On the Knowledge of Coprophilus (Zonyptilus) pennifer (Motschulsky, 1845) and Coprophilus (Zonyptilus) marginalis (Reitter, 1894) (Coleoptera,Staphylinidae)

Entomological Review - The type and other extensive material of Coprophilus (Zonyptilus) pennifer (Motschulsky, 1845) and some of its synonyms was examined. Coprophilus (Zonyptilus) marginalis...     

Structural characterization, kinetic studies, and in vitro biological activity of new cis-diamminebis-cholylglycinate(O,O') Pt(II) and cis-diamminebis-ursodeoxycholate(O,O') Pt(II) complexes

The complexes cis-diamminebis-cholylglycinate (O,O') [Pt(II) C(52)H(90)N(4)O(12)Pt, for convenience referred to as Bamet-R1] and cis-diamminebis-ursodeoxycholate (O,O') Pt(II) (C(48)H(84)N(2)O(8)Pt, Bamet-UD2) were prepared. The structural integrity of the compounds was confirmed by elemental analysis, FT-IR, NMR, FAB-MS, and UV spectroscopies. The kinetic study of both compounds was accomplished by combining the conductivity measurement and those of the analysis of the electronic spectra in aqueous solution for NaCl concentrations of 4 mM (similar to cytoplasmatic concentration), 150 mM (similar to plasmatic concentration), and 500 mM. In water, the compound Bamet-R1 showed a half-life, t(1/2), of 3.0 h. This compound forms the chelate species through loss of a ligand, and the other one acts as a bidentate ligand. Ring opening in the presence of chloride ion was produced with a k(Cl)()-of 0.25 M(-)(1) h(-)(1). The half-life of Bamet-UD2 in aqueous solution was 3.2 h. However, since this species is not able to chelate and has a lower degree of solubility in the presence of chloride ion, its kinetic behavior was very different from that of the other compound. We consider this to be of great interest with regards to its cytostatic activity. All kinetic measurements were performed under pseudo-first-order conditions, and a pseudo-first-order behavior was found. The antitumoral effect of Bamet-UD2 on several cell lines derived from rat hepatoma, human hepatoma, mouse leukemia, and human colon carcinoma was found to be, in general, similar to that of cisplatin, but higher than that observed for Bamet-R1.     

Spermatozoa and spermiogenesis of Holocnemus pluchei (Scopoli, 1763) (Pholcidae, Araneae)

Until now, the knowledge on pholcid spermatozoa is based on two species, Pholcus phalangioides and, incompletely, Holocnemus pluchei. To complete this knowledge and to reveal more potential phylogenetic characters, we have investigated sperm ultrastructure and spermiogenesis of H. pluchei. We found that the sperm cells of this species are clearly different from those of P. phalangioides with respect to: (1) the lack of specialization in the cylindrical acrosomal vacuole; (2) a nuclear canal which is located in the periphery and not in the center of the nucleus; (3) a more prominent postcentriolar elongation of the nucleus; (4) the presence of "inner microtubules" in the implantation fossa in early and mid-spermatids; (5) the absence of a helical band of nuclear material; (6) the proximal centriole which is not prolonged; (7) the types of secretion in the seminal fluid (only two types in H. pluchei). Similarities in the spermatozoa of both species concern: (1) a large implantation fossa which contains large amounts of glycogen in mature spermatozoa; (2) absence of a centriolar adjunct; (3) an axonemal basis located in the posterior part of the implantation fossa; (4) the formation of the so-called cleistospermia in the vas deferens. Our results strongly support systematic relationships within Pholcidae placing these two species in different subgroups.     

三种常见实蝇的形态学、生物学和生态学比较

对瓜实蝇Bactrocera (Tetradacus) minax (Enderlein)、桔小实蝇Bactrocera (Bactrocera) dorsalis (Hendel)和桔大实蝇Bactrocera (Zeugodacus) cucurbitae (Coquillett)的形态学、生物学、生态学等方面进行了比较和分析,包括三种实蝇在国内外的分布情况,对寄主选择的差异,各种虫态的形态特征,发育历期和生活史,并对它们的危害状况和防治方法分别作了介绍,可为3种实蝇的鉴定和防治提供参考.     

Electronic structures of collagen model polymers: (Gly-Pro)n, (Gly-Hyp)n, (Ala-Pro)n, (Ala-Hyp)n, (Gly-Pro-Gly)n, (Gly-Hyp-Gly)n, (Gly-Pro-Pro)n, and (Gly-Pro-Hyp)n

In order to investigate the relationship existing between the electronic structures of collagen and its biochemical functions in vivo, the semiempirical CNDO/2 SCF MO calculations were carried out on several model polymers of collagen, (Gly-Pro)_n, (Gly-Hyp)_n, (Ala-Pro)_n, (Ala-Hyp)_n, (Gly-Pro-Gly)_n, (Gly-Hyp-Gly)_n, (Gly-Pro-Pro)_n and (Gly-Pro-Hyp)_n. Geometries of the skeleton of these polymers were assumed to be the same as those of poly(l-proline) I (cis) and II (trans) and the calculations were performed only on infinite polymers in a single chain. The results show that the cis form is always more stable than the trans form for all the polymers treated. This energy difference between the cis and trans forms depends, for example, on the kind of amino acid residue, Gly or Ala, but this could not be seen in the Pro or Hyp residue. The flexibility or mobility of the collagen structure was explained using the energy difference between the cis and trans forms of the polymers, i.e. the cis-trans conversion of the collagen was discussed in connection with the energy difference. The reason why the collagen has the constitution of (Gly-Pro-Hyp)_n is briefly discussed.     

On the Synonymy of Coprophilus (Zonyptilus) pennifer (Motschulsky, 1845) (Coleoptera,Staphylinidae, Oxytelinae)

Entomological Review - The type material of several synonyms of Coprophilus (Zonyptilus) pennifer (Motschulsky, 1845) is revised. Both Coprophilus (Zonyptilus) striatipennis (Eppelsheim, 1894) and...     

Spontaneous epimerization of (S)-deoxycoformycin and interaction of (R)-deoxycoformycin, (S)-deoxycoformycin, and 8-ketodeoxycoformycin with adenosine deaminase

(R)-Deoxycoformycin (pentostatin), (S)-deoxycoformycin, and 8-ketodeoxycoformycin were compared as inhibitors of calf intestine adenosine deaminase. In contrast to (R)-deoxycoformycin, which had been demonstrated as a tight-binding inhibitor with a dissociation constant of 2.5 X 10(-12) M [Agarwal, R. P., Spector, T., & Parks, R. E., Jr. (1977) Biochem. Pharmacol. 26, 359-367], (S)-deoxycoformycin and 8-ketodeoxycoformycin are slope-linear competitive inhibitors with respect to adenosine. The kinetic constants are 33 microM for inhibition by (S)-deoxycoformycin, 43 microM for 8-ketodeoxycoformycin, and 16 microM for the Km for adenosine. The stereochemistry of carbon 8 of the diazepine ring therefore causes a (1.3 X 10(7]-fold change in the affinity for the enzyme which is specific for the R configuration. This difference is attributed to an induced conformational change which cannot be initiated by the S isomer or the 8-keto analogue of (R)-deoxycoformycin. The studies were complicated by the need to remove traces of tight-binding inhibitor(s) from (S)-deoxycoformycin, since as little as 0.001% of the R isomer causes significant inhibition. The R and S isomers of deoxycoformycin are unstable in neutral or mildly acidic aqueous solutions. Isomerization of the secondary hydroxyl at carbon 8 of the diazepine ring is one of the reactions, resulting in S to R and R to S conversions for deoxycoformycins. Opening of the aglycon is also a major reaction. The tight-binding inhibitor generated from (S)-deoxycoformycin was identified as (R)-deoxycoformycin by high-pressure liquid chromatography, spectroscopy, circular dichroism, and chemical criteria.(ABSTRACT TRUNCATED AT 250 WORDS)     

Low-temperature (180 K) crystal structures of tetrakis-mu-(niflumato)di(aqua)dicopper(II) N,N-dimethylformamide and N,N-dimethylacetamide solvates, their EPR properties, and anticonvulsant activities of these and other ternary binuclear copper(II)niflumate complexes

Two pseudopolymorphs, solvates, of [Cu(2)(II)(niflumate)(4)(H(2)O)(2)] of unknown structure were obtained following solution of [Cu(2)(II)(niflumate)(4)(H(2)O)(2)] in N,N-dimethylacetamide (DMA) or N,N-dimethylformamide (DMF). Low-temperature crystal structures obtained for these solvates revealed that they were ternary aqua DMA and DMF solvates: [Cu(2)(II)(niflumate)(4)(H(2)O)(2)].4DMA and [Cu(2)(II)(niflumate)(4)(H(2)O)(2)].4DMF. Intermolecular hydrogen bonding interactions account for the formation of these stable DMA and DMF solvates. These pseudopolymorphs contain a centrosymmetric binuclear center with Cu-Cu bond distances ranging from 2.6439(7) to 2.6452(9) A; the coordination sphere of Cu(II) is characterized by one long Cu-O (water) bond length of 2.128(3)-2.135(3) A and four short Cu-O (carboxylate) bonds of 1.949(3)-1.977(3) A. Crystal parameters for the DMA pseudopolymorph: a=10.372(1), b=19.625(2), c=17.967(2) A, beta=97.40(1) degrees , V=3626.8(6) A(3); monoclinic system; space group: P2(1)/a and for the DMF pseudopolymorph: a=10.125(2), b=18.647(3), c=19.616(4) A, alpha=74.38(2)(o), beta=88.18(2)(o), gamma=79.28(2)(o), V=3504(1) A(3); triclinic system; space group: P1. EPR spectra of these solids are identical and show strong antiferromagnetic coupling between the copper atoms, similar to the spectrum obtained for [Cu(2)(II)(niflumate)(4)(DMSO)(2)]. The [Cu(2)(II)(niflumate)(4)(H(2)O)(2)], [Cu(2)(II)(niflumate)(4)(H(2)O)(2)].4DMA, [Cu(2)(II)(niflumate)(4)(H(2)O)(2)].4DMF, [Cu(2)(II)(niflumate)(4)(DMF)(2)], and[Cu(2)(II)(niflumate)(4)(DMSO)(2)] evidenced protection against maximal electroshock-induced seizures and Psychomotor seizures at various times after treatment, consistent with the well known antiinflammatory activities of Cu chelates, but failed to protect against Metrazol-induced seizures while evidencing some Rotorod Toxicity consistent with a mechanism of action involving sedative activity.     

Magnetic resonance studies of Mn(II)-, Mn(III)-, and Fe(III)-conalbumin complexes.

Apoconalbumin binds Mn(II) at two sites with association constants of K1 = 7 (+/- 1) X 10(4) and K2 = 0.4 (+/- 0.25) X 10(4) M-1. The binding is tighter in the presence of excess bicarbonate resulting in K1 = 1.8 (+/- 0.2) X 10(5) and K2 = 3 (+/- 2) X 10(4) M-1. The electron paramagnetic resonance spectrum (at both 9 and 35 GHz) of Mn(II) bound at the tight site reveals a rhombic distortion (lambda = E/D approximately equal to 0.25-0.31) in the protein ligand environment of the mental ion. An evaluation of the 1/pT1p, paramagnetic contribution to the longitudinal relaxation rate of solvent protons with Mn(II)-, Mn(III)-, and Fe(III)-derivatives of conalbumin revealed that the mental ion in each site of conalbumin is accessible to one water molecule. For Mn(II)-conalbumin and Mn(III)-conalbumin species, inner coordination sphere protons are rapidly exchanging with the bulk solvent, while slow exchange conditions prevail for Fe(III)-conalbumin.     

Synthesis and characterization of N-methyliminodiacetato trans-R,R-, trans-S,S-, and cis-1,2-diaminocyclohexane platinum (IV) complexes: crystal structure of chloro(trans-R,R-1,2-diaminocyclohexane) (N-methyliminodiacetato) platinum(IV) chloride.

The compounds, chloro(trans-R,R-1,2-diaminocyclohexane) (N-methyliminodiacetato)platinum(IV) chloride, chloro(trans-S,S-1,2-diaminocyclohexane)(N-methyliminodiacetato) platinum(IV) chloride, and chloro(cis-1,2-diaminocyclohexane)(N-methyliminodiacetato)platinum (IV) chloride, were prepared and characterized by elemental analysis, IR, and 195Pt NMR. The crystal structure of one of these three compounds, chloro(trans-R,R-1,2-diaminocyclohexane) (N-methyliminodiacetato) platinum(IV) chloride, was determined by x-ray single crystal diffraction. This compound is particularly interesting because the 1,2-diaminocyclohexane (DACH) ring is in a twist-boat configuration rather than the chair configuration previously reported for other DACH platinum compounds. The crystal structure consists of two independent cations and anions, with all atoms between these two independent molecules (except those in the chiral DACH) related by a pseudo-inversion center. Both platinum atoms have slightly distorted octahedral coordination, with angles ranging from 81.8 to 100.8 degrees. Crystallographic details: space group P2(1) (monoclinic); a = 19.864(5) A, b = 7.026(2) A, c = 12.446(3) A, beta = 106.64(2) degrees; Z = 4; R = 0.036 for 2333 reflections.     

(Dien)M(II) (M=Pd, Pt) and (NH3)3Pt(II) complexes of 1-methylcytosine: Linkage and rotational isomerism, metal-promoted deamination, and pathways to dinuclear species

Despite their structural similarity, [Pt(dien)(1-MeC-N3)](2+) (1), [Pd(dien)(1-MeC-N3)](2+) (2), and [Pt(NH(3))(3)(1-MeC-N3)](2+) (3) (with dien=diethylenetriamine and 1-MeC=neutral 1-methylcytosine) behave in part markedly different at strongly alkaline pH (12-13) and at room temperature. While 1 and 2, yet not 3 show linkage isomerization from N3 to N4, deamination of the cytosine nucleobase to 1-methyluracilate occurs with 1 and 3, yet not with 2. Pathways leading to N3,N4-diplatinated 1-MeC(-) complexes (1-MeC(-)=1-methylcytosine, deprotonated at exocyclic amino group N4) have been studied at high pH by starting from 1 and 3, respectively, and adding (dien)Pt(II). It appears that initial migration of the metal entity from N3 to N4, followed by binding of the second metal to the available N3 site, is favored over sequential coordination to N3 and then N4. X-ray crystal data of 1-3 density functional theory (DFT) calculations, and NMR ((1)H, (195)Pt) data are presented.     

Trans-bis(benzo(1,3)-thiazole)bis(N,N-dimethylformamide)bis(N-thiocyanato)-cobalt(II): spectroscopy,thermal analysis and crystal structure

Disolution of Co(bzt)₂(NCS)₂ (bzt = benzo 1,3- thiazole) in dimethyl formamide (dmf) produces Co(bzt)₂(NCS)₂(dmf)₂. The stoichionmetry of the complex has been established by a combination of chemical (C, H, N) and thermal analysis. The comlex has an octahedral structure with pairs of ligands in trans configuration as well as a CoN₄O₂ coordination sphere with CoN distances of 2.185(2) Å (bzt); 2.082(2) Å (NCS) and CoN(dmf) of 2.118(2) Å. The infrared and electronic absorption spectra are consistent with this arrangement.     

Synthesis, characterization, and antitumor activity of 1,2-bis(diphenylphosphino) ethane platinum(II) and palladium(II) complexes

A number of 1,2-bis(diphenylphosphino)ethane monomeric platinum(II) and palladium(II) complexes have been synthesized in light of their potential antitumor activity. The metal center is coordinated with a number of carboxylate anions in the cis-configuration. These complexes have been characterized by elemental analysis, conductivity measurement, and various spectroscopic techniques [IR and 195Pt NMR]. In vivo screening tests for activity of these complexes were performed against the L1210/0 murine leukemia cancer model, but none displayed a significant level of antitumor activity.     

Synthesis, structures, and characterization of benzildiimine complexes of rhodium(III) and iridium(I)

The reactions of trans-[(PPh₃)₂M(CO)Cl] (M = Rh and Ir) with benzildiimine (H₂BDI = 2) derived from benzil-bis(trimethylsilyl)diimine (Si₂BDI) (1) in a 1:2 and 1:1 molar ratio afforded the cationic bis-benzildiiminato complexes [Rh(PPh₃)₂(HBDI)₂]Cl (3) and the mono-benzildiimine complex [Ir(PPh₃)₂(CO)(H₂BDI)]Cl (4), respectively. Both complexes are fully characterized using IR, FAB-MS, NMR spectroscopy and elemental analysis. The single crystal X-ray structure analysis reveals a distorted octahedral coordination geometry for the Rh(III) in 3 and a highly distorted square pyramidal geometry for Ir(I) in 4. In addition, the solid-state structure of Si₂BDI is reported here for the first time showing the substituents highly twisted because of steric reasons.     

Diamminetetrakis(carboxylato)platinum(IV) Complexes - Synthesis, Characterization, and Cytotoxicity

A series of eight novel diamminetetrakis(carboxylato)platinum(IV) complexes was synthesized and characterized by multinuclear (1) H-, (13) C-, (15) N-, and (195) Pt-NMR spectroscopy. Their antiproliferative potency was evaluated in three human cancer cell lines representing ovarian (CH1), lung (A549), and colon carcinoma (SW480). In cisplatin-sensitive CH1 cancer cells, cytotoxicity was found in the low micromolar range, whereas, in inherently cisplatin-resistant A549 and SW480 cells, the activity was very low or negligible. Astonishingly, raise in lipophilicity of the complexes, as found in the case of cisplatin analogs, did not result in a significant enhancement of the cytotoxic effect.     

Inhibition of peroxidase, trypsin, and alpha-chymotrypsin by platinum (II) and platinum (IV) complexes

Effects of various complexes of platinum (II) and platinum (IV) on activities of trypsin, alpha-chymotrypsin, and peroxidase were compared. The platinum (II) complexes were found to inhibit these enzymes, though with variable efficiency. The platinum (IV) complexes at concentrations < or = 0.2 mM efficiently inhibited peroxidase but had no effect on the proteases. An enzymatic assay was developed to measure the most effective peroxidase inhibitor (cisplatin) at concentrations of 5-50 microM in the presence of fivefold excess of its isomer (transplatin).     

Chaetotaxy and surface structures of the miracidia of Ichthyocotylurus erraticus (Rudolphi, 1809), I. variegatus (Creplin, 1825) and Apatemon gracilis (Szidat, 1928) (Digenea,Strigeidae)

Silver nitrate staining was used to investigate the number and arrangement of argentophillic structures (epidermal plates, sensilla, excretory pores) of three species of strigeid miracidia, Ichthyocotylurus erraticus (Rudolphi, 1809), I. variegatus (Creplin, 1825) and Apatemon gracilis (Szidat, 1928). The epidermal plates of all three species of miracidia were arranged in four tiers according to the formula (6 + 9 + 4 + 3) = 22, while the number and distribution of sensilla were also found to be identical. Modifications to the nomenclature of Dimitrov et al. (1989) for miracidial chaetotaxy are proposed.Scanning electron microscopy (SEM) was also employed to examine the surface structures of deciliated miracidia of Ichthyocotylurus spp., confirming the position and revealing the form of body sensilla.     

Synthesis, catalytic activity, phosphatase inhibition activity, and X-ray structural characterization of vanadium scorpionate complexes, (Tpms)VCl2(DMF) and (Tpms)VOCl(DMF)

The complexes (Tpms)VCl₂(DMF) (1), and (Tpms)VOCl(DMF) (2), have been synthesized and characterized. Complex 2 has also been structurally characterized via X-ray diffractometry. The vanadium(IV) center possesses a square pyramidal/distorted octahedral geometry with a facially coordinating Tpms⁻ ligand in a κ³-N,N,O coordination mode. The complex is the first structurally characterized example of a vanadium(IV) complex with Tpms⁻. Complex 2 shows catalytic activity towards oxidation of 3,5-di-tert-butyl catechol and also exhibits phosphatase inhibition characteristics on alkaline phosphatase. Tpms⁻ = trispyrazolylmethanesulfonate; DMF = N,N-dimethylformamide.