Synthesis and characterization of Ru2(DMBA)4X2 (X = CN, N3, N(CN)2, I): controlling structural, redox, and magnetic properties with axial ligands

Metathesis reactions between Ru(2)(DMBA)(4)Cl(2) (DMBA = N,N'-dimethylbenzamidinate) and MX (M = Na and K) yielded bis-adduct derivatives Ru(2)(DMBA)(4)X(2) (X = CN (1), N(3) (2), N(CN)(2) (3)). Metathesis reactions between Ru(2)(DMBA)(4)(NO(3))(2) and KI resulted in Ru(2)(DMBA)(4)I(2) (4). Compound 1 is diamagnetic, while compounds 2-4 are paramagnetic (S = 1). Both compounds 1 and 2 undergo two reversible one-electron processes, an oxidation and a reduction, while compound 3 features a quasireversible reduction. Single-crystal X-ray diffraction studies revealed that the Ru-Ru bond lengths are 2.4508(9), 2.3166(7), 2.304[1], and 2.328(1) A for compounds 1-4, respectively. Structural and electrochemical data clearly indicate that the axial ligands impart a significant influence on the electronic structures of diruthenium species.     

Some results on the geometry of Choquet simplices

In this paper, we give some properties of Choquet simplices which lead to the characterization of the closed Choquet simplices of ⁿ.The results of this paper were presented at the Conference on Convexity and Foundation of Geometry held in Haifa (10–14 March 1975).     

IR, MS studies on (+/-)-1-[3-(2-methoxyphenoxy)-2-hydroxypropyl]-4-[(2,6-dimethylphenyl)aminocarbonylmethyl]piperazine dihydrochloride salt

The vibration spectrum and FAB mass spectrum of (+/-)-1-[3-(2-methoxyphenoxy)-2-hydroxypropyl]-4-[(2,6-dimethylphenyl)aminocarbonylmethyl]piperazine dihydrochloride salt was studied. By comparing with the spectra of free base, different bands of IR were found in the NH+ stretching, the NH+ deformation motion, the CH2 of NCH2 group symmetric stretching, the CH2 of N-CH2 group twisting and the CN stretching. FAB shows the basic peak is M + H. Other m/e peaks are consistent with the structure.     

Adaption of a fragment analysis technique to an automated high-throughput multicapillary electrophoresis device for the precise qualitative and quantitative characterization of microbial communities

The analysis of microbial communities is of increasing importance in life sciences and bioengineering. Traditional techniques of investigations like culture or cloning methods suffer from many disadvantages. They are unable to give a complete qualitative and quantitative view of the total amount of microorganisms themselves, their interactions among each other and with their environment. Obviously, the determination of static or dynamic balances among microorganisms is of fast growing interest. The generation of species specific and fluorescently labeled 16S ribosomal DNA (rDNA) fragments by the terminal restriction fragment length polymorphism (T-RFLP) technique is a suitable tool to overcome the problems other methods have. For the separation of these fragments polyacrylamide gel sequencers are preferred as compared to capillary sequencers using linear polymers until now because of their higher electrophoretic resolution and therefore sizing accuracy. But modern capillary sequencers, especially multicapillary sequencers, offer an advanced grade of automation and an increased throughput necessary for the investigation of complex communities in long-time studies. Therefore, we adapted a T-RFLP technique to an automated high-throughput multicapillary electrophoresis device (ABI 3100 Genetic Analysis) with regard to a precise qualitative and quantitative characterization of microbial communities.     

钙与 DBC-偶氮氯膦显色反应的研究及其在高纯氧化钇中钙的测定的应用

在PH8.5-9的液中,钙可与DBC-偶氮氯膦形成一种紫色的稳定配合物。该配合物在625nm处有最大吸收,表观摩尔吸光系数为2.6×10~4L.mol~(-1).cm~(-1),配合物组成为Ca:DBC-偶氮氯膦=1:1。在Zn-DTPA和乙二胺的存在下,较大量的Y~(3+)、Fe~(3+)及Cu~(2+)、Mo(Ⅵ)、Cr~(3+)等三十余种离子不干扰钙的测定。方法的选择性较好,利用本方法,并经简单萃取分离基体后,测定了高纯氧化钇和易切削钢中的微量钙,结果令人满意。标准加入试验回收率好。方法简便实用。     

3D H-bonding networks self-assembly from pyridinium derivatives and bis(maleonitriledithiolato)zincate(II)

The two ion-pair complexes, [pyH]₂[Zn(mnt)₂] (1) and [4,4′-bipyH₂]-[Zn(mnt)₂] (2), were synthesized, where mnt²⁻ denotes maleonitriledithiolate, and [pyH]⁺, [4,4′-bipyH₂]²⁺ represent pyridinium and diprotonated 4,4′-bipyridinium, respectively. Their single crystal structures show that there are strong bifurcated H-bonding interactions between the cations of the pyridinium derivative and the [Zn(mnt)₂]²⁻ anions in both 1 and 2. The bifurcated H-bonding interactions between the N–H of the pyridiniums and the CN groups of the mnt²⁻ ligands give rise to a 2D layered H-bonding network, the adjacent layers come together in such way as mutual embrace to give a tight pack, thus 2D hydrogen-bonding sheets further develop into 3D H-bonding networks through weak C–HS and ππ stacking interactions in 1. As for 2, the cations and anions connect into several types of H-bonding macrorings ([2+2], [3+3] and [4+4]), these H-bonding macrorings fuse to extend into 2D layered structure, the interpenetration between [3+3] and [4+4] type H-bonding macrorings in the adjacent layers give further rise to novel 3D extended H-bonding networks, in which there are clearly parallel stacks of cations and the chelate rings of anions.     

Preparation and Characterization of a Sol-Gel Prepared Ferroelectric Sandwich Structure

A novel silicon-based PbTiO₃/Pb(Zr,Ti)O₃/PbTiO₃ (PT/PZT/PT) sandwich structure has been prepared using a sol-gel method. The annealing temperature is greatly reduced compared with those structures without PT layers. Capacitance-voltage (C-V), leakage current-voltage (I-V), polarization-field (P-E), dielectric-frequency response and polarization fatigue of the sandwich structure are examined. The relative dielectric constant, the coercive field and the remanent polarization of the PZT films are measured to be about 900, 18 kV/cm and 16 C/cm² respectively. The current density is less than 5 × 10^–9 A/cm² below 200 kV/cm. The dielectric constant of the structure remains constant at low frequency, and decreases to some degree at high frequency. The retained polarization does not change significantly after 8 × 10⁹ read/write cycles. The PZT films are proved to have very good dielectric and ferroelectric properties. The new PT/PZT/PT sandwich structure can be valuable for memory devices and other applications.     

Palladium salicylaldimine complexes containing boronate esters

Reactions of salicylaldehydes with boronate ester derivatives of aniline have been examined. Addition of these Schiff base ligands to palladium acetate or Na₂PdCl₄ afforded novel boron-containing trans-bis(N-arylsalicylaldiminato) palladium complexes.Condensation of salicylaldehyde (2-HOC₆H₄C(O)H) with H₂NC₆H₄Bpin (pin=1,2-O₂C₂Me₄) afforded the boron-containing Schiff bases, 2-HOC₆H₄C(H)=NC₆H₄Bpin (1–3a). Similar reactivity with 2-hydroxy-5-nitrobenzaldehyde and 2-hydroxy-1-naphthaldehyde gave the corresponding Schiff bases (1-3b) and (1-3c), respectively. Reaction of Schiff bases (2) and (3) with palladium acetate or Na₂PdCl₄ afforded complexes of the type PdL₂ (4,5), where L=deprotonated Schiff base. The molecular structure of the nitro-salicylaldehyde 4-Bpin palladium complex (5b) was characterized by an X-ray diffraction study. All new palladium compounds have been characterized fully and tested for their antifungal activity against Aspergillus niger and Aspergillus flavus.     

Co-C bond dissociation energy and reaction volume change of 2',5'-dideoxyadenosylcobalamin studied by laser-induced time-resolved photoacoustic calorimetry

Time resolved photoacoustic calorimetry (PAC) was applied to a study of the photolysis of a coenzyme B(12) analog 2',5'-dideoxyadenosylcobalamin, which lacks an -OH group at the 2' position of ribofuranose ring. In aqueous solution, we report for the first time the quantum yield Phi(d) (0.25+/-0.02), Co-C bond dissociation energy (BDE; 31.8+/-2.5 kcal mol(-1)) and reaction volume change deltaV(R) (6.5+/-0.5 ml mol(-1)) due to conformation changes of the corrin ring and its side chains accompanying the cleavage of the Co-C bond. These values for the analog are very similar to those for the natural cofactor. Based our results and previous studies, a possible explanation for the similarity in their structure and properties versus the large difference in their enzymatic activity is discussed.