Bone marrow biopsies have been investigated in 330 cases of Hodgkin's disease totalising 298 patients, out of which 32 with repeated biopsies. Positive biopsies with typical lesions were found in 32% of patients, the majority in stages III and IV (88.6%), rarely in stage I or II (11.4%). Nonspecific lesions were very frequent (75%), either isolated or accompanied by typical lesions. The majority of the positive biopsies were found in patients with lymphocytic predominance and lymphocytic depletion, or in polytreated patients in an advanced stage of the disease. The specific marrow involvement consisted in lymphocytic infiltrations either nodular or diffuse, Reed-Sternberg (R-St) or Hodgkin cells. The lymphocytic depletion is often accompanied by diffuse fibrosis, atypical histiocytes, fibroblasts and R-St cells. Hodgkin typical granulomas are rare. The positive biopsies were associated with nonspecific reactions including hyperplasia of granulopoiesis, megakaryocytes, territories with hyperplasia or aplasia, fibrosis, disruption of sinus walls, oedema, plasmocytosis, necrosis, myelomonoblastic cells, lymphocyte nodes, etc. The bone marrow histology has a prognostic significance. 相似文献
The stability constants of Am+3, Cm3+ and Eu3+ with ortho silicate, were measured at pH 3.50 and in ionic strengths of 0.20-1.00 M (NaClO4) by the solvent extraction method. The Am+3, Cm3+ and Eu3+ forms 1:1 complex with ortho silicate ion at pH 3.60 with the stability constant (log β1) value of 8.02 ± 0.10, 7.78 ± 0.08 and 7.81 ± 0.11, respectively. The stability of these metal ions decrease with increased ionic strength from 0.20 to 1.00 M (NaClO4) for silicic acid concentrations of 0.002-0.020 M. Increasing silicic acid concentration above 0.02 M increased the amount of M3+ extracted into the organic phase, contrary to the trend usually observed for increased ligand concentration in solvent extraction. This reversed trend is likely due to the extraction of cationic species of silicic acid by HDEHP. Aging time (60-300 min) had no effect on the stability constant of these metal ions for 0.002-0.020 M silicic acid at pH 3.50 and I = 0.20 M (NaClO4).The fraction of polymeric silicic acid present in solutions of 0.20-4.50 M NaClO4 solutions at pH 3.0-10.0, T = 0-60 °C and aging time = 5-300 min was measured for determination of the silicomolybdate reaction to ascertain the proper conditions to study metal-silicate complexation. 相似文献
Polynuclear sulfur bridged complexes where the neutral complex tris(2-aminoethanethiolato)cobalt(III) acts as a tridentate ligand to rhodium(III), iridium(III) and osmium(III) have been prepared. These complexes have been characterized by electronic spectroscopy, vibrational spectroscopy and nuclear magnetic resonance spectroscopy. Along with the previously prepared complexes of iron(III), ruthenium(III) and cobalt(III), these complexes form two series of complexes with the group 8 and group 9 elements from all three transition series. 相似文献
The reactions of AuBr?4 and Au(CN)2Br?2 with uracil in water produce gold(I) and 5-bromouracil and/or 5-bromo-6-hydroxy-5,6-dihydrouracil. The observed kinetics of the reactions are consistent with a mechanism involving a fast redox pre-equilibrium followed by bromination of the pyrimidine (X?= Br? or CN?): The calculated equilibrium constant K = k1/k?1 is 1.6 × 10?10 M for AuBr?4 and 1.7 × 10?11 M for Au(CN)2Br?2. Specific rates for the reduction of AuBr?4 are correspondingly greater than those for the reduction of Au(CN)2Br?2. 相似文献
Some new derivatives of Cr(III) with 5′AMP, 5′ATP, 5′CMP, 5′GMP, 5′IMP and 5′UMP have been obtained by reaction of the starting complexes cis and trans-[Cr(en)2Cl2]Cl with the above nucleotides.The complexes were characterized by elemental analysis, conductivity, infrared and electronic spectroscopy, and EPR for the 5′UMP derivative.In all cases, chlorine has been substituted and one ethylenediamine eliminated. The interaction of Cr(III) with the nucleotide seems to occur through the phosphate group and additional interaction through the heterocyclic ring especially for the 5′GMP and 5′IMP derivatives.The 5′UMP complex seems to be a dimer and the other complexes are polymer. 相似文献
New solid complex compounds of La(III), Ce(III), Pr(III), Nd(III), Sm(III), Eu(III) and Gd(III) ions with morin were synthesized. The molecular formula of the complexes is Ln(C15H9O7)3 · nH2O, where Ln is the cation of lanthanide and n = 6 for La(III), Sm(III), Gd(III) or n = 8 for Ce(III), Pr(III), Nd(III) and Eu(III). Thermogravimetric studies and the values of dehydration enthalpy indicate that water occurring in the compounds is not present in the inner coordination sphere of the complex. The structure of the complexes was determined on the basis of UV-visible, IR, MS, 1H NMR and 13C NMR analyses. It was found that in binding the lanthanide ions the following groups of morin take part: 3OH and 4CO in the case of complexes of La, Pr, Nd, Sm and Eu, or 5OH and 4CO in the case of complexes of Ce and Gd. The complexes are five- and six-membered chelate compounds. 相似文献
Luminescent lanthanide (III) ions have been exploited for circularly polarized luminescence (CPL) for decades. However, very few of these studies have involved chiral samarium (III) complexes. Complexes are prepared by mixing axial chiral ligands (R/S))‐2,2’‐bis(diphenylphosphoryl)‐1,1′‐binaphthyl (BINAPO) with europium and samarium Tris (trifluoromethane sulfonate) (Eu (OTf)3 and Sm (OTf)3). Luminescence‐based titration shows that the complex formed is Ln((R/S)‐BINAPO)2(OTf)3, where Ln = Eu or Sm. The CPL spectra are reported for Eu((R/S)‐BINAPO)2(OTf)3 and Sm((R/S)‐BINAPO)2(OTf)3. The sign of the dissymmetry factors, gem, was dependent upon the chirality of the BINAPO ligand, and the magnitudes were relatively large. Of all of the complexes in this study, Sm((S)‐BINAPO)2(OTf)3 has the largest gem = 0.272, which is one of the largest recorded for a chiral Sm3+ complex. A theoretical three‐dimensional structural model of the complex that is consistent with the experimental observations is developed and refined. This report also shows that (R/S)‐BINAPO are the only reported ligands where gem (Sm3+) > gem (Eu3+). 相似文献
The crystal structures of the title compounds, Ga(S2COEt)3 (1) and In(S2COEt)3 (2) have been determined by three dimensional X-ray diffraction methods. Both compounds crystallize in the trigonal space group R
with Z = 6. Cell dimensions for (1) are ahex 15.065(1) and chex 13.421(1) Å and for (2) 15.319(3) and 13.522(4) Å. Final R. and Rw values 0.044 and 0.049 for (1) and 0.040 and 0.037 for (2) for 668 and 1153 statistically significant reflections respectively.The complexes are isostructural. The metal centres are in a distorted octahedral environment, the distortion arising from the restricted bite distance of the xanthate ligands. For each compound, each xanthate moiety chelates the metal atom with similar M-S bonds. 相似文献
Bimuth(III) complexes with 1,4,7,10-tetrakis(2-pyridylmethyl)-1,4,7,10-tetraazacyclododecane have been prepared in dichloromethane and ethanol and investigated. These complexes have been characterized structurally by X-ray diffraction and NMR-2D studies. They present different coordination scheme depending on the reaction conditions: according to the nature of solvent, bismuth coordinates from six to eight nitrogen atoms and forms in the solid state a chiral structure which is maintained in solution. 相似文献
Some new chromium(III) complexes with nucleotides were obtained. For 5′ AMP derivatives, different stoichiometries were observed for the complexes obtained at pH = 2, 3.5 and 5–7. The results provide more insight on the biological role of chromium(III). 相似文献
Manganese phthalocyanine-substituted cytochrome c has been prepared by the reaction of Mn(III) tetrasulfonated phthalocyanine with apocytochrome c in acetate buffer, pH 5.8. Its structure and properties have been investigated by difference spectroscopy, circular dichroism (cd), electron paramagnetic resonance (epr), electrophoresis, molecular weight estimation, and potentiometric measurements. The epr and spectroscopic data show that the manganese phthalocyanine-substituted cytochrome c represents the low spin, six-coordinated. Mn(Ill) complex with the metal ion in the plane of the phthalocyanine ring. The sixth ligand, which is coordinated axially to the metal ion, is probably the methionine-80. Electrophoresis and molecular weight studies show this complex to be a monomer. As is shown by cd experiments, Mn(III)L-apocyt has a more ordered structure than that of apocytochrome c. Its conformation is, however, significantly altered compared to native cytochrome c. The manganese(III)-phthalocyanine complex is able to combine with cyanide. The cyanide derivative gives a stable reduced form upon dithionite reduction. If, however, Mn(IlI)Lapocyt is reduced with dithionite before addition of cyanide, it loses its ability to coordinate with cyanide. Nitric oxide reacts with the manganese(III) complex to form, in all probability, the nitrosyl derivative. The half-reduction potential of Mn(IlI)L-apocyt is about +400 mV, and the complex is reduced by cytochrome c. Spectroscopic data suggest that the mechanism of this process is complicated. 相似文献
The preparation of well-defined adducts of the M(guH)(2Cl3 (M = Cr, Fe) and VO(guH)Cl2 types (guH = neutral guanine), by refluxing ligand and metal chloride mixtures in ethanol-triethyl orthoformate, is reported. Characterization studies suggest that the new complexes are probably linear chain-like polymeric species, involving single bridges of bidentate guH ligands between adjacent metal ions. Bidentate bridging guH is most probably coordinated through the N(7) and N(9) imidazole nitrogens. The chloro ligands present in the adducts are exclusively terminal. Infrared evidence rules out the possibility of coordination of guanine through either of its exocyclic potential binding sites (i.e., CO oxygen and NH2 nitrogen) [1]. 相似文献
The lanthanide ion catalyzed trans-cis isomerizations of trans-bis(oxalato)diaquochromate(II) and trans-bis(malonato)diaquochromate(III) have been studied. A linear free energy relationship was found correlating the catalytic rate constants for the oxalate reaction with the corresponding formation constants of complexes formed between simple monocarboxylic acids and the light (LaGd) members of the lanthanide series. The results indicates that for this portion of the series, the reaction mechanism is related to the formation of monocarboxylate complex intermediates. When the ionic radius of the lanthanide ion decreases below a particular value (as in the latter half of the series), the metal ion remains coordinated to both carboxylates of the oxalate ion rather than simply binding to only one carboxylate. In either situation, isomerization to the cis product eventually occurs, and the lanthanide ion is released.The reaction rates associated with the trans-bis(malonato)diaquochromate(III) reaction were found to be significantly slower than those of the corresponding oxalate system. However, in the malonate system, no linear free energy relationship was found relating the catalytic rate constants with the corresponding formation constants of monocarboxylic acids. One does find a linear relationship between the catalytic rate constants for the malonate reaction and the log K1 values for the corresponding lanthanide/malonate complexes. During the course of the trans-cis isomerization, the lanthanide ion chelates the dissociated malonate group of a pentavalent Cr(III) intermediate. In the mechanism the lanthanide ion does not aid in ring opening, and neither does it singly bond to the intermediate 相似文献
New La(III) and Dy(III) complexes of deprotonated 4-hydroxy-3[1-(4-nitrophenyl)-3-oxobutyl]-2H-1-benzopyran-2-one (Acenocoumarol) were synthesized and characterized using FT-IR, FT-Raman, 1H NMR spectra, and elemental analyses. The ligand and its lanthanide(III) complexes were tested for their cytotoxic/cytostatic activity against two tumor cell lines and peritoneal mouse macrophages. The La(III) and Dy(III) complexes exhibit good activity against melanoma B16 and fibrosarcoma L929 and they are stronger inhibitors of tumor cell proliferation compared to the ligand without influencing normal cell viability and NO release by mouse peritoneal macrophages. 相似文献
We have previously shown that ristocetin, an activator of glycoprotein Ib/IX/V, induces release of soluble CD40 (sCD40) ligand via thromboxane (TX) A(2) production from human platelets. In the present study, we investigated the effect of antithrombin-III (AT-III), an anticoagulant, on the ristocetin-induced glycoprotein Ib/IX/V activation in human platelets. AT-III inhibited ristocetin-stimulated platelet aggregation. The ristocetin-induced production of 11-dehydro-TXB(2), a stable metabolite of TXA(2), and the release of sCD40 ligand were suppressed by AT-III. AT-III also reduced the ristocetin-stimulated secretion of platelet-derived growth factor (PDGF)-AB. AT-III failed to affect U46619-, a TXA(2) receptor agonist, induced levels of p38 mitogen-activated protein kinase phosphorylation or sCD40 ligand release. AT-III reduced the binding of SZ2, a monoclonal antibody to the sulfated sequence in the α-chain of glycoprotein Ib, to the ristocetin-stimulated platelets. These results strongly suggest that AT-III reduced ristocetin-stimulated release of sCD40 ligand due to inhibiting TXA(2) production in human platelets. 相似文献
To study the effect of chelation of iron ions by quinones on the generation of OH radicals in biological redox systems, we have synthesized quinones that can form complexes with Fe(III) ions: 2-phenyl-4-(butylamino)naphtho[2,3-h]quinoline-7,12-dione (Qbc) and 2-phenyl-4-(octylamino)naphtho[2,3-h]quinoline-7,12-dione (Qoc). A quinone with a similar structure without chelating group was synthesized as a control sample: 2-phenyl-5-nitronaphtho[2,3-g]indole-6,11-dione (Qn). Using optical spectroscopy, we determined the stability constant of Qbc with Fe(III) [Ks = (7 +/- 1) x 10(18) M-3] and the stoichiometry of the complex Fe(Qbc)3 in chloroform solutions. One-electron reduction potentials of Qbc, Qn, and adriamycin in dimethyl sulfoxide were measured by cyclic voltammetry. In the presence of Fe(III) the one-electron reduction potentials shifted toward positive values by 0.16 and 0.1 V for Qbc and adriamycin, respectively. Using the spin trap 5,5'-dimethyl-1-pyroline N-oxide (DMPO) and EPR, it was found that Qbc in the Fe(III) complex stimulated the formation of OH radicals in the enzymatic system consisting of NADPH and NADPH-cytochrome P-450 reductase more efficiently than adriamycin and quinone Qn. This is indicated by the absence of a lag period in the spin adduct appearance for Qbc and by a significantly higher rate of the spin adduct production, as well as by a larger absolute concentration of the spin adduct obtained for Qbc in comparison with Qn in the presence of Fe(III).(ABSTRACT TRUNCATED AT 250 WORDS) 相似文献
The crystal structures of the title compounds Sb(C9H6NO)2(S2COC2H5) (1) and Sb(S2COC2H5)3 (2) have been determined by three dimensional X-ray diffraction techniques and refined by a least squares method; final R 0.049 for 2911 reflections [I ? 3σ(I)] for (1) and R 0.047, Rw 0.046 for 846 reflections [I ? 2σ(I)] for (2). Crystals of (1) are triclinic, space group P1, a = 10.825(2), b = 11.131(2), c = 8.911(1) Å, α = 109.45(1), β = 95.92(1) and γ = 93.02(1)° with Z = 2. Crystals of (2) are rhombohedral, space group R, arhomb = 10.138(3) Å and α = 103.43(2)°. The environment of the Sb atom in (1) is based on a pentagonal bipyramidal geometry consisting of the six donor atoms of the three chelating ligands and a stereochemically active lone-pair of electrons which occupies the remaining axial position. The xanthate ligand chelates the Sb atom almost symmetrically with two long SbS bonds of 3.059(2) and 3.171(2) Å. In contrast the xanthate ligands in (2) chelate the Sb atom with asymmetric SbS bonds of 2.511(2) and 3.002(3) Å. 相似文献
Complexes of the type [Al(HL)(OH)Cl(2)], [M(HL)(OH)(2)Cl] and [M'(HL)(L')(OH)Cl], where HL = 5-iodouracil; HL' = histidine; M = Cr(III), Fe(III) and M' = Al(III), Cr(III), Fe(III), were synthesized and characterized. The complexes are polymeric showing high decomposition points and are insoluble in water and common organic solvents. The mu(eff) values, electronic spectral bands and ESR spectra suggest a polymeric 6-coordinate spin-free octahedral stereochemistry for the Cr(III) and Fe(III) complexes. 5-Iodouracil acts as a monodentate ligand coordinating to the metal ion through the O atom of C((4)) = O while histidine through the O atom of -COO(- ) and the N atom of -NH(2) group. In vivo antitumour effect of 5-iodouracil and its complexes was examined on C(3)H /He mice against P815 murine mastocytoma. As evident from their T/C values, Cr(III) and Fe(III) complexes display significant and higher antitumour activity compared to the 5-iodouracil ligand. The in vitro results of the complexes on the same cells indicate that Cr(III) and Fe(III) complexes show higher inhibition on (3)H-thymidine and (3)H-uridine incorporation in DNA and RNA replication, respectively, at a dose of 5 microg/mL. 相似文献