Stereoselective synthesis of atropisomeric korupensamines A and B utilizing planar chiral arene chromium complex

Naphthyl tetrahydroisoquinoline alkaloids, atropisomeric korupensamines A and B and ent-korupensamine B, were synthesized by syn-selective cross-coupling of a planar chiral arene chromium complex with naphthylboronic acid and subsequent axial isomerization or tricarbonylchromium migration to the inverted arene face as a key step. Palladium(0)-catalyzed cross-coupling of planar chiral arene chromium complex 12 with naphthylboronic acid 9 gave syn-biaryl coupling product 13. syn-Biaryl chromium complex 13 was heated in 1:1 mixture of di-n-butyl ether and 1,2-dichloroethane to give a face-inverted anti-biaryl chromium complex 14 without axial isomerization. Korupensamine A was synthesized from the syn-biaryl chromium complex 13 via o-formyl syn-biaryl chromium complex 10, and ent-korupensamine B was prepared from the face-inverted anti-biaryl chromium complex 14. On the other hand, difluoro-substituted syn-biaryl chromium complex 40 with a formyl group afforded anti-biaryl chromium complex 41 containing a rotated central bond by heating in xylene. The chromium-complexed fluorine atom was easily substituted with an isopropoxy group by nucleophilic substitution. Use of these reactions allowed (+)-2-bromo-3,5-difluorobenzaldehyde chromium complex (37) as a single chiral source to be converted to atropisomeric korupensamines A and B, respectively.     

Complexation of aminoglycoside antibiotics with metal cations as a derivatization reaction: Determination of gentamicin by equilibrium electrochemical and spectrophotometric methods

The complexation of aminoglycoside antibiotics with metal cations was proposed as a derivatization method for the further determination of the complex obtained by potentiometry with ion-selective electrodes (ISE), voltammetry at the interface between two immiscible electrolyte solutions (ITIES), and spectrophotometry. It was shown by the spectrophotometric method that gentamicin formed a 1: 1 complex with copper(II). For the potentiometric determination of gentamicin, we obtained ionophores that were ion associates formed by the gentamicin complex of copper(II) and tetraphenylborate derivatives as counterions. The transfer of the gentamicin complex of copper(II) was studied voltammetrically at the ITIES. The results obtained indicate that l antibiotic gentamicin can be directly determined as a complex with copper(II) by potentiometric, voltammetric, and spectrophotometric methods.     

Anion directed synthesis of paddlane and trisilver tweezer complexes based upon silver coordination chemistry

Addition of AgBF4 or Ag(O3SCF3) to the tripodal ligand, Me3tacnRh(CCPh)3, yields a paddlane complex as well as a novel trinuclear silver "tweezer" complex based upon silver acetylene coordination chemistry. The paddlane is composed of two Me3tacnRh(CCPh)3 moieties held together by silver acetylene interactions. The tweezer complex is composed of one tripodal moiety with three silver atoms coordinated to each acetylene-Rh-acetylene face. The tweezer complex is stabilized by additional interactions, including a triflate anion which serves to cap the complex.     

Synthesis and biodistribution of the 99m TcN-DMSA complex as a potential bone imaging agent

In this study, the preparation of the 99m TcN complex of DMSA (dimercaptosuccinicacid) was carried out as a freeze-dried formulation, through a simple procedureinvolving the initial of 99m TcO 4 – with succinic dihydrazide in thepresence of stannous chloride as reducing agent, followed by the additionof the ligand DMSA to afford the final product. The radiochemical purity ofthe 99m TcN-DMSA complex was over 90% determined by thin layer chromatography.It was stable over 8 hours at room temperature. Its partition coefficientindicated that it was a good hydrophilic complex. Biodistribution in miceshowed that the 99m TcN-DMSA complex was accumulated in bone with high uptakeand good retention, suggesting it would be potentially useful as a bone imagingagent containing the [ 99m TcN] 2+ core. The biodistribution comparison inmice of the 99m TcN-DMSA complex and the 99m Tc-DMSA complex indicate thatthe presence of the 99m Tc nitrido group significantly alters the biologicalproperties of the 99m Tc complex.     

基于多金属氧簇的手性超分子液晶

以手性诱导为切入点,采用含胆固醇基团的季铵盐表面活性剂静电包覆缺位的Keggin结构多金属氧簇K7PW11O39·12H2O,得到了手性介晶阳离子修饰的多金属氧簇杂化超分子复合物。圆二色谱对该复合物光学活性的表征说明外围的手性表面活性剂可以通过静电相互作用诱导复合物显示出手性。利用差示扫描量热曲线法、偏光显微镜观察和变温X射线衍射详细研究了该复合物的热性质和相行为,结果表明该复合物在较宽的温度范围内具有热致液晶性质,是一种典型的手性近晶A相离子液晶材料。     

基于多金属氧簇的手性超分子液晶

以手性诱导为切入点,采用含胆固醇基团的季铵盐表面活性剂静电包覆缺位的Keggin结构多金属氧簇K₇PW₁₁O₃₉·12H₂O,得到了手性介晶阳离子修饰的多金属氧簇杂化超分子复合物。圆二色谱对该复合物光学活性的表征说明外围的手性表面活性剂可以通过静电相互作用诱导复合物显示出手性。利用差示扫描量热曲线法、偏光显微镜观察和变温X射线衍射详细研究了该复合物的热性质和相行为,结果表明该复合物在较宽的温度范围内具有热致液晶性质,是一种典型的手性近晶A相离子液晶材料。     

交联木质素负载钯催化剂的制备及对Heck反应的催化性能研究

以天然木质素为原料, 用甲醛对其进行交联得到了交联木质素, 通过简单的方法合成了负载钯催化剂, 用XPS、 TG、 DTA等对其进行了表征. 该催化剂在空气氛围中能很好的催化乙烯基化合物与芳基碘的Heck反应. 如在较低的温度下(40 ℃)催化丙烯酸与碘苯的反应, 产率高达73.7%, 显示了较高的催化活性. 该催化剂重复使用5次, 产率仍高达90%, 显示该催化剂有良好的重复使用性能.     

Indenyl-functionalised triethylborane adduct of N-heterocyclic carbene: stepwise coordination of indenyl and NHC ligands toward molybdenum fragment

Indenyl-functionalised BEt(3)-adduct NHCs were prepared by the reaction of imidazolium pro-ligands with LiBEt(3)H. This compound was converted into the indenyl-coordinate molybdenum complex dangling the NHC·BEt(3) moiety as a substituent. The stepwise coordination of NHC afforded a chelate-type mononuclear complex as well as a bimetallic complex.     

QUENCHING OF PHOTOEXCITED 4,4'-DICARBOXY-2,2'-BIPYRIDINEBIS(2,2'-BIPYRIDINE)RUTHENIUM(II) BY OXYGEN IN AQUEOUS SOLUTION AND IN SILK FIBROIN MEMBRANE

Abstract— Photoluminescence and quenching of 4,4'-dicarboxy-2,2'-bipyridinebis(2,2'-bipyridine)-ruthenium(II) complex (Ru(DCbpy)(bpy)²₂⁺) in an aqueous solution as well as in a silk fibroin membrane were studied. Emission quenching by oxygen in an aqueous solution showed a linear relationship with respect to oxygen concentration. When the complex was incorporated into a silk fibroin membrane by adsorption from an aqueous solution into a preformed membrane, the photoexcited state of the complex was not quenched by oxygen in an aqueous phase. However, when the complex was incorporated into a silk fibroin membrane by casting a mixture of the complex and silk fibroin, the photoexcited complex was quenched by oxygen in an aqueous phase. In this case the Stern-Volmer plots showed a downward-deviating curve indicating heterogeneity of the probe site. Emission intensity decreased with an increase of the water content in the silk fibroin membrane.     

Light‐Controlled Release and Uptake of Zinc Ions in Solution by a Photochromic Terthiazole‐Based Ligand

We have synthesized and fully characterized a photochromic zinc complex with a terphenylthiazole‐based ligand with a salen‐like cavity. The solution stability of the complex was found to be greatly dependent on the state of the photochromic ligand and an interesting photo‐triggered release and uptake of zinc ions was found as well as monitored by its fluorescence. The contrasting stability difference of the zinc complex between its two isomeric states was rationalized by DFT calculations.     

Evaluation of 99mTc-HIDA complex as a cholescintigraphic agent (author's transl)

In the reaction labeling N-(2,6-dimethylphenylcarbamoylmethyl) iminodiacetic acid (HIDA) with 99mTc, several complexes with different chemical characteristics were observed to occur with slight changes in the labeling conditions. Among these complexes, a complex detected in the bile of rats was limited to one complex, named as complex II. The preparation method of 99mTc-HIDA complex II and the exchange reaction between this complex and penicillamine indicate that 99mTc is coordinated with HIDA as low-hydrolyzed 99mTc in this complex. This complex is excreted rapidly through the bile and within 1 hr, about 65% of the total activity injected is recovered from bile in rats. The organ distribution of this complex was studied in mice by radioassay and in rabbits by scintillation camera and, in both cases, the radioactivity was accumulated in the gallbladder. These results suggest that the 99mTc chemical state, low-hydrolyzed state, relates to the bile excretion behavior of this complex, a potentially useful cholescintigraphic agent.     

High-energy complex copper(II) perchlorate with 1,5-pentamethylenetetrasole as ligand

Possibility of obtaining an energy-saturated metal complex, copper tetrakis[cyclopentamethylenetetrasol] perchlorate, was studied by reacting copper(II) perchlorate hexahydrate with cyclopentamethylenetetrazol. The composition and structure of the complex were confirmed by elemental analysis and UV, IR, ¹H NMR, and ESR spectroscopies. The thermal decomposition of the metal complex synthesized was analyzed and its explosive characteristics and combustion law, as well as the combustion law of a model formulation of a composite solid propellant with addition of the complex, were determined.     

Synthesis, structural characterization and catalytic activity of a multifunctional enzyme mimetic oxoperoxovanadium(V) complex

The synthesis and structural characterization of a novel oxoperoxovanadium(V) complex [VO(O(2))(PAH)(phen)] containing the ligands 2-phenylacetohydroxamic acid (PAHH) and 1,10-phenanthroline (phen) has been accomplished. The oxoperoxovanadium(V) complex was found to mimic both vanadate-dependent haloperoxidase (VHPO) activity as well as nuclease activity through effective interaction with DNA. The complex is the first example of a structurally characterized stable oxoperoxovanadium(V) complex with a coordinated bi-dentate hydroximate moiety (-CONHO(-)) from 2-phenylacetohydroximate (PAH). The oxoperoxovanadium(V) complex has been used as catalyst for the peroxidative bromination reaction of some unsaturated alcohols (e.g. 4-pentene-1-ol, 1-octene-3-ol and 9-decene-1-ol) in the presence of H(2)O(2) and KBr. The catalytic products have been characterized by GC-MS analysis and spectrophotometric methods. The DNA binding of this complex has been established with CT DNA whereas the DNA cleavage was demonstrated with plasmid DNA. The interactions of the complex with DNA have been monitored by electronic absorption and fluorescence emission spectroscopy. Viscometric measurements suggest that the compound is a DNA intercalator. The nuclease activity of this complex was confirmed by gel electrophoresis studies.     

Preparation of Tc-HA complex by displacement of thiourea from the hexakis(thiourea-S)technetium(III) complex

The complexation of technetium with humic acid is usually done by a reduction of pertechnetate by Sn²⁺ ions. A Tc-HA complex can be scavenged in a Sn-HA complex, if tin is present as reductant. The main aim of the study was a preparation of the Tc-HA complex without impurities of Sn ions or other metal reductant, which was performed by a ligand exchange with hexakis(thiourea-S)technetium(III) under nitrogen atmosphere at pH 5.5. The [Tc(tu)₆]³⁺ complex was prepared from TcO₄ ^- in acidic solution with thiourea as a reductant. Presence of the Tc-HA complex and other technetium species was determined by gel chromatography, paper chromatography and dialysis. Yield of Tc-HA complex was about 80% and reaction mixture contains about 20% of technetium dioxide, which is a side product of ligand-exchange.     

水溶性茂钛配合物的表征及其在芳香酸茂钛衍生物合成中的应用

二氯二茂钛与5－磺基水杨酸形成了较为稳定的水溶性配合物。由等摩尔系列 法确定了其组成为1:1,通过对含5－磺基水杨酸二茂钛配离子的不溶性配合物1的 结构分析表明,其中的羧基以双齿形式与钛配位,形成了四元环状结构。首次利用 该水溶性配合物在水相和两体系中得到了八种新的二茂钛芳香酸衍生物,为配合物 2 ～ 9。运用元素分析、IR及~1H NMR对它们的组成和结构进行了表征,结果表明 ,这八种配合物中羧基均以单齿形式与钛配位,且不含5－磺基水杨酸配体。     

Monitoring the DNA binding kinetics of a binuclear ruthenium complex by energy transfer: evidence for slow shuffling

The semirigid binuclear ruthenium complex Delta,Delta-[mu-(11,11'-bidppz)(phen)(4)Ru(2)](4+) has been shown to rearrange slowly from an initial groove-bound nonluminescent state to a final intercalated emissive state by threading one of its bulky Ru(phen)(2) moieties through the DNA base stack. When this complex binds to poly[d(A-T)(2)], a further increase in emission from the complex is observed after completion of the intercalation, assigned to reorganization of the intercalated complex. We here report a study of the threading process in poly[d(A-T)(2)], in which the minor groove binding dye DAPI is used as an energy transfer probe molecule to assess the distribution of ruthenium complex during and also after the actual threading phase. The emission from DAPI is found to change with the same rate as the emission from the ruthenium complex, and furthermore, DAPI does not disturb the binding kinetics of the latter, justifying it as a good probe of both the threading and the reorganization processes. We conclude from the change in the emission from both DAPI and the ruthenium complex with time that DAPI-ruthenium interactions are most pronounced during the process of threading of the complex, suggesting that the complexes are initially threaded slightly anticooperatively and thereafter redistribute along the DNA to reach their thermodynamically most favorable distribution. The final distribution is characterized by a small but significant binding cooperativity, probably as a result of hydrophobic interactions between the complex ions despite their tetravalent positive charges. The mechanism of "shuffling" the complex along the DNA chain is discussed, i.e., whether the ruthenium complex remains threaded (requiring sequential base-pair openings) or if unthreading followed by lateral diffusion within the ionic atmosphere of the DNA and rethreading occurs.     

Investigations into sulfobetaine-stabilized Cu nanoparticle formation: toward development of a microfluidic synthesis

The mechanistic aspects of the formation of sulfobetaine-stabilized copper nanoparticles were investigated by using in situ XANES (X-ray absorption near edge structure), UV-vis spectroscopy, and reaction calorimetry. The tetracoordinated sulfobetaine-Cu(II) complex was reduced to a stable sulfobetaine-Cu(I) complex prior to the formation of sulfobetaine-stabilized copper nanoparticles. The stability of the Cu(I) complex was found to be sensitive to the concentration of the sulfobetaine stabilizer and the addition rate of the reducing agent. It appears to exist primarily as a linear complex. A tetracoordinated Cu(I) complex as an intermediate has also been postulated. Based on the understanding from these investigations, a microfluidic process for copper nanoparticle synthesis was designed by using sulfobetaine-Cu(I) complex as the starting material. When compared with the copper nanoparticles synthesized by a conventional batch process, the microfluidic reactor process provided particles with a smaller size and narrower size distribution. The copper nanoparticles from the microreactor process could also be more easily purified and the particles were relatively stable in air. Both XRD and SAED indicated that the Cu nanoparticles synthesized have fcc structure.     

A highly reactive mononuclear non-heme manganese(IV)-oxo complex that can activate the strong C-H bonds of alkanes

A mononuclear non-heme manganese(IV)-oxo complex has been synthesized and characterized using various spectroscopic methods. The Mn(IV)-oxo complex shows high reactivity in oxidation reactions, such as C-H bond activation, oxidations of olefins, alcohols, sulfides, and aromatic compounds, and N-dealkylation. In C-H bond activation, the Mn(IV)-oxo complex can activate C-H bonds as strong as those in cyclohexane. It is proposed that C-H bond activation by the non-heme Mn(IV)-oxo complex does not occur via an oxygen-rebound mechanism. The electrophilic character of the non-heme Mn(IV)-oxo complex is demonstrated by a large negative ρ value of -4.4 in the oxidation of para-substituted thioanisoles.     

Oxygen quenching of tris(2,2′-bipyridine) ruthenium(II) complexes in thin organic films

A study is presented of the quenching, by oxygen, of the luminescence of tris(2,2′-bipyridine) ruthenium(II) complexes immobilized in thin, transparent, polymer-based films. The film media consist of a water-insoluble linear polymer plasticized with a trialkylphosphate ester, in which the complex ruthenium cations are solubilized by ion pairing with organophilic anions such as tetraphenylborate.

Luminescence lifetimes were studied in relation oxygen concentration in a gas stream contiguous with the film medium, film thickness and concentration of the metal complex within the film medium. It is shown that the microheterogeneous environment of the luminescent complex, which has recently been implicated in the non-linear quenching responses of polymer-immobilized, transition metal complex oxygen sensors, may arise simply as a consequence of the limited solubility of the complex in the film medium. When solubility is limited, the partial precipitation of the complex results in a colloidal of luminescent particles which exhibit non- uniform susceptibilities to quenching by oxygen. Good solubility, and therefore linear quenching characteristics, are promoted by methyl substitution of the bipyridyl ligand and by use of a plasticizer (tributylphosphate) with marked cation solvating powers.     

Visible Light‐Triggered Photoswitchable Diarylethene‐Based Iridium(III) Complexes for Imaging Living Cells

A novel diarylethene‐based iridium(III) complex was synthesized as a phosphorescence probe for monitoring living cells. The switchable phosphorescence complex in solution and within living cells was controlled by two distinguishable visible‐light irradiations, which suggests that this complex can be developed as a promising probe with weak photodamage for biological samples.