Effects of Heterogeneous Fracture Aperture on Multiphase Production from Shale Reservoirs

Production simulation from fractured shale reservoirs is often performed by simplifying the hydraulic fractures as rectangular planes with homogeneous aperture. This study investigates the effects of heterogeneous fracture aperture and proppant distribution in realistic, non-rectangular fractures on the multi-phase production from shales. The heterogeneous hydraulic fractures are generated with the GEOS multiphysics simulator under realistic 3D stress field. These fractures are embedded into the TOUGH+ multi-phase flow simulator for production simulation. The results emphasize the importance of flow barriers within the hydraulic fractures, due both to low-aperture regions caused by the stress-shadow effect and the settling of proppant. The production rate is particularly sensitive to aperture heterogeneity if the flow barriers are close to the wellbore such that a great portion of fracture volume is isolated from the well. A stage-to-stage comparison reveals that production from different stages could vary significantly because the local stress field leads to different fracture area and aperture. The use of proppant prevents fracture closure, but if the propped regions are far from the well, they do not enhance production because flow barriers between these regions and the well act as bottlenecks. The present study highlights the importance of incorporating aperture heterogeneity into production simulation, provides insights on the relationship between flow barriers, proppant concentration, and well production, and proposes a practical method to mitigate numerical difficulties when modeling heterogeneous fractures.

     

Universality in lattice models of dynamic arrest: introduction of an order parameter

We introduce an order parameter for dynamical arrest. Dynamically available volume (unoccupied space that is available to the motion of particles) is expressed as holes for the simple lattice models we study. Near the arrest transition the system is dilute in holes, so we expand dynamical quantities in a series of hole density. Unlike the situation when presented in particle density, all cases of simple models that we examine have a quadratic dependence of the diffusion constant on hole density. This observation implies that in certain regimes ideal dynamical arrest transitions may possess a hitherto unnoticed degree of universality.     

Ozonolytic cleavage of cycloalkenes to terminally differentiated products

Conditions are reported which convert cycloalkenes to terminally differentiated products through the intermediacy of α-alkoxy hydroperoxides.     

Exploring the Link between Reformed Teaching Practices and Pupil Learning in Elementary School Mathematics

This study examined the classroom practices of beginning elementary school teachers' instruction of mathematics and how it connected to their pupils' learning. The Reformed Teaching Observation Protocol (RTOP) was used to measure the extent to which beginning teachers used reformed teaching practices. As a measure of pupil learning, we utilized assessment scores specific to the mathematics unit observed and correlated them with teachers' RTOP scores. We found that beginning teachers who implemented reformed teaching practices tended to have pupils who scored higher on the district mathematics test with a statistically significant correlation of 0.56 (p < .05). Implications of these findings and others are discussed in terms of using the RTOP to improve practice at the elementary school level and for future school‐based research.     

High throughput screening for orphan and liganded GPCRs

GPCRs had significant representation in the drug discovery portfolios of most major commercial drug discovery organizations for many years. This is due in part to the diverse biological roles mediated by GPCRs as a class, as well as the empirical discovery that they have proven relatively tractable to the development of small molecule therapeutics. Publication of the human genome sequence in 2001 confirmed GPCRs as the largest single gene superfamily with more than 700 members, furthering the already strong appeal of addressing this target class using efficient and highly parallelized platform approaches. The GPCR research platform implemented at Amgen is used as a case study to review the evolution and implementation of available assays and technologies applicable to GPCR drug discovery. The strengths, weaknesses, and applications of assay technologies applicable to G alpha s, G alpha i and G alpha q-coupled receptors are described and their relative merits evaluated. Particular consideration is made of the role and practice of "de-orphaning" and signaling pathway characterization as a pre-requisite to establishing effective screens. In silico and in vitro methodology developed for rapid, parallel high throughput hit characterization and prioritization is also discussed extensively.     

Characterization and Optimization of Injectable In Situ Crosslinked Chitosan-Genipin Hydrogels

In recent years, there has been an increased interest in injectable, in situ crosslinking hydrogels due to their minimally invasive application and ability to conform to their environment. Current in situ crosslinking chitosan hydrogels are either mechanically robust with poor biocompatibility and limited biodegradation due to toxic crosslinking agents or the hydrogels are mechanically weak and undergo biodegradation too rapidly due to insufficient crosslinking. Herein, the authors developed and characterized a thermally-driven, injectable chitosan-genipin hydrogel capable of in situ crosslinking at 37 °C that is mechanically robust, biodegradable, and maintain high biocompatibility. The natural crosslinker genipin is utilized as a thermally-driven, non-toxic crosslinking agent. The chitosan-genipin hydrogel's crosslinking kinetics, injectability, viscoelasticity, swelling and pH response, and biocompatibility against human keratinocyte cells are characterized. The developed chitosan-genipin hydrogels are successfully crosslinked at 37 °C, demonstrating temperature sensitivity. The hydrogels maintained a high percentage of swelling over several weeks before degrading in biologically relevant environments, demonstrating mechanical stability while remaining biodegradable. Long-term cell viability studies demonstrated that chitosan-genipin hydrogels have excellent biocompatibility over 7 days, including during the hydrogel crosslinking phase. Overall, these findings support the development of an injectable, in situ crosslinking chitosan-genipin hydrogel for minimally invasive biomedical applications.     

Bifunctional diphosphorus Lewis acids from cyclodiphosphadiazanes

The quantitative displacement of triflate groups in 1,3-ditriflato-2,4-bis(2,6-dimethylphenyl)cyclodiphospha-2,4-diazane by DMAP (4-dimethylaminopyridine) or Me(3)P gives dicationic complexes containing bifunctional diphosphorus Lewis acceptors.     

Rearrangements in an alkylthiolate self-assembled monolayer using electrostatic interactions between nanoscale asperity and organomercaptan molecules

Chemically induced rearrangements of amphifunctional molecules have been demonstrated using strong nonuniform electric fields (10(8)-10(10) V m(-1)) induced in the vicinity of nanoscale asperities. Electrostatic interactions utilizing these rearrangements of alkylthiolates assembled on Au(111) result in the nanopatterning of raised nanostructure (1.5-9 nm high, 15-100 nm wide) arrays on a second time scale by manipulating an atomic force microscope (AFM) tip above the monolayer. It is suspected that, as a result of the oxidative cleavage initiated by a weak bias of the tip, the S end of the alkylthiolate chain carrying a sulfenium cation is attracted to the (lifting) tip, forming bi- and higher-layer structures in the vicinity of the tip apex. Stabilization of the multiple-layered structures is accomplished via mutual attraction and entanglement of hydrocarbon chains. The rearrangements suggest a novel and general approach for nanoscale architecture in self-assembled systems.     

Demonstration of a 100 Hz repetition rate gain-saturated diode-pumped table-top soft x-ray laser

We demonstrate the operation of a gain-saturated table-top soft x-ray laser at 100?Hz repetition rate. The laser generates an average power of 0.15?mW at λ=18.9 nm, the highest laser power reported to date from a sub-20-nm wavelength compact source. Picosecond laser pulses of 1.5?μJ energy were produced at λ=18.9 nm by amplification in a Mo plasma created by tailoring the temporal intensity profile of single pump pulses with 1?J energy produced by a diode-pumped chirped pulse amplification Yb:YAG laser. Lasing was also obtained in the 13.9?nm line of Ni-like Ag. These results increase by an order of magnitude the repetition rate of plasma-based soft x-ray lasers opening the path to milliwatt average power table-top lasers at sub-20?nm wavelengths.     

Cross and ring-closing metathesis of 1,3-diynes: metallotropic [1,3]-shift of ruthenium carbenes

The regio- and stereoselective enyne CM and RCM reactions involving 1,3-diynes have been developed. The ring-closing metathesis of enediynes induces a facile metallotropic [1,3]-shift of alkynyl ruthenium carbene species, thereby providing a unique entry into the synthesis of fully conjugated 1,5-diene-3-ynes.