Functional nonparametric estimation of conditional extreme quantiles

We address the estimation of quantiles from heavy-tailed distributions when functional covariate information is available and in the case where the order of the quantile converges to one as the sample size increases. Such “extreme” quantiles can be located in the range of the data or near and even beyond the boundary of the sample, depending on the convergence rate of their order to one. Nonparametric estimators of these functional extreme quantiles are introduced, their asymptotic distributions are established and their finite sample behavior is investigated.     

Circularly Polarized Luminescence and Circular Dichroism of Bichromophoric Difluoroboron-β-diketonates: Inversion and Enhanced Chirality Based on Spatial Arrangements and Self-Assembly

We synthesized two bichromophoric difluoroboron-β-diketonates (DFB) connected in para and meta positions by using cyclohexane diamine as a chiral bridge ( para and meta (R/S)-CyDFB ). TD-DFT calculations revealed that the variation in connectivity of the DFB units leads to different spatial arrangements and a chirality inversion of the bichromophoric DFB. Higher g_abs values were obtained in (R/S)-CyDFB connected in para as compared to meta position. Aggregation of para (R/S)-CyDFB in mixture of solvents increase the g_lum values as compared to its monomeric form. Ultrasonication and heating induced the formation of highly ordered nano-helical wires of para (R/S)-CyDFB that increased the g_lum values to 0.015. On the other hand, meta (R/S)-CyDFB failed to form highly ordered self-assembled wires due to hindered H-binding sites. These observations indicate that the chiroptical properties of DFB bi-chromophore system can be modulated with self-assembly and spatial arrangement of the chromophores.     

Einstein’s equations and Clifford algebra

Einstein’s equations of the general theory of relativity are rewritten within a Clifford algebra. This algebra is otherwise isomorphic to a direct product of two quaternion algebras. A multivector calculus is developed within this Clifford algebra which differs from the corresponding complexified algebra used in the standard spacetime algebra approach.     

A short and stereoselective synthesis of carbocyclic alpha-l-dideoxyhomonucleosides

A stereoselective five-step total synthesis of the hitherto unknown carbocyclic alpha-L-dideoxyhomonu-cleosides starting from readily available (1R,5S)-2-oxabicyclo[3.3.0]oct-6-en-3-one is described.     

Peculiar field-dependent magnetic behavior of cyano-bridged coordination polymer Er(H2O)4[W(CN)8

The two-dimensional cyano-bridged coordination polymer Er(H(2)O)(4)[W(CN)(8)] exhibits a magnetic transition at 12 K and an unusual field-dependent transition from short-range to ferromagnetic ordering.     

Tandem CH Activation/Arylation Catalyzed by Low‐Valent Iron Complexes with Bisiminopyridine Ligands

Tandem C?H activation/arylation between unactivated arenes and aryl halides catalyzed by iron complexes that bear redox‐active non‐innocent bisiminopyridine ligands is reported. Similar reactions catalyzed by first‐row transition metals have been shown to involve substrate‐based aryl radicals, whereas our catalytic system likely involves ligand‐centered radicals. Preliminary mechanistic investigations based on spectroscopic and reactivity studies, in conjunction with DFT calculations, led us to propose that the reaction could proceed through an inner‐sphere C?H activation pathway, which is rarely observed in the case of iron complexes. This bielectronic noble‐metal‐like behavior could be sustained by the redox‐active non‐innocent bisiminopyridine ligands.     

Frontier estimation with local polynomials and high power-transformed data

We present a new method for estimating the frontier of a sample. The estimator is based on a local polynomial regression on the power-transformed data. We assume that the exponent of the transformation goes to infinity while the bandwidth goes to zero. We give conditions on these two parameters for obtaining almost complete convergence. The asymptotic conditional bias and variance of the estimator are provided and its good performance is illustrated for some finite sample situations.     

Two New Constituents from the Soft Coral Nephthea hainansis

Two new compounds, namely 7α, 10α-dimethyl-3β-isopropene-1, 2-ene-octahydro-naphthalene (1) and ethyl 5Z,8Z, 11Z, 14Z-nonadecatetraenoate (2) were isolated from the soft coralNephthea hainansis. Compound 1 was a pseutosesquiterpene and 2 was a polyunsaturated fattyacid ethylate. Their structures were established on the basis of spectroscopic methods.     

Quantitative Proteomic Analysis of Optimal Cutting Temperature (OCT) Embedded Core-Needle Biopsy of Lung Cancer

With recent advances in understanding the genomic underpinnings and oncogenic drivers of pathogenesis in different subtypes, it is increasingly clear that proper pretreatment diagnostics are essential for the choice of appropriate treatment options for non-small cell lung cancer (NSCLC). Tumor tissue preservation in optimal cutting temperature (OCT) compound is commonly used in the surgical suite. However, proteins recovered from OCT-embedded specimens pose a challenge for LC-MS/MS experiments, due to the large amounts of polymers present in OCT. Here we present a simple workflow for whole proteome analysis of OCT-embedded NSCLC tissue samples, which involves a simple trichloroacetic acid precipitation step. Comparisons of protein recovery between frozen versus OCT-embedded tissue showed excellent consistency with more than 9200 proteins identified. Using an isobaric labeling strategy, we quantified more than 5400 proteins in tumor versus normal OCT-embedded core needle biopsy samples. Gene ontology analysis indicated that a number of proliferative as well as squamous cell carcinoma (SqCC) marker proteins were overexpressed in the tumor, consistent with the patient’s pathology based diagnosis of “poorly differentiated SqCC”. Among the most downregulated proteins in the tumor sample, we noted a number of proteins with potential immunomodulatory functions. Finally, interrogation of the aberrantly expressed proteins using a candidate approach and cross-referencing with publicly available databases led to the identification of potential druggable targets in DNA replication and DNA damage repair pathways. We conclude that our approach allows LC-MS/MS proteomic analyses on OCT-embedded lung cancer specimens, opening the way to bring powerful proteomics into the clinic.

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Unsteadiness of Flow Separation and End-Effects Regime in a Thrust-Optimized Contour Rocket Nozzle

Turbulent flow separation in over-expanded rocket nozzles is investigated experimentally in a sub-scale model nozzle fed with cold air and having a thrust-optimized contour. Depending upon the pressure ratio either a free shock separation (FSS) or a restricted shock separation (RSS) is observed with a significant hysteresis between these two flow regimes. It is shown that the RSS configuration may involve several separated regions. Analysis of wall pressure fluctuations give quantitative information on the fluctuating pressure field directly connected with the occurrence of significant side loads. Direct measurements of the evolution of the side loads with respect to the pressure ratio show the occurrence of three distinct peaks which are explained by the wall pressure fluctuations measurements.