The preparation of carrier-free102Rh and102m Rh

Long-lived rhodium radionuclides were produced by the following reactions:¹⁰³Rh(n, 2n)^102(m)Rh;¹⁰³Rh(γ,xn)¹⁰⁰Rh,¹⁰¹Rh,^102(m)Rh;¹⁰⁴Pd(d, α)^102(m)Rh; Ru(d, n)⁹⁹Rh,^101(m)Rh,^102(m)Rh; and . The average cross-section of the¹⁰³Rh(n, 2n)¹⁰²Rh reaction in a fission neutron spectrum is about 0.75 mb. Irradiation of rhodium in the bremsstrahlung spectrum of 50 MeV electrons yielded a¹⁰²Rh activity of 0.11 μCi/g after 3 days at a power of 2 kW. The thick target yield of the reaction¹⁰⁴Pd(d, α)¹⁰²Rh was 0.002 μCi/μAh for 12 MeV deuterons. The thick target yield of the reaction Ru(d,xn)¹⁰²Rh was 0.05 μCi/μAh for 12 MeV deuterons and 4.8 μCi/μAh for 18 MeV deuterons. The best yield was obtained by deuteron bombardment of ruthenium. The chemical separation of carrier-free Rh radionuclides from deuteron-irradiated ruthenium is described, with a chemical yield better than 90%. The same procedure has also been applied for the isolation of¹⁰⁵Rh from neutron-irradiated ruthenium. γ-Ray spectra of⁹⁹Rh,^101(m)Rh and^102(m)Rh from deuteron-irradiated ruthenium and of¹⁰⁵Rh from neutron-irradiated ruthenium, taken with a Ge(Li) detector, are shown; a number of γ-rays, not reported in the literature, were observed. The γ-ray energies were determined with a precision of ca. 0.3–0.4 keV.     

Measurement of activation cross sections of the proton induced nuclear reactions on palladium

Excitation functions of proton induced reactions on Pd are important for medical radioisotope production, for activation analysis, for development of low activation materials and other purposes. No experimental data exist in the literature for low and medium energy range protons. A detailed study of the excitation functions was performed up to 80 MeV proton energy by using the stacked foil irradiation technique and gamma-ray spectrometry. The irradiations were carried out at the external beam lines of the AVF cyclotron at the Tohoku University. Japan (80 and 70 MeV) and the CGR 560 cyclotron at the Vrije Universiteit Brussels (38, 29 and 17 MeV). The beam intensity, the incident energy and the energy degradation were controlled by a method based on flux constancy via normalization to the parallel measured excitation functions of ^natAl(p,x)^22,24Na and ^natCu(p,x)^56,58Co, ^62,65Zn monitor reactions. Excitation functions for direct and cumulative cross sections have been measured for the production of ^{105mg,106m,110m}Ag, ¹⁰¹Pd, ^101mRh and ⁹⁷Ru radionuclei. Calculations for the excitation functions using the Alice-IPPE code were performed with a view to estimate the weight of the different contributing reactions and to check the trend and the magnitude of the obtained experimental data.     

Isobaric yields and radiochemistry of near-target residues in the interaction of 12C and 16O with 103Rh at an incident energy of 400 MeV

Production cross sections of residues with mass near to that of the target were measured in ¹²C and ¹⁶O induced reactions on Rh at an incident energy of 400 MeV. An ion-exchange method has been developed for the separation of Rh, Pd and Ag nuclides from all other produced activities. Rh and Ag nuclides were separated from elements such as Pd, Ru, and Tc, amongst others, on an AG1-X8 anion exchange resin in 6M HCl. The Ag nuclides were then removed from the effluent using a precipitation technique so that only Rh remained in the final solution. The Pd was afterwards separated from Ru and Tc by eluting it from the resin with 5% ammonia solution. This procedure made it possible to accurately measure production cross sections for ^103mRh and ¹⁰³Pd. Cross sections for the production of various other observed residues are also presented. The results are consistent with an enhanced isobaric yield in the near-target mass region. The radiochemical separation technique is also suitable for the routine production of Pd and Rh nuclides, e.g., ¹⁰³Pd and ^101mRh, in proton-induced reactions on Rh targets     

Separation of L-DOPA and four metabolites in plasma using a porous graphitic carbon column in capillary liquid chromatography

Summary A sensitive HPLC method with marbofloxacin (MAR) as internal standard and fluorescence detection is described for the analysis of ofloxacin (OFL) enantiomers in plasma samples. Plasma samples were prepared by adding phosphate buffer (pH 7.4, 0.1m), then extracted with trichloromethane.S-OFL,R-OFL, and the internal standard were separated on a reversed-phase column with water-methanol, 85.5∶14.5, as mobile phase. The concentrations ofS-OFL andR-OFL eluting from the column (retention times 7.5 and 8.7 min, respectively) were monitored by fluorescence detection withλ _ex = 331 andλ _em = 488 nm. The detection and quantitation limits were 10 and 20 ng mL⁻¹, respectively, forS-OFL and 11 and 21 ng mL⁻¹ forR-OFL. Response was linearly related to concentration in the range 10 to 2500 ng mL⁻¹. Recovery was close to 93% for both compounds. The method was applied to determination of the enantiomers of OFL in plasma samples collected during pharmacokinetic studies.     

Redetermination of several half-lives

The half-live of⁴¹Ar,^80mBr,^94mNb,¹⁰¹Mo,¹⁰¹Tc,¹⁰⁹Pd,^109mPd,¹²²Sb,^123mSn,^152mEu and²³⁹Np have been measured more accurately compared to previous measurements.     

Oxidation of Alcohols by [Cp*Rh(ppy)(OH)]+

Summary.  Rh(III) polypyridine complexes ([Cp ^*Rh(ppy)(H₂O)]²⁺; ppy = 2,2′-bipyridine, 2,2′-bipyridine-4,4′-dicarboxylate, o-phenanthroline, tetrahydro-4,4′-dialkyl-bis-oxazole) oxidize in organic or aqueous alkaline solution primary and secondary alcohols to aldehydes or ketones and are thereby reduced to the Rh(I) complexes Cp ^*Rh(ppy). The Rh(III) form can be regenerated byoxidants like pyruvate or oxygen, making the reaction quasi-catalytic. The reaction follows anautocatalytic pathway; hydrogen transfer from the α-CH₂ group of an alcoholate complex [Cp ^*Rh(ppy)(OR)]⁺ to Cp ^*Rh(I)(ppy) is suggested to yield the Rh(II) intermediate Cp ^*Rh(ppy)H as the key and rate determining step. The knowledge of Rh(III)/Rh(I) redox potentials allows to estimate the thermodynamic driving force of the reaction which is not more than about 300 mV.     

Cyclopalladated complexes of 2-phenylbenzothiazole with 4,4′-bipyridyl

Complexes [Pd(bt)(4,4′-bpy)OOCCH₃], [Pd(bt)NO₃]₂(m-4,4′-bpy), [Pd(bt)(m-4,4′-bpy)]₄(NO₃)₄ (bt⁻ is deprotonated form of 2-phenylbenzothiazole, bpy is 4,4′-bipyridyl) are prepared and characterized by ¹H NMR, electron absorption and emission spectroscopy, as well as by voltammetry. The upfield shift of the signal of proton in the ortho-position to the donor carbon atom of the cyclopalladated ligand in the complexes [(Δδ = −(1.1–1.5) ppm] is assigned to the anisotropic effect of the ring current of the pyridine rings of the 4,4′-bipyridyl moiety, which are orthogonal to the coordination plane. Characteristic longwave absorption bands λ = (387±4) nm and the low-temperature phosphorescence bands λ = (512±3) nm in the complexes are assigned to the chromophore {Pd(bt)} metal complex fragment. The reduction waves in the complexes [E _1/2 = −(1.54±0.04) and E _p = −(1.83±0.03) V] are assigned to the ligand-centered processes of the successive electron transfer to the π* orbitals localized predominantly on the coordinated pyridine components of the 4,4′-bipyridyl moiety.     

Separation ofN-carbamoyl aspartate andl-dihydroorotate from serum by high-performance liquid chromatography with fluorimetric detection

Summary A high-performance liquid chromatographic method, with 9-anthryldiazomethane as derivatizing agent, has been developed for the simultaneous determination ofN-carbamoyl aspartate andl-dihydroorotate in serum. Sample preparation for 1 mL serum was by simple liquid-liquid extraction and then derivatization. The compounds were separated on a Luna C18(2) column by use of a gradient prepared from acetonitrile and 10 mM sodium acetate buffer, pH 6.0, and fluorimetric detection was performed at excitation and emission wavelengths of 365 nm and 412 nm, respectively. The response was found to be linearly dependent on concentration between 0.8 and 60 μg mL⁻¹ forl-dihydrooratate and between 0.9 and 90 μg mL⁻¹ forN-carbamoyl aspartate; the mean recovery rates were 50 and 51%, respectively. The limits of detection and quantification were 0.33 μg mL⁻¹ and 0.6 μg mL⁻¹, respectively, forl-dihydroorotate and 0.4 μg mL⁻¹ and 0.7 μg mL⁻¹ forN-carbamoyl aspartate. This method can be used to assess accumulation ofN-carbamoyl aspartate andl-dihydroorotate in body fluids in situations where cellular pyrimidine de novo synthesis is impaired.     

Reactions of chiral phosphoramidites with complexes Pd(COD)Cl2 and Pt(COD)Cl2

Reactions of phosphoramidites based on (−)-ephedrine and [(1S)-endo]-(−)-borneol with the complexes M(COD)Cl₂ (M is Pd or Pt, and COD is cycloocta-1,5-diene) were studied. The formation ofcis andtrans complexes of the general formulas MCl₂L₂ and M₂Cl₂(μ-Cl)₂L₂ was observed. The structures of the resulting compounds were established by³¹P,¹³C, and¹⁹⁵Pt NMR and IR spectroscopy and by plasma desorption mass spectrometry. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1627–1630, August, 1998.     

NMR studies of transformations of Pt(II) and Pd(II) complexes with amino acids in solution. 1. Glycine complexes

¹H,¹³C, and¹⁹⁵Pt NMR studies were performed for Pt(ll) and Pd(II) complexes with glycine cis- and trans-M(Gly)₂, trans-Pd(GlyH)₂Cl₂ , cis- and trans-Pt(GlyH)₂Cl₂ , Na[Pd(GIy)Cl₂], and K[Pt(Gly)CI₂] in donor type solvents DMSO and H₂O. It is shown that a cis ↔ trans equilibrium takes place in these solvents and that the equilibration rate is low for Pt(II) complexes and high for Pd(II) complexes. Therefore, the cis- and trans-complexes of Pt(II) may be recorded by NMR spectroscopy in the individual state, whereas for Pd(II) there is an equilibrium mixture of cis- and trans-isomers. Solvolysis of Cl-containing complexes in DMSO is studied. A mechanism of solvolysis involving eis ↔ trans isomerization of the dichloro complexes of Pd(II) is suggested. NMR spectral data for some solvolysis products are given. Translated fromZhurnal Strukturnoi Khimii, Vol. 41, No. 2, pp. 300–311, March–April, 2000.     

Preconcentration of noble metals on a polymer support as complexes of organic reagents and their subsequent determination in the solid phase

Conditions of the sorption preconcentration of Pt, Pd, Au, Ag, and Hg as colored complexes of azorhodanines, tyrodine, and sulfonitrophenol M from acidic solutions (pH 0–2) on a polyamide membrane in the flow mode are determined. At a flow rate of 10–20 mL/min, concentrations of determined elements of 10^-9-10^-7 M, and pressure of 10–20 mm Hg, the complexes are nearly quantitatively sorbed on a polyamide membrane disk (d = 1 cm,m = 2.7 mg, andl = 0.1 mm). The influence of the composition of the test solutions on the formation of the analytical signal in the solid phase is studied. Rapid sorption-spectrometric procedures are developed for the determination of Pt, Pd, Au, Ag, and Hg with the detection limit 5–30 ng of the element in the sorbent zone     

Transition-Metal Complexes with Nano-Sized Phosphine and Pyridine Ligands-Catalysis,Fluxional Behavior and Molecular Recognition

Nano-sized phosphine and pyridine ligands having tetraphenylphenyl-, m-terphenyl-, poly(benzylether) moieties were synthesized. These ligands showed a remarkable effect on homogeneous transition metal catalyzed reactions. Pd(II) complexes with tetraphenylphenyl substituted pyridine ligands show high catalytic activities for oxidation of ketones suppressing Pd black formation and maintains the catalytic activity for a long time. Rh(I) complex catalysts with m-terphenyl substituted phosphine ligands showed remarkable rate acceleration in the hydrosilylation of ketones. In addition, several phosphinocalixarene ligands were synthesized and their coordination studies with Pd(II), Pt(II), Ru(II), Ir(I), and Rh(I) metals were documented. Ir(I) and Rh(I) cationic complexes with a 1,3,5-triphosphinocalix[6]arene ligand showed dynamic behavior with size-selective molecular recognition.     

Rh(III), Pd(II), Pt(IV) and Au(III) complexes of 2-thiopyrimidine derivatives

Some news thiopyrimidine derivatives and complexes [4-amino-5-nitroso-6-oxo-1,2,3,6-tetrahydro-2-thio-pyrimidine (TANH), its 2-methylthio derivative (MTH), the ammonium salt ofTANH (sTANH) and six new complexes of formulas: Rh(MT)₂Cl · 2H₂O, Pd(MTH)₂Cl₂, Pt(MTH)₂Cl₄, Au(MTH)Cl₃ Pd(TANH)₂Cl₂ and Au(TAN ^–)Cl] have been synthesized and characterized by elemental analysis, IR and¹H-NMR spectroscopy techniques. The thermal behaviour of all compounds has also been studied.

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Rh(III), Pd(II), Pt(IV) und Au(III) Komplexe von 2-Thiopyrimidin Derivaten

Zusammenfassung Es wurden einige neue Thiopyrimidinderivate und deren Komplexe synthetisiert und mittels Elementaranalyse, IR und¹H-NMR charakterisiert: 4-Amino-5-nitroso-6-oxo-1,2,3,6-tetrahydro-2-thio-pyrimidin (TANH), dessen 2-Methylthio-Derivat (MTH), das Ammoniumsalz vonTANH (sTANH) und sechs neue Komplexe der Formeln Rh(MT)₂Cl · 2H₂O, Pd(MTH)₂Cl₂, Pt(MTH)₂Cl₄, Au(MTH)Cl₃, Pd(TANH)₂Cl₂ und Au(TAN ^–)Cl. Das thermische Verhalten der Verbindungen wurde ebenfalls untersucht.

     

Some transition metal complexes of new terdentate ligands: Bis[2-(diphenylphosphino)ethyl]benzylamine and bis[2-(diphenylarsino)ethyl)benzylamine

Complexes of the terdentate ligands bis[2-diphenylphosphino)ethyl]benzylamine (DPBA) and bis[2-(diphenylarsino)ethyl]benzylamine (DABA) with Co(II), Ni(II), Pd(II), Pt(II), Rh(III), Ir(III), Rh(I) and Ir(I) are reported. The ligand DPBA reacts with Co(II) ion to form two types of complexes: a high-spin, paramagnetic, tetrahedral Co(II) complex of composition [CoCl(DPBA)]Cl and a low-spin, paramagnetic, square-planar complex of composition [CoBr(DPBA)]B(C₆H₅)₄. The reaction of DPBA with Ni(II) ion in methanol yields low-spin, diamagnetic, square-planar complexes of type [NiX(DPBA)]Y [X = Cl, Br or I; Y = Cl or B(C₆H₅)₄]. Four-coordinate, square-planar, cationic complexes of type [MY(L⁺[M = Pd(II), Pt(II), Rh(I) or Ir(I); Y = Cl or P(C₆H₅)₃; L = DPBA or DABA], were obtained on reaction of L with various starting materials containing these metal ions. Reaction of DPBA and DABA with rhodium and iridium trichlorides gave octahedral, neutral complexes of general formula [MCl₃(L)] (M = Rh or Ir, L = DPBA or DABA). All the complexes were characterized on the basis of their elemental analysis, molarconductance data, magnetic susceptibilities, electronic spectra, IR spectral measurements, and¹H and³¹P-{¹H} NMR spectral data.     

Spectrophotometric and derivative spectrophotometric study of the reaction of palladium (II) and rhodium (III) with 5-(3,4-methoxyhydroxybenzylidene)rhodanine and cationic surfactants

Spectrophotometric and derivative spectrophotometric methods for the determination of Pd(II) and Rh(III) are proposed. Pd(II) forms with 5-(3,4-methoxyhydroxybenzylidene)rhodanine [3,4-MHBR], in the absence and presence of cetylpyridinium bromide [CPB], 14 binary and 134 ternary complexes having molar absorptivities of 5.77 × 10⁴ and 7.46 × 10⁴ M ^–1cm^–1 at 525 and 530 nm, respectively. Rh(III) forms a 14 complex with 3,4-MHBR in the presence of cetyltrimethylammonium bromide [CTAB], which gives a maximum absorbance at 445 nm with a molar absorptivity of 5.13 × 10⁴ M ^–1cm^–1. Derivative spectrophotometric methods are employed for the determination of Pd(II) and Rh(III) at ng ml^–1 levels utilizing these complexes. Under the optimum conditions the calibration lines for Pd(II) and Rh(III) determination fit the equations d⁴ A/d⁴ = 1.10 × 10⁶ [Pd] – 0.018 (r = 0.9967) and d⁴ A/d⁴ = 2.25 × 10⁶ [Rh] + 0.03 (r = 1.0426) and have detection limits of 5.6 and 1.2 ng ml^–1, respectively. The influences of experimental variables and foreign ions are studied. The methods are free of interference from most common metal ions and anions. The results of the analysis of some synthetic mixtures of Pd(II) and Rh(III) are reported.     

Accurate values for the nonrelativistic energies of the lowest singlet and triplet S-states of the4He-Isotop

Accurate lower and upper bounds for the nonrelativistic lowest energies¹ E ₀ and³ E ₀ of the singlet and triplet-system of the⁴He-Isotop are calculated with the linearized method of variance minimization. The same was done for¹ E ₁ the energy of the first excitedS-state 2¹ S. The results especially for¹ E ₀ and³ E ₀ in a.u. are −2.9033076997₅ ≤¹ E ₀ ≤ −2.9033076921₈ −2.1749324263₇ ≤³ E ₀ ≤ −2.1749324245₉ i.e. the values are determined with an absolute error smaller than 0.00167 cm⁻¹ for¹ E ₀ and 0.00039 cm⁻¹ for³ E ₀.     

Synthesis and biological evaluation of novel 99mTc‐oxo and 99mTc‐tricarbonyl complexes with C3′‐functionalized thymidine dithiocarbamate for tumor imaging

A novel C3′‐functionalized thymidine dithiocarbamate derivative (3’DTC‐TdR) was successfully synthesized and labelled using [^99mTcO]³⁺ core and [^99mTc(CO)₃(H₂O)₃]⁺ core with high yields. The structures of the ^99mTc complexes were verified by preparation and characterization of the corresponding stable rhenium complexes. Both of the complexes were lipophilic and stable in vitro. Cell internalization experiments indicated that the uptakes of ^99mTcO‐3’DTC‐TdR were related to nucleoside transporters. Biodistribution of these complexes in mice bearing tumor showed that they had high tumor uptakes, good tumor/muscle ratios and tumor/blood ratios. Especially for ^99mTcO‐3’DTC‐TdR, it exhibited the highest tumor/muscle ratio and tumor/blood ratio at 4 h post‐injection. SPECT/CT imaging studies indicated clear accumulation in tumor, suggesting ^99mTcO‐3’DTC‐TdR would be a promising candidate for tumor imaging.     

Thermochemical studies for determination of the molar enthalpy of formation of aniline derivatives

The standard (p ^o=0.1 MPa) molar enthalpies of combustion atT=298.15 K were measured by static bomb combustion calorimetry for liquidN,N-diethylaniline,N,N-dimethyl-m-toluidine,N,N-dimethyl-p-toluidine, andN-ethyl-m-toluidine. Vaporization enthalpies forN,N-dimethyl-m-toluidine andN-ethyl-m-toluidine were determined by correlation gas chromatography. Derived standard molar values of _f H _m ^o (g) at 298.15 K forN,N-diethylaniline (62.1±7.6);N,N-dimethyl-m-toluidine (72.6±7.3),N,N-dimentyl-p-toluidine (68.9±7.4),N-ethyl-m-toluidine (30.5±3.8 kJ· mol^–1) were obtained.     

Palladium(II) complexes with 1-allyl-3-(2-pyridyl)thiourea: Synthesis and spectroscopic characterization

New Pd(II) complexes with 1-allyl-3-(2-pyridyl)thiourea (APTU) of the formulas [Pd(C₉H₁₁N₃S)Cl₂] (I) and [Pd(C₉H₁₁N₃S)₂]Cl₂ (II) were obtained and examined by UV-Vis, IR, and 1H NMR spectroscopy. The conditions for the complexation reactions were optimized. The instability constants and molar absorption coefficients of these complexes were calculated. Comparison of the characteristic bands in the UV-Vis and IR spectra of the complexes and free APTU revealed that the ligand in both complexes is coordinated to the metal atom in the thione form in the bidentate chelating mode through the S atom of the thiourea group and the pyridine N atom. In the UV-Vis spectra of the complexes, the charge transfer bands (π → π* Py) and n → π* (C=N_Py), (C=S) experience hypsochromic shifts by 450–470 cm⁻¹ caused by the coordination of APTU to the metal ion, which gives rise to ligand-metal charge-transfer bands (C=N_Py → Pd, n → π* (C=S)) and (SPd). The protons in the 6-, 4-, and 3-positions of the pyridine ring and the thiourea NH proton in the chelate ring are most sensitive to the complexation.     

Nuclear charge distribution in the spontaneous fission of252Cf: Determination of fractional cumulative yields of133mTe and133gTe

The fractional cumulative yields (FCY) of^133mTe and^133gTe in the spontaneous fission of²⁵²Cf were measured for the first time by a radiochemical method. The values ofFCY are 0.533±0.014 and 0.291±0.042 for^133mTe and^133gTe, respectively. The isomeric state to ground state fractional independent yield (FIY) ratio of¹³³Te,R, was found to be 3.5. The root-mean-square angular momentum of the primary fragment corresponding to the fission product¹³³Te, Jr.m.s.=8.8h, was estimated according to a simple one-parameter statistical model. The fractional cumulative yields from this work together with other literature data in the mass region A=131–141 are compared with the normal yields given by the empiricalZ _p model by Whhl. It suggests that both theN=82 neutrons shell and nucleus pairing effects are not apparent for the spontaneous fission of²⁵²Cf.