A New Reactor Concept for Efficient Solar-Thermochemical Fuel Production

We describe and analyze the efficiency of a new solar-thermochemical reactor concept, which employs a moving packed bed of reactive particles produce of H-2 or CO from solar energy and H2O or CO2. The packed bed reactor incorporates several features essential to achieving high efficiency: spatial separation of pressures, temperature, and reaction products in the reactor; solid-solid sensible heat recovery between reaction steps; continuous on-sun operation; and direct solar illumination of the working material. Our efficiency analysis includes material thermodynamics and a detailed accounting of energy losses, and demonstrates that vacuum pumping, made possible by the innovative pressure separation approach in our reactor, has a decisive efficiency advantage over inert gas sweeping. We show that in a fully developed system, using CeO2 as a reactive material, the conversion efficiency of solar energy into H-2 and CO at the design point can exceed 30%. The reactor operational flexibility makes it suitable for a wide range of operating conditions, allowing for high efficiency on an annual average basis. The mixture of H-2 and CO, known as synthesis gas, is not only usable as a fuel but is also a universal starting point for the production of synthetic fuels compatible with the existing energy infrastructure. This would make it possible to replace petroleum derivatives used in transportation in the U. S., by using less than 0.7% of the U. S. land area, a roughly two orders of magnitude improvement over mature biofuel approaches. In addition, the packed bed reactor design is flexible and can be adapted to new, better performing reactive materials.

Targeting p-Conjugated Multiple Donor-Acceptor Motifs Exemplified by Tetrathiafulvalene-Linked Quinoxalines and Tetrabenz bc,ef,hi,uv ovalenes: Synthesis, Spectroscopic, Electrochemical, and Theoretical Characterization

An efficient synthetic approach to a symmetrically functionalized tetrathiafulvalene (TTF) derivative with two diamine moieties, 2-[5,6-diamino-4,7-bis(4-pentylphenoxy)-1,3-benzodithiol-2-ylidene]-4,7- bis(4-pentylphenoxy)-1,3-benzodithiole-5,6-diamine (2), is reported. The subsequent Schiff-base reactions of 2 afford large p-conjugated multiple donoracceptor (DA) arrays, for example, the triad 2-[4,9-bis(4-pentylphenoxy)-1,3-dithiolo[4,5-g]quinoxalin-2-ylidene]-4,9 -bis(4-pentylphenoxy)-1,3-dithiolo[4,5-g]quinoxaline (8) and the corresponding tetrabenz[bc,ef,hi,uv]ovalene-fused pentad 1, in good yields and high purity. The novel redox-active nanographene 1 is so far the largest known TTF-functionalized polycyclic aromatic hydrocarbon (PAH) with a well-resolved 1H NMR spectrum. The electrochemically highly amphoteric pentad 1 and triad 8 exhibit various electronically excited charge-transfer states in different oxidation states, thus leading to intense optical intramolecular charge-transfer (ICT) absorbances over a wide spectral range. The chemical and electrochemical oxidations of 1 result in an unprecedented TTF+ radical cation dimerization, thereby leading to the formation of [1+]2 at room temperature in solution due to the stabilizing effect, which arises from strong pp interactions. Moreover, ICT fluorescence is observed with large solvent-dependent Stokes shifts and quantum efficiencies of 0.05 for 1 and 0.035 for 8 in dichloromethane.

Management effects on colostrogenesis in small ruminants: a review

Colostrum feeding in small ruminants is crucial during the first hours after birth due to the lack of Ig transfer during pregnancy via the placenta. In addition the immature immune system of the neonate is slow to produce its own Ig during the first weeks of life. Colostrogenesis, i.e. the transfer of Ig from blood into mammary secretions, starts several weeks prepartum. In goat plasma, immunoglobulin G (IgG) concentration decreases by around 38% from the third month of gestation until partum, which coincides with the dry period. Thus, management during the dry period is crucial for the course of colostrogenesis. The colostrum synthesis is determined by the nutrition during the prepartum period, but the transfer of Ig is obviously independent of nutritional influences. The administration of conjugated linoleic acid during the dry period to dairy goats causes a less pronounced decrease of blood plasma IgG concentration (6%) but it did not change colostral IgG levels. In cattle, IgG1 is transported from blood into colostrum by an IgG1 specific receptor located on the surface of alveolar epithelial cells during colostrogenesis, and this is most likely similar in small ruminants. Via inactivation of this receptor, the Ig transfer is downregulated by increasing prolactin (PRL) during lactogenesis. It was recently observed in goats treated with PGF2 alpha, in order to induce parturition, lower colostrum IgG concentrations occurred concomitantly with an earlier increase of plasma PRL as compared to untreated animals. The effect of litter size and number of lactations on colostral IgG concentration in small ruminants has not been made fully clear until now most likely due to the different breeds used in the published studies.

The ω3-polyunsaturated fatty acid derivatives AVX001 and AVX002 directly inhibit cytosolic phospholipase A(2) and suppress PGE(2) formation in mesangial cells

ω3-polyunsaturated fatty acids (ω3-PUFAs) are known to exert anti-inflammatory effects in various disease models although their direct targets are only poorly characterized.

Total synthesis of (-)-zampanolide and structure-activity relationship studies on (-)-dactylolide derivatives

A new total synthesis of the marine macrolide (-)-zampanolide (1) and the structurally and stereochemically related non-natural levorotatory enantiomer of (+)-dactylolide (2), that is, ent-2, has been developed. The synthesis features a high-yielding, selective intramolecular Horner-Wadsworth-Emmons (HWE) reaction to close the 20-membered macrolactone ring of 1 and ent-2. The β-keto phosphonate/aldehyde precursor for the ring-closure reaction was obtained by esterification of a ω-diethylphosphono carboxylic acid fragment and a secondary alcohol fragment incorporating the THP ring that is embedded in the macrocyclic core structure of 1 and ent-2. THP ring formation was accomplished through a segment coupling Prins-type cyclization. Employing the same overall strategy, 13-desmethylene-ent-2 as well as the monocyclic desTHP derivatives of 1 and ent-2 were prepared. Synthetic 1 inhibited human cancer cell growth in vitro with nM IC(50) values, while ent-2, which lacks the diene-containing hemiaminal-linked side chain of 1, is 25- to 260-fold less active. 13-Desmethylene-ent-2 as well as the reduced versions of ent-2 and 13-desmethylene-ent-2 all showed similar cellular activity as ent-2 itself. The same activity level was attained by the monocyclic desTHP derivative of 1. Oxidation of the aldehyde functionality of ent-2 gave a carboxylic acid that was converted into the corresponding N-hexyl amide. The latter showed only μM antiproliferative activity, thus being several hundred-fold less potent than 1.

Synthesis and cytotoxic activity of non-naturally substituted 4-oxycoumarin derivatives

Coumarins are a large family of natural and synthetic compounds exerting different pharmacological effects, including cytotoxic, anti-inflammatory or antimicrobial. In the present communication we report the synthesis of a series of 12 diversely substituted 4-oxycoumarin derivatives including methoxy substituted 4-hydroxycoumarins, methyl, methoxy or unsubstituted 3-aryl-4-hydroxycoumarins and 4-benzyloxycoumarins and their anti-proliferative effects on breast adenocarcinoma cells (MCF-7), human promyelocytic leukemia cells (HL-60), human histiocytic lymphoma cells (U937) and mouse neuroblastoma cells (Neuro2a). The most potent bioactive molecule was the 4-hydroxy-5,7-dimethoxycoumarin (compound 1) which showed similar potency (IC(50) 0.2-2 μM) in all cancer cell lines tested. This non-natural product reveals a simple bioactive scaffold which may be exploited in further studies.

Lead discovery, chemistry optimization, and biological evaluation studies of novel biamide derivatives as CB2 receptor inverse agonists and osteoclast inhibitors

N,N'-((4-(Dimethylamino)phenyl)methylene)bis(2-phenylacetamide) was discovered by using 3D pharmacophore database searches and was biologically confirmed as a new class of CB(2) inverse agonists. Subsequently, 52 derivatives were designed and synthesized through lead chemistry optimization by modifying the rings A-C and the core structure in further SAR studies. Five compounds were developed and also confirmed as CB(2) inverse agonists with the highest CB(2) binding affinity (CB(2)K(i) of 22-85 nM, EC(50) of 4-28 nM) and best selectivity (CB(1)/CB(2) of 235- to 909-fold). Furthermore, osteoclastogenesis bioassay indicated that PAM compounds showed great inhibition of osteoclast formation. Especially, compound 26 showed 72% inhibition activity even at the low concentration of 0.1 μM. The cytotoxicity assay suggested that the inhibition of PAM compounds on osteoclastogenesis did not result from its cytotoxicity. Therefore, these PAM derivatives could be used as potential leads for the development of a new type of antiosteoporosis agent.

Spirocyclic Acylphloroglucinol Derivatives from Hypericum pyramidatum

Five spirocyclic acylphloroglucinol derivatives (1-5) have been isolated from a hexanes extract of the leaves of Hypericum pyramidatum. Pyramidatones A-D (1-3, 5) are new, and chipericumin C (4) has been previously reported. The acylphloroglucinols were characterized based on spectroscopic (NMR, IR, UV-VIS) and mass spectrometric data.

Genome-Wide Survey of Pseudogenes in 80 Fully Re-sequenced Arabidopsis thaliana Accessions

Pseudogenes (Ψs), including processed and non-processed Ψs, are ubiquitous genetic elements derived from originally functional genes in all studied genomes within the three kingdoms of life. However, systematic surveys of non-processed Ψs utilizing genomic information from multiple samples within a species are still rare. Here a systematic comparative analysis was conducted of Ψs within 80 fully re-sequenced Arabidopsis thaliana accessions, and 7546 genes, representing ~28% of the genomic annotated open reading frames (ORFs), were found with disruptive mutations in at least one accession. The distribution of these Ψs on chromosomes showed a significantly negative correlation between Ψs/ORFs and their local gene densities, suggesting a higher proportion of Ψs in gene desert regions, e.g. near centromeres. On the other hand, compared with the non-Ψ loci, even the intact coding sequences (CDSs) in the Ψ loci were found to have shorter CDS length, fewer exon number and lower GC content. In addition, a significant functional bias against the null hypothesis was detected in the Ψs mainly involved in responses to environmental stimuli and biotic stress as reported, suggesting that they are likely important for adaptive evolution to rapidly changing environments by pseudogenization to accumulate successive mutations.