave emergence (P=0.378) or day of IPRD removal (P=0.780) to ovulation. This study demonstrates that FSH secretion in B. indicus heifers treated with a combination of IPRD's and ODB to synchronise ovulation was suppressed during the period of IPRD insertion but no significant effect on growth of the DF was observed. (C) 2013 Elsevier B.V. All rights reserved.

Iron(II) and iron(III) complexes of 2,4-dithiobiuret

Ferrous and ferric complexes of 2,4-dithiobiuret (Dtb) of the type Fe(Dtb)m Xn where m, n = 1-3, and X = CI–, Br–, I– and SO 4 2– , and a neutral Fe(Dtb-H)2 complex have been synthesized and characterised by elemental analyses, magnetic susceptibility, i.r., electronic and Mössbauer spectroscopic studies. From its i.r. spectrum Dtb was found to act as a S,S-coordinating bidentate chelate. The magnetic moment, electronic and Massbauer spectra are consistent with a low spin distorted octahedral structure for the ferric complexes and a high spin form for ferrous complexes.

The Crystal Structure of Pivaloyl- D- prolyl-L- prolyl- L-alanyl-N- methylamide

Pivaloyl-D-prolyl-L-prolyl-L-analyl-N-methylam~de (I), C1UH32N40c4r,y stallizes in the orthorhombic space group P21212,w ith four molecules in a unit cell of dimensions a = 9.982 (l),b = 10.183 (3), c = 20.746 (2)A . The structure has been refined to R 0.048 for 1 745 observed reflections. All the peptide bonds in the molecule are trans and both the prolyl residues are in the CY-exo-conformation. The molecule assumes a highly folded conformation in which a Type II' DL bend is followed by a Type I LL bend, both stabilised by intramolecular 4 + 1 hydrogen bonds. This conformation, which has been observed for the first time, is of interest in relation to the structure of gramicidin S.