cssi/SciSciGPT-SciSciNet huggingface dataset:
AVA-Speech: A Densely Labeled Dataset of Speech Activity in Movies

Speech activity detection (or endpointing) is an important processing step for applications such as speech recognition, language identification and speaker diarization. Both audio- and vision-based approaches have been used for this task in various settings, often tailored toward end applications. However, much of the prior work reports results in synthetic settings, on task-specific datasets, or on datasets that are not openly available. This makes it difficult to compare approaches and understand their strengths and weaknesses. In this paper, we describe a new dataset which we will release publicly containing densely labeled speech activity in YouTube videos, with the goal of creating a shared, available dataset for this task. The labels in the dataset annotate three different speech activity conditions: clean speech, speech co-occurring with music, and speech co-occurring with noise, which enable analysis of model performance in more challenging conditions based on the presence of overlapping noise. We report benchmark performance numbers on AVA-Speech using off-the-shelf, state-of-the-art audio and vision models that serve as a baseline to facilitate future research.
Organizational culture and public diplomacy in the digital sphere: The case of South Korea

Digital diplomacy is the latest technological advance to push change in diplomatic practice. It relates to the application of digital technologies, including information and communication technologies, software engineering and big data, and artificial intelligence, to the practice of diplomacy. Positioned in the top ranks of connectivity, internet speed, smartphone ownership, and social media usage, South Korea should be a leader in the use of digital technologies in diplomatic practice. However, South Korea is not a leader; indeed, it has been left behind. I explore digital diplomacy as a “disruptive technology” and look at criteria for organizational adaptation. I then use these criteria to assess South Korea's adaptation and draw from these the specific policy challenges facing South Korea. To conclude, I propose four core criteria to aid digital diplomacy adaptation in South Korea and other similar states.
Weight loss as a predictor of mortality in patients with interstitial lung disease

Weight loss in patients with ILD was associated with increased mortality risk in those with IPF and U-ILD http://ow.ly/Nk0D30l2Apm
Transcriptome analysis of adult Caenorhabditis elegans cells reveals tissue-specific gene and isoform expression.

The biology and behavior of adults differ substantially from those of developing animals, and cell-specific information is critical for deciphering the biology of multicellular animals. Thus, adult tissue-specific transcriptomic data are critical for understanding molecular mechanisms that control their phenotypes. We used adult cell-specific isolation to identify the transcriptomes of C. elegans’ four major tissues (or “tissue-ome”), identifying ubiquitously expressed and tissue-specific “enriched” genes. These data newly reveal the hypodermis’ metabolic character, suggest potential worm-human tissue orthologies, and identify tissue-specific changes in the Insulin/IGF-1 signaling pathway. Tissue-specific alternative splicing analysis identified a large set of collagen isoforms. Finally, we developed a machine learning-based prediction tool for 76 sub-tissue cell types, which we used to predict cellular expression differences in IIS/FOXO signaling, stage-specific TGF-β activity, and basal vs. memory-induced CREB transcription. Together, these data provide a rich resource for understanding the biology governing multicellular adult animals.
The Semantic Communication Game

This paper proposes a communication framework where meanings of transmitted codewords over a noisy channel are explicitly taken into account. Furthermore, such communication takes place in the presence of an external entity, i.e., an agent, that can influence the receiver. The agent may be adversarial or helpful, and its true nature is unknown to the communicating parties. Actions taken by the agent are governed by its nature to aim to improve/deteriorate the communication performance. We characterize the optimal transmission policies to minimize the end-to-end average semantic error, that we define as the expected error between meanings of intended and recovered messages, under the uncertainty of agent’s true intentions. To do so, we first formulate the communication problem as a Bayesian game, and investigate the conditions under which a Bayesian Nash equilibrium exists. Next, we consider a dynamic communication scenario in which parties take actions sequentially, forming beliefs about the other party. By formulating this setting as a sequential game, we investigate the structure of the belief system and strategy profiles at equilibrium. Our results indicate that word semantics are instrumental in assessing communication performance when messages carry meanings, and optimal communication strategies are strongly influenced by the communicating parties’ beliefs.
Calvin Henry Kauffman

Calvin Henry Kauffman was born March 1, 1869, on a farm near Lebanon, Pennsylvania. Here his close contact with nature early developed an interest in botany. While still in prepratory school he studied the flora about Lebanon and started his herbarium of flowering plants. However, during his undergraduate years at Harvard, he specialized in languages and devoted but little attention to science, taking three courses in chemistry and one in botany. He received the A.B. degree from Harvard in 1895.
Broad-band trajectory mechanics

Author(s): Vasco, DW; Nihei, K | Abstract: We present a trajectory-based solution to the elastodynamic equation of motion that is valid across a wide range of seismic frequencies. That is, the derivation of the solution does not invoke a high-frequency assumption or require that the medium have smoothly varying properties. The approach, adopted from techniques used in quantum dynamics, produces a set of coupled ordinary differential equations for the trajectory, the slowness vector and the elastic wave amplitude along the ray path. The trajectories may be determined by a direct solution of the governing equations or derived as the by-product of a numerical wavefield simulation. Synthetic tests with interfaces and layers containing increasingly narrow transition zones indicate that the conventional high-frequency trajectories associated with the eikonal equation bend too sharply into high-velocity regions as the wavelength exceeds the transition zone width. Tests in a velocity model, based upon mapped structural surfaces from the Geysers geothermal field in California, indicate that discrepancies between high-frequency and broad-band trajectories can exceed several hundred metres at wavelengths of 1 Hz. An application to a crosswell tomographic imaging experiment demonstrates that the technique provides a basis for the seismic monitoring of fluid flow along narrow features such as fracture zones.
Blood handling and leukocyte isolation methods impact the global transcriptome of immune cells.

Transcriptional profiling with ultra-low input methods can yield valuable insights into disease, particularly when applied to the study of immune cells using RNA-sequencing. The advent of these methods has allowed for their use in profiling cells collected in clinical trials and other studies that involve the coordination of human-derived material. To date, few studies have sought to quantify what effects that collection and handling of this material can have on resulting data. We characterized the global effects of blood handling, methods for leukocyte isolation, and preservation media on low numbers of immune cells isolated from blood. We found overall that storage/shipping temperature of blood prior to leukocyte isolation and sorting led to global changes in both CD8+ T cells and monocytes, including alterations in immune-related gene sets. We found that the use of a leukocyte filtration system minimized these alterations and we applied this method to generate high-quality transcriptional data from sorted immune cells isolated from the blood of intracerebral hemorrhage patients and matched healthy controls. Our data underscore the necessity of processing samples with comparably defined protocols prior to transcriptional profiling and demonstrate that a filtration method can be applied to quickly isolate immune cells of interest while minimizing transcriptional bias.
Broadband hyperspectral stimulated Raman scattering microscopy with a parabolic fiber amplifier source.

Hyperspectral stimulated Raman scattering (hsSRS) microscopy has recently emerged as a powerful non-destructive technique for the label-free chemical imaging of biological samples. In most hsSRS imaging experiments, the SRS spectral range is limited by the total bandwidth of the excitation laser to ~300 cm−1 and a spectral resolution of ~25 cm−1. Here we present a novel approach for broadband hsSRS microscopy based on parabolic fiber amplification to provide linearly chirped broadened Stokes pulses. This novel hsSRS instrument provides >600 cm−1 spectral coverage and ~10 cm−1 spectral resolution. We further demonstrated broadband hsSRS imaging of the entire Raman fingerprint region for resolving the distribution of major biomolecules in fixed cells. Moreover, we applied broadband hsSRS in imaging amyloid plaques in human brain tissue with Alzheimer’s disease.
Propulsive design principles in a multi-jet siphonophore.

ABSTRACT Coordination of multiple propulsors can provide performance benefits in swimming organisms. Siphonophores are marine colonial organisms that orchestrate the motion of multiple swimming zooids for effective swimming. However, the kinematics at the level of individual swimming zooids (nectophores) have not been examined in detail. We used high-speed, high-resolution microvideography and particle image velocimetry of the physonect siphonophore Nanomia bijuga to study the motion of the nectophores and the associated fluid motion during jetting and refilling. The integration of nectophore and velum kinematics allow for a high-speed (maximum ∼1 m s−1), narrow (1–2 mm) jet and rapid refill, as well as a 1:1 ratio of jetting to refill time. Scaled to the 3 mm nectophore length, jet speeds reach >300 lengths s−1. Overall swimming performance is enhanced by velocity gradients produced in the nectophore during refill, which lead to a high-pressure region that produces forward thrust. Generating thrust during both the jet and refill phases augments the distance traveled by 17% over theoretical animals, which generate thrust only during the jet phase. The details of velum kinematics and associated fluid mechanics elucidate how siphonophores effectively navigate three-dimensional space, and could be applied to exit flow parameters in multijet underwater vehicles.
Building Bridges in Cardiology and Radiology: Why Collaboration Is the Future of Cardiovascular Imaging.

In 1976, an unknown early-career 37-year-old Swiss cardiologist submitted a research poster to the American Heart Association Scientific Sessions. The poster was rejected in the cardiology section, but found a welcome home in the radiology portion of the meeting [(1)][1]. This initial seminal work
Saturation and alternate pathways in four-wave mixing in rubidium

We have examined the frequency spectrum of the blue light generated via four-wave mixing in a rubidium vapor cell inside a ring cavity. At high atomic density and input laser power, two distinct frequency components separated by 116±4 MHz are observed, indicating alternate four-wave mixing channels through the 6p3/2 hyperfine states. The dependence of the generated light on excitation intensity and atomic density are explored, and they indicate that the primary process has saturated. This saturation results when the excitation rate through the 6p state becomes equal to the rate through the 5p state, giving no further gain with atomic density while a quadratic intensity dependence remains.
Acquisition of time–frequency localized mechanical properties of biofilms and single cells with high spatial resolution

Biofilms are a cluster of bacteria embedded in extracellular polymeric substances (EPS) that contain a complex composition of polysaccharides, proteins, and extracellular DNA (eDNA). Desirable mechanical properties of the biofilms are critical for their survival, propagation, and dispersal, and the response of mechanical properties to different treatment conditions also sheds light on biofilm control and eradication in vivo and on engineering surfaces. However, it is challenging yet important to investigate mechanical behaviors of biofilms with a high spatial resolution because biofilms are very heterogeneous. Moreover, biofilms are viscoelastic, and their time-dependent mechanical behavior is difficult to capture. Herein, we develop a powerful technique that combines the high spatial resolution of an atomic force microscope (AFM) with a rigorous history-dependent viscoelastic analysis to deliver highly spatial-localized biofilm properties within a wide time–frequency window. By exploiting the use of static force spectroscopy in combination with an appropriate viscoelastic framework, we highlight the intensive amount of time-dependent information experimentally available that has been largely overlooked. It is shown that this technique provides a detailed nanorheological signature of the biofilms even at the single-cell level. We share the computational routines that would allow any user to perform the analysis from experimental raw data. The detailed localization of mechanical properties in space and in time–frequency domain provides insights into the understanding of biofilm stability, cohesiveness, dispersal, and control.
Bot Electioneering Volume: Visualizing Social Bot Activity During Elections

It has been widely recognized that automated bots may have a significant impact on the outcomes of national events. It is important to raise public awareness about the threat of bots on social media during these important events, such as the 2018 US midterm election. To this end, we deployed a web application to help the public explore the activities of likely bots on Twitter on a daily basis. The application, called Bot Electioneering Volume (BEV), reports on the level of likely bot activities and visualizes the topics targeted by them. With this paper we release our code base for the BEV framework, with the goal of facilitating future efforts to combat malicious bots on social media.
Bioinformatics in Functional Genomics

Databases of DNA sequences, physical maps, genetic maps, gene polymorphisms, protein structures, and gene expression have produced a need for systematic quantitative analysis that goes by the name of bioinformatics. To manage these large datasets in the domain of functional genomics requires algorithmic implementation on computers. Functional genomics will continue to be hypothesis-driven and hypothesis-generating biological research. Because the datasets are of high dimensionality, involving relatively small numbers of cases, a large number of solutions can explain the data; the computational techniques to unravel these involve both supervised and unsupervised learning. Keywords: computer algorithms; databases; functional genomics; supervised learning; unsupervised learning
Steady streaming viscometry of Newtonian liquids in microfluidic devices

We report a novel technique capable of measuring the kinematic shear viscosity of Newtonian liquids with steady streaming flows in microfluidic devices. This probe-free microrheological method utilizes sub-kilohertz liquid oscillation frequencies around a cylindrical obstacle, ensuring that the inner streaming layer is comparable in size to the cylinder radius. To calibrate the viscometer, the evolution of the inner streaming layer as a function of the oscillation frequency for a liquid of known viscosity is characterized using standard particle tracking techniques. Once calibrated, we show how the steady streaming viscometer can be used to measure low-viscosity liquids.
Chapter 8 – Relative, Asset-Oriented, and Real Option Valuation Basics

This chapter addresses relative valuation (i.e., market-based) methods, asset-oriented methods, real options analysis (i.e., contingent claims), and replacement cost, often used as alternatives to discounted cash flow valuation. Relative valuation methods include comparable company, comparable transactions, comparable industry techniques, and value driver-based valuation. Asset-oriented methods include tangible book value and liquidation- or breakup valuation techniques. This chapter also discusses in detail how to look at merger and acquisition (M&A) valuation in the context of real options and concludes with a summary of the strengths and weaknesses of the alternative valuation methods (including discounted cash flow) and when it is appropriate to apply each methodology.
Duttonite, A New Quadrivalent Vanadium Oxide from the Peanut Mine, Montrose County, Colorado

A report about a new quadrivalent vanadium oxide from the Peanut mine named Duttonite which has the formula VO(OH)2. The mineral occurs as crusts and coatings of pale-brown transparent platy crystals.
On the Spectrum Sensing, Beam Selection and Power Allocation in Cognitive Radio Networks Using Reconfigurable Antennas

In this paper, we consider a cognitive radio (CR) system consisting of a primary user (PU) and a pair of secondary user transmitter (SU tx ) and secondary user receiver (SU rx ). The SU tx is equipped with a reconfigurable antenna (RA) which divides the angular space into M sectors. The RA chooses one sector among M sectors for its data transmission to (SU rx ). The SU tx first senses the channel and monitors the activity of PU for a duration of T sen seconds. We refer to this period as channel sensing phase. Depending on the outcome of this phase, SU tx stays in this phase or enters the next phase, which we refer to as transmission phase. The transmission phase itself consists of two phases: channel training phase followed by data transmission phase. During the former phase, SU tx sends pilot symbols to enable channel training and estimation at (SU rx ). The SU rx selects the best beam (sector) for data transmission and feeds back the index of the selected beam as well as its corresponding channel gain. We also derive the probability of determining the true beam and take into account this probability in our system design. During the latter phase, SU tx sends data symbols to SU rx over the selected beam with constant power $\Phi$ if the gain corresponding to the selected beam is bigger than the threshold $\zeta$. We find the optimal channel sensing duration T sen , the optimal power level $\Phi$ and a optimal threshold $\zeta$, such that the ergodic capacity of CR system is maximized, subject to average interference and power constraints. In addition, we derive closed form expressions for outage and symbol error probabilities of our CR system.
Changing Direction: A Practical Approach to Directing Actors in Film and Theatre

Mengubah Arah: Sebuah Pendekatan Praktis untuk Mengarahkan Aktor di Film dan Teater. Buku ini dimaksudkan sebagai panduan untuk mengarahkan aktor berdasarkan pengalaman penulis yang sudah cukup lama di dalam kelas dan di berbagai lokakarya di New York dan Los Angeles. Mencakup segala sesuatu dari script untuk pengembangan karakter, latihan, casting, dan bekerja dengan kamera. Memuat pula tentang menggabungkan teori yang mendasari bersama-sama dengan bahasa dan praktis latihan aktor untuk digunakan di bengkel atau kelas.
Lost in Interpretation: Predicting Untranslated Terminology in Simultaneous Interpretation

Simultaneous interpretation, the translation of speech from one language to another in real-time, is an inherently difficult and strenuous task. One of the greatest challenges faced by interpreters is the accurate translation of difficult terminology like proper names, numbers, or other entities. Intelligent computer-assisted interpreting (CAI) tools that could analyze the spoken word and detect terms likely to be untranslated by an interpreter could reduce translation error and improve interpreter performance. In this paper, we propose a task of predicting which terminology simultaneous interpreters will leave untranslated, and examine methods that perform this task using supervised sequence taggers. We describe a number of task-specific features explicitly designed to indicate when an interpreter may struggle with translating a word. Experimental results on a newly-annotated version of the NAIST Simultaneous Translation Corpus (Shimizu et al., 2014) indicate the promise of our proposed method.
Modeling Electron Injection at Semiconductor–Molecule Interfaces using First-Principles Dynamics Simulation: Effects of Nonadiabatic Coupling, Self-energy, and Surface Models

Excited electron transfer across semiconductor–molecule heterogeneous interfaces is central to various future electronic and optoelectronic devices. At the same time, first-principles modeling of s...
Approximating the Ideal Observer and Hotelling Observer for Binary Signal Detection Tasks by Use of Supervised Learning Methods

It is widely accepted that the optimization of medical imaging system performance should be guided by task-based measures of image quality (IQ). Task-based measures of IQ quantify the ability of an observer to perform a specific task, such as detection or estimation of a signal (e.g., a tumor). For binary signal detection tasks, the Bayesian Ideal Observer (IO) sets an upper limit of observer performance and has been advocated for use in optimizing medical imaging systems and data-acquisition designs. Except in special cases, the determination of the IO test statistic is analytically intractable. Markov-chain Monte Carlo (MCMC) techniques can be employed to approximate the IO detection performance, but their reported applications have been limited to relatively simple object models. In cases where the IO test statistic is difficult to compute, the Hotelling Observer (HO) can be employed. To compute the HO test statistic, potentially large covariance matrices must be accurately estimated and subsequently inverted, which can present computational challenges. This paper investigates the supervised learning-based methodologies for approximating the IO and HO test statistics. Convolutional neural networks (CNNs) and single-layer neural networks (SLNNs) are employed to approximate the IO and HO test statistics, respectively. The numerical simulations were conducted for both signal-known-exactly (SKE) and signal-known-statistically (SKS) signal detection tasks. The considered background models include the lumpy object model and the clustered lumpy object model. The measurement noise models considered are Gaussian, Laplacian, and mixed Poisson–Gaussian. The performances of the supervised learning methods are assessed via receiver operating characteristic (ROC) analysis, and the results are compared to those produced by the use of traditional numerical methods or analytical calculations when feasible. The potential advantages of the proposed supervised learning approaches for approximating the IO and HO test statistics are discussed.
Connectedness-Aware Copy-Adaptive Routing Protocol in Intermittently Connected Networks

In the intermittently connected networks where the complete paths from a source to a destination do not always exist, multi-copy forwarding is considered to be capable of providing more reliable transmission than single-copy forwarding. However, injecting too many copies into a network can cause unnecessary network resource consumption that degrades the network performance, especially if the network nodes are low-cost and resource-constrained. Therefore, copy control is a critical efficiency mechanism for the forwarding protocols in such situations. Using a preset threshold is a common copy-control mechanism used by many multi-copy forwarding protocols. The preset threshold is the maximum allowed number of copies of a packet in a network, calculated before running these protocols. It can effectively reduce the unnecessary copies and provide better performance than the protocols without using copy control. However, preset threshold makes the protocol less flexible with respect to the variations of network characteristics such as density or connectedness caused by node failures or new nodes joining. In this paper, we propose a multi-copy routing algorithm, Connectedness-Aware Copy-Adaptive Routing (CACAR) protocol, which adopts a novel copy-control mechanism. CACAR estimates the network connectedness locally and conducts the copy control and the next-hop selection based on the measured connectedness. This proposed protocol can achieve a higher delivery rate and lower latency without sacrificing the energy efficiency compared with other benchmark multi-copy routing protocols.
Isonitrile Formation by a Non-heme Iron(II)-dependent Oxidase/Decarboxylase

The electron-rich isonitrile is an important functionality in bioactive natural products, but its biosynthesis has been restricted to the IsnA family of isonitrile synthases. We herein provide the first structural and biochemical evidence of an alternative mechanism for isonitrile formation. ScoE, a putative non-heme iron(II)-dependent enzyme from Streptomyces coeruleorubidus, was shown to catalyze the conversion of (R)-3-((carboxymethyl)amino)butanoic acid to (R)-3-isocyanobutanoic acid through an oxidative decarboxylation mechanism. This work further provides a revised scheme for the biosynthesis of a unique class of isonitrile lipopeptides, of which several members are critical for the virulence of pathogenic mycobacteria.
Identification of BrONO as the Major Product in the Gas-Phase Reaction of Br with NO2

Products of the gas-phase reaction of Br atoms with NO2 have been quantitatively determined at temperatures between 215 and 300 K in an environmental chamber interfaced to an FT-IR spectrometer. The major product of the reaction (yield > 75%) was found to be the cis isomer of BrONO, which was identified and quantified by means of its NO stretching fundamental at 1660 cm-1; this represents the first gas-phase detection of this species. Although rapid thermal decomposition back to Br and NO2 precludes its detection at room temperature (lifetime < 1 s), BrONO was detected at temperatures at and below 263 K. Isomerization of the BrONO to BrNO2 was found to be an important fate of BrONO at low temperatures. The rate coefficient for this process was found to increase with decreasing pressure, indicative of a heterogeneous process. At 700 Torr, this isomerization rate was (0.013 ± 0.003) s-1, independent of temperature over the range 218−243 K. Evidence was also obtained for rapid reactions between Br atoms and ...
A Comment on Priors for Bayesian Occupancy Models

Understanding patterns of species occurrence and the processes underlying these patterns is fundamental to the study of ecology. One of the more commonly used approaches to investigate species occurrence patterns is occupancy modeling, which can account for imperfect detection of a species during surveys. In recent years, there has been a proliferation of Bayesian modeling in ecology, which includes fitting Bayesian occupancy models. The Bayesian framework is appealing to ecologists for many reasons, including the ability to incorporate prior information through the specification of prior distributions on parameters. While ecologists almost exclusively intend to choose priors so that they are "uninformative" or "vague", such priors can easily be unintentionally highly informative. Here we report on how the specification of a "vague" normally distributed (i.e., Gaussian) prior on coefficients in Bayesian occupancy models can unintentionally influence parameter estimation. Using both simulated data and empirical examples, we illustrate how this issue likely compromises inference about species-habitat relationships. While the extent to which these informative priors influence inference depends on the data set, researchers fitting Bayesian occupancy models should conduct sensitivity analyses to ensure intended inference, or employ less commonly used priors that are less informative (e.g., logistic or t prior distributions). We provide suggestions for addressing this issue in occupancy studies, and an online tool for exploring this issue under different contexts.
Synthesis of a novel ring-expanded (“fat”) nucleotide analogue of phosphonomethoxyethylguanine (PMEG) containing the imidazo[4,5-e][1,3]diazepine ring system

The synthesis of 6-amino-4,5-dihydro-8H-1-(2-phosphonylmethoxyethyl)imidazo[4,5-e][1,3]diazepine-4,8-dione (7), a novel ring-expanded (“fat”) acyclic nucleotide analogue of phosphonomethoxyethylguanine (PMEG), has been reported. It was prepared in 4 steps in 51% overall yield starting from dimethyl imida-zole-4,5-dicarboxylate.
Zinc-induced reduction of ethyl 2-cyano-3-(4-oxo-4H-1-benzopyran-3-yl)propenoates: a medium-dependent reaction

Reduction of acrylates 1 1 with Zn in THF containing aqueous NH 4 Cl produces the cyclopentadienones 4, whereas with Zn in acetic acid reduction produces the cyanopropanoates 5.
Downgrading disease transmission risk estimates using terminal importations.

As emerging and re-emerging infectious arboviruses like dengue, chikungunya, and Zika threaten new populations worldwide, officials scramble to assess local severity and transmissibility, with little to no epidemiological history to draw upon. Indirect estimates of risk from vector habitat suitability maps are prone to great uncertainty, while direct estimates from epidemiological data are only possible after cases accumulate and, given environmental constraints on arbovirus transmission, cannot be widely generalized beyond the focal region. Combining these complementary methods, we use disease importation and transmission data to improve the accuracy and precision of a priori ecological risk estimates. We demonstrate this approach by estimating the spatiotemporal risks of Zika virus transmission throughout Texas, a high-risk region in the southern United States. Our estimates are, on average, 80% lower than published ecological estimates—with only six of 254 Texas counties deemed capable of sustaining a Zika epidemic—and they are consistent with the number of autochthonous cases detected in 2017. Importantly our method provides a framework for model comparison, as our mechanistic understanding of arbovirus transmission continues to improve. Real-time updating of prior risk estimates as importations and outbreaks arise can thereby provide critical, early insight into local transmission risks as emerging arboviruses expand their global reach.
The one-dimensional polyselenide compound CsGaSe3

A new one-dimensional phase, CsGaSe3 has been synthesized and characterized by single crystal X-ray diffraction, differential thermal analysis, and single crystal UV/Vis spectroscopy. The structure contains infinite chain anions, [GaSe(Se2)]— separated by Cs cations. The Ga3+ cation is in a distorted tetrahedral environment coordinated by each two Se2— and Se22— ions. The red crystals of CsGaSe3 absorb visible light at energies above 2.25 eV. Differential thermal analysis revealed that the compound does not melt below 1000 °C. Crystal data: CsGaSe3, monoclinic, space group P21/c (No 14), a=7.727(1), b=13.014(3), c=6.705(1), β=106.39(3)°, Z=4, R1=0.0469. Die eindimensionale Polyselenid-Verbindung CsGaSe3 Eine neue eindimensionale Phase, CsGaSe3, wurde synthetisiert und durch Einkristall-Rontgenbeugung, Differentialthermoanalyse sowie durch Einkristall-UV/Vis-Spektroskopie charakterisiert. Die Struktur besteht aus unendlichen Anionen-Ketten, [GaSe(Se2)]—, die durch Cs-Kationen getrennt sind. Das Ga3+-Kation ist in verzerrt tetraedrischer Anordnung durch je zwei Se2—- und Se22—-Ionen koordiniert. Die roten Kristalle von CsGaSe3 absorbieren im sichtbaren Licht bei Energien uber 2, 225 eV. Die Differentialthermoanalyse zeigte, dass die Verbindung nicht unter 1000 °C schmilzt. Die Kristalldaten von CsGaSe3 sind: monoklin, Raumgruppe P21/c (No 14), a=7, 727(1), b=13, 014(3), c=6, 705(1)A, β=106, 39(3)°, Z=4, R1=0, 0469.
Syntheses and photophysical properties of fluorescent 2-aryl-3-hydroxy-4-chromenones

The particle detectors proposed for the Super-conducting Super Collider contain polystyrene scintillation fibers as a component. Scintillation fluors soluble in styrene are required which have improved light output and response time. New 2-aryl-3-hydroxy-4-chromenones related to 3-hydroxyflavone were prepared which displayed these improved properties. Improved solvent systems for chromenone formation were essential in the synthesis of two of the chromenones. One chromenone produced fluorescence emission at 560 nm with a quantum yield of 0.53 and a scintillation decay time of 5 nsec.
A novel 3-dimensional open framework sulfide based upon the [In10S20]10- supertetrahedron : DMA-InS-SB1

Hydrothermal treatment of elemental indium and sulfur in the presence of the organic structure directing agent dimethylamine yields the novel open framework material DMA-InS-SB1. This material contains [In10S20]10- supertetrahedra that corner link to form an interpenetrating “double-diamond” lattice.
Syntheses, Structures, and Catalytic Properties of Ruthenium(II) Nitrosyl Complexes with Pyridine-Functionalized N-Heterocyclic Carbenes

Ruthenium(II) nitrosyl complexes with pyridine-functionalized N-heterocyclic carbenes [(L)Ru(NO)Cl3] [L = 3-tert-butyl-1-(2-pyridyl)imidazol-2-ylidene, 2a; 3-n-butyl-1-(2-pyridyl)imidazol-2-ylidene, 2b; 3-tert-butyl-1-picolylimidazol-2-ylidene, 2c; 3-n-butyl-1-picolylimidazol-2-ylidene, 2d; and 3-benzyl-1-picolylimidazol-2-ylidene, 2e] have been prepared by transmetalation from the corresponding silver carbene complexes. Compounds 2a−c have been characterized by single-crystal X-ray crystallography. Compounds 2a−e show catalytic activities in transfer hydrogenation of ketones.
Suzuki–Miyaura synthesis of m-terphenyl thioethers and their facilitated oxidation caused by through-space π⋯S⋯π interaction

Abstract S-tert-Butyl m-terphenyl thioethers have been efficiently synthesized by Suzuki–Miyaura coupling reactions with 2,6-dibromo-S-tert-butylthio benzene. Selective monocoupling could be achieved with o-substituted boronic acids. This facilitated the synthesis of unsymmetrical S-tert-butyl m-terphenyl thioethers and bis(S-tert-butyl m-terphenyl thioether)s. The study of their electrochemistry showed facilitated oxidations resulting from through-space π⋯S⋯π interactions.
REMOTE FUNCTIONALIZATION OF THE STEROID SIDE-CHAIN

By using classical methods of organic synthesis, the introduction of chemical modifications into the saturated side-chains of steroids usually requires a multistep synthesis to construct new side-chains to be added to the steroid nucleus. In order to circumvent these earlier methods, new procedures have been developed to directly introduce functionality onto the steroid side-chain to produce useful products. These initial products may also provide an entry toward the further modification of the side-chain to produce steroids which could previously be obtained only with great difficulty.
A Spring Propelled Extreme Environment Robot for Off-World Cave Exploration

Pits on the Moon and Mars are intriguing geological formations that have yet to be explored. These geological formations can provide protection from harsh diurnal temperature variations, ionizing radiation, and meteorite impacts. Some have proposed that these underground formations are well-suited as human outposts. Some theorize that the Martian pits may harbor remnants of past life. Unfortunately, these geological formations have been off-limits to conventional wheeled rovers and lander systems due to their collapsed ceiling or “skylight” entrances. In this paper, a new low-cost method to explore these pits is presented using the Spring Propelled Extreme Environment Robot (SPEER). The SPEER consists of a launch system that flings disposable spherical microbots through skylights into the pits. The microbots are low-cost and composed of aluminium Al-6061 disposable spheres with an array of adapted COTS sensors and a solid rocket motor for soft landing. By moving most control authority to the launcher, the microbots become very simple, lightweight, and low-cost. We present a preliminary design of the microbots that can be built today using commercial components for under 500 USD. The microbots have a total mass of 1 kg, with more than 750 g available for a science instrument. In this paper, we present the design, dynamics and control, and operation of these microbots. This is followed by initial feasibility studies of the SPEER system by simulating exploration of a known Lunar pit in Mare Tranquillitatis.
Chemoselective Reduction of Some Condensates derived from Chromone-3-carbaldehyde using Sm and Zn

Abstract Condensates 4–6 undergo reductive dimerization with Sm in THF containing aqueous NH4Cl to produce 7–9, whereas with Zn under similar reaction condition 3–5 produce 10–12.
Metal-mediated two-atom carbocycle enlargement in aqueous medium ☆

Abstract The indium and tin-mediated carbonyl allylations of 1,3-dicarbonyl compounds have been studied in aqueous medium. The study led to the development of a novel two-atom carbocycle-enlargement in water. Five-, six-, seven-, eight-, and twelve-membered rings are enlarged by two carbon atoms into seven-, eight-, nine-, ten-, and fourteen-membered ring derivatives respectively. Tetralone derivatives are similarly expanded to 6–8 fused ring systems; and indanone derivatives are expanded to 5–7 fused ring systems. The use of both indium and zinc as the metal mediators provided the ring expansion products successfully. The use of water as a solvent was found to be essential for the ring expansion reaction.
A Novel Cycloaddition Reaction of α-Diazo-γ-amido Ketones Catalyzed by Rhodium(II) Acetate. Scope and Mechanistic Details of the Process†

α-Diazo ketones containing an amido group in the γ-position have been found to undergo a novel rhodium(II)-catalyzed cycloaddition reaction. Intramolecular cyclization of the keto carbenoid onto the oxygen atom of the amide group generates a carbonyl ylide dipole as a transient species. This highly stabilized dipole does not readily undergo 1,3-dipolar cycloaddition but rather transfers a proton to produce a cyclic ketene N,O-acetal. The ketene acetal is unstable to moisture and upon standing is readily hydrolyzed to a γ-keto δ-lactone and an amine. In the absence of any significant amount of water, the ketene N,O-acetal undergoes conjugate addition with the activated π-bond of the dipolarophile to give a zwitterion intermediate. The anionic portion of the zwitterion adds to the neighboring carbonyl group. This is followed by epoxide ring formation with charge dissipation leading to an amido-substituted spiro cyclopentyl epoxide. In certain cases a hydroxy lactone was also isolated and its formation can b...
WNT1-inducible signaling pathway protein 1 (WISP1/CCN4) stimulates melanoma invasion and metastasis by promoting the epithelial–mesenchymal transition

Besides intrinsic changes, malignant cells also release soluble signals that reshape their microenvironment. Among these signals is WNT1-inducible signaling pathway protein 1 (WISP1), a secreted matricellular protein whose expression is elevated in several cancers, including melanoma, and is associated with reduced survival of patients diagnosed with primary melanoma. Here, we found that WISP1 knockout increases cell proliferation and represses wound healing, migration, and invasion of mouse and human melanoma cells in multiple in vitro assays. Metastasis assays revealed that WISP1 knockout represses tumor metastasis of B16F10 and YUMM1.7 melanoma cells in both C57BL/6Ncrl and NOD-scid IL2Rγnull (NSG) mice. WT B16F10 cells having an invasion phenotype in a transwell assay possessed a gene expression signature similar to that observed in the epithelial–mesenchymal transition (EMT), including E-cadherin repression and fibronectin and N-cadherin induction. Upon WISP1 knockout, expression of these EMT signature genes went in the opposite direction in both mouse and human cell lines, and EMT-associated gene expression was restored upon exposure to media containing WISP1 or to recombinant WISP1 protein. In vivo, Wisp1 knockout–associated metastasis repression was reversed by the reintroduction of either WISP1 or snail family transcriptional repressor 1 (SNAI1). Experiments testing EMT gene activation and inhibition with recombinant WISP1 or kinase inhibitors in B16F10 and YUMM1.7 cells suggested that WISP1 activates AKT Ser/Thr kinase and that MEK/ERK signaling pathways shift melanoma cells from proliferation to invasion. Our results indicate that WISP1 present within the tumor microenvironment stimulates melanoma invasion and metastasis by promoting an EMT-like process.
Developmental exposure to perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) selectively decreases brain dopamine levels in Northern leopard frogs.

Abstract Per- and polyfluoroalkyl substances (PFAS) are synthetic compounds that are a major public health concern due to widespread use, long environmental and biological half-lives, detection in most human plasma samples, and links to multiple adverse health outcomes. The literature suggests that some PFAS may be neurotoxic. However, there are major gaps in the literature with respect to how environmentally-relevant doses during development may influence the nervous system. To address this gap, we utilized a sentinel species, Northern leopard frogs (Lithobates pipiens) to determine the effects of developmental exposure to environmentally relevant perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) on major neurotransmitter systems. Frog larvae at Gosner stage 25 were exposed to 10, 100, or 1000 ppb PFOS or PFOA for 30 days before neurochemical analysis. High performance liquid chromatography (HPLC) with electrochemical detection or fluorescent detection assays was used to measure neurotransmitter levels, which were normalized to protein levels in each sample. Dopamine (DA) decreased significantly in the brains of frogs treated with PFOA (1000 ppb) and PFOS (100 and 1000 ppb). Significant increases in DA turnover also resulted from PFOA and PFOS treatment. Neither PFOS, nor PFOA produced detectable alterations in serotonin (nor its metabolite), norepinephrine, gamma-amino butyric acid (GABA), glutamate, or acetylcholine. PFAS body burdens showed that PFOS accumulated relative to dose, while PFOA did not. These data suggest that DArgic neurotransmission is selectively affected in developmentally exposed amphibians and that PFAS should be evaluated for a potential role in diseases that target the DA system.
Intramolecular photocycloaddition of olefin-tethered benzo[a]spiro[2,5]octa-1,4-dien-3-one derivatives

Photolysis of benzo[a]spiro[2,5]octa-1,4-dien-3-one derivative 8a afforded spiro-fused tetracycles 10 as a pair of diastereomers in 1.7:1 ratio. The photochemical process occurred by cycloaddition of the intermediate-sulfone stabilized biradical 9 to the tethered olefin. Photolysis of dienone 8b gave only spiro-fused tetracycle 11 without bridged adduct 12.
Synthesis of Enantiopure C2-Symmetric VERDI Disulfonamides and Their Application to the Catalytic Enantioselective Addition of Diethylzinc to Aromatic and Aliphatic Aldehydes

The enantiopure disulfonamides 7a−c have been prepared from the C2-symmetric diketone 2, a starting material conveniently accessible from the “dimerization” of (+)-verbenone. These ligands, when treated with titanium isopropoxide and diethylzinc, function as catalysts for the enantioselective alkylation of aldehydes. Stereoselectivity levels ranging from 72 to 98% ee are seen depending on the structural characteristics of the aldehyde. In all cases, the absolute configuration of the carbinol product is R. A working mechanistic model is advanced for the purpose of rationalizing the high levels and direction of asymmetric induction exhibited by these VERDI catalysts.
Macrocyclic Bisindolylmaleimides: Synthesis by Inter- and Intramolecular Alkylation

Macrocyclic bisindolylmaleimides 1−4 have been identified as competitive reversible inhibitors of PKC β1 and β2 and are being advanced to the clinic for evaluation as a treatment of retinopathy associated with diabetic complications. Highly convergent and stereoselective syntheses of 1−4 have been developed. The key synthetic step involves intermolecular alkylation of symmetrical bisindolylmaleimide 9 with chiral bisalkylating agent 8c and is amenable to the preparation of multikilogram quantities of these compounds. The synthetic sequence to 1, the most active compound, proceeds in 11 steps and 26% overall yield (>98% ee) from (R)-1-chloro-2,3-propanediol. No chromatographic purifications are required throughout the process and the final product is isolated in >97% purity after crystallization from DMF/MeOH. Synthesis of 1−4 by intramolecular alkylation proved less efficient, requiring 17 steps and affording 1−4 in lower overall yields of 6.0−8.5%.
Site-specific vanadates Co4Fe3.33(VO4)6 and Mn3Fe4(VO4)6.

Single crystals of Co4Fe3.33(VO4)6 and Mn3Fe4(VO4)6 were grown from equivalent CoO/Fe2O3/V2O5 and MnO/Fe2O3/V2O5 melts, respectively. The former crystallizes in the orthorhombic space group Pnma with parameters a = 4.965(1) A, b = 10.211(1) A, c = 17.188(3) A, and Z = 2 and is a homeotype of such catalysts as Mg2.5VMoO8. The latter crystallizes in the triclinic space group P1 with parameters a = 6.703(2) A, b = 8.137(1) A, c = 9.801(2) A, α = 105.56(1)°, β = 105.58(2)°, γ = 102.35(1)°, and Z = 1 and is a homeotype of β-Cu3Fe4(VO4)6, the low-pressure form of α-Cu3Fe4(VO4)6. The cobalt analogue deviates in stoichiometry from the reactant melt to form the more dense α-Cu3Fe4(VO4)6 structure type comprised of partially occupied face-sharing octahedral and trigonal prismatic coordination sites.
Use of a scientific microwave apparatus for rapid optimization of reaction conditions in a monomode function and then substrate screening in a multimode function

Abstract Recently, a new apparatus has become available, which aims to bring together in one unit the advantages of a monomode and a multimode microwave device. We have assessed the applicability of the apparatus toward rapid optimization of reaction conditions in a monomode function and then substrate screening in a multimode function. We have also probed the effects of differences in microwave absorptivity of reaction mixtures on the product conversions in screening multiple substrates simultaneously in a multimode microwave apparatus. We find that when the microwave absorptivity of a reaction mixture is dictated by the solvent, there is little effect on the heating profile of varying the substrate in a screening run. However, this is not the case when reactions involving non-microwave absorbant solvents are used. In this case the characteristics of the substrate can affect significantly the outcome of the reaction.
One pot synthesis of α,α-bis(N-arylamido) lactams via iodide-catalyzed rearrangement of β,β-bis(N-arylamido) cyclic ketene-N,O-acetals

Abstract Five and six-membered cyclic ketene-N,O-acetals, generated in situ from 2,3-dimethyl-2-oxazolinium iodide or 2,3-dimethyl-2-oxazinium iodide and triethylamine, reacted with aryl isocyanates in refluxing THF producing α,α-bis(N-arylamido) lactams via the iodide-catalyzed rearrangement of β,β-bis(N-arylamido) cyclic ketene-N,O-acetal intermediates. The cyclic ketene-N,O-acetal generated in situ from 2,3,4,4-tetramethyl-2-oxazolinium iodide reacted with isocyanates to give β,β-bis(N-arylamido) cyclic ketene-N,O-acetals, which do not readily rearrange. The two methyls at C-4 hindered the nucleophilic attack of iodide on C-5, which is required for rearrangement.
Practical methodology for the asymmetric synthesis of organofluorine compounds

Abstract Pseudoephedrine α-fluoroacetamide (1), a nonvolatile, crystalline solid, is alkylated efficiently and with high diastereoselectivity with reactive alkyl halides. The alkylation products can be hydrolyzed under mild basic conditions to form α-fluoro carboxylates with high enantiomeric enrichment.