Deep XMM-Newton Observations of an X-ray Weak Broad Absorption Line Quasar at z = 6.5

We report X-ray observations of the most distant known gravitationally lensed quasar, J0439+1634 at z = 6.52, which is also a broad absorption line (BAL) quasar, using the XMM-Newton Observatory. With a 130 ks exposure, the quasar is significantly detected as a point source at the optical position with a total of 358 − 19 + 19 net counts using the EPIC instrument. By fitting a power law plus Galactic absorption model to the observed spectra, we obtain a spectral slope of Γ = 1.45 − 0.09 + 0.10 . The derived optical-to-X-ray spectral slope α ox is − 2.07 − 0.01 + 0.01 , suggesting that the X-ray emission of J0439+1634 is weaker by a factor of 18 than the expectation based on its 2500 Å luminosity and the average α ox versus luminosity relationship. This is the first time that an X-ray weak BAL quasar at z > 6 has been observed spectroscopically. Its X-ray weakness is consistent with the properties of BAL quasars at lower redshift. By fitting a model including an intrinsic absorption component, we obtain intrinsic column densities of N H = 2.8 − 0.6 + 0.7 × 10 23 cm − 2 and N H = 4.3 − 1.5 + 1.8 × 10 23 cm − 2 , assuming a fixed Γ of 1.9 and a free Γ, respectively. The intrinsic rest-frame 2–10 keV luminosity is derived as (9.4–15.1) × 1043 erg s−1, after correcting for lensing magnification (μ = 51.3). The absorbed power-law model fitting indicates that J0439+1634 is the highest redshift obscured quasar with a direct measurement of the absorbing column density. The intrinsic high column density absorption can reduce the X-ray luminosity by a factor of 3–7, which also indicates that this quasar could be a candidate intrinsically X-ray weak quasar.

Ultrasmall PEI-Decorated Bi2Se3 Nanodots as a Multifunctional Theranostic Nanoplatform for in vivo CT Imaging-Guided Cancer Photothermal Therapy

Bi-based nanomaterials, such as Bi2Se3, play an important part in biomedicine, such as photothermal therapy (PTT) and computed tomography (CT) imaging. Polyethylenimine (PEI)-modified ultrasmall Bi2Se3 nanodots were prepared using an ultrafast synthetic method at room temperature (25°C). Bi2Se3 nanodots exhibited superior CT imaging performance, and could be used as effective photothermal reagents owing to their broad absorption in the ultraviolet–visible–near infrared region. Under irradiation at 808 nm, PEI-Bi2Se3 nanodots exhibited excellent photothermal-conversion efficiency of up to 41.3%. Good biocompatibility and significant tumor-ablation capabilities were demonstrated in vitro and in vivo. These results revealed that PEI-Bi2Se3 nanodots are safe and a good nanotheranostic platform for CT imaging-guided PTT of cancer.

The new evidence from the fingerprint region in FT-IR spectra to indicate the heat treatment of blue sapphire sample

FT-IR spectroscopy is a significant method to detect the heat treatment of gemstones, especially ruby and sapphire. There are a set of certain peaks, i.e., 3309, 3232, and 3185 cm−1 in the FT-IR spectra used as an indicator to determine whether the samples have been undergone heat treatment. In this study, however, new evidence has emerged. The O-Al-O bending vibration peak at the fingerprint region around 600-700 cm−1 has been suggested as new clues to define the heated stones. The blue sapphire samples were prepared, then the heat treatment was performed separately at 800, 1000, 1200, 1400, and 1650 °C under an oxidizing atmosphere with a soaking time of 1 hour. The energy dispersive X-ray fluorescence (EDXRF) shows that there is no significant difference in the chemical composition of Al2O3, Fe2O3, TiO2, and Ga2O3 between unheated and heated samples. The alteration of blue color and the UV-Vis absorption spectra are also difficult to classify. When comparing the samples at each heating temperature, the alteration of blue color was not related to one another because the color of the samples was decreased depending on those of the unheated ones. The FT-IR spectra revealed that the broad absorption peak of O-Al-O bending at approximately 650 cm−1 was slightly shifted to a lower wavenumber (630 – 635 cm−1) after the samples were heated at higher temperatures. The broad absorption peak also turned into a sharper one when the sample has undergone heating at ≥1000 °C. It is suggested that the peak is related to the rearrangement of the Al2O3 structure of the blue sapphire sample after heat treatment.

Achieving broad absorption band and high incident angles by stochastically-distributed oblique-flat-sheet metamaterial perfect absorbers

In this work, we integrated a periodic seed layer and oblique deposition method to fabricate a stochastically-distributed oblique-flat-sheet metamaterial perfect absorber (MPA). Such design could increase its absorption bandwidth and tolerance to high angle-incidence due to the fact that various oblique flat sheets offer different resonance conditions while even a single oblique flat sheet could provide different optical paths for resonance. On the other hand, a seed layer could reduce uncertainty regarding to direct oblique deposition and provide abilities to manipulate the bandwidth of the MPA. We also setup a simulation model in the aids of Visual Basic Application and examined the absorption behavior of the MPA under TM and TE oblique incidence that could achieve high absorbance under 80° and 60° incidence, respectively. Finally, in measurement, the fabricated sample owns 65% absorbance within 80–250 THz and over 90% absorbance within 250–320 THz at x-polarization normal incidence; as for the y-polarization normal incidence, we could achieve overall 70% absorbance within 80–300 THz. The measured results reveal similar tendency compared to the simulated ones.

Naphthazarin Derivatives in the Light of Intra- and Intermolecular Forces

Our long-term investigations have been devoted the characterization of intramolecular hydrogen bonds in cyclic compounds. Our previous work covers naphthazarin, the parent compound of two systems discussed in the current work: 2,3-dimethylnaphthazarin (1) and 2,3-dimethoxy-6-methylnaphthazarin (2). Intramolecular hydrogen bonds and substituent effects in these compounds were analyzed on the basis of Density Functional Theory (DFT), Møller–Plesset second-order perturbation theory (MP2), Coupled Clusters with Singles and Doubles (CCSD) and Car-Parrinello Molecular Dynamics (CPMD). The simulations were carried out in the gas and crystalline phases. The nuclear quantum effects were incorporated a posteriori using the snapshots taken from ab initio trajectories. Further, they were used to solve a vibrational Schrödinger equation. The proton reaction path was studied using B3LYP, ωB97XD and PBE functionals with a 6-311++G(2d,2p) basis set. Two energy minima (deep and shallow) were found, indicating that the proton transfer phenomena could occur in the electronic ground state. Next, the electronic structure and topology were examined in the molecular and proton transferred (PT) forms. The Atoms In Molecules (AIM) theory was employed for this purpose. It was found that the hydrogen bond is stronger in the proton transferred (PT) forms. In order to estimate the dimers’ stabilization and forces responsible for it, the Symmetry-Adapted Perturbation Theory (SAPT) was applied. The energy decomposition revealed that dispersion is the primary factor stabilizing the dimeric forms and crystal structure of both compounds. The CPMD results showed that the proton transfer phenomena occurred in both studied compounds, as well as in both phases. In the case of compound 2, the proton transfer events are more frequent in the solid state, indicating an influence of the environmental effects on the bridged proton dynamics. Finally, the vibrational signatures were computed for both compounds using the CPMD trajectories. The Fourier transformation of the autocorrelation function of atomic velocity was applied to obtain the power spectra. The IR spectra show very broad absorption regions between 700 cm−1–1700 cm−1 and 2300 cm−1–3400 cm−1 in the gas phase and 600 cm−1–1800 cm−1 and 2200 cm−1–3400 cm−1 in the solid state for compound 1. The absorption regions for compound 2 were found as follows: 700 cm−1–1700 cm−1 and 2300 cm−1–3300 cm−1 for the gas phase and one broad absorption region in the solid state between 700 cm−1 and 3100 cm−1. The obtained spectroscopic features confirmed a strong mobility of the bridged protons. The inclusion of nuclear quantum effects showed a stronger delocalization of the bridged protons.

Structure elucidation of the novel carotenoid gemmatoxanthin from the photosynthetic complex of Gemmatimonas phototrophica AP64

Gemmatimonas phototrophica AP64 is the first phototrophic representative of the bacterial phylum Gemmatimonadetes. The cells contain photosynthetic complexes with bacteriochlorophyll a as the main light-harvesting pigment and an unknown carotenoid with a single broad absorption band at 490 nm in methanol. The carotenoid was extracted from isolated photosynthetic complexes, and purified by liquid chromatography. A combination of nuclear magnetic resonance (1H NMR, COSY, 1H-13C HSQC, 1H-13C HMBC, J-resolved, and ROESY), high-resolution mass spectroscopy, Fourier-transformed infra-red, and Raman spectroscopy was used to determine its chemical structure. The novel linear carotenoid, that we have named gemmatoxanthin, contains 11 conjugated double bonds and is further substituted by methoxy, carboxyl and aldehyde groups. Its IUPAC-IUBMB semi-systematic name is 1′-Methoxy-19′-oxo-3′,4′-didehydro-7,8,1′,2′-tetrahydro- Ψ, Ψ carotene-16-oic acid. To our best knowledge, the presence of the carboxyl, methoxy and aldehyde groups on a linear C40 carotenoid backbone is reported here for the first time.