cssi/SciSciGPT-SciSciNet huggingface dataset:
Corporate social responsibility and stock split

This study examines whether socially responsible companies are likely to conduct a stock split. We argue that these companies, compared to their counterparts, could use their strong corporate social responsibility (CSR) performance to reduce information asymmetry with shareholders, and therefore, are less likely to rely on stock splits to signal their future growth potentials. We find empirical evidence to support our hypothesis and investigate the reasons for the lower frequency of stock splits among CSR oriented firms. We find that more socially responsible firms experience a smaller increase in trading volume and a greater increase in bid-ask spread following a stock split than less socially responsible firms. Furthermore, our study finds that, when more socially responsible firms decide to conduct a stock split, they attract a greater proportion of institutional investors with long-term investment horizons.
Algorithms for Routing of Unmanned Aerial Vehicles with Mobile Recharging Stations

We study the problem of finding a tour for an energy-limited Unmanned Aerial Vehicle (UAV) to visit a set of sites in the least amount of time. We envision scenarios where the UAV can be recharged along the way either by landing on stationary recharging stations or on Unmanned Ground Vehicles (UGVs) acting as mobile recharging stations. This leads to a new variant of the Traveling Salesperson Problem (TSP). We present an algorithm that finds not only the order in which to visit the sites but also when and where to land on the charging stations to recharge. Our algorithm plans tours for the UGVs as well as determines best locations to place stationary charging stations. While the problems we study are NP-Hard, we present a practical solution using Generalized TSP that finds the optimal solution. If the UGVs are slower, the algorithm also finds the minimum number of UGVs required to support the UAV mission such that the UAV is not required to wait for the UGV. Our simulation results show that the running time is acceptable for reasonably sized instances.
Carcinocythemia: A rare entity becoming more common? A 3-year, single institution series of seven cases and literature review.

INTRODUCTION Carcinocythemia is a rare phenomenon defined as morphologically identifiable, circulating tumor cells in the peripheral blood. No modern case series of carcinocythemia exists in the literature. METHODS Blood smears from carcinocythemia patients were reviewed and associated clinicopathologic findings described and compared to the literature. When available, bone marrows were examined. RESULTS We identified 7 carcinocythemia cases over 3 years at our institution in 5 females and 2 males with a median age of 57 and compare them to 26 case reports in the literature (19 females, 10 males; median age 57). The primary neoplasms were carcinomas of breast (3 cases), lung, non-small cell (2 cases), prostate (1), and 1 case of unknown primary. Circulating tumor cells were associated with fragmentation hemolysis (2 cases), asplenic RBC changes (3 cases), and myeloid antigen expression by flow cytometry (2 cases) and were most commonly found at the feathered edge of the slide (6 cases) as single cells or in clusters. CONCLUSIONS This represents the largest series of carcinocythemia reported. The identification of 7 cases at one institution over a 3-year period suggests carcinocythemia may becoming more common. Raising awareness of this entity and its associated clinicopathologic findings may help avoid diagnostic pitfalls in blood smear examinations and may guide timely clinical management.
Drivers, timing and some impacts of global aridity change

The modeled robustness of the aridity response to climate change has already been well established: global drylands are expanding as increases in potential evapotranspiration outpace precipitation increases. This work considers three questions not previously addressed: (1) in which aridity zones are aridity trends expected to first emerge? (2) To what extent are future populations expected to experience changes in aridity? (3) For which locations and populations is aridity change determined by changes in precipitation versus temperature? Using a multi-model ensemble of general circulation models (GCMs) from the CMIP5 archives, together with population statistics from United Nations databases we find the following: (1) drier regions are projected to dry earlier, more severely and to a greater extent than humid regions. (2) By the end of the century, up to 700 million more people are projected to live in arid regions, with half of humankind living in regions experiencing drying of at least 5% and 3 billion experiencing 25% drying under a high emissions scenario. The largest populations to experience extreme drying are in Africa and Asia. According to GCMs, aridity increases have already begun to emerge in Northern Africa. Populations in sub-Saharan Africa appear to be the most vulnerable considering current water scarcity levels there. And (3) precipitation change is projected to drive the most severe drying in arid regions, contributing to the earliest emerging signals of aridity change and driving the differential drying across aridity zones. A comparison of aridity data derived from observations with model ensemble data suggests that increased aridity is already emerging in the driest regions. In sum, widespread aridity trends across a warming state imply that most of humanity will live in a more arid world.
SFV: reinforcement learning of physical skills from videos

Data-driven character animation based on motion capture can produce highly naturalistic behaviors and, when combined with physics simulation, can provide for natural procedural responses to physical perturbations, environmental changes, and morphological discrepancies. Motion capture remains the most popular source of motion data, but collecting mocap data typically requires heavily instrumented environments and actors. In this paper, we propose a method that enables physically simulated characters to learn skills from videos (SFV). Our approach, based on deep pose estimation and deep reinforcement learning, allows data-driven animation to leverage the abundance of publicly available video clips from the web, such as those from YouTube. This has the potential to enable fast and easy design of character controllers simply by querying for video recordings of the desired behavior. The resulting controllers are robust to perturbations, can be adapted to new settings, can perform basic object interactions, and can be retargeted to new morphologies via reinforcement learning. We further demonstrate that our method can predict potential human motions from still images, by forward simulation of learned controllers initialized from the observed pose. Our framework is able to learn a broad range of dynamic skills, including locomotion, acrobatics, and martial arts. (Video1)
Identification of peripheral neural circuits that regulate heart rate using optogenetic and viral vector strategies

Heart rate is under the precise control of the autonomic nervous system. However, the wiring of peripheral neural circuits that regulate heart rate is poorly understood. Here, we develop a clearing-imaging-analysis pipeline to visualize innervation of intact hearts in 3D and employed a multi-technique approach to map parasympathetic and sympathetic neural circuits that control heart rate in mice. We identify cholinergic neurons and noradrenergic neurons in an intrinsic cardiac ganglion and the stellate ganglia, respectively, that project to the sinoatrial node. We also report that the heart rate response to optogenetic versus electrical stimulation of the vagus nerve displays different temporal characteristics and that vagal afferents enhance parasympathetic and reduce sympathetic tone to the heart via central mechanisms. Our findings provide new insights into neural regulation of heart rate, and our methodology to study cardiac circuits can be readily used to interrogate neural control of other visceral organs.
Challenges in the Search for Perchlorate and Other Hydrated Minerals with 2.1-μm Absorptions on Mars

A previously unidentified artifact has been found in Compact Reconnaissance Imaging Spectrometer for Mars targeted I/F data. It exists in a small fraction (<0.05%) of pixels within 90% of images investigated and occurs in regions of high spectral/spatial variance. This artifact mimics real mineral absorptions in width and depth and occurs most often at 1.9 and 2.1 μm, thus interfering in the search for some mineral phases, including alunite, kieserite, serpentine, and perchlorate. A filtering step in the data processing pipeline, between radiance and I/F versions of the data, convolves narrow artifacts (“spikes”) with real atmospheric absorptions in these wavelength regions to create spurious absorption‐like features. The majority of previous orbital detections of alunite, kieserite, and serpentine we investigated can be confirmed using radiance and raw data, but few to none of the perchlorate detections reported in published literature remain robust over the 1.0‐ to 2.65‐μm wavelength range.
Hybridité et voix auctoriale

This article analyzes three hybrid narratives – Sylvie Gracia’s Le livre des visages (2012), Pascal Quignard’s Les ombres errantes (2002), and Helene Cixous’s Hyperreve (2006). Although their hybridity can be found at different levels, such as the generic level, or the lexical level, all three texts attempt to catch the Mother in their narrative subterfuges in order to bring her back to life (or in the case of Cixous, to keep her alive), in vain. In the process, the authorial voice is reinforced as the voice leading the reader through narrative transgressions.
High-throughput assessment of vacancy formation and surface energies of materials using classical force-fields

In this work, we present an open access database for surface and vacancy-formation energies using classical force-fields (FFs). These quantities are essential in understanding diffusion behavior, nanoparticle formation and catalytic activities. FFs are often designed for a specific application, hence, this database allows the user to understand whether a FF is suitable for investigating particular defect and surface-related material properties. The FF results are compared to density functional theory and experimental data whenever applicable for validation. At present, we have 17 506 surface energies and 1000 vacancy formation energies calculation in our database and the database is still growing. All the data generated, and the computational tools used, are shared publicly at the following websites: www.ctcms.nist.gov/~knc6/periodic.html, https://jarvis.nist.gov and https://github.com/usnistgov/jarvis. Approximations used during the high-throughput calculations are clearly mentioned. Using some of the example cases, we show how our data can be used to directly compare different FFs for a material and to interpret experimental findings such as using Wulff construction for predicting equilibrium shape of nanoparticles. Similarly, the vacancy formation energies data can be useful in understanding diffusion related properties.
Evidence and rationalization

Suppose that you have to take a test tomorrow but you do not want to study. Unfortunately you should study, since you care about passing and you expect to pass only if you study. Is there anything you can do to make it the case that you should not study? Is there any way for you to ‘rationalize’ slacking off? I suggest that such rationalization is impossible. Then I show that if evidential decision theory is true, rationalization is not only possible but sometimes advisable.
Exploring the impact of R&D on patenting activity in small women-owned and minority-owned entrepreneurial firms

The relevant economics literature on the impact of R&D on patenting activity falls within two methodological areas of inquiry. The first area might be classified as a test of the Schumpeterian hypothesis. The second and lesser research area might be classified as an estimation of the knowledge production function relationship between R&D and patenting. This paper focuses on estimates of the R&D-to-patenting relationship for a random sample of small, entrepreneurial firms whose research projects were supported through the US Small Business Innovation Research (SBIR) program. Our paper contributes to the R&D-to-patenting literature in two ways. It examines empirically a unique set of small, entrepreneurial firms funded by the public sector, and it explores the effect of the gender and ethnicity of firm owners on the propensity of their firms to patent from funded research projects.
On the Solution of a Painlevé III Equation

In a 1977 paper of B. M. McCoy, C. A. Tracy and T. T. Wu there appeared for the first time the solution of a Painleve equation in terms of Fredholm determinants of integral operators. Their proof is quite complicated. We present here one which is more straightforward and makes use of recent work of the author and C. A. Tracy.
Hydrocephalus in a rat model of Meckel Gruber syndrome with a TMEM67 mutation.

Transmembrane protein 67 (TMEM67) is mutated in Meckel Gruber Syndrome type 3 (MKS3) resulting in a pleiotropic phenotype with hydrocephalus and renal cystic disease in both humans and rodent models. The precise pathogenic mechanisms remain undetermined. Herein it is reported for the first time that a point mutation of TMEM67 leads to a gene dose-dependent hydrocephalic phenotype in the Wistar polycystic kidney (Wpk) rat. Animals with TMEM67 heterozygous mutations manifest slowly progressing hydrocephalus, observed during the postnatal period and continuing into adulthood. These animals have no overt renal phenotype. The TMEM67 homozygous mutant rats have severe ventriculomegaly as well as severe polycystic kidney disease and die during the neonatal period. Protein localization in choroid plexus epithelial cells indicates that aquaporin 1 and claudin-1 both remain normally polarized in all genotypes. The choroid plexus epithelial cells may have selectively enhanced permeability as evidenced by increased Na+, K+ and Cl− in the cerebrospinal fluid of the severely hydrocephalic animals. Collectively, these results suggest that TMEM67 is required for the regulation of choroid plexus epithelial cell fluid and electrolyte homeostasis. The Wpk rat model, orthologous to human MKS3, provides a unique platform to study the development of both severe and mild hydrocephalus.
LHC SUSY and WIMP dark matter searches confront the string theory landscape

The string theory landscape of vacua solutions provides physicists with some understanding as to the magnitude of the cosmological constant. Similar reasoning can be applied to the magnitude of the soft SUSY breaking terms in supersymmetric models of particle physics: there appears to be a statistical draw towards large soft terms which is tempered by the anthropic requirement of the weak scale lying not too far from ∼ 100 GeV. For a mild statistical draw of m soft with n = 1 (as expected from SUSY breaking due to a single F term) then the light Higgs mass is preferred at ∼ 125 GeV while sparticles are all pulled beyond LHC bounds. We confront a variety of LHC and WIMP dark matter search limits with the statistical expectations from a fertile patch of string theory landscape. The end result is that LHC and WIMP dark matter detectors see exactly that which is expected from the landscape: a Standard Model-like Higgs boson of mass 125 GeV but as yet no sign of sparticles or WIMP dark matter. SUSY from the n = 1 landscape is most likely to emerge at LHC in the soft opposite-sign dilepton plus jet plus MET channel. Multi-ton noble liquid WIMP detectors should be able to completely explore the n = 1 landscape parameter space.
Perpendicular magnetic anisotropy and spin mixing conductance in polycrystalline europium iron garnet thin films

Polycrystalline single-phase europium iron garnet films (EuIG, Eu3Fe5O12, a ferrimagnetic insulator), with thicknesses from 25 to 50 nm and roughness <1 nm, have been grown on various substrates using pulsed laser deposition followed by a rapid thermal anneal. The films are under strain that originates primarily from thermal mismatch and leads to a magnetoelastic anisotropy that dominates the net anisotropy. EuIG grown on quartz (0001) demonstrated perpendicular magnetic anisotropy (PMA) attributed to the in-plane (IP) compressive thermal mismatch strain, whereas films on (11 2¯ 0) quartz, Si, fused silica, and yttria-stabilized zirconia exhibited an IP easy axis due to tensile strain, consistent with the positive magnetostriction of polycrystalline EuIG. For the PMA EuIG, the saturation magnetization was close to that of bulk EuIG, and the out-of-plane coercivity ranged from 600 to 900 Oe, depending on the film thickness. Spin transport measurements on Pt/EuIG/quartz heterostructures gave an anomalous Hall effect-like spin Hall magnetoresistance similar to that of Pt/epitaxial single crystal EuIG. These results show that high quality polycrystalline garnets can be grown with PMA making them useful for applications in spintronic devices.
Quantitative analysis of the ThrbCRM1-centered gene regulatory network

Enhancer activity is determined by both the activity and occupancy of transcription factors as well as the specific sequences they bind. Experimental investigation of this dynamic requires the ability to manipulate components of the system, ideally in as close to an in vivo context as possible. Here we use electroporation of plasmid reporters to define critical parameters of a specific cis-regulatory element, ThrbCRM1, during retinal development. ThrbCRM1 is associated with cone photoreceptor genesis and activated in a subset of developing retinal cells that co-express the Otx2 and Onecut1 (OC1) transcription factors. Variation of reporter plasmid concentration was used to generate dose response curves and revealed an effect of binding site availability on the number and strength of cells with reporter activity. Critical sequence elements of the ThrbCRM1 element were defined using both mutagenesis and misexpression of the Otx2 and OC1 transcription factors in the developing retina. Additionally, these experiments suggest that the ThrbCRM1 element is co-regulated by Otx2 and OC1 even under conditions of sub-optimal binding of OC1.
Minimal Images in Deep Neural Networks: Fragile Object Recognition in Natural Images

The human ability to recognize objects is impaired when the object is not shown in full. "Minimal images" are the smallest regions of an image that remain recognizable for humans. Ullman et al. 2016 show that a slight modification of the location and size of the visible region of the minimal image produces a sharp drop in human recognition accuracy. In this paper, we demonstrate that such drops in accuracy due to changes of the visible region are a common phenomenon between humans and existing state-of-the-art deep neural networks (DNNs), and are much more prominent in DNNs. We found many cases where DNNs classified one region correctly and the other incorrectly, though they only differed by one row or column of pixels, and were often bigger than the average human minimal image size. We show that this phenomenon is independent from previous works that have reported lack of invariance to minor modifications in object location in DNNs. Our results thus reveal a new failure mode of DNNs that also affects humans to a much lesser degree. They expose how fragile DNN recognition ability is for natural images even without adversarial patterns being introduced. Bringing the robustness of DNNs in natural images to the human level remains an open challenge for the community.
Assessing the Value of Market Access from Belt and Road Projects

This paper describes a parsimonious approach to the economic analysis of transportation investments. In a gravity model of trade, project benefits may be summarized by a money metric for the change in market access experienced by all cities due to the investment. This metric is equivalent to the change in the value of all payments to urban land—the fixed factor of production. Using this model and an original geographic information system data set of Belt and Road Initiative projects in Eurasia, the paper predicts additional income paid to owners of urban land, for each project and city. Individually, nearly half of the proposed infrastructure is estimated to provide significant gains; however, the rest is estimated to be of little value because it fails to create new least-cost paths between large populations centers. Considering the proposed new transport infrastructure as a system, the share of projects that provide gains increases to almost two-thirds. While gains in market access accrue primarily to low-income countries, gains from many projects accrue outside the project country, and in dollar terms more so to richer countries. This finding is consistent with the idea that infrastructure investment along international trade corridors can be a public good. These estimates should be taken as lower bounds, because they do not include direct benefits to users, for instance, time savings. Even so, they offer a useful way for governments to estimate the short-run gains from infrastructure and prioritize infrastructure spending.
Effect of functionalization on the properties of silsesquioxane: a comparison to silica

While similar in nature, the properties of silica and silsesquioxane are very different, but little is known about these differences. In this paper, functionalized silsesquioxane microparticles are synthesized by adapting the modified Stober method and post-functionalized with rhodamine B. The as-synthesized silsesquioxane particles are characterized by a variety of physical and chemical methods. The synthesized particles are amorphous and nonporous in nature and are less dense than silica. While silsesquioxane and silica have some similar physical properties from their siloxane core, the organic functional group of silsesquioxane and the one-half oxygen difference in its structure impact many other properties of these particles like their charging behavior in liquids. These differences not only allow for the ease of surface modification as compared to that necessary to modify silica but also allow for the use in a variety of colloidal systems that due to pH or electrolyte concentrations may not be suitable for silica particles.
Enhanced blebbing as a marker for metastatic prostate cancer.

Highly metastatic prostate cancer cells flowing through a microfluidic channel form plasma membrane blebs: they form 27% more than normal cells and have a lower stiffness (about 50%). Hypo-osmotic stress assays (with ∼ 50 % osmolarity) show 22% more blebbing of highly metastatic than moderately metastatic and 30% more than normal cells. Plasma membrane blebbing is known to provide important metastatic capabilities to cancer cells by aiding cell detachment from the primary tumor site and increasing cell deformability to promote cell migration through the extracellular matrix. Increased blebbing was attributed by others to decreased phosphorylated ezrin, radixin, and moesin (ERM) (p-ERM) protein expression—p-ERMs bind the plasma membrane to the actin cortex and reduced p-ERM expression can weaken membrane-cortex attachment. Myosin II also influences blebbing as myosin’s natural contraction generates tension in the actin cortex. This increases cellular hydrostatic pressure, causes cortex rupture, cytoplasm flow out of the cortex, and hence blebbing. Highly metastatic cells are surprisingly found to express similar ezrin and myosin II levels but higher moesin levels in comparison with lowly metastatic or normal cells—suggesting that their levels, contrary to the literature [G. Charras and E. Paluch, Nat. Rev. Mol. Cell Biol. 9(9), 730–736 (2008); J.-Y. Tinevez, U. Schulze, G. Salbreux, J. Roensch, J.-F. Joanny, and E. Paluch, Proc. Natl. Acad. Sci. U.S.A. 106(44), 18581–18586 (2009); M. Bergert, S. D. Chandradoss, R. A. Desai, and E. Paluch, Proc. Natl. Acad. Sci. U.S.A. 109(36), 14434–14439 (2012); E. K. Paluch and E. Raz: Curr. Opin. Cell Biol. 25(5), 582–590 (2013)], are not important in metastatic prostate cell blebbing. Our results show that reduced F-actin is primarily responsible for increased blebbing in these metastatic cells. Blebbing can thus serve as a simple prognostic marker for the highly incident and lethal metastatic prostate cancer.
Highly Efficient Enantioselective Synthesis of Optically Active Carboxylic Acids by Ru(OCOCH3)2[(S)-H8-BINAP]

In the presence of a catalytic amount of Ru(OCOCH3)2[(S)-H8-BINAP] [H8-BINAP = 2,2‘-bis(diphenylphosphino)-5,5‘,6,6‘,7,7‘,8,8‘-octahydro-1,1‘-binaphthyl], the asymmetric hydrogenation of α,β- and β...
Time-Course Analysis of Early Meiotic Prophase Events Informs Mechanisms of Homolog Pairing and Synapsis in Caenorhabditis elegans.

Segregation of homologous chromosomes during meiosis depends on their ability to reorganize within the nucleus, discriminate among potential partners, and stabilize pairwise associations through assembly of the synaptonemal complex (SC). Here we report a high-resolution time-course analysis of these key early events during Caenorhabditis elegans meiosis. Labeled nucleotides are incorporated specifically into the X chromosomes during the last 2 hr of S phase, a property we exploit to identify a highly synchronous cohort of nuclei. By tracking X -labeled nuclei through early meiotic prophase, we define the sequence and duration of chromosome movement, nuclear reorganization, pairing at pairing centers (PCs), and SC assembly. Appearance of ZYG-12 foci (marking attachment of PCs to the nuclear envelope) and onset of active mobilization occur within an hour after S-phase completion. Movement occurs for nearly 2 hr before stable pairing is observed at PCs, and autosome movement continues for ∼4 hr thereafter. Chromosomes are tightly clustered during a 2–3 hr postpairing window, during which the bulk of SC assembly occurs; however, initiation of SC assembly can precede evident chromosome clustering. SC assembly on autosomes begins immediately after PC pairing is detected and is completed within ∼3.5 hr. For the X chromosomes, PC pairing is contemporaneous with autosomal pairing, but autosomes complete synapsis earlier (on average) than X chromosomes, implying that X chromosomes have a delay in onset and/or a slower rate of SC assembly. Additional evidence suggests that transient association among chromosomes sharing the same PC protein may contribute to partner discrimination.
Disruption of endosperm development is a major cause of hybrid seed inviability between Mimulus guttatus and Mimulus nudatus

Divergence of developmental mechanisms within populations could lead to hybrid developmental failure, and might be a factor driving speciation in angiosperms. We investigate patterns of endosperm and embryo development in Mimulus guttatus and the closely related, serpentine endemic Mimulus nudatus, and compare them to those of reciprocal hybrid seed. We address whether disruption in hybrid seed development is the primary source of reproductive isolation between these sympatric taxa. M. guttatus and M. nudatus differ in the pattern and timing of endosperm and embryo development. Some hybrid seeds exhibit early disruption of endosperm development and are completely inviable, while others develop relatively normally at first, but later exhibit impaired endosperm proliferation and low germination success. These developmental patterns are reflected in mature hybrid seeds, which are either small and flat (indicating little to no endosperm) or shriveled (indicating reduced endosperm volume). Hybrid seed inviability forms a potent reproductive barrier between M. guttatus and M. nudatus. We shed light on the extent of developmental variation between closely related species within the M. guttatus species complex, an important ecological model system, and provide a partial mechanism for the hybrid barrier between M. guttatus and M. nudatus.
ABOUT THE REACTION OF 2,3-DIBROMO-2-METHYL-N-(1-ADAMANTYL)-PROPANAMIDE WITH SODIUM TERT-BUTOXIDE. A COMPETITION EXPERIMENT

2,3-Dibromo-2-methyl-N-(1-adamantyl)propanamide (4), a precursor equally suited for the preparation of an α-lactam and a β-lactam, upon treatment with sodium tert-butoxide ether gives no α-lactam (5), but an excellent yield of the isomeric β-lactam, 1-(1-adamantyl)-3-bromo-3-methylazetidinone (6) as the only product. Repeating the experiment using a large excess of sodium tert-butoxide still leads to β-lactam 6 in 76.1% yield, but now accompanied by its dehydrobrominated derivative, β-lactam 7, in 17.4% yield, and no trace of α-lactam 5
Excitable RhoA dynamics drive pulsed contractions in the early C. elegans embryo

Pulsed actomyosin contractility underlies diverse modes of tissue morphogenesis, but the underlying mechanisms remain poorly understood. Here, we combined quantitative imaging with genetic perturbations to identify a core mechanism for pulsed contractility in early Caenorhabditis elegans embryos. We show that pulsed accumulation of actomyosin is governed by local control of assembly and disassembly downstream of RhoA. Pulsed activation and inactivation of RhoA precede, respectively, the accumulation and disappearance of actomyosin and persist in the absence of Myosin II. We find that fast (likely indirect) autoactivation of RhoA drives pulse initiation, while delayed, F-actin–dependent accumulation of the RhoA GTPase-activating proteins RGA-3/4 provides negative feedback to terminate each pulse. A mathematical model, constrained by our data, suggests that this combination of feedbacks is tuned to generate locally excitable RhoA dynamics. We propose that excitable RhoA dynamics are a common driver for pulsed contractility that can be tuned or coupled differently to actomyosin dynamics to produce a diversity of morphogenetic outcomes.
Distinct solubility and cytotoxicity regimes of paclitaxel-loaded cationic liposomes at low and high drug content revealed by kinetic phase behavior and cancer cell viability studies.

Abstract Lipid-based particles are used worldwide in clinical trials as carriers of hydrophobic paclitaxel (PTXL) for cancer chemotherapy, albeit with little improvement over the standard-of-care. Improving efficacy requires an understanding of intramembrane interactions between PTXL and lipids to enhance PTXL solubilization and suppress PTXL phase separation into crystals. We studied the solubility of PTXL in cationic liposomes (CLs) composed of positively charged 2,3-dioleyloxypropyltrimethylammonium chloride (DOTAP) and neutral 1,2-dioleoyl- sn -glycero-3-phosphatidylcholine (DOPC) as a function of PTXL membrane content and its relation to efficacy. Time-dependent kinetic phase diagrams were generated from observations of PTXL crystal formation by differential-interference-contrast microscopy. Furthermore, a new synchrotron small-angle x-ray scattering in situ methodology applied to DOTAP/DOPC/PTXL membranes condensed with DNA enabled us to detect the incorporation and time-dependent depletion of PTXL from membranes by measurements of variations in the membrane interlayer and DNA interaxial spacings. Our results revealed three regimes with distinct time scales for PTXL membrane solubility: hours for >3 mol% PTXL (low), days for ≈ 3 mol% PTXL (moderate), and ≥20 days for PTXL nanoparticles (NPs) in the distinct CL PTXL solubility regimes reveal an unexpected dependence of efficacy on PTXL content in NPs. Remarkably, formulations with lower PTXL content and thus higher stability show higher efficacy than those formulated at the membrane solubility limit of ≈3 mol% PTXL (which has been the focus of most previous physicochemical studies and clinical trials of PTXL-loaded CLs). Furthermore, an additional high-efficacy regime is seen on occasion for liposome compositions with PTXL ≥9 mol% applied to cells at short time scales (hours) after formation. At longer time scales (days), CL PTXL NPs with ≥3 mol% PTXL lose efficacy while formulations with 1–2 mol% PTXL maintain high efficacy. Our findings underscore the importance of understanding the relationship of the kinetic phase behavior and physicochemical properties of CL PTXL NPs to efficacy.
Solid-solution catalysts for CO2 reforming of methane

Abstract One of the important developments in CO2 reforming of methane is highly effective MgO-based solid-solution catalysts. Herein, their high activity and selectivity as well as excellent stability for CO2 reforming of methane were briefly reviewed. How to inhibit carbon deposition via the formation of NiO–MgO or CoO–MgO solid solution was discussed. The reduction of NiO (or CoO) in the NiO–MgO (or CoO–MgO) solid solution is much more difficult than that of pure NiO (or CoO), which contributes to the formation of very small Ni particles to inhibit carbon deposition. It is generally recognized that the reduction of a metal oxide is determined by its metal–oxygen bond strength. Herein, however, it was showed that the reduction of a metal oxide is strongly dependent on both metal–oxygen bond strength of the metal oxide and the metal–metal bond strength of its metal product. Furthermore, it was proposed that a critical factor to control the reduction of NiO (or CoO) in the solid solution is the isolation effect that NiO (or CoO) is isolated by MgO, which inhibits the metal–metal bond formation during the reduction.
Methyl substitution in carbenes : lack of steric or hyperconjugative stabilization effects on the CH3CH singlet-triplet splitting

Ab initio GVB-CI (generalized valence bond theory with configuration interaction) and MCSCF (multiconfiguration self-consistent-field) calculations have been carried out on methylene and ethylidene (CH3CH) to investigate the effects of methyl substitution on the singlet-triplet splitting of methylene. We predict that ethylidene has a singlet-triplet splitting of 3 f 2 kcal/mol, about 6 kcal/mol less than the value for methylene. Furthermore, our investigations show that neither steric effects nor hyperconjugative singlet stabilization effects are large enough to account for this decrease in the singlet-triplet splitting. Rather, the dominant effects of the CH3 group are to (i) decreasep character in the nonbonding u orbital of the triplet state, (ii) reduce electron donation to the methylenic carbon, and (iii) induce repulsions in the triplet state between the CH3 and the singly occupied methylenic C PA orbital. All of these effects destabilize the triplet ground state and thus decrease the singlet-triplet splitting. I. Introduction The geometric and electronic structure of substituted carbenes is of importance in synthetic chemistry. The diverse reactivity of such molecules can be understood in terms of their electronic structure. The singlet state (u2) has both of its nonbonding electrons in a u orbital localized on the carbenoid carbon while the triplet state (uW) has one electron in that u orbital and one in a a orbital also localized on the carbenoid carbon. As a result, the chemistry in which they participate is very different: singlet carbenes undergo one-step stereospecific reactions while triplet carbenes participate in two-step, nonspecific reactions.’ The trends in the reactivity of carbenes can thus be better understood upon determination of their singlet-triplet splittings. The singlet-triplet gap in a substituted carbene depends strongly on the hybridization of the u and a orbitals of the central carbon. For both the triplet and the singlet states, the A orbital is essentially a pure p-like orbital while the u orbital is a hybrid of s- and p-like atomicorbitals. Thus, u orbitals with increased p character favor
Metal catalyzed diazo transfer for the synthesis of azides from amines

Abstract An improved method for the synthesis of azides is described. Diazo transfer from trifly azide effectively with Cu++, Ni++ or Zn++ as a catalyst. The process is amenable to scaleup, can be carried out using commercially available reagents and does not require anhydrous conditions. When metals are scavenged from the reaction, the rate drops by many orders of magnitude.
Challenges and opportunities in correlating bimetallic model surfaces and supported catalysts

Abstract In this paper, we use the hydrogenation and reforming reactions to demonstrate the success and challenges in correlating bimetallic model surfaces with supported catalysts. For hydrogenation reactions, results from ultra-high vacuum (UHV) experiments and density functional theory (DFT) calculations of model surfaces typically show strong correlation with reactor evaluations of the corresponding supported catalysts. However, such correlation is less clear for reforming reactions, which require a strong bonding of oxygenates on the bimetallic surfaces. One of the challenges is to understand the bimetallic structures and their stability under reaction conditions, which would in turn provide critical input for constructing relevant model surfaces for UHV and DFT studies. In order to truly achieve the design of bimetallic catalysts from first principles, it is essential that the structures of model surfaces are as close as possible to those under reaction conditions.
Total synthesis of both methyl 4a-carba-D-arabinofuranosides.

The total synthesis of methyl 4a-carba-α-d-arabinofuranoside (1) and methyl 4a-carba-β-d-arabinofuranoside (2) has been achieved starting from d-mannose (5). Key transformations included a ring-closing metathesis of diene 11 employing Schrock's catalyst followed by a stereoselective hydrogenation with Wilkinson's catalyst.
Energetics of Formation and Oxidation of Microporous Calcium Aluminates: A New Class of Electrides and Ionic Conductors

Microporous calcium aluminates with a common formula [Ca12Al14O33-δ]2δ+(2δe-), (0 < δ ≤ 1), represent a new family of electrides with conducting extraframework electrons encaged within the framework. Their enthalpies of oxidation to eliminate these electrons and obtain a stoichiometric Ca12Al14O33 compound, and formation enthalpies relative to the most stable annealed calcium aluminate Ca12Al14O33.46 (which contains excess oxygen probably as O- and O2- species), are studied by transposed temperature drop calorimetry and drop solution calorimetry in molten lead borate at 1080 K. The standard enthalpy of oxidation per O2 consumed is −579.4 ± 9.4 kJ/mol (or −144.8 ± 9.4 kJ per encaged electron). The enthalpies obtained for samples with variable amounts of electrons (and less than 33 oxygens per formula unit) are compared to that for oxidation of a stoichiometric Ca12Al14O33 sample to an oxygen-rich composition. The study supports the idea that the oxidation of the stoichiometric Ca12Al14O33 sample results in...
Microwave-assisted oxidation of alcohols under solvent-free conditions using clayfen

Abstract Adsorbed on clayfen, alcohols are readily oxidized to carbonyl compounds upon exposure to microwaves under solvent-free conditions. This rapid, selective and environmentally benign method conserves the use of excess solvents and toxic oxidants usually employed.
Fast atom bombardment-promoted reductive ring opening of 1,2-benzisothiazoles

Abstract Fast atom bombardment mass spectral examination of molecules containing a 1,2-benzisothiazole ring, using a thiol reducing agent matrix, promotes reductive ring opening of the benzisothiazole ring, giving an [M+H] + two daltons higher than expected. Measurements using a non-reducing matrix produce the expected [M+H] + . This is a general phenomenon, observed with a number of molecules containing the benzisothiazole ring. The ring-opened structure has been confirmed by chemical synthesis and observed in metabolic studies.
NEW IMPLICATIONS OF LORENTZ VIOLATION

In this proceedings, I summarize two recently discovered theoretical implications that Lorentz violation has on physical systems. First, I discuss new models for neutrino oscillations in which relatively simple combinations of Lorentz-violating parameters can mimic the major features of the current neutrino oscillation data. Second, I will present results on Yang-Mills instantons in Lorentz-violating background fields. An explicit solution is presented for unit winding number in SU(2).
Distributed representation of context by intrinsic subnetworks in prefrontal cortex

Human prefrontal cortex supports goal-directed behavior by representing abstract information about task context. The organizational basis of these context representations, and of representations underlying other higher-order processes, is unknown. Here, we use multivariate decoding and analyses of spontaneous correlations to show that context representations are distributed across subnetworks within prefrontal cortex. Examining targeted prefrontal regions, we found that pairs of voxels with similar context preferences exhibited spontaneous correlations that were approximately twice as large as those between pairs with opposite context preferences. This subnetwork organization was stable across task-engaged and resting states, suggesting that abstract context representations are constrained by an intrinsic functional architecture. These results reveal a principle of fine-scaled functional organization in association cortex.
Unusual tosyl transfer solvolysis reaction to 3‐n‐butyl‐4‐methyl‐5,5‐di‐p‐toluenesulfonyl‐ 3 ‐pyrrolin‐2‐one

The title compound (1) was isolated in 20-30% recovery following solvolysis of a mixture of 5-bromo-3-n-butyl-4-methyl-2-p-toluenesulfonylpyrrole (4b) and 5-bromo-4-n-butyl-3-methyl-2-p-toluenesulfonyl-pyrrole (4a) in trifluoroacetic acid and water, a reaction designed to produce 5-p-toluenesulfonyl-3-pyrrolin-2-ones, e.g., 5a and 5b.
Birch reduction and reduction-alkylations of 3,4-dihydro-3-methyl-8-phenylisocoumarin

Abstract Birch reduction and reduction-alkylations of 4 provide 3-methyl-8-phenyl-3,4,5,6,7,8-hexahydroisocoumarin 6 (88% yield) and a series of 8a-substituted-3-methyl-8-phenyl-3,4,6,7,8,8a-hexahydroisocoumarins 5a-d (84–89%). Conversions of 5a and 6 to cyclohexenones 12 and 13, and 6 to butadiene carboxylic acid 14 also are described.
[Co(en)3][B2P3O11(OH)2]: A Novel Borophosphate Templated by a Transition-Metal Complex

The structure of the title compound is made of chains of corner-sharing phosphate and borate tetrahedra that are separated by stacks of the octahedral Co(III) complex with ethylenediamine.
Maximum Likelihood Estimation of Fitness Components in Experimental Evolution.

Estimating fitness differences between allelic variants is a central goal of experimental evolution. Current methods for inferring such differences from allele frequency time series typically assume that the effects of selection can be described by a fixed selection coefficient. However, fitness is an aggregate of several components including mating success, fecundity, and viability. Distinguishing between these components could be critical in many scenarios. Here, we develop a flexible maximum likelihood framework that can disentangle different components of fitness from genotype frequency data, and estimate them individually in males and females. As a proof-of-principle, we apply our method to experimentally evolved cage populations of Drosophila melanogaster , in which we tracked the relative frequencies of a loss-of-function and wild-type allele of yellow . This X-linked gene produces a recessive yellow phenotype when disrupted and is involved in male courtship ability. We find that the fitness costs of the yellow phenotype take the form of substantially reduced mating preference of wild-type females for yellow males, together with a modest reduction in the viability of yellow males and females. Our framework should be generally applicable to situations where it is important to quantify fitness components of specific genetic variants, including quantitative characterization of the population dynamics of CRISPR gene drives.
ELECTRODEPOSITION OF TANTALUM CARBIDE COATINGS FROM MOLTEN SALTS

Des revetements denses et adherents de siliciure de tantale ont ete deposes sur des substrats nickel a 750°C a partir bains de fluorure (Li, Na, K) F contenant quelques pour-cent de K 2 TaF 7 et K 2 SiF 6 . Les compositions et les morphologies des surfaces des revetements ont ete etudies en fonction de la composition des bains et du potentiel applique entre la cathode de nickel et l'electrode de reference de platine
Energetics of Dysprosia-Stabilized Bismuth Oxide Electrolytes

With ionic conductivities superior to conventional doped zirconia and ceria at intermediate temperatures (IT, 700–800 °C), bismuth oxide (BiO1.5) materials based on the defect fluorite structure are promising electrolyte candidates for solid oxide fuel cells (SOFCs) operating at reduced temperatures. In order to investigate the energetics of stabilized BiO1.5 in the fluorite structure, DyO1.5-stabilized BiO1.5 (DSB) over a range of compositions was synthesized by solid state reaction and quenched. Using high temperature oxide melt solution calorimetry in molten 3Na2O·4MoO3 at 702 °C, enthalpies of formation at 25 °C were determined. Relative to the phases of the oxide end-members stable at room temperature (monoclinic BiO1.5 and C-type DyO1.5), the formation of Bi1-xDyxO1.5 is endothermic at x < 0.30 and becomes slightly exothermic toward the upper phase boundary (x = 0.50). These data suggest that this system is slightly stabilized, and there is only a moderate (1–2 orders of magnitude) decrease in the v...
Synthesis of both enantiomers of C2 symmetric trans-2,5- bis(hydroxymethyl)pyrrolidine. Lipase mediated sequential kinetic resolutions

Abstract Lipase mediated sequential kinetic resolution has been employed to give both enantiomers of trans -2,5-bis(hydroxymethyl)pyrrolidine in optically pure form. The effect of different parameters on the ee and yields in these resolutions are also reported.
Lithium perchlorate catalyzed conjugate addition of o-silylated ketene acetals to hindered α,β-unsaturated carbonyl compounds at atmospheric pressure

Abstract O-Silylated ketene acetals undergo 1,4 conjugate addition to hindered α,β-unsaturated carbonyl systems at atmospheric pressure in the presence of lithium perchlorate.
Persistent Increases of PKMζ in Sensorimotor Cortex Maintain Procedural Long-Term Memory Storage

Summary Procedural motor learning and memory are accompanied by changes in synaptic plasticity, neural dynamics, and synaptogenesis. Missing is information on the spatiotemporal dynamics of the molecular machinery maintaining these changes. Here we examine whether persistent increases in PKMζ, an atypical protein kinase C (PKC) isoform, store long-term memory for a reaching task in rat sensorimotor cortex that could reveal the sites of procedural memory storage. Specifically, perturbing PKMζ synthesis (via antisense oligodeoxynucleotides) and blocking atypical PKC activity (via zeta inhibitory peptide [ZIP]) in S1/M1 disrupts and erases long-term motor memory maintenance, indicating atypical PKCs and specifically PKMζ store consolidated long-term procedural memories. Immunostaining reveals that PKMζ increases in S1/M1 layers II/III and V as performance improved to an asymptote. After storage for 1 month without reinforcement, the increase in M1 layer V persists without decrement. Thus, the persistent increases in PKMζ that store long-term procedural memory are localized to the descending output layer of the primary motor cortex.
Synthesis and the determination of the absolute configuration of matsuone, sex pheromone of female Matsucoccus pine scales

Abstract The four possible optical isomers of matsuone ( 1 ), female sex pheromone of Matsucoccus resinosae pine scales, were convergently synthesized in high optical purities. The absolute configuration of the natural product has been assigned as (2 E , 4 E , 6 R , 10 R )-4,6,10,12-tetramethyltridecan-2,4-dien-7-one. Bioassays with M. resinosae using these stereoisomers reveal that the unnatural (6 R , 10 S )-isomer mimics the natural pheromone.