Investigation of an alternative chemical agent to recover valuable metals from anode slime

Anode slime (AS) including high content of precious metals is a by-product obtained after the electro-refining stage in copper production. In this study, it is aimed to recover Cu, Au, and Ag from the AS by using 1-butyl-3-methyl-imidazolium hydrogen sulphate ([Bmim]HSO₄) ionic liquid (IL) as a green solvent. The effects of IL concentration, temperature, reaction time and pulp density on recovery of valuable metals were statistically investigated. A high copper recovery of 87.52% was obtained under optimum condition as in 60% (v/v) [Bmim]HSO₄ at 50 °C after 2 h, pulp density at 40 g/L (1/25 solid/liquid ratio). Also, a remarkable gold recovery as 97.32% has been achieved in 80% (v/v) [Bmim]HSO₄ at 95 °C after 4 h, pulp density at 40 g/L. Temperature and IL concentration were detected as the most effective parameters for copper and gold recovery from AS, respectively. Silver could not be recovered from the AS due to the lower solubility in [Bmim]HSO₄ IL media. According to experimental results, [Bmim]HSO₄ could be offered as an alternative leaching agent, instead of conventional solvents, to recover valuable metals from copper anode slime.     

Drinfeld modules and torsion in the Chow groups of certain threefolds

Let E B be an elliptic surface defined over the algebraic closureof a finite field of characteristic greater than 5. Let W bea resolution of singularities of E x _B E. We show that the l-adicAbel–Jacobi map from the l-power-torsion in the secondChow group of W to H³(W, _l(2)) _l/_l is an isomorphism for almostall primes l. A main tool in the proof is the assertion thatcertain CM-cycles in fibres of W B are torsion, which is provenusing results from the theory of Drinfeld modular curves.     

Novel estradiol derivatives labeled with Ru,W, and Co complexes. Influence on hormone-receptor affinity of several organometallic groups at the 17 alpha position

In order to elucidate the extent to which recognition of the estrogen receptor is influenced by addition of an organometallic substituent at the 17 alpha position, modification of 17 beta-estradiol at this position was carried out by using the organometallic groups -C identical to C(eta 5-C5H4)RuCp, CH2-(eta 5-C5H4)RuCp, -C identical to C-(eta 5-C5H4)-W(CO)3(Me), -(C identical to CCHO)Co2(CO)6, and -(C identical to CCH2OH)Co2(CO)6. The relative binding affinity (RBA) values for estradiol receptor alpha showed that recognition was good (RBA between 20 and 13.5%) when the organometallic moiety was attached at the end of a rigid alkyne spacer. However, the affinity of the modified hormone for the receptor was severely reduced (RBA = 1%) for a substituent such as -CH2-(eta 5-C5H4)RuCP, in which the spacer is reduced to a single flexible sp3 carbon atom, allowing the organometallic moiety greater freedom of movement around the attachment point. The RBA values found were in agreement with results obtained from a molecular-modeling study in which 5, an organometallic hormone with a rigid spacer, or 7, a molecule with a flexible spacer, was inserted into the cavity of the recently characterized Ligand-Binding Domain of estrogen receptor alpha.     

Reactivity and reaction pathways of electrochemically generated 17-electron tricarbonyl steroid chromium cations

Electrochemical oxidation of α- and β-diastereomers of a range of steroid hormone receptor marker chromium tricarbonyl complexes, (steroid)Cr(CO)₃, have been examined at platinum electrodes in dichloromethane. Data confirm the general nature of previously published conclusions on the oxidation of (arene)Cr(CO)₃ complexes (arene = benzene or steroid). That is, with 0.1 M Bu₄NPF₆ as the electrolyte, and in the absence of nucleophiles, a reversible oneelectron process, (steroid)Cr(CO)₃ ? [(steroid)Cr(CO)₃]⁺ + e^?, is observed, followed by an irreversible one-electron process at considerably more positive potentials. The reversible half-wave potentials (approximately E°-values) calculated for the [(steroid)Cr(CO)₃]⁺/(steroid)Cr(CO)₃ redox couple are shown to be dependent on whether the α- or β-diastereomer is oxidized. Similarly the rate of nucleophilic attack on the 17-electron cation [(steroid)Cr(CO)₃]⁺ by nucleophiles such as ClO, PPh₃ and bis(diphenylphosphine)methane confirms a previous observation that the stereochemistry of this class of compound is important with respect to redox, kinetic and hormone receptor properties. The nature of the electrochemical data obtained on the (arene)Cr(CO)₃ complexes in the presence of nucleophiles suggests that reactions associated with the nucleophilic attack on the 17-electron cations are complex and that a range of reaction pathways occur simultaneously. Electrochemical studies on the oxidation of (benzene)Cr(CO)₂PPh₃ and (oestradiol)Cr(CO)₂PPh₃ confirm some aspects of the proposed mechanisms, although it is clear that a great deal still has to be learned concerning mechanistic aspects of nucleophilic attack on these 17-electron complexes.     

Synthesis, biochemical properties and molecular modelling studies of organometallic specific estrogen receptor modulators (SERMs), the ferrocifens and hydroxyferrocifens: evidence for an antiproliferative effect of hydroxyferrocifens on both hormone-dependent and hormone-independent breast cancer cell lines

A series of ferrocene derivatives based upon the structure of the antiestrogenic drug tamoxifen or of its active metabolite hydroxytamoxifen has been prepared and named by analogy ferrocifens and hydroxyferrocifens. This series includes 1-[4-(O(CH(2))(n)NMe(2))phenyl]-1-phenyl-2-ferrocenyl-but-1-ene and 1-[4-(-O(CH(2))(n)NMe(2))phenyl]-1-(4-hydroxyphenyl)-2-ferrocenyl-but-1-ene, with n=2, 3, 5 and 8, and 1-[4-(-O(CH(2))(2)NMe(2))phenyl]-1-(4-hydroxyphenyl)-2-ferrocenylethene. Most of these molecules have been synthesised by McMurry cross-coupling of the appropriate ketones, except for the ethene complexes, which were prepared by a four-step reaction sequence starting from the ferrocenylacetic acid. All these compounds were obtained as mixtures of Z and E isomers. The isomers were separated in the cases of the ferrocenyl derivatives of tamoxifen and hydroxytamoxifen (n=2). No isomerisation of the Z and E isomers occurred in DMSO after one day, while a 50:50 mixture of the isomers was obtained within one hour in chloroform. The X-ray structure of (E)-1-[4-(-O(CH(2))(2)NMe(2))phenyl]-1-(4-hydroxyphenyl)-2-ferrocenyl-but-1-ene has been determined. The relative binding affinity (RBA) values of the hydroxyferrocifens for the estrogen receptor alpha (ERalpha) was good to moderate, with values decreasing progressively with the length of the basic chain. The RBA values found for the estrogen receptor beta (ERbeta) are equal to or slightly less than those found for the alpha form. The lipophilicity of the hydroxyferrocifens are superior to the values found for estradiol and increase with lengthening of the chain. The antiproliferative effects of the four hydroxyferrocifens with n=2, 3, 5 and 8 were studied on four breast cancer cell lines (MCF7, MDA-MB231, RTx6 and TD5) possessing different levels of ERalpha. On MCF7 cells containing high levels of ERalpha, hydroxyferrocifens behave as antiestrogens. At a molarity of 1 microM the effect is close to that of hydroxytamoxifen (used for reference) when n=2 or 5, more marked when n=3, and weaker when n=8. Ferrocene alone has no effect. For the MDA-MB231 cells, classed as a hormone-independent breast cancer cell line, on the other hand, the hydroxyferrocifens show remarkable antiproliferative behaviour while the hydroxytamoxifen is completely inactive. Hydroxyferrocifens therefore show the unique property of being active both on hormone-dependent and on hormone-independent breast cancer cell lines. The molecular modelling study provides some clues for understanding of the antagonist effect of these molecules, while an additional cytotoxic effect due to the vectorised ferrocenyl unit is revealed in some occasions.     

羟烷基壳聚糖制备及应用研究进展

壳聚糖是由甲壳素通过脱乙酰作用得到的一种天然高分子多糖,具有良好的生物相容性、抗菌性、无毒和可生物降解等优点,但壳聚糖水溶性差限制了其在很多方面的应用。为克服壳聚糖在水溶性上的不足,利用壳聚糖结构中氨基和羟基上的活泼氢进行化学改性以引进羟烷基等亲水性基团成为重要手段。本文主要对壳聚糖羟烷基化改性的方法及羟烷基壳聚糖在医药、水处理和组织工程材料等领域的研究和应用现状进行介绍,并对羟烷基壳聚糖未来的发展趋势进行了展望。     

Acetylene chemistry,part XXII [1, 2]: Synthesis of noracronycine and some of its analogs via Mitsunobu-reaction

Summary The natural product noracronycine as well as some of its analogs were synthesized by Mitsunobu-etherisation, using propinol derivatives.

---

Acetylenchemie, 22. Mitt.: Synthese von Noracronycin und einiger Analoga mittels Mitsunobu-Reaktion (Kurze Mitt.)

Zusammenfassung Der Naturstoff Noracronycin sowie einige seiner Analoga konnten durch Mitsunobu-Veretherung unter Verwendung von Propinol-Derivaten synthetisiert werden.

     

Diterpenoids from Salvia ceratophylla

Salvia ceratophylla L. has yielded four known and two new diterpenoids together with two triterpenic acids, a steroid and a flavone. The structures of the compounds were established by spectroscopic analyses. One of the known compounds candidissiol exhibited a high antibacterial activity against Staphylococcus epidermidis and Proteus mirabilis.