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1.
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.
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.
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2.
The effect of the nature of organic electron transfer agents and of PtII, PdII, RhII, CoII, NiII, CuII, CrIII, MnII, TiIII, VIII, ZnII, and AgI metal ions on the kinetics of the homogeneous reduction ofgem-dichlorocyclopropanes has been studied. PtII, PdII, RhIII, CoII, and NiII ions accelerate this process, VIII and AgI 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.  相似文献   

3.
Zusammenfassung Es wird über die Möglichkeit berichtet, Metallionen aus wäßriger Lösung mit Hilfe organischer Lösungsmittel als Verbindungen der Diphenylarsinsäure extrahieren zu können. Von den untersuchten Ionen Fe3+, Al3+, Bi3+, Cr3+, UO2 2+, Zn2+, Cd2+, Cu2+, Co2+, Ni2+, Mn2+, Be2+, Pb2+, Ca2+ und Mg2+ sind mit Chloroform nur Pb2+, Bi3+, Be2+, Zn2+ und Al3+ extrahierbar. Mit Trichloräthylen ist praktisch nur mehr Pb2+ extrahierbar, während Benzol und Essigester keinerlei Extraktionswirkung zeigen. Vergleiche mit dem Verhalten aliphatischer Arsinsäuren werden angestellt.
Summary A report is given concerning the possibility of extracting metal ions from aqueous solution by means of organic liquids as compounds of diphenylarsinic acid. The ions investigated included Fe3+, Al3+, Bi3+, UO2 2+, Zn2+, Cr3+, Cd2+, Cu2+, Co2+, Ni2+, Mn2+, Be2+, Pb2+, Ca2+, and Mg2+. Of these only Pb2+, Bi3+, Be2+, Zn3+ and Al3+ are extractable with chloroform. With trichloro ethylene only Pb2+ is extractable, whereas benzene and acetic ester show no extraction action. Comparisons were made with the behavior of aliphatic arsinic acids.

Résumé On décrit la possibilité d'extraction d'ions métalliques à l'état de composés de l'acide diphénylarsinique, à partir de leur solution aqueuse, à l'aide d'un solvant organique. Parmi les ions étudiés, Fe3+, Al3+, Bi3+, Cr3+, UO2 2+, Zn2+, Cd2+, Cu2+, Co2+, Ni2+, Mn2+, Be2+, Pb2+, Ca2+ et Mg2+, seuls Pb2+, Bi3+, Be2+, Zn2+ et Al3+ peuvent être extraits par le chloroforme. Le trichloréthyléne ne permet que l'extraction du Pb2+, cependant que le benzène et l'ester acétique ne manifestent aucune activité d'extraction. On établit une comparaison avec le comportement des acides arsiniques aliphatiques.
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4.
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.  相似文献   

5.
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.  相似文献   

6.
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.  相似文献   

7.
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: CuII, FeIII, CoII, BiIII, NiII, CrVI, TeIV, SeIV, AgI, HgII, AsIII, SnIV, PbIV, CdII, MoVI, MnII, VV, ZnII, InIII, TlI, WVI, OsVIII and NbV.
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: CuII, FeIII, CoII, BiIII, NiII, CrVI, TeIV, SeIV, AgI, HgII, AsIII, SnIV, PbIV, CdII, MoVI, MnII, VVI, ZnII, InIII, TlI, WVI, OsVIII sowie NbV.
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8.
9.
Summary The chelation behaviour of the complexes of La3+, Ce3+, Pr3+, Nd3+, Sm3+, Eu3+, Gd3+, Y3+, Tb3+, Dy3+, Ho3+ with biologically active 2-Hydroxy-1-naphthaldehyde semicarbazone (HNAS) has been studied potentiometrically in 75% (v/v) dioxane-water medium at various ionic strengths. The method of Bjerrum and Calvin, as modified by Irving and Rossotti has been used to find out the values of n andpL. The formation constants of metal chelates and the values ofS min have been calculated. The order of formation constants of chelates was found to be: La3+3+3+3+3+3+3+3+3+3+3+.
Physikochemische Untersuchungen zur Komplexierung von biologisch aktivem 2-Hydroxy-1-naphthaldehyd-Semicarbazon (HNAS) mit Lanthanoiden
Zusammenfassung Das Chelierungsverhalten von La3+, Ce3+, Pr3+, Nd3+, Sm3+, Eu3+, Gd3+, Y3+, Tb3+, Dy3+ und Ho3+ mit 2-Hydroxy-1-naphthaldehydsemicarbazon (HNAS) wurde potentiometrisch in 75% (v/v) Dioxan-Wasser bei verschiedenen Ionenstärken untersucht. Die Werte für n undpL wurden nach der Methode von Bjerrum und Calvin in der Modifikation von Irving und Rossotti bestimmt. Die Komplexbildungskonstanten der Metallchelate und die WerteS min wurden ermittelt. Die Reihung der Komplexbildungskonstanten war La3+3+3+3+3+3+3+3+3+33+.
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10.
The cross-sections for the production of the short-lived nuclides:26mAl,197mAu,136mBa,79mBr,139mCe,34Cl,167mEr,114m3In,114m2In,38mK,38mCl,26Na,20F,192Re,207mPb,203mPb,46mSc,183mW,90mZr obtained from (n, 2n), (n, n′), (n, alpha), (n,p) reactions using 14 MeV neutrons, were evaluated by the activation method. The experimental results of this work were compared with those obtained by other authors.  相似文献   

11.
设计合成基于苯并噻唑Zn2+荧光增强型探针BHP,在HEPES缓冲液中测其对Zn2+识别性能。实验结果表明,BHP对Zn2+有较高的选择性,对其他金属离子如Cd2+,Fe2+,Ni2+,Pb2+,Hg2+,Al3+,Mn2+,Ag+,Cu2+,Co2+,Na+,K+,Mg2+和Ca2+无明显荧光增强响应。BHP与Zn2+按1:1计量比配位,在生理条件下荧光强度不受pH值影响。在HeLa细胞中对Zn2+的造影表明BHP可用于生物体Zn2+检测。  相似文献   

12.
The ligand H6ioan has been used to synthesize the three dinuclear complexes [(ioan)MnIITiIV], [(ioan)FeIITiIV], and [(ioan)FeIIITiIV]+. The face-sharing bridging mode of the three phenolates provides short M-TiIV distances of ≈3.0 Å. Mössbauer spectra of [(ioan)FeIIITiIV]+ show a magnetically split six-line spectrum at 3 K in zero magnetic field demonstrating a slow magnetic relaxation. Magnetic measurements provide a zero-field splitting of |D|=5 cm−1 in [(ioan)FeIITiIV]. EPR spectroscopy demonstrates sizable zero-field splittings of the S=5/2 spin systems of [(ioan)MnIITiIV] (D=0.246 cm−1) and [(ioan)FeIIITiIV]+ (D<−1 cm−1) that can be related to enforced covalency of the M-Oph bonds. [(ioan)FeIIITiIV]+ exhibits a reversible reduction at −0.26 V vs. Fc+/Fc demonstrating the facile accessibility of FeIII and FeII. In contrast to an irreversible oxidation in [(ioan)NiIITiIV] at 0.78 V vs. Fc+/Fc, the reversible oxidation at 0.25 V vs. Fc+/Fc in [(ioan)MnIITiIV] indicates even the access of MnIII. These results indicate that pentanuclear complexes [(ioan)FeM1M2M1Fe(ioan)]n+ are meaningful targets to access electron delocalization in mixed-valence systems over five ions due to the facile accessibility of both FeII and FeIII in the terminal positions. This study provides important local spin-Hamiltonian and Mössbauer parameters that will be essential for the understanding of the potentially complicated electronic structure in the anticipated pentanuclear complexes.  相似文献   

13.
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.  相似文献   

14.
The addition of54Mn and65Zn to a nine-radionuclide standard (containing241Am.,109Cd.57Co,139Ce,203Hg.113Sn,137Cs,88Y, and60Co) provides the capability to determine the extent of coincidence summing for gamma rays from88Y and60Co. A method for correcting the efficiency points at 1332 keV (60Co) and 1836 keV (88Y) for coincidence summing is presented.  相似文献   

15.
Zusammenfassung Die Trennung der Ionenpaare Rb+/Cs+, K+/Rb+, K+/Cs+, Na+/K+, Li+/Na+ mit Salzsäure oder Ammoniumchloridlösung als Elutionsmittel gelingt quantitativ oder nahezu quantitativ mit Hilfe von Titanhexacyanoferrat(II)-säulen. Die Cäsiumionen können nicht eluiert werden. Ebenso gelingt die Trennung der lonenpaare Sr2+/Ba2+, Ca2+/Ba2+, Ba2+/Cs+ und Sr2+/Cs+ quantitativ oder nahezu quantitativ. Auch eine partielle Trennung der Seltenen Erden ist möglich; Yttrium ist leichter eluierbar als die Lanthanide.
Summary The quantitative or nearly quantitative separation of the ion pairs Rb+/Cs+, K+/Rb+, k+/Cs+, Na+/K+ and Li+/Na+ can be achieved with hydrochloric acid or ammonium chloride solutions as eluents by means of columns of titanium hexacyanoferrate(II). The elution of the Cs+ ions is not possible. In the same way the quantitative or nearly quantitative separation of the ion pairs Sr2+/Ba2+, Ca2+/Ba2+, Ba2+/Cs+ and Sr2+/Cs+ can be achieved. Also a partial separation of the rare-earth elements is possible; yttrium is more easily eluted than the lanthanides.
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16.
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.  相似文献   

17.
In this study, the titanyl and vanadyl phthalocyanine (Pc) salts (Bu4N+)2[MIVO(Pc4?)]2? (M=Ti, V) and (Bu3MeP+)2[MIVO(Pc4?)]2? (M=Ti, V) with [MIVO(Pc4?)]2? dianions were synthesized and characterized. Reduction of MIVO(Pc2?) carried out with an excess of sodium fluorenone ketyl in the presence of Bu4N+ or Bu3MeP+ is exclusive to the phthalocyanine centers, forming Pc4? 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 MIVO(Pc2?) was reduced to [MIVO(Pc . 3?)] . ? and [MIVO(Pc4?)]2?. From magnetic measurements, [TiIVO(Pc4?)]2? was found to be diamagnetic and (Bu4N+)2[VIVO(Pc4?)]2? and (Bu3MeP+)2[VIVO(Pc4?)]2? were found to have magnetic moments of 1.72–1.78 μB corresponding to an S=1/2 spin state owing to VIV electron spin. As a result, two latter salts show EPR signals with VIV hyperfine coupling.  相似文献   

18.
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, Trp3,4, D-Trp1,3,4 Phe8, D-Trp3,4 Phe8 D-Glu9, D-pF-Phe3,4 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.  相似文献   

19.
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.  相似文献   

20.
The reaction of the hydrated positron, eaq+ with Cl?, Br?, and I? ions in aqueous solutions was studied by means of positron The measured angular correlation curves for [Cl?, e+], [Br?, e+, and [I?, e+] bound states were in good agreement with th Because of this agreement and the fact that the calculated positron wavefunctions penetrate far outside the X? ions in the [X?, e+] sta propose that a bubble is formed around the [X?, e+] state, similar to the Ps bubble found in nearly all liquids. F?ions did not react w Preliminary results showed that CN? ions react with eaq+ while OH?ions are non reactive. The rate constants were 3.9 × 1010 M?1 s?1, 4.4 × 1010 M?1 s?1, and 6.3 × 1010 M?1 s?1 for Cl?, Br?, and I?, respectively, at low (? 0.03 M) X? concentrations. A 25% decrease in the rate constant caused by the addition of 1 M ethanol to the I? solutions was i The influence of halide ions on the positronium (Ps) yields in pure water was studied by use of lifetime measurements. The Cl?, Br?, and I? ions reduced the Ps yields at low concentrations (? 0.03 M), while F? ions only reduced the Ps-yield However, the Ps yields saturated (e.g. at ≈ 21% ortho-Ps yield in the Cl? case) at higher concentrations. This saturation and the high-concentration effects-in the angular correlation results were interpreted as caused by rather complicated spur effects, wh It is proposed that spur electrons may pick off the positron from the [X?, e+ states with an efficiency which depends on the structure of the  相似文献   

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