Thermoplastic polymers quality control

A technique is proposed for improving the accuracy of the heat of fusion of semicrystalline polymers by DSC. The results of three commercially available instruments are compared.     

Ion pair charge-transfer complexes between anionic and cationic metal-dithiolenes [M(II) = Pd,Pt

New [M(R(2)pipdt)(2)](BF(4))(2) salts [R(2)pipdt = N,N'-dialkyl-piperazine-2,3-dithione; M = Pd(II), R = Me and M = Pt(II), R = Me, Et, Pr(i)] bearing redox-active cationic dithiolene complexes have been prepared and characterized. These cations react with the redox-active [M(mnt)(2)](2-) [M = Pd(II), Pt(II); mnt = maleonitrile-2,3-dithiolate] anionic dithiolenes to form salts describable as ion pair charge-transfer complexes. X-ray crystallographic studies have shown that [M(Me(2)pipdt)(2)][M(mnt)(2)] complexes, with M = Pd(II) and Pt(II), are isomorphous. Crystal data of the Pt salt (3a): triclinic, Ponemacr; (No. 2); Z = 1; T = 293(2) K; a = 6.784(7) A, b = 8.460(6) A, c = 13.510(5) A, alpha = 100.63(2) degrees, beta = 104.04(2) degrees, gamma = 96.90(2) degrees; R1 = 0.0691 [wR2 = 0.2187 (all data)]. Structural data show that approximately square-planar [Pt(Me(2)pipdt)(2)] dications and regular square-planar [Pt(mnt)(2)] dianions form an infinite anion-cation one-dimensional stack along axis a with a Pt...Pt a/2 distance of 3.392 A and a Pt...Pt...Pt angle of 180 degrees. Anions and cations arrange themselves face-to-face so as to take on a staggered arrangement. These salts exhibit strong absorptions in the visible-near-infrared region assigned to ion pair charge-transfer transitions. A relation between the optical and thermal electron transfer in the solid state is obtained using a "Marcus-Hush model", and a solid-state electrical conductivity in agreement with expectations is observed. Vibrational spectroscopy is in agreement with the existence of charge-transfer interactions between the cationic and anionic components of the salts.     

Novel P‐Stereogenic PCP Pincer‐Aryl Ruthenium(II) Complexes and Their Use in the Asymmetric Hydrogen Transfer Reaction of Acetophenone

Achiral P‐donor pincer‐aryl ruthenium complexes ([RuCl(PCP)(PPh₃)]) 4c , d were synthesized via transcyclometalation reactions by mixing equivalent amounts of [1,3‐phenylenebis(methylene)]bis[diisopropylphosphine] ( 2c ) or [1,3‐phenylenebis(methylene)]bis[diphenylphosphine] ( 2d ) and the N‐donor pincer‐aryl complex [RuCl{2,6‐(Me₂NCH₂)₂C₆H₃}(PPh₃)], ( 3 ; Scheme 2). The same synthetic procedure was successfully applied for the preparation of novel chiral P‐donor pincer‐aryl ruthenium complexes [RuCl(P*CP*)(PPh₃)] 4a , b by reacting P‐stereogenic pincer‐arenes (S,S)‐[1,3‐phenylenebis(methylene)]bis[(alkyl)(phenyl)phosphines] 2a , b (alkyl=ⁱPr or ^tBu, P*CHP*) and the complex [RuCl{2,6‐(Me₂NCH₂)₂C₆H₃}(PPh₃)], ( 3 ; Scheme 3). The crystal structures of achiral [RuCl(equation/tex2gif-sup-3.gifPCP)(PPh₃)] 4c and of chiral (S,S)‐[RuCl(equation/tex2gif-sup-6.gifPCP)(PPh₃)] 4a were determined by X‐ray diffraction (Fig. 3). Achiral [RuCl(PCP)(PPh₃)] complexes and chiral [RuCl(P*CP*)(PPh₃)] complexes were tested as catalyst in the H‐transfer reduction of acetophenone with propan‐2‐ol. With the chiral complexes, a modest enantioselectivity was obtained.     

Degradation of imazosulfuron in different soils-HPLC determination

Imazosulfuron, 1-(2-chloroimidazo [1,2-a] pyridin-3-ylsulfonyl)-3-(4,6-dimethoxypyrimidin-2-yl)urea, is a new sulfonylurea herbicide applied once per growing season. It is highly active at low application levels and is used to control most annual and perennial broad-leaf weeds and some grasses in cereal crop. In this work the degradation of imazosulfuron in four different soils was investigated under aerobic laboratory conditions to evaluate its environmental fate. Test soils were treated with this herbicide in acetonitrile to obtain a final concentration of 0.2 mg kg(-1) (100 g ha(-1)), extracted with methylene chloride and analyzed by reversed-phase liquid chromatography (RP-HPLC) using a C(18) column coupled with UV detection. Recoveries of spiked soils ranged from 84.3 to 99.8% (RDS 0.0-4.9%; n = 4). The limits of quantitation ranged from 0.002 to 0.004 mg kg(-1). Imazosulfuron half-life, t(1/2), was calculated in each of the investigated soil. In aerobic conditions it ranged between 1 and 50 days.     

Interactions modes and physical properties in transition metal chalcogenolene-based molecular materials

Molecule-based materials are extremely versatile materials as they can be built from specifically designed building blocks with the desired size, shape, charge and electronic properties which determine their intermolecular interactions and, thus, their organization in the solid. The intermolecular interactions, therefore, in particular van der Waals interactions, π–π and π–d interactions, H-bonding, etc., play a crucial role in self-assembling these pre-designed molecular units and may provide a powerful way to afford layered mono- and multifunctional molecular materials with new or unknown physical properties. In this review the relationship between interaction modes and physical properties of organic/inorganic hybrids based on transition metal complexes with chalcogenolene ligands will be examined and an outlook will be proposed. With this goal, magnetic materials, highly conducting and metallic single-component materials containing dithiolene complex building blocks, multifunctional materials where the dithiolene complex is the magnetic or conducting component in addition to more complex systems involving other types of building block such as the metal oxalate complexes, will be discussed.     

Pd-Dissolution through a mild and effective one-step reaction and its application for Pd-recovery from spent catalytic converters

We describe here an innovative method for Pd-dissolution using the reagent N,N'-dimethylperhydrodiazepine-2,3-dithione diiodine adduct which, being safe and powerful, is appealing for practical applications: remarkably almost quantitative Pd-recovery from model spent three-way catalysts has been obtained, showing that the effectiveness of the method is maintained when palladium is contained in a complex system such as a car catalyst, a ceramic material which has undergone severe thermal stress.     

Synthesis, crystal structure and properties of the semiconducting salts (TTF)2[Ni(dtcr)2] and (ET)2[Ni(dtcr)2] based on [Ni(dtcr)2] dianions (dtcr = dithiocroconate)

The first examples of CT salts based on [Ni(dtcr)2] dianions (1) (dtcr = dithiocroconate = 4,5-disulfanylcyclopent-4-ene-1,2,3-trionate), (TTF)2[Ni(dtcr)2] (TTF = tetrathiafulvalene) (2) and (ET)2[Ni(dtcr)2] [ET = bis(ethylenedithio)tetrathiafulvalene] (3) are reported. The redox-active dianion 1, containing oxo-groups in the periphery of the molecule, has been selected to investigate the role of the oxo-groups in promoting intermolecular interactions and hopefully their conducting properties. The salts 2 and 3 have been prepared by electrocrystallisation methods and 3 shows a semi-metallic behaviour: sigma = 1 x 10(-3) omega(-1) cm(-1) at room temperature, with a low activation energy 60 meV, while crystals of 2 were unsuitable for conductivity measurements. The X-ray structural characterisation shows an alternate dianion-(cation)2 stacking and the capability of the oxo-groups to promote interstack contacts. In 2, the TTF donors are present as face-to-face dimers of monocations (D2)2+. The stacking arrangement is different in 3, where ET monocations stack along two directions ([110] and [110]) in the same manner, with the repeating sequence (ET)-(ET)-[Ni(dtcr)2]-(ET)-(ET) and are almost parallel to each other, with interplanar distances of 3.575 angstroms. Both structures are built on a dianion and two donor molecules, each one with a charge of +1. Diffuse reflectance combined with vibrational spectra complement structural results well. Crystal data: both 2 and 3 crystallise in the monoclinic space group P2(1)/c with a = 8.6340(8) angstroms, b = 21.586(2) angstroms, c = 7.5960(8) angstroms, beta = 95.625(11) degrees and V = 1408.9(2) angstroms3 for 2 and with a = 9.3700(7), b = 7.4410(6), c = 28.278(2) angstroms, beta = 99.039(6) degrees, V = 1947.1(3) angstroms3 for 3.     

Multidimensional NMR spectroscopy for the study of histone H4-Ni(II) interaction

The N-terminal 30-amino acid tail of histone H4, a nuclear protein, was studied as a model for the interaction of this protein with Ni(ii) ions. The behaviour of the ends-blocked Ac-SGRGKGGKGLGKGGA(15)K(16)R(17)H(18)R(19)KVLRDNIQGIT-Am fragment towards Ni(ii) was analyzed with multidimensional NMR (1D, 2D TOCSY, NOESY) and UV-Vis spectroscopy. As expected, the coordination involved the imidazolic nitrogen of the His(18) residue and the three deprotonated amidic nitrogens of the His(18), Arg(17) and Lys(16) residues, respectively. A model for the structure of the complex was calculated from the inter-residual NOEs recorded in 2D NOESY spectra. The structure obtained shows that the interaction with the metal is responsible for deep changes in the conformation of the peptide, blocking the side chain of Arg(17) and Lys(16) residues above the coordination plane. These structural modifications may be physiologically relevant to the mechanism of nickel carcinogenesis.     

Mn(II) and Zn(II) interactions with peptide fragments from Parkinson's disease genes

Two peptide sequences from PARK9 Parkinson's disease gene, ProAspGluLysHisGluLeu, (P(1)D(2)E(3)K(4)H(5)E(6)L(7)) (1) and PheCysGlyAspGlyAlaAsnAspCysGly (F(1)C(2)G(3)D(4)G(5)A(6)N(7)D(8)C(9)G(10)) (2) were tested for Mn(II), Zn(II) and Ca(II) binding. The fragments are located from residues 1165 to 1171 and 1184 to 1193 in the PARK9 encoded protein. This protein can protect cells from poisoning of manganese, which is an environmental risk factor for a Parkinson's disease-like syndrome. Mono- and bi-dimensional NMR spectroscopy has been used to understand the details of metal binding sites at different pH values and at different ligand to metal molar ratios. Mn(II) and Zn(II) coordination with peptide (1) involves imidazole N(ε) or N(δ) of His(5) and carboxyl γ-O of Asp(2), Glu(3) and Glu(6) residues. Six donor atoms participate in Mn(II) binding resulting in a distorted octahedral geometry, possibly involving bidentate interaction of carboxyl groups; four donor atoms participate in Zn(II) binding resulting in a tetracoordinate geometry. Mn(II) and Zn(II) coordination involves the two cysteine residues with peptide (2); Mn(II) accepts additional ligand bonds from the carboxyl γ-O of Asp(4) and Asp(8) to complete the coordination sphere; the unoccupied sites may contain solvent molecules. The failure of Ca(II) ions to bind to either peptide (1) or (2) appears to result, under our conditions, from the absence of chelating properties in the chosen fragments.     

A New Conducting Molecular Solid Based on the Magnetic [Ni(dmf)6] Cation and on [Ni(dsit)2]2 (dsit=1,3-dithiole-2-thione-4,5-diselenolate) Showing an Unprecedented Anion Packing

The synthesis, X-ray structure, magnetic and transport properties of the compound Ni(dmf)₆[Ni(dsit)₂]₂ (dmf=dimethylformamide, dsit=1,3-dithiole-2-thione-4,5-diselenolate) are described. This compound crystallizes in the monoclinic space group P2₁/c, with a=18.709(6), b=22.975(5), c=20.418(5) Å, β=99.31(2)° and Z=6; its structure consists of [Ni(dsit)₂]₂²⁻ dimers and isolated [Ni(dmf)₆]²⁺ cations both centrosymmetric and non-centrosymmetric. The dimers are packed forming chains along the [101] direction with short Se·Se interdimer contacts. Additional interchains S·S contacts render this structure a three-dimensional character, never observed so far in other [Ni(dsit)₂]⁻ salts. This compound exhibits semiconducting behavior with a room temperature conductivity (1 S cm⁻¹) much higher than those reported for other salts of the [Ni(dsit)₂]⁻ anion. Tight-binding band structure calculations were used to analyze the origin of the semiconducting properties of this salt. The magnetic susceptibility shows Curie behavior with C=1.25 emu K mol⁻¹, typical of isolated Ni(II) ions as expected for the octahedrally coordinated [Ni(dmf)₆]²⁺ cations.