Bayesian Trend Filtering via Proximal Markov Chain Monte Carlo.

Proximal Markov Chain Monte Carlo is a novel construct that lies at the intersection of Bayesian computation and convex optimization, which helped popularize the use of nondifferentiable priors in Bayesian statistics. Existing formulations of proximal MCMC, however, require hyperparameters and regularization parameters to be prespecified. In this work, we extend the paradigm of proximal MCMC through introducing a novel new class of nondifferentiable priors called epigraph priors. As a proof of concept, we place trend filtering, which was originally a nonparametric regression problem, in a parametric setting to provide a posterior median fit along with credible intervals as measures of uncertainty. The key idea is to replace the nonsmooth term in the posterior density with its Moreau-Yosida envelope, which enables the application of the gradient-based MCMC sampler Hamiltonian Monte Carlo. The proposed method identifies the appropriate amount of smoothing in a data-driven way, thereby automating regularization parameter selection. Compared with conventional proximal MCMC methods, our method is mostly tuning free, achieving simultaneous calibration of the mean, scale and regularization parameters in a fully Bayesian framework.

Robust Low-rank Tensor Decomposition with the L2 Criterion.

The growing prevalence of tensor data, or multiway arrays, in science and engineering applications motivates the need for tensor decompositions that are robust against outliers. In this paper, we present a robust Tucker decomposition estimator based on the L2 criterion, called the Tucker-L2E. Our numerical experiments demonstrate that Tucker-L2E has empirically stronger recovery performance in more challenging high-rank scenarios compared with existing alternatives. The appropriate Tucker-rank can be selected in a data-driven manner with cross-validation or hold-out validation. The practical effectiveness of Tucker-L2E is validated on real data applications in fMRI tensor denoising, PARAFAC analysis of fluorescence data, and feature extraction for classification of corrupted images.

Pathologic complete response after neoadjuvant tislelizumab and chemotherapy for Pancoast tumor: A case report.

A 60-year-old man was hospitalized because of numbness and weakness in the right upper limb. Magnetic resonance imaging revealed a large mass in the right upper lobe invading the right eighth cervical and first thoracic nerve root. Biopsy pathology confirmed primary lung adenocarcinoma with a clinical stage of cT4N0M0 IIIA, negative for anaplastic lymphoma kinase fusion gene and epidermal growth factor receptor mutations but positive for programmed death ligand 1 (3%). Neoadjuvant tislelizumab and chemotherapy were offered to this patient with Pancoast tumor, and tumor shrinkage of 71% was achieved. After the operation, surgical pathology indicated pathologic complete response (pCR). Circulating tumor cells testing was negative after the first adjuvant treatment. In this case, we provide real-world evidence of encouraging pCR with neoadjuvant tislelizumab and chemotherapy for a patient with Pancoast tumor.

Effect of Different Hot Air Drying Methods on Chemical Constituents of Trichosanthis Fructus / 中国实验方剂学杂志

Objective:To compare the effects of different drying methods on the chemical constituents of Trichosanthis Fructus. Method:Trichosanthis Fructus was dried by means of air drying， sun drying， hot air drying （40， 60， 80 ℃） and variable temperature drying （50-80， 80-50 ℃）. The contents of nucleosides and flavonoids in Trichosanthis Fructus peels and seeds treated by different methods were compared by high performance liquid chromatography （HPLC）， mobile phase was acetonitrile-0.2% acetic acid aqueous solution （3∶7） （A）-acetonitrile （B） for gradient elution （0-15 min， 97-95%B； 15-30 min， 95%-90%B； 30-35 min， 90%-87%B； 35-40 min， 87%-86.5%B； 40-48 min， 86.5%-97%B； 48-50 min， 97%B）， the detection wavelength was 260 nm， and the flow rate was 0.4 mL·min^-1. Gas chromatography-ion mobility spectrometry （GC-IMS） was used to compare the changes of volatile components in the samples treated by different treatments. The volatile components were incubated on a SE-54 capillary column （0.32 mm×30 m， 0.25 μm） at 80 ℃ and 500 r·min^-1 for 15 min， the injection temperature was 85 ℃， the injection volume was 400 μL， the analysis time was 35 min， carrier gas was high purity nitrogen， the flow rate of carrier gas was 2.0 mL·min^-1， the flow rate of drift gas was 150 mL·min^-1， and the temperature of IMS detector was 45 ℃. Result:The contents of uridine， adenosine and adenine were higher after hot air drying at >50 ℃. Low temperature drying was conducive to maintaining the stability of cytidine， cytosine， rutin， luteolin and 2ʹ-deoxyadenosine. GC-IMS technology could realize the analysis and identification of Trichosanthis Fructus samples after different treatments. There were more volatile components after hot air drying at 80 ℃ and variable temperature drying. Conclusion:Hot air drying at 40 ℃ and 60 ℃ can retain nucleosides and flavonoids， and the volatile components are similar to those in traditional drying methods， which has the advantages of high efficient， controllable and suitable for industrial production.

The Circular RNome of Developmental Retina in Mice.

Circular RNAs (circRNAs) represent a class of noncoding RNAs with a wide expression pattern, and they constitute an important layer of the genome regulatory network. To date, the expression pattern and regulatory potency of circRNAs in the retina, a key part of the central nervous system, are not yet well understood. In this study, RNAs from five stages (E18.5, P1, P7, P14, and P30) of mouse retinal development were sequenced. A total of 9,029 circRNAs were identified. Most circRNAs were expressed in different stages with a specific signature, and their expression patterns were different from those of their host linear transcripts. Some circRNAs could act as sponges for several retinal microRNAs (miRNAs). Furthermore, circTulp4 could function as a competitive endogenous RNA (ceRNA) to regulate target genes. Remarkably, silencing circTulp4 in vivo led to mice having a thin outer nuclear layer (ONL) and defective retinal function. In addition, we found that circRNAs were dysregulated at a much earlier time point than that of disease onset in a retinal degeneration model (rd8 mice). In summary, we provide the first circRNA expression atlas during retinal development and highlight a key biological role for circRNAs in retinal development and degeneration.

Oxadiazole-Based Highly Efficient Bipolar Fluorescent Emitters for Organic Light-Emitting Diodes.

In this study, a series of bipolar fluorescence emitters named 2DPAc-OXD, DPAc-OXD, 2PTZ-OXD and PTZ-OXD were designed and synthesized with excellent yields. The characterization of materials was investigated by using nuclear magnetic resonance (NMR) (¹H, 13C), mass spectrometry and thermogravimetric analysis (TGA). To investigate device efficiencies, two different OLED devices (Device 1, Device 2) were fabricated with two different host materials (Bepp2, DPEPO). The Device 2 with 2PTZ-OXD as fluorescent emitter exhibited excellent power and current efficiencies of 6.88 Lm/W and 10.10 cd/A, respectively. The external quantum efficiency of 2PTZ-OXD was around 3.99% for Device 2. The overall device properties of phenothiazine donor were better than acridine derivatives.

Direct observation of solid-state reversed transformation from crystals to quasicrystals in a Mg alloy.

Phase transformation of quasicrystals is of interest in various fields of science and technology. Interestingly, we directly observed unexpected solid-state epitaxial nucleation and growth of Zn6Mg3Y icosahedral quasicrystals in a Mg alloy at about 573 K which is about 300 K below the melting point of Zn6Mg3Y, in contrast to formation of quasicrystals through solidification that was usually found in many alloys. Maximizing local packing density of atoms associated with segregation of Y and Zn in Mg adjacent to Mg/Zn3MgY interfaces triggered atomic rearrangement in Mg to form icosahedra coupled epitaxially with surface distorted icosahedra of Zn3MgY, which plays a critical role in the nucleation of icosahedral clusters. A local Zn:Mg:Y ratio close to 6:3:1, corresponding to a valence electron concentration of about 2.15, should have been reached to trigger the formation of quasicrystals at Mg/Zn3MgY interfaces. The solid-state icosahedral ordering in crystals opens a new window for growing quasicrystals and understanding their atomic origin mechanisms. Epitaxial growth of quasicrystals onto crystals can modify the surface/interface structures and properties of crystalline materials.

Crystal structure of (4Z)-4-{[(2-chloro-phen-yl)amino](furan-2-yl)methyl-idene}-3-methyl-1-phenyl-4,5-di-hydro-1H-pyrazol-5-one.

In the title compound, C21H16ClN3O2, the pyrazolone ring and the O=C-C=C-N mean plane [maximum deviation = 0.022 (2) Å] are nearly coplanar, making a dihedral angle 4.56 (8)°, while the phenyl and pyrazole rings subtend a dihedral angle of 19.75 (8)°. The compound is in the enamine-keto form and its structure is stabilized by an intra-molecular N-H⋯O hydrogen bond. In the crystal, mol-ecules are linked via C-H⋯N hydrogen bonds, forming chains along [010]. Between the chains there are π-π inter-actions [inter-centroid distances = 3.3902 (9) and 3.5956 (11) Å], linking the chains to form sheets parallel to (10-1).

Characterization of nucleosides and nucleobases in natural Cordyceps by HILIC-ESI/TOF/MS and HILIC-ESI/MS.

A method combining hydrophilic interaction chromatography (HILIC) and electrospray ionization mass spectrometry (ESI-MS) was developed for the characterization and determination of natural Cordyceps. Separation was achieved on a Waters Xbridge Amide column with gradient elution. Identification of 15 target nucleosides and nucleobases was based on retention time, UV spectra and mass measurements of the protonated molecules ([M+H]⁺) and main fragment ions (ESI-TOF/MS). Eight non-target compounds were tentatively identified by ESI-TOF/MS. The 15 target compounds were quantified by HILIC-ESI-MS/MS using time-programmed selective ion monitoring or multiple reaction monitoring in positive-ion mode under optimized mass conditions. This technique showed good linearity, repeatability and recovery. This approach was also successfully implemented in the analysis of nucleosides and nucleobases in 12 batches of natural Cordyceps samples that were collected from different regions in China. The developed HILIC-ESI-MS method exhibited clear advantages in identifying and determining highly polar bioactive components in Cordyceps, as well as their quality control.

Identification of active components in Syngnathus acus by HILIC-ESI-TOF/MS and study on their specific fingerprint chromatograms / 中草药

Objective: To develop a new method based on hydrophilic interaction chromatography-electrospray ionization-time of flight-mass spectrometry (HILIC-DAD-ESI-TOF/MS) for the rapid identification of the active components in Syngnathus acus and the development of their specific fingerprint chromatograms. Methods: Samples were extracted by accelerated solvent extraction, and the extraction conditions were optimized. The developed HILIC-DAD-ESI-TOF/MS method was used to identify the components in water extract from S. acus, and a chromatographic fingerprint based on HILIC analysis was established. Results: Ten compounds in S. acus extract could be primarily identified by HILIC-DAD-ESI-TOF/MS on-line detection, in which seven nucleosides were determined. The HPLC characteristic fingerprint was established on the basis of analysis on the multi batches of S. acus, which could be used to evaluate the quality of S. acus combined with similarity calculation. Conclusion: This method is simple and rapid, and is a powerful tool for the identification of S. acus.

(4Z)-4-[(2-Chloro-anilino)(phen-yl)methyl-idene]-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one.

The title compound, C(23)H(18)ClN(3)O, exists in an enamine-keto form with the amino group involved in an intra-molecular N-H⋯O hydrogen bond. The five-membered ring is nearly planar, the largest deviation being 0.0004 (7) Å, and makes dihedral angles of 16.62 (6), 41.89 (5) and 71.27 (4)° with the phenyl rings. In the crystal, weak C-H⋯O hydrogen bonds link the mol-ecules into supra-molecular chains along the b axis.

Redetermination of µ-oxido-bis-[bis-(N,N-diethyl-hydroxyl-aminato)-oxido-vanadium(V)].

In comparison with the previous determination [Saussine, Mimoun, Mitschler & Fisher (1980 ▶). Nouv. J. Chim.4, 235-237] of the title compound, [V(2)(C(4)H(10)NO)(4)O(3)], the current study reports an improved precision of the derived geometric parameters, along with the deposition of all coordinates and displacement parameters. The two V(V) atoms are each surrounded by two deprotonated N,O-bidentate diethyl-hydroxy-laminate groups, and a terminal and a bridging oxide ligand, in a distorted octa-hedral coordination geometry. The crystal packing is accomplished by van der Waals inter-actions.

Poly[[aqua-(µ(5)-1H-benzimidazole-5,6-dicarboxyl-ato)(µ(4)-1H-benzimidazole-5,6-dicarboxyl-ato)dibarium] 4.5-hydrate].

The polymeric title compound, {[Ba(2)(C(9)H(4)N(2)O(4))(2)(H(2)O)]·4.5H(2)O}(n), adopts a layer structure parallel to (001) in which adjacent Ba(II) atoms are connected by two benzimidazole-5,6-dicarboxyl-ate dianions, one functioning in a µ(4)-bridging mode and the other in a µ(5)-bridging mode. The Ba atom having water in its coordination environment as well as the Ba atom without water exist in a nine-coordinate polyhedron of O atoms; the geometry is difficult to derive. Lattice water mol-ecules occupy the space between layers and inter-act with the layers through O-H⋯O, O-H⋯N and N-H⋯O hydrogen bonds. ne of the five lattice water molecules is equally disordered around an inversion centre and shows half-occupancy.

Molecularly imprinted polymer for selective extraction of domoic acid from seafood coupled with high-performance liquid chromatographic determination.

In this work, a highly selective sample cleanup procedure that combining molecular imprinting technique (MIT) and solid phase extraction (SPE) was developed for the isolation of domoic acid (a fascinating marine toxin) from seafood samples. The molecular imprinting polymer (MIP) for domoic acid was prepared using 1,3,5-pentanetricarboxylic acid as the template molecule instead of domoic acid. 4-Vinyl pyridine was used as the functional monomer and ethylene glycol dimethacrylate was used as the cross-linking monomer. The obtained imprinted polymer showed high affinity to domoic acid and was used as selective sorbent for the SPE of domoic acid from seafood samples. An off-line molecularly imprinted solid phase extraction (MISPE) method followed by high-performance liquid chromatography (HPLC) with diode-array detection for the detection of domoic acid was also established. Good linearity was obtained from 0.5 mg L(-1) to 25 mg L(-1) (R(2)>0.99) with a quantitation limit of 0.1 mg L(-1), which was sufficient to determine domoic acid at the maximum level permitted by several authorities. The mean recoveries of domoic acid from mussel extracts were 93.4-96.7%. It was demonstrated that the proposed MISPE-HPLC method could be applied to direct determination of domoic acid from seafood samples.

[Water-soluble anions of atmosphere on Tianwan nuclear power station].

Three major water-soluble anions (Cl-, SO4(2-) and NO3-) in the atmosphere of the Tianwan nuclear power station in Lianyungang were determined by ion chromatography from June 2005 to May 2006. The results showed that the annual average concentration of Cl-, SO4(2-) and NO3- in the atmosphere of Tianwan nuclear power station was (33.12 +/- 53.63) microg x m(-3), (53.34 +/- 30.34) microg x m(-3) and (8.34 +/- 4.47) microg x m(-3), respectively. The concentrations of the three water-soluble anions showed evident trend of seasonal variation. The concentrations of Cl-, SO4(2-) reached the highest level in summer and the lowest level in winter, while the concentration of NO3- in autumn and winter was higher than those in summer and spring. Meteorological parameters such as wind direction, wind speed, temperature and relative humidity were studied and showed definite influence to the anions concentration of the atmosphere. This is the first simultaneous monitoring of corrosive anions in the atmosphere of Chinese coastal nuclear power plant, and it will provide basis for the prevention of marine atmospheric corrosion, which will ensure the safely operating of our nuclear power industry.

[Identification of active components in Styela clava by HPLC-eSI-Tof/MS and the study on their HPLC specific chromatograms].

A new method based on high performance liquid chromatography-electrospray ionization time of flight-mass spectrometry (HPLC-ESI-TOF/MS) was developed for the rapid identification of active compounds in Styela clava and the development of its specific chromatograms. Samples were extracted by ultrasonic-assisted extraction, and the extraction conditions were optimized. The developed HPLC-ESI-TOF/MS method was used to identify the components in Styela clava extract, and a specific chromatogram based on HPLC analysis was established. Ten compounds in Styela clava extract have been primary identified by HPLC-ESI-TOF/MS on-line detection combined with literature review. The result of similarity evaluation for specific chromatograms indicated that the quality of different Styela clava samples was not entirely consistent. This method has the advantages of simple operation, rapid measurement and it is a powerful tool for identification of active components in Styela clava and its quality control.

Erratum: 4-[(Z)-(2-Fur-yl)(2-naphthyl-amino)methyl-ene)]-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one. Corrigendum.

The title of the paper by Li, Li, Li, Zhang & Li [Acta Cryst. (2009), E65, o1824] is corrected.[This corrects the article DOI: 10.1107/S1600536809025586.].

Identification of active components in Styela clava by HPLC-eSI-Tof/MS and the study on their HPLC specific chromatograms / 药学学报

A new method based on high performance liquid chromatography-electrospray ionization time of flight-mass spectrometry (HPLC-ESI-TOF/MS) was developed for the rapid identification of active compounds in Styela clava and the development of its specific chromatograms. Samples were extracted by ultrasonic-assisted extraction, and the extraction conditions were optimized. The developed HPLC-ESI-TOF/MS method was used to identify the components in Styela clava extract, and a specific chromatogram based on HPLC analysis was established. Ten compounds in Styela clava extract have been primary identified by HPLC-ESI-TOF/MS on-line detection combined with literature review. The result of similarity evaluation for specific chromatograms indicated that the quality of different Styela clava samples was not entirely consistent. This method has the advantages of simple operation, rapid measurement and it is a powerful tool for identification of active components in Styela clava and its quality control.

Molecularly imprinted polymer as SPE sorbent for selective extraction of melamine in dairy products.

In this paper, a highly selective sample cleanup procedure combining molecular imprinting and solid-phase extraction (MI-SPE) was developed for the isolation of melamine in dairy products. The molecularly imprinted polymer (MIP) was prepared using melamine as the template molecule, methacrylic acid as the functional monomer and ethylene glycol dimethacrylate as the cross-linking monomer. The melamine imprinted polymer was used as selective sorbent for the solid-phase extraction of melamine from dairy products. An off-line MI-SPE method followed by high-performance liquid chromatography with diode-array detection for the detection of melamine was also established. The mean recoveries of melamine from ultra-heat treatment (UHT) milk and milk powders were 92.9-98.0% and 91.6-102.8%, respectively. Good linearity was obtained from 0.5 microM to 10 microM (r>0.999) with a quantitation limit of 0.5 micromol/L (0.06 ppm) which was sufficient to analyse melamine at the maximum level permitted by U.S. Food and Drug Administration (1 ppm) in dairy products. It was demonstrated that the proposed MI-SPE-HPLC method could be applied to direct determination of melamine in dairy products.

A three-dimensional supramolecular vanadium hydroxylamide complex: poly[di-mu2-aqua-bis(hydroxylamido)-mu3-malonato-oxidosodiumvanadium(V)].

The crystal structure of the title compound, [NaV(C3H2O4)(NH2O)2O(H2O)2], is built up of NaO6 and VO5N2 polyhedra connected through malonate bridges. The NaO6 octahedra are linked by edge sharing in the equatorial plane to form one-dimensional infinite chains. These chains are linked together by the malonate bridges to form two-dimensional layers. The distorted VO5N2 pentagonal bipyramid is grafted on to the layer by a malonate carboxylate O atom. Adjacent layers are connected through O-H...O and N-H...O hydrogen bonds to build up a three-dimensional supramolecular structure.