Kinetics of the mediatory reduction ofgem-dichlorocyclopropanes

The effect of the nature of organic electron transfer agents and of Pt^II, Pd^II, Rh^II, Co^II, Ni^II, Cu^II, Cr^III, Mn^II, Ti^III, V^III, Zn^II, and Ag^I metal ions on the kinetics of the homogeneous reduction ofgem-dichlorocyclopropanes has been studied. Pt^II, Pd^II, Rh^III, Co^II, and Ni^II ions accelerate this process, V^III and Ag^I ions exert practically no effect on the reduction rate, and the rest of the metal ions exhibit inhibitor properties.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1407–1410, August, 1993.     

Multielement (H,C, N,O, S) stable isotope characteristics of lamb meat from different Italian regions

The study focuses on the ²H/H, ¹³C/¹²C, ¹⁵N/¹⁴N, ¹⁸O/¹⁶O and ³⁴S/³²S values of defatted dry matter (DFDM) and on the ²H/H, ¹³C/¹²C and ¹⁸O/¹⁶O values of the fat fraction of meat samples from various lamb types reared in seven Italian regions, following different feeding regimes (forage, concentrate, milk). The ¹³C/¹²C (r = 0.922), ²H/H (r = 0.577) and ¹⁸O/¹⁶O (r = 0.449) values of fat and DFDM are significantly correlated, the fat values being significantly lower for C and H and higher for O than for DFDM values and the differences between the two fractions not being constant for different lamb types. The feeding regime significantly affected the ¹³C/¹²C, ¹⁵N/¹⁴N, ¹⁸O/¹⁶O and ²H/H of fat. The DFDM ²H/H, and ¹⁸O/¹⁶O values, excluding an outlier, are significantly correlated with the corresponding values in meteoric waters, thus allowing us to trace the variability of geoclimatic factors. ¹⁵N/¹⁴N is influenced by pedoclimatic conditions, whereas ³⁴S/³²S is influenced by the sea spray effect and the surface geology of the provenance area. By applying stepwise linear discriminant analysis only the ²H/H of fat was found not to be significant and 97.7% of the samples were correctly assigned to the lamb type and more than 90% cross‐validated. With the feeding regime, 97.7% of the samples were both correctly assigned and cross‐validated using a predictive model including ¹³C/¹²C, ¹⁵N/¹⁴N, ¹⁸O/¹⁶O, ³⁴S/³²S of DFDM and ¹⁸O/¹⁶O of fat. Copyright © 2009 John Wiley & Sons, Ltd.     

The development of nuclear microprobe techniques for the spatial determination of13C and13C/12C ratios

Sensitive and selective nuclear reaction methods have been sought for the nuclear microprobe measurement of the spatial distributions of¹³C and¹³C/¹²C ratios. The¹³C(α, n)¹⁶O reaction, with neutron detection, is the most selective for¹³C, and has a sensitivity of ca. 100 ppm. The reactions¹³C(d, p)¹⁴C and¹²C(d, p)¹³C, with proton detection, are the most sensitive for the simultaneous measurement of¹³C and¹²C, with detection limits of 30 and 2 ppm respectively. Less sensitive alternative reaction pairs are;¹³C(³He, p)¹⁵N and¹²C(³He, p)¹⁴N;¹³C(d, nγ)¹⁴N and¹²C(d, pγ)¹³C;¹³C(³He, pγ)¹⁵N and¹²C(³He, pγ)¹⁴N. The conditions governing their use, particularly light element interferences, are detailed.     

The spectrophotometric and titrimetric determination of gold with ferroin as reagent

A spectrophotometric and a photometric titration method in a two-phase system for the determination of gold with ferroin is reported. Both methods are rapid and reproducible with an accuracy of ±1%. In the spectrophotometric determination Co²⁺, Cu²⁺, Ni²⁺ , Fe³⁺, Zn²⁺, Mn²⁺ and Cr³⁺ do not interfere with the determination of gold and Pt⁴⁺, Pd²⁺, Hg²⁺, Ir⁴⁺ and Os⁴⁺ can be tolerated up to a ratio of 1:1. The titrations can also be carried out in the presence of a number of diverse ions, e.g. Ni²⁺, Cu²⁺, Co²⁺, Fe³⁺, Zn²⁺, Cr³⁺, Mn²⁺, without interference; the platinum metals and Hg²⁺ cause interference but, by the use of the spectrophotometric procedure, this can be reduced.     

Studies on the structure-activity relationship of delta-sleep inducing peptide

DSIP and its fourteen analogs as well as three short peptides were synthesized by solid phase method. The design of the analogs was based on the consideration of the introduction of D-amino acid into the molecules to inhibit the enzymatic hydrolysis and the introduction of amino acids with a hydrophobic side chain. The modification was placed on the position of 1, 3, 4, 5, 8 and 9, e.g. D- Trp¹, Tyr¹, Tyr¹ Phe⁵, D-Trp¹ Phe⁸, Trp^3,4, D-Trp^1,3,4 Phe⁸, D-Trp3^,4 Phe⁸ D-Glu⁹, D-pF-Phe^3,4 Phe⁸ D-Glu⁹, Phe⁵, Glu⁵ Asp⁹, Tyr⁶ Asp⁹, Asp⁹ and Ala⁷-DSIP as well as Trp-Ala-Gly-Gly-Asp, Trp-Ala-Gly-Gly-Glu and Trp-Gly-Glu. DSIP and Phe⁵-DSIP were also prepared by pentafluorophenyl ester method. The purity of the synthetic peptides was checked by amino acid analysis, elemental analysis, thin layer chromatography and paper electrophoresis. The biological assay showed that the analogs of D-Trp¹, Tyr¹, Tyr¹ Phe⁵ and Ala⁷-DSIP as well as three short peptides were inactive whereas Phe⁵-DSIP showed similar activity as that of synthetic DSIP.     

Production of charge-induced X-rays during PIXE studies using light and heavy ion-beams

A recently discovered phenomenon of excessively high X-ray production is discussed. The high yield is attributed to the build-up of potential on non-conducting targets irradiated with accelerated ion beams, and the subsequent discharge. Ion-beams of¹H⁺,¹H₂ ⁺,²H⁺,²H₂ ⁺,³He⁺,³He²⁺,⁴He⁺,¹⁴N⁺,¹⁴N²⁺,¹⁶O⁺ and²⁰Ne⁺ were used. A new mechanism of X-ray excitation is proposed. The increased X-ray fluxes produced by this process are suitable for analytical applications of high specificity. The mechanism of excitation associated with the process, factors affecting the high X-ray yields, applications and a general overview of the studies undertaken with the various ion beams are given.     

Fe3+和Fe2+对原代培养的成骨细胞增殖、分化和矿化功能的影响

采用噻唑蓝(MTT)法、碱性磷酸酶(ALP)比活性测定、油红O染色和茜素红染色及定量分析,研究了不同浓度的Fe3+和Fe2+对原代培养的成骨细胞增殖、分化及矿化功能的影响.结果表明:浓度为1×10-9～1×10-4 mol·L-1的Fe3+和Fe2+促进成骨细胞增殖,但是在较高浓度1×10-3 mol·L-1时,它们则抑制成骨细胞增殖.与成骨细胞作用48 h,浓度为1×10-8～1×10-4 mol·L-1的Fe3+和Fe2+抑制其分化,但在较低的浓度1×10-9 mol·L-1时则对其分化没有影响:进一步延长作用时间为72 h,Fe3+对成骨细胞分化没有影响,除1×10-6mol·L-1浓度的Fe2+促进成骨细胞分化外,其他浓度的Fe2+则抑制其分化;测试浓度下的Fe3+对成骨细胞向脂肪细胞的横向分化表现为抑制或没有影响,而Fe2+的影响则依赖于浓度和作用时间.在1×10-8～1×10-5mol·L-1浓度范围内,Fe3+和Fe2+对矿化结节的影响表现出相反的效应.在较高浓度(1×10-4mol·L-1)下,它们促进矿化节结的形成,而在较低浓度(1×10-9mol·L-1)下,Fe3+抑制矿化节结的形成,Fe2+则没有影响.结果提示:浓度.作用时间和铁离子的价态都是影响Fe3+和Fe2+生物效应(从毒性到活性,从损伤到保护,从上调到下调)转变的关键因素.     

脯氨酸类N-酰胺衍生物的核磁共振研究

脯氨酸类衍生物结构独特,鲜有报道利用核磁共振（nuclear magnetic resonance,NMR）技术对氨基酸的手性进行鉴别.利用多种NMR技术:1H NMR、1H-1H同核位移相关谱（1H-1H COSY）、1H-1H质子全相关谱（1H-1H TOCSY）、1H-1H核Overhauser效应谱（1H-1H NOESY）、13C NMR、无畸变的极化转移增强法（DEPT135°）、1H-13C检出1H的异核单量子相干（1H-13C HSQC）和1H-13C检出1H的异核多键相关（1H-13C HMBC）,对脯氨酸类N-酰胺衍生物两种构象异构体的1H和13C NMR进行了全归属,确定了室温下在二甲基亚砜（DMSO）中L型和D型的顺反异构体以相同的比例同时存在.     

Radioactivity of coals and fly ashes

The level and the behavior of the naturally occurring primordial radionuclides ²³⁸U, ²²⁶Ra, ²¹⁰Pb, ²³²Th, ²²⁸Ra and ⁴⁰K in coals and fly ashes are described. The activity concentrations of the examined coals and originated from coal mines in Greece ranged from 117 to 435 Bq·kg⁻¹ for ²³⁸U, from 44 to 255 Bq·kg⁻¹ for ²²⁶Ra, from 59 to 205 Bq·kg⁻¹ for ²¹⁰Pb, from 9 to 41 Bq·kg⁻¹ for ²²⁸Ra and from 59 to 227 Bq·kg⁻¹ for ⁴⁰K. These levels are comparable to those appeared in coals of different countries worldwide. The activity concentrations of the examined fly ashes and produced in coal-fired power plants in Greece ranged from 263 to 950 Bq·kg⁻¹ for ²³⁸U, from 142 to 605 Bq·kg⁻¹ for ²²⁶Ra, from 133 to 428 Bq·kg⁻¹ for ²¹⁰Pb, from 27 to 68 Bq·kg⁻¹ for ²²⁸Ra and from 204 to 382 Bq·kg⁻¹ for ⁴⁰K. The results showed that there is an enrichment of the radionuclides in fly ash relative to the input coal during the combustion process. The enrichment factors (EF) ranged from 0.60 to 0.76 for ²³⁸U, from 0.69 to 1.07 for ²²⁶Ra, from 0.57 to 0.75 for ²¹⁰Pb, from 0.86 to 1.11 for ²²⁸Ra and from 0.95 to 1.10 for ⁴⁰K.     

Synthesis of a Dithiocarbamate Chelate Resin and Its Oxidized form and Their Adsorption Properties for Heavy Metal Ions

A series of macroporous dithiocarbamate chelate resins, III and V, and an oxidized resin, VI, with high adsorption capacity were prepared. The influence of various reaction conditions of amination, dithiocarboxylation, and oxidation were examined. The structure and the conversion of functional groups of resins were confirmed by IR spectra and elemental analysis. The adsorption capacities of Resin II for Hg²⁺, Cu²⁺, Zn²⁺, and Cd²⁺ are 4.40, 2.44, 1.77, and 1.36 mmol/g, respectively. The adsorption capacities of Resins V and VI for Cu²⁺. Zn²⁺, Ni²⁺, Co³⁺, Ag⁺, Hg²⁺, Cd²⁺, Pb²⁺, and Au³⁺ are 4.07–0.51 and 3.81–0.59 meq ion/g, respectively. The adsorption rate and the influence of pH on the adsorption percentage of the resins for metal ions were examined. Noble metal, transitional metal, and heavy metal ions can be quantitatively adsorbed by the resins. The adsorbed Cu²⁺, Pb²⁺, Cd²⁺, Co³⁺, and Ni²⁺ can be quantitatively eluted with 5N HNO₃, and the presence of large amounts of Ca²⁺, Mg²⁺, Fe³⁺, and Al³⁺ did not interfere.     

Chelatbildung mit N-unsubstituierten 1.2-Diiminliganden

Fe^II, Co^III, Ni^II, Pd^II, and Rh^III chelates with the N-unsubstituted 1-2-diimine ligands benzildiimine and 9.10-phenanthrenequinonediimine have been prepared. The compounds are characterised chemically, spectroscopically (uv, vis, ir) and polarographically. The results indicate remarkable π-back bonding in the chelates. The unusual magnetic moments of the Fe^II, Co^III and Rh^III chelates are caused by temperature-independent paramagnetism. Fe^II, Co^III, Ni^II and Cu^II chelates of the partially deprotonated phenanthrenequinone diimine are obtained.     

Solvent extraction and spectrophotometric determination of uranium (VI)

Summary Solvent extraction of uranium-sodium diethyldithiocarbamate with ethylmethyl ketone and separation from titanium, zirconium, thorium, lanthanum and cerium has been described. It has been found that 11.75 to 47.00 mg of uranium can be extracted from a binary mixture containing 4.78 to 19.04 mg of titanium, 9.12 to 36.48 mg of zirconium, 116.0 to 460.0 mg of thorium, 6.95 to 27.8 mg of lanthanum or 7.06 to 28.24 mg of cerium at pH 3.0. The pH range between which the separations may be carried out successfully is 2.0 to 3.5. The following cations interfere in the separations: Cu^II, Fe^III, Co^II, Bi^III, Ni^II, Cr^VI, Te^IV, Se^IV, Ag^I, Hg^II, As^III, Sn^IV, Pb^IV, Cd^II, Mo^VI, Mn^II, V^V, Zn^II, In^III, Tl^I, W^VI, Os^VIII and Nb^V.

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Zusammenfassung Uran kann durch Extraktion als Diäthyldithiocarbamidat mit Methyläthylketon von Ti, Zr, Th, La oder Ce getrennt werden. Der günstigste pH-Bereich liegt zwischen 2,0 und 3,5. Die Trennungen wurden mit folgenden Mengen durchgeführt: U (11,75–47,00 mg); Ti (4,78 bis 19,04 mg), Zr (9,12–36,48 mg) Th (116,0–460,0 mg), La (6,95–27,8 mg), Ce (7,06–28,24 mg). Folgende Ionen verursachen Störungen: Cu^II, Fe^III, Co^II, Bi^III, Ni^II, Cr^VI, Te^IV, Se^IV, Ag^I, Hg^II, As^III, Sn^IV, Pb^IV, Cd^II, Mo^VI, Mn^II, V^VI, Zn^II, In^III, Tl^I, W^VI, Os^VIII sowie Nb^V.

     

Theoretical study of electronic structure of rhodium mononitride and interpretation of experimental spectra

Potential energy curves of 22 electronic states of RhN have been calculated by the complete active space second‐order perturbation theory method. The X¹Σ₀⁺ is assigned as the ground state, and the first excited state a³Π₀+ is 978 cm^?1 higher. The ¹Δ(I) and B¹Σ⁺ states are located at 9521 and 13,046 cm^?1 above the ground state, respectively. The B¹Σ⁺ state should be the excited state located 12,300 cm^?1 above the ground state in the experimental study. Moreover, two excited states, C¹Π and b³Σ⁺, are found 14,963 and 15,082 cm^?1 above the X¹Σ⁺ state, respectively. The transition C¹Π₁–X¹Σ₀⁺ may contribute to the experimentally observed bands headed at 15,071 cm^?1. There are two excited states, D¹Δ and E¹Σ⁺, situate at 20,715 and 23,145 cm^?1 above the X¹Σ⁺ state. The visible bands near 20,000 cm^?1 could be generated by the electronic transitions D¹Δ₂–a³Π₁ and E¹Σ⁺₀–X¹Σ⁺₀ because of the spin–orbit coupling effect. © 2013 Wiley Periodicals, Inc.     

Radionuclides used for therapy and suggestion for new candidates

Summary Targeted radiotherapy has the potential to provide radiation doses from a wide range of radionuclides, some of them suitable for killing single cells while others are more suitable for killing tumor cell clusters of various sizes. A list of 64 radionuclides, including 20 new potential candidates for therapy (⁷³Ga, ⁷⁵Se, ^87mSr, ⁹⁷Ru, ¹⁰³Ru, ¹¹³Sn, ^113mIn, ¹¹⁷Sb, ¹²³Sn, ¹³¹Cs, ¹³⁹Ce, ¹⁴¹Ce, ¹⁴⁹Eu, ¹⁶⁷Tm, ¹⁷⁰Tm, ¹⁷³Tm, ¹⁹⁵Au, ^195mPt, ¹⁹⁷Pt and ¹⁹⁷Hg) were analyzed in terms of the suitability of their energies for killing tumor cells which grow as single, small, intermediate and large clusters. In addition, their possible production routes were studied.     

Radioactivity in coffee

This research was dedicated to the study of the background levels of ²¹⁰Po and natural gamma emitters as ⁴⁰K, ²¹⁴Pb, ²¹⁴Bi, ²²⁸Ac, ²¹²Pb and ²¹²Bi in coffee powder and in coffee beverage; also the artificial ¹³⁷Cs was determined. In the coffee powder the mean ²¹⁰Po activity resulted 7.25 ± 2.25 × 10^?2 Bq kg^?1. ⁴⁰K showed a mean activity of 907.4 ± 115.6 Bq kg^?1. The mean activity concentration of ²¹⁴Pb and ²¹⁴Bi, indicators of ²²⁶Ra, given as mean value of the two radionuclides, resulted 10.61 ± 4.02 Bq kg^?1. ²²⁸Ac, ²²⁸Ra indicator, showed a mean activity concentration of 13.73 ± 3.20 Bq kg^?1. The mean activity concentration of ²¹²Pb, ²²⁴Ra indicator, was 8.28 ± 2.88 Bq kg^?1. ²⁰⁸Tl, ²²⁴Ra indicator, presented a mean activity concentration of 11.03 ± 4.34 Bq kg^?1. In all samples, the artifical ¹³⁷Cs resulted below the detection limit (2.0 Bq kg^?1). The arithmetical mean value of percentage of ²¹⁰Po extraction in coffee beverage resulted 20.5 ± 6.9. The percentage of transfer of gamma emitters,⁴⁰K, ²¹⁴Pb, ²¹⁴Bi, ²²⁸Ac, ²¹²Pb, ²⁰⁸Tl resulted of 80.0, 33.5, 24.7, 30.0, 35.1 and 53.5 % for ⁴⁰K, ²¹⁴Pb, ²¹⁴Bi, ²²⁸Ac, ²¹²Pb and ²⁰⁸Tl respectively.     

Dianionic Titanyl and Vanadyl (Cation+)2[MIVO(Pc4−)]2− Phthalocyanine Salts Containing Pc4− Macrocycles

In this study, the titanyl and vanadyl phthalocyanine (Pc) salts (Bu₄N⁺)₂[M^IVO(Pc^4?)]^2? (M=Ti, V) and (Bu₃MeP⁺)₂[M^IVO(Pc^4?)]^2? (M=Ti, V) with [M^IVO(Pc^4?)]^2? dianions were synthesized and characterized. Reduction of M^IVO(Pc^2?) carried out with an excess of sodium fluorenone ketyl in the presence of Bu₄N⁺ or Bu₃MeP⁺ is exclusive to the phthalocyanine centers, forming Pc^4? species. During reduction, the metal +4 charge did not change, implying that Pc is an non‐innocent ligand. The Pc negative charge increase caused the C?N(pyr) bonds to elongate and the C?N(imine) bonds to alternate, thus increasing the distortion of Pc. Jahn–Teller effects are significant in the [eg(π*)]² dianion ground state and can additionally distort the Pc macrocycles. Blueshifts of the Soret and Q‐bands were observed in the UV/Vis/NIR when M^IVO(Pc^2?) was reduced to [M^IVO(Pc ^{. 3?})] ^{. ?} and [M^IVO(Pc^4?)]^2?. From magnetic measurements, [Ti^IVO(Pc^4?)]^2? was found to be diamagnetic and (Bu₄N⁺)₂[V^IVO(Pc^4?)]^2? and (Bu₃MeP⁺)₂[V^IVO(Pc^4?)]^2? were found to have magnetic moments of 1.72–1.78 μ_B corresponding to an S=1/2 spin state owing to V^IV electron spin. As a result, two latter salts show EPR signals with V^IV hyperfine coupling.     

Study on the synthesis of novel fluorescent macrocyclic sensors and their sensitive properties for Cu2+ and Fe3+ in aqueous solution

In this work, we synthesised and characterised three novel fluorescence macrocyclic sensors containing optically active dansyl groups. The studies for the interaction of the synthesised compounds with various mental ions (Li⁺, Na⁺, K⁺, Ag⁺, Mg²⁺, Ca²⁺, Ba²⁺, Pb²⁺, Zn²⁺, Co²⁺, Cd²⁺, Hg²⁺, Ni²⁺, Cu²⁺, Mn²⁺, Cr³⁺, Al³⁺, Fe³⁺) were performed by fluorescence titration, Job’s plot, ESI-MS and DFT calculations. The results showed that the sensors 1a–1c displayed selective recognition for Cu²⁺ and Fe³⁺ ions and formed stoichiometry 1:1 complex through PET mechanism in DMSO/H₂O solution (1:1, v/v, pH 7.4 of HEPES). The binding constant (K) and detection limit were calculated.     

Synthesis and reactivity of metal-containing monomers

Acid and neutral Co^II, Cu^II, Ni^II, Zn^II, Fe^II, and Fe^III maleates, fumarates, and itaconates were obtained and characterized. The methods for their synthesis were optimized, and the valence state and coordination of metals were studied. Co^II and Fe^II hydrogen maleates, Co^II maleate, and Co^II fumarate were examined by X-ray diffraction analysis. The ligands based on unsaturated dicarboxylic acids can be mono-, bi-, and tetradentate, which results in the formation of acid salts, chain and three-dimensional coordination polymers, whose double bond is not involved in the coordination. The strong antiferromagnetic exchange (μ_elf=1.41 and 0.34 μ_B at 290 and 80 K, respectively) was detected in Cu^II itaconate. Based on the data of Mössbauer spectroscopy, the partial reduction of Fe^III to Fe^II during the synthesis of Fe^III maleate was shown to occur: δFe=0.43 and 1.27 mm s^?1, ΔE _Q=0.57 and 3.13 mm s^?1 and Γ=0.37 and 0.28 mm s^?1 atT=298 K for Fe^III and Fe^II, respectively.     

Synthesis, ion-exchange properties and analytical applications of stannic selenoarsenate: Comparison with other heteropolyacid salts

Summary Stannic selenoarsenate samples have been prepared by adding a mixture which is 0.05 M in sodium arsenate and 0.05 M in sodium selenite to a 0.05 M solution of stannic chloride in different volume ratios at pH 1. Its ion-exchange properties, pH titration curves and X-ray pattern were studied. Adsorption behaviour of 24 metal ions in different solvent systems has been examined. The analytical importance of this material has been demonstrated by achieving the following binary and ternary separations: Hg²⁺-Cd²⁺, Co²⁺-Fe³⁺, Cu²⁺-Fe³⁺, Hg²⁺-Zn²⁺-Al³⁺, Hg²⁺-Cu²⁺-Al³⁺, Hg²⁺-Ni²⁺-Al³⁺, Hg²⁺-Zn²⁺-Fe³⁺ and Hg²⁺-Ni²⁺-Fe³⁺. A comparison of the ion-exchange properties of this material has also been made with some other tin(IV) based ion-exchangers.

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Synthese, Ionenaustauscher-Eigenschaften und analytische Anwendungen von Zinn-Selenoarsenat: Vergleich mit anderen Heteropolysalzen

Zusammenfassung Zinn-Selenoarsenat wurde durch Mischen von 0,05 M Natriumarsenat-, 0,05 M Natriumselenitund 0,05 M Zinn(IV)-Chlorid-Lösungen bei pH 1 in verschiedenen Verhältnissen hergestellt. Die Ionenaustauscher-Eigenschaften, pH-Titrationskurven sowie Röntgendiagramme wurden untersucht und das Adsorptionsverhalten von 24 Metallionen in verschiedenen Lösungsmittelsystemen geprüft. Die analytische Verwertbarkeit wurde an Hand der folgenden Trennungsmöglichkeiten gezeigt: Hg²⁺-Cd²⁺, Co²⁺-Fe³⁺, Cu²⁺-Fe³⁺, Hg²⁺-Zn²⁺-Al³⁺, Hg²⁺-Cu²⁺-Al³⁺, Hg²⁺-Ni²⁺-Al³⁺, Hg²⁺-Zn²⁺-Fe³⁺, Hg²⁺-Ni²⁺-Fe³⁺. Vergleiche mit anderen Ionenaustauschern auf Zinn(IV)-Basis werden ebenfalls beschrieben.