An interpretation of the yield behaviour of polymers in terms of correlated motion

An interpretation of yield behaviour in polymers is given in terms of the stress-activated flow of structural units over an energy barrier together with an additional correlated component to the motion. This correlated contribution takes account, in the simplest way possible, of the state of other conformations, and it is shown to lead to an effective activation-energy barrier which depends in part on the strain present at any time in the material. In this manner, the present work relates to previous work by M.G. Brereton, S.G. Croll, R.A. Duckett and I.M. Ward (1974), who, on purely phenomenological grounds, proposed a relation between stress and strain which had the form of a feedback equation. Specifically, the strain resulting from an applied stress was assumed to modify the material in a way which reduced its resistance to stress. The basic equation obtained here is non-linear and shows a yield-like behaviour resulting from a dynamical (as opposed to a geometrical) instability. Furthermore, it indicates a consistent relation between yield in creep tests and in constant strain-rate tests.     

Hyperpolarising Pyruvate through Signal Amplification by Reversible Exchange (SABRE)

Hyperpolarisation methods that premagnetise agents such as pyruvate are currently receiving significant attention because they produce sensitivity gains that allow disease tracking and interrogation of cellular metabolism by magnetic resonance. Here, we communicate how signal amplification by reversible exchange (SABRE) can provide strong ¹³C pyruvate signal enhancements in seconds through the formation of the novel polarisation transfer catalyst [Ir(H)₂(η²‐pyruvate)(DMSO)(IMes)]. By harnessing SABRE, strong signals for [1‐¹³C]‐ and [2‐¹³C]pyruvate in addition to a long‐lived singlet state in the [1,2‐¹³C₂] form are readily created; the latter can be observed five minutes after the initial hyperpolarisation step. We also demonstrate how this development may help with future studies of chemical reactivity.     

Palladium catalysed alkyne hydrogenation and oligomerisation: a parahydrogen based NMR investigation

The role phosphine ligands play in the palladium(ii)-bis-phosphine-hydride cation catalysed hydrogenation of diphenylacetylene is explored through a PHIP (parahydrogen induced polarization) NMR study. The precursors Pd(LL')(OTf)(2) () [LL' = dcpe (PCy(2)CH(2)CH(2)PCy(2)), dppe, dppm, dppp, cppe (PCy(2)CH(2)CH(2)PPh(2))] are used. Alkyl palladium intermediates of the type [Pd(LL')(CHPhCH(2)Ph)](OTf) ( and ) are detected and demonstrated to play an active role in hydrogenation catalysis. Magnetization transfer experiments reveal chemical exchange from the alpha-H of the alkyl ligand of (LL' = dcpe) and linkage isomer ' (LL' = cppe) into trans-stilbene on the NMR timescale. Activation parameters (DeltaH( not equal) and DeltaS( not equal)) for this transformation have been determined. These experiments, coupled with GC/MS data, indicate that the catalytic activity is greater in methanol, where it follows the order: dcpe > cppe > dppp > dppe > dppm, than in CD(2)Cl(2). All five of the phosphine systems described are less active than those based on bcope [where bcope is (C(8)H(14))PCH(2)-CH(2)P(C(8)H(14))] and (t)bucope [where (t)bucope is (C(8)H(14))PC(6)H(4)CH(2)P((t)Bu)(2)]. cis, cis-1,2,3,4-Tetraphenyl-buta-1,3-diene is detected as a minor reaction product with Pd(LL')(PhCH-CHPh-CPh[double bond, length as m-dash]CHPh)(+) () also being shown to play a role in the alkyne dimerisation step.     

Palladium-catalyzed hydrogenation: detection of palladium hydrides. A joint study using para-hydrogen-enhanced NMR spectroscopy and density functional theory

Pd(PEt3)2(OTf)2, acting as an in situ source of Pd(PEt3)2, reacts with an alkyne and hydrogen via phosphine loss to form the detectable hydride-containing species Pd(PEt3)2(H)(CHPhCH2Ph), cis- and trans-Pd(PEt3)2(H)(CPh=CHPh), and Pd2(PEt3)3(H)(CHPhCH2Ph)2+, which map onto the reaction scheme predicted by density functional theory.     

The dependence of yield behavior on temperature,pressure, and strain rate for linear polyethylenes of different molecular weight and morphology

The temperature, strain-rate, and pressure dependences of the yield stress have been determined for two polyethylene homopolymers of differing molecular weights and for a polyethylene copolymer. Samples were prepared by slowly cooling from the melt, and also by quenching in order to assess the effects of morphology on the yield behavior. The data have been analyzed on the basis of two Eyring processes acting in parallel. Comparison of all data sets reveals the existence in general of three distinct activated processes each with its own temperature, strain-rate, and pressure dependences. The relative contribution of each process is dependent on the molecular weight, morphology, etc. Also discussed is the relation of these three yield processes to the well-known loss processes of linear viscoelasticity.     

Hyperpolarisation of weakly binding N-heterocycles using signal amplification by reversible exchange

Signal Amplification by Reversible Exchange (SABRE) is a catalytic method for improving the detection of molecules by magnetic resonance spectroscopy. It achieves this by simultaneously binding the target substrate (sub) and para-hydrogen to a metal centre. To date, sterically large substrates are relatively inaccessible to SABRE due to their weak binding leading to catalyst destabilisation. We overcome this problem here through a simple co-ligand strategy that allows the hyperpolarisation of a range of weakly binding and sterically encumbered N-heterocycles. The resulting ¹H NMR signal size is increased by up to 1400 times relative to their more usual Boltzmann controlled levels at 400 MHz. Hence, a significant reduction in scan time is achieved. The SABRE catalyst in these systems takes the form [IrX(H)₂(NHC)(sulfoxide)(sub)] where X = Cl, Br or I. These complexes are shown to undergo very rapid ligand exchange and lower temperatures dramatically improve the efficiency of these SABRE catalysts.

The scope of the hyperpolarisation method Signal Amplification by Reversible Exchange (SABRE) is dramatically expanded through the use of co-ligands to substrates that weakly interact with the active cataylst.

Hyperpolarised magnetic resonance is receiving increasing attention from both the analytical science and medical communities due to its ability to create signals that are many orders of magnitude higher than those normally detected under Boltzmann control.^1–6 The time and cost benefits associated with this improvement have propelled this area of research forward over the past few decades. Two of the most prominent techniques used to create hyperpolarisation are dissolution Dynamic Nuclear Polarisation (d-DNP) and Para-Hydrogen Induced Polarisation (PHIP),^7,8 which derive their non-Boltzmann spin energy level populations from interactions with unpaired electrons and para-hydrogen (p-H₂, the singlet spin isomer of hydrogen), respectively. Both of these methods have been reviewed in detail.^3–5,9,10Signal Amplification by Reversible Exchange (SABRE) is a PHIP method that does not involve the chemical incorporation of p-H₂ into the target substrate.^11,12 Instead, under SABRE, spin order transfer proceeds catalytically through the temporary formation of a scalar coupling network between p-H₂ derived hydride ligands and the substrate''s nuclei whilst they are located in a transient metal complex. The most common catalysts are of the type [Ir(H)₂(NHC)(sub)₃]Cl (where NHC = N-heterocyclic carbene and sub = the substrate of interest, Fig. 1a),^13,14 although other variants are known.^15–17 For SABRE to be accomplished, the target substrate must be able to reversibly ligate to the metal centre and this limits the methods applicability; although several routes to overcome this have been reported.^18–20 Recently, the use of bidentate ancillary ligands such as NHC-phenolates¹⁶ and phosphine-oxazoles²¹ has been shown to expand the applicability of SABRE for a variety of different ligands and solvents (Fig. 1b). For example, use of the PHOX ligand (PHOX = (2-diphenylphosphanyl)phenyl-4,5-dihydrooxazole) gives ¹H NMR signal gains of up to 132-fold for 2-picoline; a substrate previously shown to be unpolarised under classic SABRE conditions.²²Open in a separate windowFig. 1Development of the SABRE method for hyperpolarisation of a range of substrates.The use of co-ligands to stabilise the active SABRE catalyst has proven successful for substrates that weakly associate to the catalyst (Fig. 1c). Of particular note is the hyperpolarisation of sodium [1,2]-¹³C₂-pyruvate²³ and sodium ¹³C-acetate²⁴ which could be used as in vivo metabolic probes. The importance of co-ligands in breaking the chemical symmetry of the SABRE catalyst is also well established and co-ligands such as acetonitrile,²⁵ sulfoxides,^23,26 1-methyl-1,2,3-triazole²⁷ and substrate isotopologues²⁸ have been employed.We report here on the use of co-ligands to allow the NMR hyperpolarisation of weakly binding N-heterocyclic derived substrates with functionality in the ortho-position that have proven to be routinely inaccessible to the SABRE technique (Fig. 1d). ¹H signal gains of up to 1442 ± 84-fold were obtained for some of these substituted pyridines at 9.4 T and the expansion of this approach to ¹³C and ¹⁵N detection and other N-heterocyclic motifs is also exemplified.     

Development and validation of a NANOGold™ immunoassay for the detection of vascular endothelial growth factor (VEGF) in human serum using inductively coupled plasma mass spectrometry

This work aimed to develop and validate a NANOGold? based assay, quantified using inductively coupled plasma mass spectrometry (ICP‐MS), for the detection of human vascular endothelial growth factor (hVEGF) in serum. The initial assay range based on calibration standards was 62.5–2000 pg/mL with a detection limit of approximately 30 pg/mL. After validation using spiked validation controls, a quantification range between 175 and 1928 pg/mL was obtained. The inter‐assay precision was between 2.3 and 18.9% with accuracy between ?8.8 and ?3.1%. Additional performance parameters, including dilutional linearity, matrix specificity and time‐factored drift, were within ±20%, as defined by the validation acceptance criteria for the validation of macromolecule immunoassays used within our clinical environment. Serum samples from healthy donors were analysed to determine the endogenous levels of VEGF present; these ranged from 164 to 580 pg/mL with a mean of 273 pg/mL. The intra‐ and inter‐assay precision obtained from the healthy donor samples were 1.3–10.7% and 4.2–17.5%, respectively. This demonstration of a validated immunoassay opens further possibilities, utilising the simultaneous detection capabilities of ICP‐MS for the detection of multiple analytes in a single validated immunoassay, for routine use within a clinical environment. Copyright © 2010 John Wiley & Sons, Ltd.     

Photochemical isomerization of N-heterocyclic carbene ruthenium hydride complexes: in situ photolysis, parahydrogen, and computational studies

Low-temperature UV irradiation of the N-heterocyclic carbene complex Ru(IEt2Me2)(PPh3)2(CO)H2 (IEt2Me2 = 1,3-bis(ethyl)-4,5-dimethylimidazol-2-ylidene) leads to a remarkable photoisomerization reaction. By combining in situ photolysis and parahydrogen experiments to characterize the ultimate photoproducts and DFT calculations to interrogate the structures of the key 16-electron intermediates, the importance of both PPh3 and H2 loss pathways has been established.     

A model iridium hydroformylation system with the large bite angle ligand xantphos: reactivity with parahydrogen and implications for hydroformylation catalysis

Iridium complexes containing the large bite angle bisphosphine ligand xantphos have been synthesized and their reactivity studied. Several of these complexes are the first reported Ir(xantphos) systems to be characterized by X-ray diffraction. Variable-temperature NMR spectroscopic studies of IrI(CO)2(xantphos) (1-I) and Ir(COEt)(CO)2(xantphos) (8) show two separate dynamic processes in which the phosphorus donors and the backbone methyl groups of the xantphos ligand are exchanged. The addition of parahydrogen (p-H2) to 1-I leads to the formation of two dihydride isomers including one in which both hydride ligands are trans to the phosphorus donors, suggestive of an Ir(I) xantphos intermediate with the ligand chelated in a trans-spanning fashion (2b). The bromide and chloride Ir(I) analogues (1-Br and 1-Cl) also form this isomer upon reaction with parahydrogen, with 1-Cl yielding only this dihydride species. The trihydride complex IrH3(CO)(xantphos) (7) has been prepared, and its exchange with free hydrogen at elevated temperature is confirmed by reaction with p-H2. The hydride complexes IrH(CO)2(xantphos) (6) and IrH3(CO)(xantphos) (7), as well as the propionyl complex 8, are modest catalysts for the hydroformylation of 1-hexene and styrene under mild conditions. The addition of p-H2 to 8 permits direct observation of the propionyl dihydride species IrH2(COEt)(CO)(xantphos) (9) under both thermal and photolytic conditions, as well as unusual but weak polarization of the aldehydic proton of the propanal product that forms upon reductive elimination from 9.     

Parahydrogen studies of H2 addition to Ir(I) complexes containing chiral phosphine-thioether ligands: implications for catalysis

Ir(CO)[CpFe{eta5-C5H3(PPh2)CH2SR}]Cl [R = Ph and (t)Bu], containing a kappa2:P,S ligand, undergoes H2 addition across the S-Ir-CO axis under kinetic control to form two distinct diastereoisomeric products, which then rearrange via S dissociation in a process that can be hijacked for useful catalysis, but ultimately form a single diastereoisomer of the thermodynamic product where the hydride ligands are trans to chloride and phosphine.