Quantitative and Stereoisomeric Determination of Light Biomarkers in Crude Oil and Coal Samples

Indans and tetralins are considered biological markers (biomarkers). These C9-C11 hydrocarbons are present in small amounts in organic geological samples. Methyl substituted indans or tetralins may possess a stereogenic center (carbon). Thus they can exist as enantiomers and, in the case of disubstituted enties, also as diastereoisomers. The concentrations of 1-methylindan, 1,3-dimethylindan, 1-methyltetralin, and 2-methyltetralin were determined in 16 crude oil samples of different sources and in 14 coal samples of different sources and ranks. Deuterated homologues were synthesized as standards to spike the samples and to assure accurate quantitative analysis. A procedure using HPLC fractionation followed by GC/MS analysis allowed the determination of μng/g (ppm) amounts of these compounds in oils. The concentration of substituted indans and tetralins was 3-4 orders of magnitude less in coal than in crude oil. The select ion mass spectrometry (SIM) mode in GC/MS and the deuterated standards allowed detection of the much lower amounts (ng/g, ppb down to pg/g, ppt) of these compounds in coal samples. The stereochemistry of the biomarkers was determined, and the relationship between their relative concentrations and the location and type of the deposits was examined. Racemic mixtures of the indans and tetralins studied were found in all samples of oil and coal. It is postulated that there is an inverse relationship between the retention of stereochemical configuration and the molecular weight of hydrocarbons in crude oil. The chiral retention of configuration cut-off is thought to be between molecular weights of 146 and 208. An excess of cis-1,2-dimethylindan was found in al oil samples (average cis/trans ratio: 3/2). The 2-methyltetralin concentration was found to be about twice that of 1-methyltetralin in all oil and coal samples. Similar concentration correlations were found for the indan derivatives in oils and coals

The Density of States in High-Tc Superconductors Vortices

We calculated the electronic structure of a vortex in a pseudogapped superconductor within a model featuring strong correlations. With increasing strength of the correlations, the BCS core states are suppressed and the spectra in and outside the core become similar. If the correlations are short-range, we find new core states in agreement with the observations in YBaCuO and BiSrCaCuO. Our results point to a common phenomenology for these two systems and indicate that normal-state correlations survive below Tc without taking part in the overall phase coherence.Comment: REVTeX 4, 5 pages, 2 EPS figures. Some changes to the text; new figures; references update

Competition of Superconductivity and Antiferromagnetism in a d-Wave Vortex Lattice

The d-wave vortex lattice state is studied within the framework of Bogoliubov-de Gennes (BdG) mean field theory. We allow antiferromagnetic (AFM) order to develop self-consistently along with d-wave singlet superconducting (dSC) order in response to an external magnetic field that generates vortices. The resulting AFM order has strong peaks at the vortex centers, and changes sign, creating domain walls along lines where $\nabla \times j_s \approx 0$. The length scale for decay of this AFM order is found to be much larger than the bare d-wave coherence length, $\xi$. Coexistence of dSC and AFM order in this system is shown to induce $\pi$-triplet superconducting order. Competition between different orders is found to suppress the local density of states at the vortex center and comparison to recent experimental findings is discussed.Comment: 10 pages, 7 figure

Soil carbon stock impacts following reversion of Miscanthus x giganteus and short rotation coppice willow commercial plantations into arable cropping

There are posited links between the establishment of perennial bioenergy, such as Short Rotation Coppice (SRC) willow and Miscanthus x giganteus, on low carbon soils and enhanced soil C sequestration. Sequestration provides additional climate mitigation, however, few studies have explored impacts on soil C stocks of bioenergy crop removal, thus the permanence of any sequestered C is unclear. This uncertainty has led some authors to question the handling of soil C stocks with carbon accounting e.g. through LCA. Here we provide additional data for this debate, reporting on the soil C impacts of the reversion (removal and return) to arable cropping of commercial SRC willow and Miscanthus across four sites in the UK, two for each bioenergy crop, with 8 reversions nested within these sites. Using a paired‐site approach, soil C stocks (0–1 m) were compared between 3 and 7 years after bioenergy crop removal. Impacts on soil C stocks varied, ranging from an increase of 70.16 ± 10.81 Mg C ha‐1 7 years after reversion of SRC willow to a decrease of 33.38 ± 5.33 Mg C ha‐1 3 years after reversion of Miscanthus compared to paired arable land. The implications for carbon accounting will depend on the method used to allocate this stock change between current and past land use. However, with, published life cycle assessment values for the lifetime C reduction provided by these crops ranging from 29.50 to 138.55 Mg C ha‐1, the magnitude of these changes in stock are significant. We discuss the potential underlying mechanisms driving variability in soil C stock change, including the age of bioenergy crop at removal, removal methods, and differences in the recalcitrant of the crop residues, and highlight the need to design management methods to limit negative outcomes

QED3 theory of pairing pseudogap in cuprates: From d-wave superconductor to antiferromagnet via "algebraic" Fermi liquid

High-$T_c$ cuprates differ from conventional superconductors in three crucial aspects: the superconducting state descends from a strongly correlated Mott-Hubbard insulator, the order parameter exhibits d-wave symmetry and superconducting fluctuations play an all important role. We formulate a theory of the pseudogap state in the cuprates by taking the advantage of these unusual features. The effective low energy theory within the pseudogap phase is shown to be equivalent to the (anisotropic) quantum electrodynamics in (2+1) space-time dimensions (QED$_3$). The role of Dirac fermions is played by the nodal BdG quasiparticles while the massless gauge field arises through unbinding of quantum vortex-antivortex degrees of freedom. A detailed derivation of this QED$_3$ theory is given and some of its main physical consequences are inferred for the pseudogap state. We focus on the properties of symmetric QED$_3$ and propose that inside the pairing protectorate it assumes the role reminiscent of that played by the Fermi liquid theory in conventional metals.Comment: 31 pages, 4 figures; replaced with revised versio

Scanning tunneling spectroscopy of high-temperature superconductors

Tunneling spectroscopy played a central role in the experimental verification of the microscopic theory of superconductivity in the classical superconductors. Initial attempts to apply the same approach to high-temperature superconductors were hampered by various problems related to the complexity of these materials. The use of scanning tunneling microscopy/spectroscopy (STM/STS) on these compounds allowed to overcome the main difficulties. This success motivated a rapidly growing scientific community to apply this technique to high-temperature superconductors. This paper reviews the experimental highlights obtained over the last decade. We first recall the crucial efforts to gain control over the technique and to obtain reproducible results. We then discuss how the STM/STS technique has contributed to the study of some of the most unusual and remarkable properties of high-temperature superconductors: the unusual large gap values and the absence of scaling with the critical temperature; the pseudogap and its relation to superconductivity; the unprecedented small size of the vortex cores and its influence on vortex matter; the unexpected electronic properties of the vortex cores; the combination of atomic resolution and spectroscopy leading to the observation of periodic local density of states modulations in the superconducting and pseudogap states, and in the vortex cores.Comment: To appear in RMP; 65 pages, 62 figure

Vaccination with LAG-3Ig (IMP321) and Peptides Induces Specific CD4 and CD8 T-Cell Responses in Metastatic Melanoma Patients-Report of a Phase I/IIa Clinical Trial.

PURPOSE: Cancer vaccines aim to generate and maintain antitumor immune responses. We designed a phase I/IIa clinical trial to test a vaccine formulation composed of Montanide ISA-51 (Incomplete Freund's Adjuvant), LAG-3Ig (IMP321, a non-Toll like Receptor agonist with adjuvant properties), and five synthetic peptides derived from tumor-associated antigens (four short 9/10-mers targeting CD8 T-cells, and one longer 15-mer targeting CD4 T-cells). Primary endpoints were safety and T-cell responses. EXPERIMENTAL DESIGN: Sixteen metastatic melanoma patients received serial vaccinations. Up to nine injections were subcutaneously administered in three cycles, each with three vaccinations every 3 weeks, with 6 to 14 weeks interval between cycles. Blood samples were collected at baseline, 1-week after the third, sixth and ninth vaccination, and 6 months after the last vaccination. Circulating T-cells were monitored by tetramer staining directly ex vivo, and by combinatorial tetramer and cytokine staining on in vitro stimulated cells. RESULTS: Side effects were mild to moderate, comparable to vaccines with Montanide alone. Specific CD8 T-cell responses to at least one peptide formulated in the vaccine preparation were found in 13 of 16 patients. However, two of the four short peptides of the vaccine formulation did not elicit CD8 T-cell responses. Specific CD4 T-cell responses were found in all 16 patients. CONCLUSIONS: We conclude that vaccination with IMP321 is a promising and safe strategy for inducing sustained immune responses, encouraging further development for cancer vaccines as components of combination therapies. Clin Cancer Res; 22(6); 1330-40. ©2015 AACR

Counter-current chromatography for the separation of terpenoids: A comprehensive review with respect to the solvent systems employed

Copyright @ 2014 The Authors.This article is distributed under the terms of the Creative Commons Attribution License which permits any use, distribution, and reproduction in any medium, provided the original author(s) and the source are credited.Natural products extracts are commonly highly complex mixtures of active compounds and consequently their purification becomes a particularly challenging task. The development of a purification protocol to extract a single active component from the many hundreds that are often present in the mixture is something that can take months or even years to achieve, thus it is important for the natural product chemist to have, at their disposal, a broad range of diverse purification techniques. Counter-current chromatography (CCC) is one such separation technique utilising two immiscible phases, one as the stationary phase (retained in a spinning coil by centrifugal forces) and the second as the mobile phase. The method benefits from a number of advantages when compared with the more traditional liquid-solid separation methods, such as no irreversible adsorption, total recovery of the injected sample, minimal tailing of peaks, low risk of sample denaturation, the ability to accept particulates, and a low solvent consumption. The selection of an appropriate two-phase solvent system is critical to the running of CCC since this is both the mobile and the stationary phase of the system. However, this is also by far the most time consuming aspect of the technique and the one that most inhibits its general take-up. In recent years, numerous natural product purifications have been published using CCC from almost every country across the globe. Many of these papers are devoted to terpenoids-one of the most diverse groups. Naturally occurring terpenoids provide opportunities to discover new drugs but many of them are available at very low levels in nature and a huge number of them still remain unexplored. The collective knowledge on performing successful CCC separations of terpenoids has been gathered and reviewed by the authors, in order to create a comprehensive document that will be of great assistance in performing future purifications. © 2014 The Author(s)