Ab initio instanton rate theory made efficient using Gaussian process regression

Ab initio instanton rate theory is a computational method for rigorously including tunnelling effects into calculations of chemical reaction rates based on a potential-energy surface computed on the fly from electronic-structure theory. This approach is necessary to extend conventional transition-state theory into the deep-tunnelling regime, but is also more computationally expensive as it requires many more ab initio calculations. We propose an approach which uses Gaussian process regression to fit the potential-energy surface locally around the dominant tunnelling pathway. The method can be converged to give the same result as from an on-the-fly ab initio instanton calculation but requires far fewer electronic-structure calculations. This makes it a practical approach for obtaining accurate rate constants based on high-level electronic-structure methods. We show fast convergence to reproduce benchmark H + CH4 results and evaluate new low-temperature rates of H + C2H6 in full dimensionality at a UCCSD(T)-F12b/cc-pVTZ-F12 level.Comment: 12 pages, 4 figures; submitted to Faraday Discussion: Quantum effects in small molecular system

Feasibility study to realize an anaerobc digester fed with vegetables matrices in central Italy

In the present paper we have analysed the possibility to realize an anaerobic digester in a bio-Energy Park located in Città della Pieve, a small town in Central Italy. The use of anaerobic digesters is quite common in Europe for reducing the environmental impact of manure in a co-digestion procedure with vegetables materials. In addition, for several areas of Central Italy there is the need to find alternative productions to improve farmer's incomes, as traditional cropping systems are loosing convenience. An interesting alternative seems to be cultivation of energy crops because of the favourable conditions of the electric energy market. We are suggesting a low input cropping system to be implemented in areas where low input food/feed crops are no more profitable. In particular our case-study is an example based on the use of a forage legume, alfalfa (Medicago sativa L.), together with other crops, like sorghum, to realize small-size bio-digesters plants. Alfalfa: is a highly sustainable crop as it is able to fix nitrogen and therefore it does not require this fertilization with the consequence of avoiding underground water pollution. Moreover alfalfa residual products are nitrogen rich thus improving soil structure and fertility more than popular graminaceous energy crops such as corn. Beside, alfalfa mostly does not need irrigation in the typical Central Italy environment, all these traits make it one of the species with the lowest energy needs for growing. The aims of this feasibility study are: i) optimization of plant materials feeding the bio-digester, ii) typology of bio-digester, iii) size of bio-digester in relation with land availability for growing energetic cultures, iv) the utilization of bio-gas produced by bio-digester plant to produce electric and thermal energy using cogeneration engines, vi) disposal of waste-water produced according to regional and national laws. The final aim of this study is to verify the possibility to develop an alternative economical use of marginal soils in relatively dry areas of Central Italy that would be replicable in other European areas with a similar climatic situation

CYP72A67 catalyses a key oxidative step in Medicago truncatula hemolytic saponin biosynthesis

In the Medicago genus, triterpenic saponins are bioactive secondary metabolites constitutively synthesized in the aerial and subterranean parts of plants via the isoprenoid pathway. Exploitation of saponins as pharmaceutics, agrochemicals and in the food and cosmetic industries has raised interest in identifying the enzymes involved in their synthesis. We have identified a cytochrome P450 (CYP72A67) involved in hemolytic sapogenin biosynthesis by a reverse genetic TILLING approach in a Medicago truncatula ethylmethanesulfonate (EMS) mutagenized collection. Genetic and biochemical analyses, mutant complementation, and expression of the gene in a microsome yeast system showed that CYP72A67 is responsible for hydroxylation at the C-2 position downstreamof oleanolic acid synthesis. The affinity of CYP72A67 for substrates with different substitutions at multiple carbon positions was investigated in the same in vitro yeast system, and in relation to two other CYP450s (CYP72A68) responsible for the production of medicagenic acid, the main sapogenin in M. truncatula leaves and roots. Full sib mutant and wild-type plants were compared for their sapogenin profile, expression patterns of the genes involved in sapogenin synthesis, and response to inoculation with Sinorhizobium meliloti. The results obtained allowed us to revise the hemolytic sapogenin pathway in M. truncatula and contribute to highlighting the tissue specificities (leaves/roots) of sapogenin synthesis

OeBAS and CYP716C67 catalyze the biosynthesis of health-beneficial triterpenoids in olive (Olea europaea) fruits

center dot The bioactive properties of olive (Olea europaea) fruits and olive oil are largely attributed to terpenoid compounds, including diverse triterpenoids such as oleanolic, maslinic and ursolic acids, erythrodiol, and uvaol. They have applications in the agri-food, cosmetics, and pharmaceutical industries. Some key steps involved in the biosynthesis of these compounds are still unknown.center dot Genome mining, biochemical analysis, and trait association studies have been used to identify major gene candidates controlling triterpenoid content of olive fruits.center dot Here, we identify and functionally characterize an oxidosqualene cyclase (OeBAS) required for the production of the major triterpene scaffold beta-amyrin, the precursor of erythrodiol, oleanolic and maslinic acids, and a cytochrome P450 (CYP716C67) that mediates 2 alpha oxidation of the oleanane- and ursane-type triterpene scaffolds to produce maslinic and corosolic acids, respectively. To confirm the enzymatic functions of the entire pathway, we have reconstituted the olive biosynthetic pathway for oleanane- and ursane-type triterpenoids in the heterologous host, Nicotiana benthamiana. Finally, we have identified genetic markers associated with oleanolic and maslinic acid fruit content on the chromosomes carrying the OeBAS and CYP716C67 genes.center dot Our results shed light on the biosynthesis of olive triterpenoids and provide new gene targets for germplasm screening and breeding for high triterpenoid content

A high purity measurement of RbR_b at SLD

Precision measurement of Rb can provide important information about the Standard Model and beyond. SLD has developed a new method for measuring Rb with very high purity. This measurement has the lowest systematic error reported to date and future measurements using this method will likely have the lowest total uncertainty. This paper will be divided into the five sections: introduction, hardware, topological vertexing tag method, results and conclusions. The introduction will discuss the importance of Rb and the problems with other measurement techniques. The hardware section will give a brief description of the SLC/SLD system concentrating on its advantages over LEP. An outlook towards the future of SLD Rb measurements will be included in the conclusions

Discovery of Potent, Selective, and Orally Bioavailable Small-Molecule Modulators of the Mediator Complex-Associated Kinases CDK8 and CDK19.

The Mediator complex-associated cyclin-dependent kinase CDK8 has been implicated in human disease, particularly in colorectal cancer where it has been reported as a putative oncogene. Here we report the discovery of 109 (CCT251921), a potent, selective, and orally bioavailable inhibitor of CDK8 with equipotent affinity for CDK19. We describe a structure-based design approach leading to the discovery of a 3,4,5-trisubstituted-2-aminopyridine series and present the application of physicochemical property analyses to successfully reduce in vivo metabolic clearance, minimize transporter-mediated biliary elimination while maintaining acceptable aqueous solubility. Compound 109 affords the optimal compromise of in vitro biochemical, pharmacokinetic, and physicochemical properties and is suitable for progression to animal models of cancer

Search for the glueball candidates f0(1500) and fJ(1710) in gamma gamma collisions

Data taken with the ALEPH detector at LEP1 have been used to search for gamma gamma production of the glueball candidates f0(1500) and fJ(1710) via their decay to pi+pi-. No signal is observed and upper limits to the product of gamma gamma width and pi+pi- branching ratio of the f0(1500) and the fJ(1710) have been measured to be Gamma_(gamma gamma -> f0(1500)). BR(f0(1500)->pi+pi-) < 0.31 keV and Gamma_(gamma gamma -> fJ(1710)). BR(fJ(1710)->pi+pi-) < 0.55 keV at 95% confidence level.Comment: 10 pages, 3 figure

Prototype ATLAS IBL Modules using the FE-I4A Front-End Readout Chip

The ATLAS Collaboration will upgrade its semiconductor pixel tracking detector with a new Insertable B-layer (IBL) between the existing pixel detector and the vacuum pipe of the Large Hadron Collider. The extreme operating conditions at this location have necessitated the development of new radiation hard pixel sensor technologies and a new front-end readout chip, called the FE-I4. Planar pixel sensors and 3D pixel sensors have been investigated to equip this new pixel layer, and prototype modules using the FE-I4A have been fabricated and characterized using 120 GeV pions at the CERN SPS and 4 GeV positrons at DESY, before and after module irradiation. Beam test results are presented, including charge collection efficiency, tracking efficiency and charge sharing.Comment: 45 pages, 30 figures, submitted to JINS

Shaking table tests and numerical analyses on a scaled dry-joint arch undergoing windowed sine pulses

The damages occurred during recent seismic events have emphasised the vulnerability of vaulted masonry structures, one of the most representative elements of worldwide cultural heritage. Although a certain consensus has been reached regarding the static behaviour of masonry arches, still more efforts are requested to investigate their dynamic behaviour. In this regard, the present paper aims to investigate the performance of a scaled dry-joint arch undergoing windowed sine pulses. A feature tracking based measuring technique was employed to evaluate the displacement of selected points, shading light on the failure mechanisms and gathering data for the calibration of the numerical model. This was built according to a micro-modelling approach of the finite element method, with voussoirs assumed very stiff and friction interface elements. Comparisons with existing literature are also stressed, together with comments about scale effects.This work was partly financed by FEDER funds through the Competitivity Factors Operational Programme-COMPETE and by national funds through FCT-Foundation for Science and Technology within the scope of the Project POCI-01-0145-FEDER-007633.info:eu-repo/semantics/publishedVersio