cssi/SciSciGPT-SciSciNet huggingface dataset:
Intercostal and Glissonian Pedicle Approach in Laparoscopic Liver Resection for Bilobar Tumors.

Bilobar liver metastasis is challenging for laparoscopic liver resection. Especially, subphrenic liver tumors in S7 or S8 are technically difficult to be resected out because the space is limited and the angle of instruments to lesions cannot be perpendicular.1,2 Major liver lobectomy is also challenging for laparoscopic liver resection. Glissonian pedicle approach has benefit that any variation of vascular and bile duct elements does not need to be considered in the hepatoduodenal ligament under the hilar plate. Glissonian pedicle approach is simpler and faster than individual dissection of hepatoduodenal ligament. This video illustrates a hand-assisted laparoscopic left lobectomy and partial liver resection of S8 in a 48-year-old male with metastatic colorectal carcinoma to the liver. He received 6 cycle of FOLFOX as neoadjuvant chemotherapy. The patient was positioned in semi left lateral decubitus so that a lesion in S8 was easily approached. A tumor in S8 was approached after right lobe mobilization. The liver resection was performed by a harmonic scalpel. A 5-mm balloon port was placed in 6th intercostal space to approach the lesion perpendicular. For left hepatectomy, glissonian pedicle approach was applied to control vascular inflow. Dissections was performed at bifurcation on the right glissonian and left glissonian pedicles. Dissection direction to the left side was above hepatogastric ligament. The tunnel was created including all left glissonian sheath, and a vessel loop was taped. An endovascular stapler was inserted and fired with dividing the left glissonian pedicle as en bloc. Hepatic parenchymal dissection was performed by the harmonic scalpel. Left hepatic vein was divided using an endoscopic vascular stapler. The specimens were removed from a hand-port. The operative time was 290 min. Blood loss was 250 ml, and no blood transfusion was required. He resumed a regular diet the next day and was discharged on postoperative day 4. Intercostal approach is useful for subphrenic liver tumors, and glissonian pedicle approach is also useful for major lobectomy for laparoscopic liver resection.
Early Life Adversity with Height Stunting Is Associated with Cardiometabolic Risk in Adolescents Independent of Body Mass Index.

Objective To evaluate cardiovascular and metabolic function in youths adopted internationally from orphanages/institutions (postinstitutionalized) who were height-stunted at adoption. Study design A total of 30 postinstitutionalized youths (age, 9-18 years; body mass index [BMI] percentile, 7.2-90.4) who were height-stunted at adoption were compared with age- and BMI percentile-matched youths (n = 90). Measurements included total body fat and visceral adipose tissue (dual radiograph absorptiometry), arterial stiffness (augmentation index and pulse wave velocity), cardiac autonomic function (heart rate variability), blood pressure, and fasting lipid, glucose, and insulin levels. Linear regression analyses were computed controlling for parent education, age, trunk tissue fat, height-for-age, sex, and race. Results Compared with controls of the same age, sex, and BMI, the postinstitutionalized children had higher systolic blood pressure (P = .018), augmentation index (P = .033), total cholesterol (P = .047), low-density lipoprotein cholesterol (P = .03), triglycerides (P = .048), insulin (P = .005), and HOMA-IR (P = .01) values. The postinstitutionalized children had a lower low-frequency to high-frequency ratio (P = .008), indicating lower sympathetic tone, as well as a lower total lean mass (P = .016), a lower gynoid lean mass (P = .039), and a higher proportion of trunk tissue fat (P = .017). The postinstitutionalized and control children did not differ in any other body composition measures. Conclusions Early life stress, as represented by height-stunted growth in institutional care, may be associated with early pathways to cardiovascular and metabolic risk in youths even after moving into well-resourced homes early in life and in the absence of increased adiposity. These findings suggest that postinstitutionalized youths with a history of height stunting may need to be closely monitored for emergent cardiometabolic risk factors.
Route of immunization defines multiple mechanisms of vaccine-mediated protection against SIV

Antibodies are the primary correlate of protection for most licensed vaccines; however, their mechanisms of protection may vary, ranging from physical blockade to clearance via the recruitment of innate immunity. Here, we uncover striking functional diversity in vaccine-induced antibodies that is driven by immunization site and is associated with reduced risk of SIV infection in nonhuman primates. While equivalent levels of protection were observed following intramuscular (IM) and aerosol (AE) immunization with an otherwise identical DNA prime-Ad5 boost regimen, reduced risk of infection was associated with IgG-driven antibody-dependent monocyte-mediated phagocytosis in the IM vaccinees, but with vaccine-elicited IgA-driven neutrophil-mediated phagocytosis in AE-immunized animals. Thus, although route-independent correlates indicate a critical role for phagocytic Fc-effector activity in protection from SIV, the site of immunization may drive this Fc activity via distinct innate effector cells and antibody isotypes. Moreover, the same correlates predicted protection from SHIV infection in a second nonhuman primate vaccine trial using a disparate IM canarypox prime-protein boost strategy, analogous to that used in the first moderately protective human HIV vaccine trial. These data identify orthogonal functional humoral mechanisms, initiated by distinct vaccination routes and immunization strategies, pointing to multiple, potentially complementary correlates of immunity that may support the rational design of a protective vaccine against HIV.
Health information management practices in informal caregiving: An artifacts analysis and implications for IT design.

Abstract Introduction Unpaid informal caregivers of adult care recipients, including persons with dementia, experience multiple unmet information needs and information management challenges. Objectives To understand the current personal health information management (PHIM) practices in informal caregiving for adults with and without dementia. Methods Semi-structured interviews were performed with ten informal caregivers—half of whom were caring for persons with dementia—and four formal caregivers at an adult day service. Interviews centered on a paper-based tool distributed by the day service, the CARE Kit, permitting an artifacts analysis of the tools used by participants for PHIM. Qualitative thematic analysis was applied to interview data. Results Caregivers’ PHIM practices aimed to support daily care management and decision-making on behalf of care recipients, through: 1) information acquisition and integration across multiple sources and records; 2) information maintenance, updating, and use over time; and 3) information sharing and communication with healthcare professionals and other family caregivers. Participants reported advantages and challenges of their PHIM practices and tools, including fitting PHIM into their daily lives, managing PHIM-related cognitive workload, the functionality of PHIM tools, and the dynamic, longitudinal nature of PHIM. Conclusion The study produced a number of implications for caregiver health information management information technology (CHIM IT), based on findings about the nature of caregivers’ practices for managing information for adult care recipients. We present CHIM IT requirements related to privacy and security, customization and flexibility, ease of use, credibility and sensitivity, situation awareness, information integration, delegation and shared use, updating and maintenance, archiving and versioning, communication, agency and information access, and validation.
Optimal Investment with Costly Reversibility

price and sell capital at a lower price. We solve for the optimal investment of a firm that faces costly reversibility under uncertainty and we extend the Jorgensonian concept of the user cost of capital to this case. We define and calculate cv and cL as the user costs of capital associated with the purchase and sale of capital, respectively. Optimality requires the firm to purchase and sell capital as needed to keep the marginal revenue product of capital in the closed interval [CL, cu]. This prescription encompasses the case of irreversible investment as well as the standard neoclassical case of costlessly reversible investment.
Public Sentiment and the Price of Corporate Sustainability

Combining environmental, social, and governance (ESG) data with “big data” measuring public sentiment about corporate sustainability performance, I found that the valuation premium for strong susta...
A Multi-variable Stacked Long-Short Term Memory Network for Wind Speed Forecasting

Precisely forecasting wind speed is essential for wind power producers and grid operators. However, this task is challenging due to the stochasticity of wind speed. To accurately predict short-term wind speed under uncertainties, this paper proposed a multi-variable stacked LSTMs model (MSLSTM). The proposed method utilizes multiple historical meteorological variables, such as wind speed, temperature, humidity, pressure, dew point and solar radiation to accurately predict wind speeds. The prediction performance is extensively assessed using real data collected in West Texas, USA. The experimental results show that the proposed MSLSTM can preferably capture and learn uncertainties while output competitive performance.
Estimation of the Rashba Strength from Second Harmonic Generation in 2D and 3D Hybrid Organic–Inorganic Perovskites

The Rashba effect (RE), caused by concurrent spin–orbit coupling and structural inversion asymmetry (SIA), has been invoked to explain outstanding optoelectronic properties of hybrid organic inorganic perovskites (HOIPs). The SIA in HOIPs also manifests itself in second harmonic generation (SHG). Here, we establish a quantitative relation between the RE strength and the low-frequency SHG value in two-dimensional (2D) and three-dimensional (3D) HOIPs using a newly developed effective-mass model. The calculated SHG, which exhibits one- and two-photon resonances between the valence and conduction bands, approaches a finite value at low frequencies. Using the measured SHG values in literature, the estimated RE strength is 10–3 eV A for 3D CH3NH3PbI3 and 4 × 10–2 eV A for 2D (C4H9NH3)2PbI4. Our results facilitate a simple and reliable determination of the RE strengths of 2D and 3D HOIPs and help quantify the impact of RE on various properties in HOIPs.
An Automated Image Analysis Pipeline Enables Genetic Studies of Shoot and Root Morphology in Carrot ( Daucus carota L.).

Carrot is a globally important crop, yet efficient and accurate methods for quantifying its most important agronomic traits are lacking. To address this problem, we developed an automated image analysis platform that extracts components of size and shape for carrot shoots and roots, which are necessary to advance carrot breeding and genetics. This method reliably measured variation in shoot size and shape, petiole number, petiole length, and petiole width as evidenced by high correlations with hundreds of manual measurements. Similarly, root length and biomass were accurately measured from the images. This platform also quantified shoot and root shapes in terms of principal components, which do not have traditional, manually measurable equivalents. We applied the pipeline in a study of a six-parent diallel population and an F2 mapping population consisting of 316 individuals. We found high levels of repeatability within a growing environment, with low to moderate repeatability across environments. We also observed co-localization of quantitative trait loci for shoot and root characteristics on chromosomes 1, 2, and 7, suggesting these traits are controlled by genetic linkage and/or pleiotropy. By increasing the number of individuals and phenotypes that can be reliably quantified, the development of a rapid, automated image analysis pipeline to measure carrot shoot and root morphology will expand the scope and scale of breeding and genetic studies.
Energy Crowdsourcing and Peer-to-Peer Energy Trading in Blockchain-Enabled Smart Grids

The power grid is rapidly transforming, and while recent grid innovations increased the utilization of advanced control methods, the next-generation grid demands technologies that enable the integration of distributed energy resources (DERs)—and consumers that both seamlessly buy and sell electricity. This paper develops an optimization model and blockchain-based architecture to manage the operation of crowdsourced energy systems (CESs), with peer-to-peer (P2P) energy trading transactions (ETTs). An operational model of CESs in distribution networks is presented considering various types of ETT and crowdsourcees. Then, a two-phase operation algorithm is presented: Phase I focuses on the day-ahead scheduling of generation and controllable DERs, whereas Phase II is developed for hour-ahead or real-time operation of distribution networks. The developed approach supports seamless P2P energy trading between individual prosumers and/or the utility. The presented operational model can also be used to operate islanded microgrids. The CES framework and the operation algorithm are then prototyped through an efficient blockchain implementation, namely, the IBM Hyperledger Fabric. This implementation allows the system operator to manage the network users to seamlessly trade energy. Case studies and prototype illustration are provided.
Demonstration of a Framework for Comparing Aviation Environmental Impact Mitigation Strategies

By modeling compatibilities, benefits, and penalties of various technology packages at the subsystem level in a vehicle design tool, bottom-up assessments of projected technological benefits can be...
Jumping the Line, Charitably: Analysis and Remedy of Donor-Priority Rule

The ongoing shortage of organs for transplantation has generated an expanding literature on efficient and equitable allocation of the donated cadaveric organs. By contrast, organ donation has been ...
Iterative broadening

Conventional blind search techniques generally assume that the goal nodes for a given problem are distributed randomly along the fringe of the search tree. We argue that this is often invalid in practice, suggest that a more reasonable assumption is that decisions made at each point in the search carry equal weight, and show that a new search technique that we call iterative broadening leads to orders-of-magnitude savings in the time needed to search a space satisfying this assumption. Both theoretical and experimental results are presented.
Average Gaps and Oaxaca–Blinder Decompositions: A Cautionary Tale about Regression Estimates of Racial Differences in Labor Market Outcomes:

Using a recent result from the program evaluation literature, the author demonstrates that the interpretation of regression estimates of between-group differences in wages and other economic outcom...
Variations in endorsed and perceived mental health treatment stigma across U.S. higher education institutions.

This study examines the association between six higher education institutional-level characteristics (institutional type, enrollment size, sector, housing, admissions selectivity, and graduation rate) and individual endorsed and perceived mental health treatment stigma scores among college students. We use nine years (2009-2017) of data from the Healthy Minds Study and our analysis sample includes 89,644 students at 105 unique institutions. We find a negative association between individual-level stigma scores and small enrollment institutions, private institutions, highly residential institutions, and institutions with the highest admissions selectivity and highest graduation rates. Moreover, these findings are generally similar across both individual measures of endorsed stigma and perceived stigma. Overall, our findings suggest that institutional environments where interactions are perhaps more frequent and personal (small enrollment institutions and highly residential institutions) are less likely to cultivate individual-level endorsements and perceptions of mental health treatment stigma. Our results have implications about higher education institutions’ ability to reduce stigma and increase mental health treatment-seeking behavior on campuses.
Near-optimal Linear Decision Trees for k-SUM and Related Problems

We construct near-optimal linear decision trees for a variety of decision problems in combinatorics and discrete geometry. For example, for any constant k, we construct linear decision trees that solve the k-SUM problem on n elements using O(n log2 n) linear queries. Moreover, the queries we use are comparison queries, which compare the sums of two k-subsets; when viewed as linear queries, comparison queries are 2k-sparse and have only l −1,0,1r coefficients. We give similar constructions for sorting sumsets A+B and for solving the SUBSET-SUM problem, both with optimal number of queries, up to poly-logarithmic terms. Our constructions are based on the notion of “inference dimension,” recently introduced by the authors in the context of active classification with comparison queries. This can be viewed as another contribution to the fruitful link between machine learning and discrete geometry, which goes back to the discovery of the VC dimension.
Learning Longer-term Dependencies in RNNs with Auxiliary Losses.

Despite recent advances in training recurrent neural networks (RNNs), capturing long-term dependencies in sequences remains a fundamental challenge. Most approaches use backpropagation through time (BPTT), which is difficult to scale to very long sequences. This paper proposes a simple method that improves the ability to capture long term dependencies in RNNs by adding an unsupervised auxiliary loss to the original objective. This auxiliary loss forces RNNs to either reconstruct previous events or predict next events in a sequence, making truncated backpropagation feasible for long sequences and also improving full BPTT. We evaluate our method on a variety of settings, including pixel-by-pixel image classification with sequence lengths up to 16\,000, and a real document classification benchmark. Our results highlight good performance and resource efficiency of this approach over competitive baselines, including other recurrent models and a comparable sized Transformer. Further analyses reveal beneficial effects of the auxiliary loss on optimization and regularization, as well as extreme cases where there is little to no backpropagation.
Nostalgin: Extracting 3D City Models from Historical Image Data

What did it feel like to walk through a city from the past? In this work, we describe Nostalgin (Nostalgia Engine), a method that can faithfully reconstruct cities from historical images. Unlike existing work in city reconstruction, we focus on the task of reconstructing 3D cities from historical images. Working with historical image data is substantially more difficult, as there are significantly fewer buildings available and the details of the camera parameters which captured the images are unknown. Nostalgin can generate a city model even if there is only a single image per facade, regardless of viewpoint or occlusions. To achieve this, our novel architecture combines image segmentation, rectification, and inpainting. We motivate our design decisions with experimental analysis of individual components of our pipeline, and show that we can improve on baselines in both speed and visual realism. We demonstrate the efficacy of our pipeline by recreating two 1940s Manhattan city blocks. We aim to deploy Nostalgin as an open source platform where users can generate immersive historical experiences from their own photos.
Design of optical neural networks with component imprecisions.

For the benefit of designing scalable, fault resistant optical neural networks (ONNs), we investigate the effects architectural designs have on the ONNs’ robustness to imprecise components. We train two ONNs – one with a more tunable design (GridNet) and one with better fault tolerance (FFTNet) – to classify handwritten digits. When simulated without any imperfections, GridNet yields a better accuracy (∼98%) than FFTNet (∼95%). However, under a small amount of error in their photonic components, the more fault tolerant FFTNet overtakes GridNet. We further provide thorough quantitative and qualitative analyses of ONNs’ sensitivity to varying levels and types of imprecisions. Our results offer guidelines for the principled design of fault-tolerant ONNs as well as a foundation for further research.
Freeze casting of iron oxide subject to a tri-axial nested Helmholtz-coils driven uniform magnetic field for tailored porous scaffolds

Abstract In this research, Fe3O4 particles were magnetically manipulated to create porous scaffolds using a tri-axial nested Helmholtz coils-based freeze-casting setup. This novel setup allowed for a uniform magnetic field to be applied in any direction and for it to effectively change directions at any time. Applying a uniform low magnetic field of 7.8 mT in various directions was investigated to fabricate a variety of tailored microstructures and mechanical properties in the resultant scaffolds. It was observed that using the magnetic field aligned up to 81% of the lamellar walls and also altered the area and shape of the pores of the resultant scaffolds. This lamellar wall alignment occurred at every applied magnetic field direction due to the Fe3O4 particles aligning during the freeze-casting process. As a result of this alignment, increases in the mechanical properties of up to 4.1× were observed. The results provide a novel experimental technique for the fabrication of user-defined microstructures in Fe3O4-based freeze-cast materials that provides significant advantages over previous experimental setups for magnetic freeze casting.
CRISPR-directed mitotic recombination enables genetic mapping without crosses

Linkage and association studies have mapped thousands of genomic regions that contribute to phenotypic variation, but narrowing these regions to the underlying causal genes and variants has proven much more challenging. Resolution of genetic mapping is limited by the recombination rate. We developed a method that uses CRISPR (clustered, regularly interspaced, short palindromic repeats) to build mapping panels with targeted recombination events. We tested the method by generating a panel with recombination events spaced along a yeast chromosome arm, mapping trait variation, and then targeting a high density of recombination events to the region of interest. Using this approach, we fine-mapped manganese sensitivity to a single polymorphism in the transporter Pmr1. Targeting recombination events to regions of interest allows us to rapidly and systematically identify causal variants underlying trait differences.
Cortex-wide neural interfacing via transparent polymer skulls

Neural computations occurring simultaneously in multiple cerebral cortical regions are critical for mediating behaviors. Progress has been made in understanding how neural activity in specific cortical regions contributes to behavior. However, there is a lack of tools that allow simultaneous monitoring and perturbing neural activity from multiple cortical regions. We engineered ‘See-Shells’—digitally designed, morphologically realistic, transparent polymer skulls that allow long-term (>300 days) optical access to 45 mm2 of the dorsal cerebral cortex in the mouse. We demonstrate the ability to perform mesoscopic imaging, as well as cellular and subcellular resolution two-photon imaging of neural structures up to 600 µm deep. See-Shells allow calcium imaging from multiple, non-contiguous regions across the cortex. Perforated See-Shells enable introducing penetrating neural probes to perturb or record neural activity simultaneously with whole cortex imaging. See-Shells are constructed using common desktop fabrication tools, providing a powerful tool for investigating brain structure and function. Imaging the mouse brain using glass cranial windows has limitations in terms of flexibility and long-term imaging. Here the authors engineer transparent polymer skulls that can fit various skull morphologies and can be implanted for over 300 days, enabling simultaneous high resolution brain imaging and electrophysiology across large cortical areas.
Primary Photoprocesses in Transition Metal Complexes

The kinetic approach to the analysis of photoprocesses has been summarized. Kinetic data are seldom sufficient for evaluation of all the primary rate constants. Nonetheless, it has been possible by combining photophysical and photochemical results to determine some of the rate constants in a variety of transition metal complexes. Identification of the photoactive state is a prerequisite to the calculation of the photochemical rates by comparison of the photochemical yields and luminescence lifetimes
Enolate Ions as β-Activators of Ortho-Metalation: Direct Synthesis of 3-Aminoindenones

β-Ketonitriles derived from a Claisen condensation of benzoate esters with alkyl- or phenylacetonitriles lead to 3-aminoindenones in the presence of excess LDA. This new reaction is also applicable to pyridine carboxylic esters. All of the 3-aminoindenones and their aza analogues can be hydrolyzed by acid to give the corresponding 1,3-indandiones. The mechanism of the reaction falls into the directed-ortho-metalation class in which the initial enolate ion of the keto-nitrile directs self-metalation at an ortho position. The new anion then cyclizes onto the nitrile group to generate an aminoindenone. Surprisingly the simplest member of the series, benzoylacetonitrile, does not undergo cyclization. Mechanistic isotope studies revealed that this substance preferentially and directly forms a dianion on the side chain, which is not further deprotonated at the ortho position of the aromatic ring.
Can an aromatic ring alter the reactions of a nearby unsaturated imide? A study of the rate and selectivity of nitrile oxide cycloaddition reactions of acryloyl derivatives of the Rebek imide benzoxazole

Abstract Cycloadditions of acryloyl derivatives of the Rebek imide benzoxazole are extraordinarily stereoselective, but have rates and regioselectivities that otherwise parallel those of a simple achiral model. It appears that the benzoxazole ring of these compounds completely shields the inner face of the nearby alkene, but has no measurable effect on the rate of reactions on the outer face.
Diverse roles of guanine nucleotide exchange factors in regulating collective cell migration

Efficient collective migration depends on a balance between contractility and cytoskeletal rearrangements, adhesion, and mechanical cell-cell communication, all controlled by GTPases of the RHO family. By comprehensive screening of guanine nucleotide exchange factors (GEFs) in human bronchial epithelial cell monolayers, we identified GEFs that are required for collective migration at large, such as SOS1 and β-PIX, and RHOA GEFs that are implicated in intercellular communication. Down-regulation of the latter GEFs differentially enhanced front-to-back propagation of guidance cues through the monolayer and was mirrored by down-regulation of RHOA expression and myosin II activity. Phenotype-based clustering of knockdown behaviors identified RHOA-ARHGEF18 and ARHGEF3-ARHGEF28-ARHGEF11 clusters, indicating that the latter may signal through other RHO-family GTPases. Indeed, knockdown of RHOC produced an intermediate between the two phenotypes. We conclude that for effective collective migration, the RHOA-GEFs → RHOA/C → actomyosin pathways must be optimally tuned to compromise between generation of motility forces and restriction of intercellular communication.
A GENERAL SYNTHETIC ROUTE TO 4-SUBSTITUTED-2,2'-BITHIOPHENES

A new synthetic route to 4-substituted-2,2′-bithiophenes has been developed utilizing 4-bromo-2,2′-bithiophene (1). Formation of the bithienyllithium adduct via halogen-metal exchange was found to be problematic and resulted in complex mixtures of products. The Grignard reagent of 1 can be obtained easily via the “entrainment” method, allowing the production of 4-substituted-2,2′-bithiophenes (where sub-stituent = octyl, hydroxyethyl, hydroxymethyl, carboxy, carbomethoxy, acetoxyethyl, and acetoxymethyl).
First stereoselective synthesis of an optically pure β-substituted histidine: (2S,3S)-β-methylhistidine

Abstract We report the first example of the asymmetric synthesis of the β-substituted histidine, (2S,3S)-β-methylhistidine. A key in the synthesis is the use of the protecting group, 2-mesitylenesulfonyl (Mts-), for the imidazole ring to minimize epimerization during synthesis.
FIRST SYNTHESIS OF CYTOTOXIC 8,9-SECOKAURENE DITERPENOIDS. AN ENANTIOSELECTIVE ROUTE TO (-)-O-METHYLSHIKOCCIN AND (+)-O-METHYLEPOXYSHIKOCCIN

A practical route for the total synthesis of 8,9-secokaurene diterpenes is described. The central step is the [3.3]sigmatropic rearrangement of spirocyclic intermediates such as 35, 40, and 41. All three compounds must necessarily respond identically to properly install the absolute configuration of the bridgehead methine carbon. The total synthesis of (−)-O-methylshikoccin (2b) was realized in 8% overall yield from the Wieland−Miescher ketone 9. Its naturally occurring epoxide 47 was prepared with comparable efficiency. The preparative route developed herein should provide a general entry into this important class of diterpenoids.
A facile and rapid route for the synthesis of novel 1,5-substituted tetrazole hydantoins and thiohydantoins via a TMSN3-Ugi/RNCX cyclization

Abstract This Letter describes novel methodology for the rapid assembly of new and biologically appealing 1,5-substituted tetrazole-hydantoins and thiohydantoins. The product of a TMSN 3 -Ugi multi-component reaction is treated with an excess of isocyanate or isothiocyanate to generate the final scaffold in moderate to good yields. The applicability of this solution phase methodology to the preparation of a small collection of compounds is discussed.
Directed regioselective Ni-catalyzed alkylation and hydride addition of allylic ethers. A remarkable turnover in regioselectivity

Abstract Various allylic ethers are reduced efficiently in the presence of Ni(PPh 3 ) 2 Cl 2 (5 mol%) and EtMgCl (5 equiv) with excellent regioselectivity (>99:1). The sense of regiochemical control in these reactions is opposite to that observed in Ni-catalyzed alkylations of the same substrates. A mechanistic working model that accounts for the observed levels and trends in selectivity is presented.
Cationic bis(oxazoline)Cu(II) lewis acid catalysts. Application to the asymmetric synthesis of ent-Δ1-tetrahydrocannabinol

Abstract The Diels-Alder reaction of acryloyl oxazolidinone and 1-acetoxy-3-methylbutadiene is catalyzed by the cationic bis(oxazoline)Cu(II) complex 4 in high enantioselectivity. The cycloadduct is converted to ent - Δ 1 -tetrahydrocannabinol (THC) in four steps.
A bright, slow cryogenic molecular beam source for free radicals

We demonstrate and characterize a cryogenic buffer gas-cooled molecular beam source capable of producing bright beams of free radicals and refractory species. Details of the beam properties (brightness, forward velocity distribution, transverse velocity spread, rotational and vibrational temperatures) are measured under varying conditions for the molecular species SrF. Under typical conditions we produce a beam of brightness 1.2 × 1011 molecules/sr/pulse in the X2Σ+(v = 0, Nrot = 0) state, with forward velocity and a rotational temperature of ≈ 1 K. This source compares favorably to other methods for producing beams of free radicals and refractory species for many types of experiments. We provide details of construction that may be helpful for others attempting to use this method.
A MILD AND HIGHLY SELECTIVE N-BENZOYLATION OF CYTOSINE AND ADENINE BASES IN NUCLEOSIDES WITH N-BENZOYLTETRAZOLE

Abstract N -Benzoyltetrazole has been developed as a mild and selective reagent for monobenzoylation of the exocyclic amino group in nucleic acid bases. Its usefulness is demonstrated by protection of adenine and cytosine bases, an important procedure in the nucleic acid chemistry field.
In situ infrared study of the absorption of nitric oxide by 12-tungstophosphoric acid

An extensive diffuse reflectance infrared investigation of the interaction of 12-tungstophosphoric acid (HPW) and its potassium salt with NOx (x = 1 or 2) was performed. In the presence of KBr, HPW yielded a spectrum identical to that of the potassium salt. Using pure powders, spectra of HPW·6H2O showing the (O−H) bands of H5O2+ and the correct appearance of the Keggin anion bands are presented. At 423 K, NO(g) with or without O2(g) interacted weakly or not at all with the potassium salt; however, NO2(g) adsorbed onto the surface as loosely bound NO with ν(NO) at 1870 cm-1. The hexahydrate did not sorb NO in the absence of oxygen at 423 K or higher. In the presence of oxygen at 423 K, the surface of HPW is involved in catalytic oxidation of NO(g) to NO2(g) via an adsorbed NOxy- intermediate. This species can be absorbed into the HPW structure as a form of NOH+, displacing water, or leave as NO2(g). Not all structural water is displaced by NO, and water plays a role in holding the new structures together b...
Reconsidering Spatial Priors In EEG Source Estimation : Does White Matter Contribute to EEG Rhythms?

Electroencephalogram (EEG) has been a core tool used in functional neuroimaging in humans for nearly a hundred years. Because it is inexpensive, easy to implement, and noninvasive, it also represents an excellent candidate modality for use in the BCI setting. Nonetheless, a complete understanding of how EEG measurements (voltage fluctuations) relate to information processing in the brain remains somewhat elusive. A deeper understanding of the neuroanatomical underpinnings of the EEG signal may help explain inter-individual variability in evoked and induced potentials, which may improve BCI therapies targeted to the individual. According to classic biophysical models, EEG fluctuations are primarily a reflection of locally synchronized neuronal oscillations within the gray matter oriented approximately orthogonal to the scalp. In contrast, global models ignore local signals due to dendritic processing, and suggest that propagation delays due to white matter architecture are responsible for the EEG signal, and are capable of explaining the coherence between numerous rhythms (e.g., alpha) at spatially distinct areas of the scalp. Recently, combined local-global models suggest that the EEG signal may reflect a superposition of local processing along with global contributors including transduction along white matter tracts in the brain. Incorporating both local and global (e.g., white matter) priors into EEG source models may therefore improve source estimates. These models may also help disentangle which aspects of the EEG signal are predicted to colocalize spatially with measurements from functional MRI (fMRI). Here, we explore the possibility that white matter conductivity contributes to EEG measurements via a generative model based on classic axonal transduction models, and discuss its potential implications for source estimation.
Generation and reactions of 2,3-dilithio-N-methylindole. Synthesis of 2,3-disubstituted indoles

Abstract Generation of 2,3-dilithio- N -methylindole ( 7 ) from 2,3-diiodo- N -methylindole ( 6 ) and subsequent reaction with various electrophiles (NH 4 Cl, DMF, ClCO 2 Me, CO 2 , phthalic anhydride) affords the corresponding 2,3-disubstituted indoles in good to excellent yields (41–99%).
Cross-platform mechanical characterization of lung tissue

Published data on the mechanical strength and elasticity of lung tissue is widely variable, primarily due to differences in how testing was conducted across individual studies. This makes it extremely difficult to find a benchmark modulus of lung tissue when designing synthetic extracellular matrices (ECMs). To address this issue, we tested tissues from various areas of the lung using multiple characterization techniques, including micro-indentation, small amplitude oscillatory shear (SAOS), uniaxial tension, and cavitation rheology. We report the sample preparation required and data obtainable across these unique but complimentary methods to quantify the modulus of lung tissue. We highlight cavitation rheology as a new method, which can measure the modulus of intact tissue with precise spatial control, and reports a modulus on the length scale of typical tissue heterogeneities. Shear rheology, uniaxial, and indentation testing require heavy sample manipulation and destruction; however, cavitation rheology can be performed in situ across nearly all areas of the lung with minimal preparation. The Young’s modulus of bulk lung tissue using micro-indentation (1.4±0.4 kPa), SAOS (3.3±0.5 kPa), uniaxial testing (3.4±0.4 kPa), and cavitation rheology (6.1±1.6 kPa) were within the same order of magnitude, with higher values consistently reported from cavitation, likely due to our ability to keep the tissue intact. Although cavitation rheology does not capture the non-linear strains revealed by uniaxial testing and SAOS, it provides an opportunity to measure mechanical characteristics of lung tissue on a microscale level on intact tissues. Overall, our study demonstrates that each technique has independent benefits, and each technique revealed unique mechanical features of lung tissue that can contribute to a deeper understanding of lung tissue mechanics.
Stereoselective synthesis of cis- or trans-2,4-disubstituted butyrolactones from Wynberg lactone

Abstract (R)-Wynberg lactone was used to prepare various asymmetric 2,4-disubstituted butyrolactones in three to four steps. Attainment of any possible stereoisomer, based upon commencement from (R)- or (S)-4-trichloromethyl-2-oxetanone, and the capacity to install disparate substituents at C2 make this approach particularly versatile.
N-Chlorosuccinimide is a convenient oxidant for the synthesis of 2,4-disubstituted 1,2,4-thiadiazolidine-3,5-diones

Abstract N -Chlorosuccinimide has been identified as a convenient and safe alternative oxidant for the oxidative condensation of isothiocyanates and isocyanates to afford 1,2,4-thiadiazolidine-3,5-diones.
Multiple Phenotypic Changes Associated with Large-Scale Horizontal Gene Transfer

Horizontal gene transfer often leads to phenotypic changes within recipient organisms independent of any immediate evolutionary benefits. While secondary phenotypic effects of horizontal transfer (i.e., changes in growth rates) have been demonstrated and studied across a variety of systems using relatively small plasmids and phage, little is known about the magnitude or number of such costs after the transfer of larger regions. Here we describe numerous phenotypic changes that occur after a large-scale horizontal transfer event (∼1 Mb megaplasmid) within Pseudomonas stutzeri including sensitization to various stresses as well as changes in bacterial behavior. These results highlight the power of horizontal transfer to shift pleiotropic relationships and cellular networks within bacterial genomes. They also provide an important context for how secondary effects of transfer can bias evolutionary trajectories and interactions between species. Lastly, these results and system provide a foundation to investigate evolutionary consequences in real time as newly acquired regions are ameliorated and integrated into new genomic contexts.
Enantioselective fluorescent recognition of chiral acids by 3- and 3,3′-aminomethyl substituted BINOLs

Abstract Benzylaminomethyl groups are introduced to the 3,3′-positions of BINOL. The resulting compounds can be used to conduct the enantioselective fluorescent recognition of mandelic acid and N-benzyloxycarbonylphenylglycine. In the presence of (S)-mandelic acid, compound (R)-2 showed over 30-fold fluorescence enhancement with the ef [ef=enantiomeric fluorescence difference ratio=(IS−I0)/(IR−I0)] up to 4.2. In the presence of d -N-benzyloxycarbonylphenylglycine, compound (RR)-4 showed up to 15-fold fluorescence enhancement with the ef up to 5.0. These high fluorescence sensitivity and enantioselectivity make compounds (R)-2 and (RR)-4 practically useful sensors for the recognition of the chiral acids in apolar solvents.
ATRX, DAXX or MEN1 mutant pancreatic neuroendocrine tumors are a distinct alpha-cell signature subgroup

The commonly mutated genes in pancreatic neuroendocrine tumors (PanNETs) are ATRX, DAXX, and MEN1. We genotyped 64 PanNETs and found 58% carry ATRX, DAXX, and MEN1 mutations (A-D-M mutant PanNETs) and this correlates with a worse clinical outcome than tumors carrying the wild-type alleles of all three genes (A-D-M WT PanNETs). We performed RNA sequencing and DNA-methylation analysis to reveal two distinct subgroups with one consisting entirely of A-D-M mutant PanNETs. Two genes differentiating A-D-M mutant from A-D-M WT PanNETs were high ARX and low PDX1 gene expression with PDX1 promoter hyper-methylation in the A-D-M mutant PanNETs. Moreover, A-D-M mutant PanNETs had a gene expression signature related to that of alpha-cells (FDR q-value < 0.009) of pancreatic islets including increased expression of HNF1A and its transcriptional target genes. This gene expression profile suggests that A-D-M mutant PanNETs originate from or transdifferentiate into a distinct cell type similar to alpha cells.
Defective RNA polymerase III is negatively regulated by the SUMO-Ubiquitin-Cdc48 pathway.

Transcription by RNA polymerase III (Pol III) is an essential cellular process, and mutations in Pol III can cause neurodegenerative disease in humans. However, in contrast to Pol II transcription, which has been extensively studied, the knowledge of how Pol III is regulated is very limited. We report here that in budding yeast, Saccharomyces cerevisiae, Pol III is negatively regulated by the S mall U biquitin-like MO difier (SUMO), an essential post-translational modification pathway. Besides sumoylation, Pol III is also targeted by ubiquitylation and the Cdc48/p97 segregase; these three processes likely act in a sequential manner and eventually lead to proteasomal degradation of Pol III subunits, thereby repressing Pol III transcription. This study not only uncovered a regulatory mechanism for Pol III, but also suggests that the SUMO and ubiquitin modification pathways and the Cdc48/p97 segregase can be potential therapeutic targets for Pol III-related human diseases.
The symmetries of fermion fluids at low dimensions

We point out that the quasiparticle spectrum of the Landau Fermi liquid theory has an extra Z2 symmetry, local in momentum space, which is not generic to the Hamiltonian with interactions. Thus the Fermi liquid is in this sense a (quantum) zero-temperature critical point.
Sampling Native-like Structures of RNA-Protein Complexes through Rosetta Folding and Docking

RNA-protein complexes underlie numerous cellular processes including translation, splicing, and posttranscriptional regulation of gene expression. The structures of these complexes are crucial to their functions but often elude high-resolution structure determination. Computational methods are needed that can integrate low-resolution data for RNA-protein complexes while modeling de novo the large conformational changes of RNA components upon complex formation. To address this challenge, we describe RNP-denovo, a Rosetta method to simultaneously fold-and-dock RNA to a protein surface. On a benchmark set of diverse RNA-protein complexes not solvable with prior strategies, RNP-denovo consistently sampled native-like structures with better than nucleotide resolution. We revisited three past blind modeling challenges involving the spliceosome, telomerase, and a methyltransferase-ribosomal RNA complex in which previous methods gave poor results. When coupled with the same sparse FRET, crosslinking, and functional data used previously, RNP-denovo gave models with significantly improved accuracy. These results open a route to modeling global folds of RNA-protein complexes from low-resolution data.
Highly diastereoselective synthesis of new, carbostyril-based type of conformationally-constrained β-phenylserines

Abstract We have demonstrated that the readily available amido–keto compounds 5 , with prearranged carbonyl and glycine moieties, under strongly basic conditions easily undergo complete and highly diastereoselective cyclization, affording a generalized and practical access to the conformationally constrained phenylserine derivatives 4 . High chemical yields, virtually complete diastereoselectivity combined with the operational convenience of the experimental procedures render this method useful for preparation of these diastereomerically pure derivatives.
Synthesis of pyrazolo[3,4‐c][1,2]thiazin‐4(3H)‐one 2,2‐dioxides, new heterocycles

The reaction of substituted ethyl 5-aminopyrazole-4-carboxylates with two equivalents of methanesul-fonyl chloride gave the substituted ethyl 5-[bis(methylsufonyl)amino]-1H.-pyrazole-4-carboxylates II. Removal of one of the methanesulfonyl groups, followed by alkylation of the ethyl 5-[(methylsulfonyl)amino]-1H-pyrazole-4-carboxylates III with methyl iodide produced the substituted ethyl 5-[methyl(methylsulfonyl)amino]-1H-pyrazole-4-carboxylates IV. Treatment of IV with sodium hydride gave the 7-substituted 1,7-dihydro-1-methylpyrazolo[3,4-c][1,2]thiazin-4(3H)-one 2,2-dioxides V.
Comparison of mechanistic models for correlation of activation energies of liquid‐phase addition of carbon‐centered radicals to terminal olefins

The performance of different models for the influence of enthalpy and polar effects on the activation energies for liquid-phase addition of carbon-centered radicals to terminal olefins is compared for the extensive data set from the Fischer group, supplemented by additional data. The best correlations result from the Fischer-Radom (FR) model, but it also contains the largest number of adjustable radical-dependent parameters that are not based on physical observables; hence its predictive power for new radicals is limited. Updating the literature values of fH, IP, and EA that are the independent variables in the FR model led to some deterioration in the quality of the correlations; this is symptomatic of remaining deficiencies in the thermochemical data bases. In contrast, the Lalevee-Allonas-Fouassier (LAF) model gives poorer correlation but this is in part compensated because it uses the same independent variables but with no adjustable parameters. Hammett-type models based on polar and radical substituent constants rather than on molecular properties of the reactants perform even more poorly than the LAF model. In all cases, poorer correlation, as judged by increasing ( E), is accompanied by a systematic bias to over-predict the lower E values and under-predict the higher ones. The enthalpy contribution inmore » both the FR and LAF models is expressed as a linear Evans-Polanyi dependence of E on H. Replacement by non-linear Marcus dependences for these exothermic reactions does not significantly improve performance. An attempt to significantly reduce the number of adjustable parameters in the FR model by anchoring them to a base set applicable to all radicals, which is then modulated for spin delocalization based on observable ESR hyperfine constants in the initial and adduct radicals, showed modest success.« less
Synthesis of Li2MgIr and LiMgIrH6: Guidance from DFT

Abstract Our theoretical modeling of Li2MgX systems and their hydrides with density functional theory (DFT) suggested the existence of Li2MgIr. Verifying the DFT results, we have synthesized Li2MgIr and determined its crystal structure and hydrogen sorption behavior. The phase crystallizes in the cubic P 4 ¯ 3 m space group and is isostructural to the known ternary Li2MgSi. Its reaction with hydrogen proceeds according to Li2MgIr + (7/2)H2 → LiMgIrH6 + LiH The hydride LiMgIrH6 also features P 4 ¯ 3 m symmetry; its detailed crystal structure is established via a combination of X-ray diffraction and DFT analyses. A metal → insulator transition accompanies formation of the hydride.