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1.
The complexes trans-[Ni(4-MP)2(NCS)2]·MeCN (1) and trans-[Ni(3-MP)2(NCS)2] (2) (4-MP = tri(4-methylphenyl)phosphine, 3-MP = tri(3-methylphenyl)phosphine) were prepared and characterized by IR, UV–visible, NMR spectra, CV, TGA and single crystal X-ray crystallography. Both the complexes have planar geometry and are diamagnetic. The Ni–P distances in both complexes are relatively short as a result of strong back donation from nickel to phosphorus. The phenyl rings in the 3-MP analogue (2) show increased pitching with reference to the plane formed by the ipso carbons due to increased steric effects. For complex (2), the N–Ni–N and P–Ni–P angles are significantly lower than the almost linear N–Ni–N and N–Ni–P angles observed for both complex (1) and trans-[Ni(PPh3)2(NCS)2]. This observation indicates that the 3-methylphosphine ligand forces complex (2) to distort towards a tetrahedral geometry. IR spectra of both complexes show strong bands around 2,090 cm−1 due to N-coordinated thiocyanate, while the electronic spectra contain d–d transitions around 452 nm. Cyclic voltammograms show that the irreversible one-electron reduction potentials increase in the following order: trans- [Ni(PPh3)2(NCS)2] < trans- [Ni(3-MP)2(NCS)2] < trans-[Ni(4-MP)2(NCS)2], revealing the electron releasing effect of the methyl groups. The planar complexes exhibit interallogony in coordinating solvents.  相似文献   

2.
Inventories and fluxes of 210Pb, 228Ra and 226Ra were determined in sediment cores collected at nine stations covering of the southern South China Sea and Malacca Straits with the thickness of water column between 42 and 83 m depth. The inventories of 210Pb, 228Ra and 226Ra were calculated range from 0.15–2.55 Bq cm−2, 0.05–0.40 Bq cm−2 and 6.83–83.63 Bq cm−2, meanwhile the fluxes ranged from 0.005–0.079 Bq cm−2 yr−1, 0.009–0.048 Bq cm−2 yr−1 and 0.003–0.037 Bq cm−2 yr−1, respectively. The results show that the highest inventories and fluxes for 210Pb, 228Ra and 226Ra were found at station WC 01 and EC 05. Because there are additional sources of 210Pb, 228Ra and 226Ra, where water transport will brings more dissolved isotopes, influence of the transportation and deposition of suspended particles, fast rate of regeneration and greater production of those radionuclides and others.  相似文献   

3.
In the present study, ytterbium-169 was produced via the 169Tm(p, n)169Yb nuclear process at the AMIRS (Cyclone-30, IBA, Belgium) cyclotron, irradiating Tm2O3 with proton particles of 15 MeV primary energy and 20 μA current for 20 min. Deposition of Tm2O3 on Cu substrate was carried out via by the sedimentation method. The 543 mg of thulium(III)oxide with 108 mg of ethyl cellulose and 8 mL of acetone were used to prepare a Tm2O3 layer of 11.69 cm2. Yields of about 0.643 MBq 169Yb per μAh were experimentally obtained. 169Yb was separated in 80 ± 5% radiochemical yield using liquid–liquid extraction. Solvent extraction of no-carrier-added 169Yb from irradiated thulium(III)oxide target hydrochloric solution was investigated using di-(2-ethylhexyl)phosphoric acid (HDEHP).  相似文献   

4.
In recent years, there has been a rapid expansion in the use of radio nuclides for therapeutic purposes. Thulium–167 is an important radionuclide (T 1/2 = 9.25 d) due to it could be used for tumor and bone studies in nuclear medicine. 167Tm complexed with hydroxy ethylene diamine tetra-acetic acid (HEDTA) could be used with the aim of bone imaging. 167Tm emits a prominent γ ray of 208 keV energy and low energy electrons. This study describes calculations on the excitation functions of 165Ho(α,2n)167Tm, 167Er(p,n)167Tm, natEr(d,xn)167Tm and natEr(p,xn)167Tm reactions by ALICE/ASH (hybrid and GDH models) and TALYS-1.0 codes. In addition, calculated data by codes were compared to experimental data that earlier were published and TENDL-2010 database. Moreover, optimal thickness of the targets and physical yield were obtained by SRIM (stopping and range of ions in matter) code for each reaction. According to the results, the 167Er(p,n)167Tm and 165Ho(α,2n)167Tm reactions are suggested as the best method to produce 167Tm owing to minimum impurities. The TALYS-1.0 code, predict the maximum cross-section of about 382 mb at 11 MeV and 849 mb at 26 MeV for 167Er(p,n)167Tm and 165Ho(α,2n)167Tm reactions, respectively. Finally, deposition of natEr2O3 on Cu substrate was carried out via the sedimentation method. The 516 mg of erbium(III)oxide with 103.2 mg of ethyl cellulose and 8 mL of acetone were used to prepare a natEr2O3 layer of 11.69 cm2. 167Tm was produced via the natEr(p,n)167Tm nuclear process at 20 μA current and 15 → 7 MeV protons beam (1 h). Yield of about 3.2 MBq 167Tm per μA h were experimentally obtained.  相似文献   

5.
Rituximab was successively labeled with 177Lu-lutetium chloride. 177Lu chloride was obtained by thermal neutron flux (4 × 1013 n cm−2 s−1) of natural Lu2O3 sample with a specific activity of 2.6–3 GBq/mg. The macrocyclic bifunctional chelating agent, N-succinimidyl-1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA-NHS) was prepared at 25 °C using DOTA, N-hydroxy succinimide (NHS) in CH2Cl2. DOTA-rituximab was obtained by the addition of 1 mL of a rituximab pharmaceutical solution (5 mg/mL, in phosphate buffer, pH 7.8) to a glass tube pre-coated with DOTA-NHS (0.01–0.1 mg) at 25 °C with continuous mild stirring for 15 h. Radiolabeling was performed at 37 °C in 24 h. Radio-thin layer chromatography showed an overall radiochemical purity of >98% at optimized conditions (specific activity = 444 MBq/mg, labeling efficacy; 82%). The final isotonic 177Lu-DOTA-rituximab complex was checked by gel electrophoresis for structure integrity control. Radio-TLC was performed to ensure that only one species was present after filtration through a 0.22 μm filter. Preliminary biodistribution studies in normal rats were carried out to determine complex distribution of the radioimmunoconjugate up to 168 h. The biodistribution data were in accordance with other antiCD20 radioimmunoconjugates already reported.  相似文献   

6.
The sorption of 63Ni(II) from aqueous solution using ZSM-5 zeolite was investigated by batch technique under ambient conditions. ZSM-5 zeolite was characterized by point of zero net proton charge (PZNPC) titration. The sorption was investigated as a function of shaking time, pH, ionic strength, foreign ions, humic acid (HA), fulvic acid (FA) and temperature. The results indicate that the sorption of 63Ni(II) on ZSM-5 zeolite is strongly dependent on pH. The sorption is dependent on ionic strength at low pH, but independent of ionic strength at high pH values. The presence of HA/FA enhances 63Ni(II) sorption at low pH values, whereas reduces 63Ni(II) sorption at high pH values. The sorption isotherms are simulated by Langmuir model very well. The thermodynamic parameters (i.e., ∆H 0, ∆S 0 and ∆G 0) for the sorption of 63Ni(II) are determined from the temperature dependent sorption isotherms at 293.15, 313.15 and 333.15 K, respectively, and the results indicate that the sorption process of 63Ni(II) on ZSM-5 zeolite is spontaneous and endothermic.  相似文献   

7.
A new insoluble solid functionalized ligand system bearing chelating ligand group of the general formula P-(CH2)3-N[CH2CONH(C6H4)NH2]2, where P represents [Si–O] n polysiloxane network, was prepared by the reaction of the immobilized diethyliminodiacetate polysiloxane ligand system, P-(CH2)3N(CH2CO2Et)2 with 1,2-diaminobenzene in toluene. 13C CP-MAS NMR, XPS and FTIR results showed that most ethylacetate groups (–COOEt) were converted into the amide groups (–N–C=O). The new functionalized ligand system exhibits high capacity for extraction and removal of the metal ions (Fe3+, Co2+, Ni2+, Cu2+ and Zn2+) with efficiency of 95–97% after recovery from its primary metal complexes. This functionalized ligand system formed 1:1 metal to ligand complexes.  相似文献   

8.
Gas-phase infrared photodissociation spectroscopy is reported for the microsolvated [Mn(ClO4)(H2O) n ]+ and [Mn2(ClO4)3(H2O) n ]+ complexes from n = 2 to 5. Electrosprayed ions are isolated in an ion-trap where they are photodissociated. The 2600–3800 cm−1 spectral region associated with the OH stretching mode is scanned with a relatively low-power infrared table-top laser, which is used in combination with a CO2 laser to enhance the photofragmentation yield of these strongly bound ions. Hydrogen bonding is evidenced by a relatively broad band red-shifted from the free OH region. Band assignment based on quantum chemical calculations suggest that there is formation of water—perchlorate hydrogen bond within the first coordination shell of high-spin Mn(II). Although the observed spectral features are also compatible with the formation of structures with double-acceptor water in the second shell, these structures are found relatively high in energy compared with structures with all water directly bound to manganese. Using the highly intense IR beam of the free electron laser CLIO in the 800–1700 cm−1, we were also able to characterize the coordination mode (η2) of perchlorate for two clusters. The comparison of experimental and calculated spectra suggests that the perchlorate Cl—O stretches are unexpectedly underestimated at the B3LYP level, while they are correctly described at the MP2 level allowing for spectral assignment.  相似文献   

9.
We report vibrational predissociation spectra of the four protonated dipeptides derived from glycine and sarcosine, GlyGlyH+•(H2)1,2, GlySarH+•(D2)2, SarGlyH+•(H2)2, and SarSarH+•(D2)2, generated in a cryogenic ion trap. Sharp bands were recovered by monitoring photoevaporation of the weakly bound H2 (D2) molecules in a linear action regime throughout the 700–4200 cm–1 range using a table-top laser system. The spectral patterns were analyzed in the context of the low energy structures obtained from electronic structure calculations. These results indicate that all four species are protonated on the N-terminus, and feature an intramolecular H-bond involving the amino group. The large blue-shift in the H-bonded N–H fundamental upon incorporation of a methyl group at the N-terminus indicates that this modification significantly lowers the strength of the intramolecular H-bond. Methylation at the amide nitrogen, on the other hand, induces a significant rotation (~110o) about the peptide backbone.  相似文献   

10.
A novel electrochemical process to avail clinical grade 99mTc from (n,γ)99Mo has been demonstrated. The electrochemical parameters were optimized to maximize the 99mTc yield with minimal 99Mo contamination. 99Mo/99mTc generators containing up to 29.6 GBq (800 mCi) 99Mo were developed and their performance were extensively evaluated for 10 days without changing the operating conditions. Very high radioactive concentration of 99mTcO4 of acceptable quality, commensurate with hospital radiopharmacy requirements could be availed from the system with >90% yield. The compatibility of the product for the formulation of 99mTc labeled radiopharmaceuticals such as 99mTc-DMSA and 99mTc-EC was found to be satisfactory in terms of high labeling yields. The proposed route represents an important step for enhancing the scope of accessing clinical grade 99mTc from low specific activity (n, γ)99Mo.  相似文献   

11.
3-(Diphenylphosphino)-1,3-diphenyltriazene Ph2P-NPh-N=NPh was synthesized. The reactions of this compound with bis(cycloocta-1,5-diene)nickel, (cod)2Ni, and nickel(I) bis(triphenylphosphino)bis(trimethylsilyl)amide, (Ph3P)2Ni-N(SiMe3)2, afforded the anionic nickel complex [Ph4P]+[Ni(PhNNNPh)3] in 15 and 78% yields, respectively. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1585–1589, July, 2005.  相似文献   

12.
14C releases in the stack air of the NPPs V1 and V2, Jaslovske Bohunice was determined during the year 2004–2010. Radioactivity concentration of 14C in the stack air was determined in the forms of inorganic 14CO2 and 14C n H m . The annual average activity concentration in the stacks air samples varies between 12 and 121 Bq m−3. NPP V1, starting with 45 Bq m−3 in 2005 is decreasing due to the shutting down of the reactors (the first reactor was shut down in December 2006 and the second reactor in December 2008). The average value of radioactivity concentration for power unit V2 was 32 Bq m−3 in 2004 and reached the value of 102 Bq m−3 in the first-quarter of the 2010. The average normalized yearly discharge rates were between 0.39 and 0.64 TBq GWe−1 year−1 (2005–2008), NPP V1 and 0.19–0.61 TBq GWe−1 year−1 (2004–first-quarter 2010) for NPP V2, Jaslovske Bohunice. Most of the discharged 14C is in a hydrocarbon form, (95% for Jaslovske Bohunice NPP V2), but the CO2 fraction may reach 37% in the air stack for Jaslovske Bohunice V1.  相似文献   

13.
This article presents, 122Sb (T 1/2 = 2.723 days, I β- = 97.59%) was produced via the natSn(p,xn) nuclear process at the AMIRS (Cyclone-30, IBA, Belgium). The electrodeposition experiments were carried out by potassium stannate trihydrate (K2Sn(OH)6) and potassium hydroxide. The optimum conditions of the electrodeposition of tin were as follows: 40 g/L natSn, 20 g/L KOH, 115 g/L K2Sn(OH)6, DC current density of 5 A/dm2 with a bath temperature of 75 °C. The electroplated Tin-target was irradiated with 26.5 MeV protons at current of 180 μA for 20 min. Solvent extraction of no-carrier-added 122Sb from irradiated Tin-natural target hydrochloric solution was investigated using di-n-butyl ether (C8H18O). Yields of about 3.61 MBq/μAh were experimentally obtained.  相似文献   

14.
Ag+ assisted aquation of blue cis-trans-cis-RuCl2(RaaiR′)2 (4–6) leads to the synthesis of solvento species, blue-violet cis-trans-cis-[Ru(OH2)2(RaaiR′)2](ClO4)2 [Raai R′=p-R-C6H4 N=N–C3H2–NN–1–R′, (1–3), abbreviated as N,N′-chelator, where N(imidazole) and N(azo) represent N and N′, respectively; R = H (a), OMe (b), NO2 (c) and R′ = Me (1/4/7/10), CH2CH3 (2/5/8/11), CH2Ph (3/6/9/12)] that have been reacted with NO2in warm EtOH resulting in violet dinitro complexes of the type, Ru(NO2)2(RaaiR′)2 (7–9). The nitrite complexes are useful synthons of electrophilic nitrosyls, and on triturating the compounds, (7b–9b) with conc. HClO4 nitro-nitrosyl derivatives, [Ru(NO2)(NO)(OMeaaiR′)2](ClO4)2 (10b–12b) are isolated. The solution structure and stereoretentive transformation in each step have been established from 1H n.m.r. results. All the complexes exhibit strong MLCT transitions in the visible region. They are redox active and display one metal-centred oxidation and successive ligand-based reductions. The redox potentials of Ru(III)/Ru(II) (E1/2M) of (10b–12b) are anodically shifted by ∼ ∼0.2 V as compared to those of dinitro precursors, (7b–9b). The ν(NO) >1900 cm−1 strongly suggests the presence of linear Ru–NO bonding. The electrophilic behaviour of metal bound nitrosyl has been proved in one case (12b) by reacting with a bicyclic ketone, camphor, containing an active methylene group and an arylhydrazone with an active methine group, and the heteroleptic tris chelates thus formed have been characterised.  相似文献   

15.
Electrochromic titanium oxide (TiO2) films were deposited on ITO/glass substrates by chemical solution deposition (CSD). The stock solutions were spin-coated onto substrates and then heated at various temperatures (200–500 °C) in various oxygen concentrations (0–80%) for 10 min. The effects of the processing parameters on the electrochromic properties of TiO2 films were investigated. X-ray diffraction measurements demonstrated that the amorphous TiO2 films were crystallized to form anatase films above 400 °C. The electrochromic properties and transmittance of TiO2 films were measured in 1 M LiClO4–propylene carbonate (PC) non-aqueous electrolyte. An amorphous 350 nm-thick TiO2 film that was heated at 300°C in 60% ambient oxygen exhibited the maximum transmittance variation (ΔT%), 14.2%, between the bleached state and the colored state, with a ΔOD of 0.087, Q of 10.9 mC/cm2, η of 7.98 cm2/C and x in Li x ClO4 of 0.076 at a wavelength (λ) of 550 nm.  相似文献   

16.
Isothermal titration calorimetry has been used to determine the stoichiometry, formation constants and thermodynamic parameters (ΔG o, ΔH, ΔS) for the formation of the citrate complexes with the Mn2+, Co2+, Ni2+ and Zn2+ ions. The measurements were run in Cacodylate, Pipes and Mes buffer solutions with a pH of 6, at 298.15 K. A constant ionic strength of 100 mM was maintained with NaClO4. The influence of a metal ion on its interaction energy with the citrate ions and the stability of the resulting complexes have been discussed.  相似文献   

17.
Abstract  Formal [2 + 2 + 2] addition reaction of [Cp*Ru(H2O)(NBD)][BF4] (NBD = norbornadiene) with 4,4′-Diethynylbiphenyl generates [C9H96-C6H4(RuCp*)–C6H4(RuCp*)-η6-C9H9][BF4]2. The reaction of [Cp*Ru(H2O)(NBD)][BF4] with 1,4-diphenylbutadiyne generates the unusual [2 + 2 + 2] additional organic compound Ph–C≡C–C9H8–Ph in addition to the organometallic compound [Cp*Ru(η6-C6H5–C≡C–C≡C–Ph)][BF4]. [C9H96-C6H4(RuCp*)–C6H4(RuCp*)-η6-C9H9][BPh4]2 is generated after the reaction of compound [C9H96-C6H4(RuCp*)–C6H4(RuCp*)-η6-C9H9][BF4]2 with Na[BPh4]. The structure of this compound was confirmed by X-ray diffraction. A possible approach to form Ph–C≡C–C9H8–Ph and [Cp*Ru(η6-C6H5–C≡C–C≡C–Ph)][BF4] is suggested. Graphical Abstract  Formal [2 + 2 + 2] addition reaction of [Cp*Ru(H2O)(NBD)]BF4 (NBD = norbornadiene) with 4,4′-Diethynylbiphenyl generates [C9H96-C6H4(RuCp*)–C6H4(RuCp*)-η6-C9H9][BF4]2. The reaction of [Cp*Ru(H2O)(NBD)][BF4] with 1,4-diphenylbutadiyne simply generates unusual [2 + 2 + 2] additional organic compound Ph–C≡C–C9H8–Ph in addition to the organometallic compound [Cp*Ru(η6-C6H5–C≡C–C≡C–Ph)][BF4]. [C9H96-C6H4(RuCp*)–C6H4(RuCp*)-η6-C9H9][BPh4]2 is generated after the reaction of compound [C9H96-C6H4(RuCp*)–C6H4(RuCp*)-η6-C9H9][BF4]2 with Na[BPh4]. The structure of this compound was confirmed by X-ray diffraction. And the possible approach to form Ph–C≡C–C9H8–Ph and [Cp*Ru(η6-C6H5–C≡C–C≡C–Ph)][BF4] was suggested. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

18.
We report herein a comprehensive study of the gas-phase Fe+-mediated oxidation of ethane by N2O on both the sextet and quartet potential energy surfaces (PESs) using density functional theory. The geometries and energies of all the relevant stationary points are located. Initial oxygen-atom transfer from N2O to iron yields FeO+. Then, ethane oxidation by the nascent oxide involves C–H activation forming the key intermediate of (C2H5)Fe+(OH), which can either undergo C–O coupling to Fe+ + ethanol or experience β-H shift giving the energetically favorable product of FeC2H4 + + H2O. Reaction of FeC2H4 + with another N2O constitutes the third step of the oxidation. N2O coordinates to FeC2H4 + and gets activated by the metal ion to yield (C2H4)Fe+O(N2). After releasing N2 through the direct H abstraction and/or cyclization pathways, the system would be oxidized to ethenol, acetaldehyde, and oxirane, regenerating Fe+. Oxidation to acetaldehyde along the cyclization –C–to–C hydrogen shift pathway is the most energetically favored channel.  相似文献   

19.
Ba1−x Sr x TiO3(x = 0–0.5, BST) nanofibers with diameters of 150–210 nm were prepared by using electrospun BST/polyvinylpyrrolidone (PVP) composite fibers by calcination for 2 h at temperatures in the range of 650–800 °C in air. The morphology and crystal structure of calcined BST/PVP nanofibers were characterized as functions of calcination temperature and Sr content with an aid of XRD, FT-IR, and TEM. Although several unknown XRD peaks were detected when the fibers were calcined at temperatures less than 750 °C, they disappeared with increasing the temperature (above 750 °C) due to its thermal decomposition and complete reaction in the formation of BST. In addition, the FT-IR studies of BST/PVP fibers revealed that the intensities of the O–H stretching vibration bands (at 3430 and 1425 cm−1) became weaker with increasing the calcination temperature and a broad band at 540 cm−1, Ti–O vibration, appeared sharper and narrower after calcination above 750 °C due to the formation of metal oxide bonds. However, no effect of Sr content on the crystal structure of the composites was detected.  相似文献   

20.
[67Ga]labeled tetraphenyl porphyrin ([67Ga]-TPP) was prepared using freshly prepared [67Ga]GaCl3 and tetraphenyl porphyrin (TPPH2) for 30–60 min at 25 °C (radiochemical purity: >97 ± 1% ITLC, >98 ± 0.5% HPLC, specific activity: 13–14 GBq/mmol). Stability of the complex was checked in final formulation and human serum for 24 h. The partition coefficient was calculated for the compound (log P 1.89). The biodistribution of the labeled compound in vital organs of wild-type rats was studied using scarification studies and SPECT imaging up to 24 h. A detailed comparative pharmacokinetic study performed for 67Ga cation and [67Ga]-TPP. The complex is mostly washed out from the circulation through kidneys and can be an interesting tumor imaging/targeting agent due to low liver uptake and rapid excretion through the urinary tract.  相似文献   

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