Boronate Ligands in Materials: Determining Their Local Environment by Using a Combination of IR/Solid‐State NMR Spectroscopies and DFT Calculations

Boronic acids (R‐B(OH)₂) are a family of molecules that have found a large number of applications in materials science. In contrast, boronate anions (R‐B(OH)₃^?) have hardly been used so far for the preparation of novel materials. Here, a new crystalline phase involving a boronate ligand is described, Ca[C₄H₉‐B(OH)₃]₂, which is then used as a basis for the establishment of the spectroscopic signatures of boronates in the solid state. The phase was characterized by IR and multinuclear solid‐state NMR spectroscopy (¹H, ¹³C, ¹¹B and ⁴³Ca), and then modeled by periodic DFT calculations. Anharmonic OH vibration frequencies were calculated as well as NMR parameters (by using the Gauge Including Projector Augmented Wave—GIPAW—method). These data allow relationships between the geometry around the OH groups in boronates and the IR and ¹H NMR spectroscopic data to be established, which will be key to the future interpretation of the spectra of more complex organic–inorganic materials containing boronate building blocks.     

Excitation dependent quenching of luminescence in LED phosphors

Droop, the decrease of efficiency with increased power density, became a major topic with InGaN LEDs, after its introduction in 2007. This paper provides insight into droop in localized center luminescence phosphors, exemplified here by Eu²⁺ doped materials. This topic is of increasing importance, as high brightness blue LEDs have reached outputs >1 W/mm². The nonlinearities in phosphor quantum efficiency result in drive‐dependent color point shift and reduction of overall efficiency of phosphor converted white LEDs which utilize Eu²⁺ activated phosphors. The efficiency quenching can be traced back to two processes, well‐known in laser physics, excited state absorption or/and cross relaxation by Foerster/Dexter transfer. Both processes lead to reduction in phosphor efficiency, but they can be differentiated. Understanding the root cause of efficiency quenching opens ways to minimize the practical consequences. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Tuning Thiophene with Phosphorus: Synthesis and Electronic Properties of Benzobisthiaphospholes

1,4‐Dimercapto‐2,5‐diphosphinobenzene and 3,6‐bis(hexyloxy)‐1,4‐dimercapto‐2,5‐diphosphinobenzene were synthesized and combined with various acid chlorides to obtain a series of benzobisthiaphospholes. Electrochemical and photophysical properties of the substituted benzobisthiaphospholes have been evaluated, and the observed reductions are more facile than the related benzothiaphospholes and 2,6‐diphenylbenzobisthiazole. A benzobisthiaphosphole with C₆H₄‐p‐CN substituents was reduced at E_1/2=?1.08 V (vs. saturated calomel electrode (SCE)). X‐ray diffraction data for several of these phosphorus heterocycles has been obtained, and DFT calculations at the B3LYP level have been performed.     

Longitudinal 3D Blood Flow Distribution Provided by Diffuse Correlation Tomography during Bone Healing in a Murine Fracture Model

Noninvasive monitoring of vascularization can potentially diagnose impaired bone healing earlier than current radiographic methods. In this study, a noncontact diffuse correlation tomography (DCT) technique was employed to measure longitudinal blood flow changes during bone healing in a murine femoral fracture model. The three-dimensional distribution of the relative blood flow was quantified from one day pre-fracture to 48 days post-fracture. For three mice, frequent DCT measurements were performed every other day for one week after fracture, and then weekly thereafter. A decrease in blood flow was observed in the bone fracture region at one day post-fracture, followed by a monotonic increase in blood flow beyond the pre-injury baseline until five to seven days post-fracture. For the remaining 12 mice, only weekly DCT measurements were performed. Data collected on a weekly basis show the blood flow for most mice was elevated above baseline during the first two post-fracture weeks, followed by a subsequent decrease. Torsional strength of the excised femurs was measured for all 15 mice after 7 weeks of healing. A metric based on the early blood flow changes shows a statistically significant difference between the high strength group and the low strength group.     

Photoinitiated cationic polymerisation of multifunctional systems

Different types of tridimensional polymer networks have been synthetised by photoinitiated cationic polymerisation of vinyl ether and epoxy-functionalised oligomers and polymers. The polymerisation kinetics was followed by real-time infrared (RTIR) spectroscopy, a technique that records directly conversion versus time profiles in a timescale as short as 1 s. The addition of a diacrylate monomer was shown to accelerate the ring-opening polymerisation of epoxidized polyisoprene, with formation of interpenetrating polymer networks having well contrasted properties. A dual polymer network has been generated by photocrosslinking of a polyisoprene functionalised with both epoxy and acrylate groups.     

13 C Saturation-Transfer Difference (STD)-NMR Experiments Using INEPT Polarization Transfer

Saturation-transfer difference (STD)-NMR spectroscopy has been widely used to screen potential ligands for binding to large receptor molecules. The STD-NMR experiment is typically based on a proton NMR spectrum, which can suffer from spectral overlap, leading to missing information in STD-based epitope mapping. Two-dimensional STD-NMR experiments can alleviate spectral overlap, but are time consuming. Here, we examine the feasibility of saturating protons in a receptor molecule and observing the STD effect on nearby carbon nuclei after transferring polarization from protons to carbons using the insensitive nuclei enhanced by polarization transfer (INEPT) pulse sequence. We show that under favorable conditions, a 1H→13C STD-INEPT experiment can give information similar to that obtained from a two-dimensional heteronuclear experiment, but in significantly less time. The STD-INEPT experiment could be especially useful when studying mixtures of ligands in which the peak positions in the proton and HSQC spectrum change significantly, and in particular, when using high-throughput, automated methods to analyze the data.     

Ankyrin repeat and SOCS box containing protein 4 (Asb-4) colocalizes with insulin receptor substrate 4 (IRS4) in the hypothalamic neurons and mediates IRS4 degradation

Background

Cigarette smoking enhances the risk of stroke. However, the underlying molecular mechanisms are largely unknown. The present study established an in vivo rat secondhand cigarette smoking (SHS) model and examined the hypothesis that SHS upregulates endothelin receptors with increased cerebrovascular contraction via the Raf/extracellular signal-regulated kinase (ERK)/mitogen-activated protein kinases (MAPK) pathway.

Results

Rats were exposed to SHS for up to 8 weeks. The cerebral artery vasoconstriction was recorded by a sensitive myograph. The mRNA and protein expressions for endothelin receptors in cerebral arteries were studied by real-time PCR and Western blot. Compared to fresh air exposed rats, cerebral arteries from SHS rats exhibited stronger contractile responses (P < 0.05) mediated by endothelin type A (ET_A) receptors. The expressions of mRNA and protein for ET_A receptors in the cerebral arteries from SHS rats were higher (P < 0.05) than that in control. SHS did not affect endothelin type B (ET_B) receptor-mediated contractions, mRNA or protein levels. The results suggest that SHS upregulates ET_A, but not ET_B receptors in vivo. After SHS exposure, the mRNA levels of Raf-1 and ERK1/2, the protein expression of phosphorylated (p)-Raf-1 and p-ERK1/2 were increased (P < 0.05). Raf-1 inhibitor, GW5074 suppressed the enhanced ET_A receptor-mediated contraction, mRNA and protein levels induced by SHS. In addition, GW5074 inhibited the SHS-caused increased mRNA and phosphorylated protein levels of Raf-1 and ERK1/2, suggesting that SHS induces activation of the Raf/ERK/MAPK pathway.

Conclusions

SHS upregulates cerebrovascular ET_A receptors via the Raf/ERK/MAPK pathway, which provides novel understanding of mechanisms involved in SHS-associated stroke.     

Determination of cocaine adulterants in human urine by dispersive liquid-liquid microextraction and high-performance liquid chromatography

Analytical and Bioanalytical Chemistry - This study aimed to determine simultaneously five major street cocaine adulterants (caffeine, lidocaine, phenacetin, diltiazem, and hydroxyzine) in human...     

Optical Spectroscopy as a Method for Skin Cancer Risk Assessment

Skin cancer is the most prevalent cancer, and its assessment remains a challenge for physicians. This study reports the application of an optical sensing method, elastic scattering spectroscopy (ESS), coupled with a classifier that was developed with machine learning, to assist in the discrimination of skin lesions that are concerning for malignancy. The method requires no special skin preparation, is non‐invasive, easy to administer with minimal training, and allows rapid lesion classification. This novel approach was tested for all common forms of skin cancer. ESS spectra from a total of 1307 lesions were analyzed in a multi‐center, non‐randomized clinical trial. The classification algorithm was developed on a 950‐lesion training dataset, and its diagnostic performance was evaluated against a 357‐lesion testing dataset that was independent of the training dataset. The observed sensitivity was 100% (14/14) for melanoma and 94% (105/112) for non‐melanoma skin cancer. The overall observed specificity was 36% (84/231). ESS has potential, as an adjunctive assessment tool, to assist physicians to differentiate between common benign and malignant skin lesions.     

The effect of a low-frequency sound source (acoustic thermometry of the ocean climate) on the diving behavior of juvenile northern elephant seals,Mirounga angustirostris

Changes in the diving behavior of individual free-ranging juvenile northern elephant seals, Mirounga angustirostris, exposed to the acoustic thermometry of the ocean climate (ATOC) sound source were examined using data loggers. Data loggers were attached to the animals and measured swim speed, maximum depth of dive, dive duration, surface interval, descent and ascent rate, and descent and ascent angle along with sound pressure level (SPL). The ATOC sound source was at a depth of 939 m and transmitted at 195 dB re: 1 microPa at 1 m centered at 75 Hz with a 37.5-Hz bandwidth. Sound pressure levels (SPL) measured at the seal during transmissions averaged 128 dB and ranged from 118 to 137 dB re: 1 microPa for the 60-90 Hz band, in comparison to ambient levels of 87-107 dB within this band. In no case did an animal end its dive or show any other obvious change in behavior upon exposure to the ATOC sound. Subtle changes in diving behavior were detected, however. During exposure, deviations in descent rate were greater than 1 s.d. of the control mean in 9 of 14 seals. Dive depth increased and descent velocity increased in three animals, ascent velocity decreased in two animals, ascent rate increased in one animal and decreased in another, and dive duration decreased in only one animal. There was a highly significant positive correlation between SPL and descent rate. The biological significance of these subtle changes is likely to be minimal. This is the first study to quantify behavioral responses of an animal underwater with simultaneous measurements of SPL of anthropogenic sounds recorded at the animal.