Raman and UV-visible absorption spectra of ion-paired aggregates of copper porphyrins

Raman and UV-visible absorption spectra of ion-paired aggregate constructed from two copper porphyrins, copper tetrakis(4-N-methylpyridyl)porphyrin (CuTMPyP) and copper tetrakis(4-sulfonatophenyl)pophyrin (CuTSPP), are reported in this paper. The absorption bands of the aggregate was found exhibiting obvious shift and broadening, which are attributed to the excitonic coupling between the two paired porphyrin rings. The excitonic coupling in the aggregates also induces evident alteration for Raman intensities compared with monomer spectrum. Aggregation results in only small shifts (2-3 cm(-1)) for Raman lines connecting with the vibrations of porphyrin rings, manifesting only slight structural change of porphyrin skeletons. On the other hand, evident downshift (5 cm(-1)) was observed for the Cm-pyridyl stretch mode (1254 cm(-1)) of CuTMPyP, suggesting weakening of the Cm-pyridyl bonds by aggregation. Raman depolarization ratios of the aggregates are different from those of the monomers, implying a lowering of effective symmetry due to the molecular packing in the aggregates.     

Preparation and characterization of biodegradable nanoparticles based on amphiphilic poly(3-hydroxybutyrate)-poly(ethylene glycol)-poly(3-hydroxybutyrate) triblock copolymer

Amphiphilic triblock copolymers of poly(3-hydroxybutyrate)-poly(ethylene glycol)-poly(3-hydroxybutyrate) (PHB-PEG-PHB) were directly synthesized by the ring-opening copolymerization of β-butyrolactone monomer using PEG as macroinitiator. Their structure, thermal properties and crystallization were investigated by ¹H NMR, differential scanning calorimetry (DSC) and X-ray diffraction. It was found that both PHB and PEG blocks were miscible. With the increase in the PHB block length, the triblock copolymers became amorphous because amorphous PHB block remarkably depressed the crystallization of the PEG block. Biodegradable nanoparticles with core-shell structure were prepared in aqueous solution from the amphiphilic triblock copolymers, and characterized by ¹H NMR, SEM and fluorescence. The hydrophobic PHB segments formed the central solid-like core, and stabilized by the hydrophilic PEG block. The nanoparticle size was close related to the initial concentrations of the nanoparticle dispersions and the compositions of the triblock copolymers. Moreover, the PHB-PEG-PHB nanoparticles also showed good drug loading properties, which suggested that they were very suitable as delivery vehicles for hydrophobic drugs.     

Insertion reactions of hydridonitrosyltetrakis(trimethylphosphine) tungsten(0)

[W(H)(NO)(PMe3)4] (1) was prepared by the reaction of [W(Cl)(NO)(PMe3)4] with NaBH4 in the presence of PMe3. The insertion of acetophenone, benzophenone and acetone into the W-H bond of 1 afforded the corresponding alkoxide complexes [W(NO)(PMe3)4(OCHR1R2)](R1 = R2 = Me (2); R1 = Me, R2 = Ph (3); R1 = R2 = Ph (4)), which were however thermally unstable. Insertion of CO2 into the W-H bond of yields the formato-O complex trans-W(NO)(OCHO)(PMe3)4 (5). Reaction of trans-W(NO)(H)(PMe3)4 with CO led to the formation of mer-W(CO)(NO)(H)(PMe3)3 (6) and not the formyl complex W(NO)(CHO)(PMe3)4. Insertion of Fe(CO)(5), Re2(CO)10 and Mn2(CO)10 into trans-W(NO)(H)(PMe3)4 resulted in the formation of trans-W(NO)(PMe3)4(mu-OCH)Fe(CO)4 (7), trans-W(NO)(PMe3)4(mu-OCH)Re2(CO)9 (8) and trans-W(NO)(PMe3)4(mu-OCH)Mn2(CO)9 (9). For Re2(CO)10, an equilibrium was established and the thermodynamic data of the equilibrium reaction have been determined by a variable-temperature NMR experiments (K(298K)= 104 L mol(-1), DeltaH=-37 kJ mol(-1), DeltaS =-86 J K(-1) mol(-1)). Both compounds 7 and 8 were separated in analytically pure form. Complex 9 decomposed slowly into some yet unidentified compounds at room temperature. Insertion of imines into the W-H bond of 1 was also additionally studied. For the reactions of the imines PhCH=NPh, Ph(Me)C=NPh, C6H5CH=NCH2C6H5, and (C6H5)2C=NH with only decomposition products were observed. However, the insertion of C10H7N=CHC6H5 into the W-H bond of led to loss of one PMe3 ligand and at the same time a strong agostic interaction (C17-H...W), which was followed by an oxidative addition of the C-H bond to the tungsten center giving the complex [W(NO)(H)(PMe3)3(C10H6NCH2Ph)] (10). The structures of compounds 1, 4, 7, 8 and 10 were studied by single-crystal X-ray diffraction.     

Preparation of aromatic copolyesteramides by the direct polycondensation with a vilsmeier adduct derived from tosyl chloride and N,N-dimethylformamide

The reaction promoted by Vilsmeier adduct derived from tosyl chloride (TsCl) with N,N-dimethylformamide (DMF) was successfully applied to the preparation of copolyesteramides of high molecular weights directly from aromatic dicarboxylic acids, diamines, and bisphenols. The polycondensation was significantly affected by the reaction of activated dicarboxylic acids with bisphenols and diamines. Addition of a mixture of bisphenols and diamines likely caused gelation of the reaction mixtures, resulting in insoluble polymers, especially with high mol % diamines. Stepweise addition of them, however, gave the homogeneous reaction mixtures and copolymers of better solubility. These phenomena were studied in terms of sequence length distribution of polyester units, which was estimated by thermal analyses of the random copolymers prepared under various conditions for the initial reaction with bisphenols.     

242Pu as tracer for simultaneous determination of 237Np and 239,240Pu in environmental samples

A procedure has been developed using ²⁴²Pu as tracer for simultaneous determination of ²³⁷Np and ^239,240Pu in environmental samples. The validity of the method has been demonstrated by ICPMS and a-spectroscopy for up to 10 gram soil and sediment, seawater up to 200 litres. The paper describes a suitable chemical procedure for Np and Pu including a quantitative pre-concentration of neptunium and plutonium, preparation of Np⁴⁺ and Pu⁴⁺, Np(NO₃)₆ ^2- and Pu(NO₃)₆ ^2-. The ratio of ²³⁷Np/²⁴²Pu (or ²³⁷Np/²³⁹Pu) before and after the procedure has been determined using 10 g soil (free from Np and Pu) R _before/R _after = 1.004±3.3% (S.D n = 20) and 1 litre seawater R _before/R _after = 1.019±1.9% (S.D., n = 12). Results from the intercomparison samples IAEA-135, IAEA-381 and from environmental samples are presented.     

Enantioselective total syntheses of manzamine a and related alkaloids

As a prelude to undertaking the total syntheses of the complex manzamine alkaloids, a series of model studies were conducted to establish the scope and limitations of intramolecular [4 + 2] cycloadditions of N-acylated vinylogous ureas with the trienic substrates 17a,b, 28a,b, and 34. These experiments clearly demonstrated that the geometry of the internal double bond and the presence of an electron-withdrawing group on the diene moiety were essential for the facile and stereoselective formation of the desired cycloadducts. The enantioselective syntheses of the manzamine alkaloids ircinol A (75), ircinal A (5), and manzamine A (1) were then completed by employing a convergent strategy that featured a novel domino Stille/Diels-Alder reaction to construct the tricyclic ABC ring core embodied in these alkaloids. Thus, the readily accessible chiral dihydropyrrole 58 was first converted in a single chemical operation into the key tricyclic intermediate 60. Two ring-closing metathesis reactions were then used to form the 13- and 8-membered rings leading to Z-72 and 74, the latter of which was quickly elaborated into ircinal A (5) via ircinol A (75). The synthetic 5 thus obtained was converted into manzamine A (1) following literature precedent. This concise synthesis of ircinal A required a total of 24 operations from commercially available starting materials with the longest linear sequence being 21 steps.     

Synthesis and Structure of MnCl2(HDpyF) (HDpyF = N,N′‐di(2‐pyridyl)formamidine): New Crystallographic Disorder and Bonding Mode of the HDpyF Ligand

The reaction of N,N′‐di(2‐pyridyl)formamidine (HDpyF) with MnCl₂‐4H₂O afforded the complex MnCl₂(HDpyF), which was characterized by X‐ray crystallography. The HDpyF ligand chelates to the Mn(II) center through the first and the third nitrogen atoms to form a six‐membered ring, leaving the second and the fourth nitrogen atoms uncoordinated. The HDpyF ligand is crystallographically disordered such that two different molecules can be solved. The neutral HDpyF ligand adopts the new s‐cis‐syn‐s‐trans conformation.     

Optical second-harmonic generation from a monolayer of centrosymmetric molecules adsorbed on silver

An increase in the optical second-harmonic signal arising from an electrochemically treated silver surface upon adsorption of a monolayer of the centrosymmetric molecule pyrazine is reported and an effective second-order non-linear polariz-ability for the adsorbed species deduced. These investigations illustrate the potential of second-harmonic generation in the elucidation of interfaces.     

Preparative isolation and purification of lutein from the microalga chlorella vulgaris by high-speed counter-current chromatography

High-speed counter-current chromatography (HSCCC) was applied to the isolation and purification of lutein from microalgae. Analytical HSCCC was used for the preliminary selection of a suitable solvent system composed of n-hexane-ethanol-water (4:3:1, v/v). Using the above solvent system, preparative HSCCC was successfully performed yielding lutein at 98% purity from 200 mg of the crude extract in a one-step separation.     

Prediction of soil organic carbon partition coefficients by soil column liquid chromatography

To avoid the limitation of the widely used prediction methods of soil organic carbon partition coefficients (KOC) from hydrophobic parameters, e.g., the n-octanol/water partition coefficients (KOW) and the reversed phase high performance liquid chromatographic (RP-HPLC) retention factors, the soil column liquid chromatographic (SCLC) method was developed for KOC prediction. The real soils were used as the packing materials of RP-HPLC columns, and the correlations between the retention factors of organic compounds on soil columns (ksoil) and KOC measured by batch equilibrium method were studied. Good correlations were achieved between ksoil and KOC for three types of soils with different properties. All the square of the correlation coefficients (R2) of the linear regression between log ksoil and log KOC were higher than 0.89 with standard deviations of less than 0.21. In addition, the prediction of KOC from KOW and the RP-HPLC retention factors on cyanopropyl (CN) stationary phase (kCN) was comparatively evaluated for the three types of soils. The results show that the prediction of KOC from kCN and KOW is only applicable to some specific types of soils. The results obtained in the present study proved that the SCLC method is appropriate for the KOC prediction for different types of soils, however the applicability of using hydrophobic parameters to predict KOC largely depends on the properties of soil concerned.