Photochemistry and photopolymerisation of substituted 2-methylanthraquinones and novel 2-acryloxymethylanthraquinone in radiation curing

© 2018 Elsevier B.V. Anthraquinones have been the subject of numerous photochemical studies and their photopolymerization activities have been examined under various conditions to improve more efficient photochemical systems. This article involves further detailed investigations into the photophysical, photochemistry and photopolymerisation properties of 4 commercial derivatives of 2-substituted anthraquinone, namely, 2-Bromomethylanthraquinone (2BA), 2 Chloromethylanthraquinone (2CA), 2 Ethylanthraquinone (2EA), 2 Hydroxymethylanthraquinone (2HA) and one novel synthesized anthraquinone, 2 Acryloxymethylanthraquinone (2AA). 2AA is synthesized from 2HA. The results from both spectroscopic and analysis studies proved the 2AA to having the ester link. Absorption spectroscopy and solvent shift data are used to characterise their spectral activity. Luminescence studies involving fluorescence and phosphorescence analysis indicates efficient intersystem crossing to triplet state and n-π* nature of the lowest excited triplet state. The polymerisation activity was studied using methyl methacrylate (MMA) and analysis of the cure rate was measured using the gravimetric method. All the compounds are shown to be highly dependent on the structure. However, the rate of polymerisation (Rp) was reduced in the presence of amine. This is consistent with other results, proving the behaviour of derivatives with n-π* configuration. Hardness tests for all compounds took place using a different formula of acrylated resin/monomer systems. The excited state characteristics of the methyl derivatives have also been examined using micro and nanosecond flash photolysis. Triplet absorption spectra of all the anthraquinone derivatives show a significant red shift in the region of 340–370 nm with increasing solvent polarity due to stabilisation of the lowest triplet state by solvent reorganization. Hydrogen atom abstraction takes place in 2 propanol, forming a semiquinone radical. In the presence of the tertiary amine, triethylamine, all anthraquinone derivatives show the formation of intermediary species related to either the exciplex or the radical ion pair. Under aerobic conditions, the first decay rate for all anthraquinone derivatives increases and showed oxygen to be a good quencher with a bimolecular rate constant of around 2 × 10 8 mol. dm −3 s −1 . Relative to benzophenone, the molar absorption coefficient, ε, and quantum yield of intersystem crossing, Φisc were calculated, and it is summarised that the value for Φisc for all compound is less than 1.00 and controls to a major extent their photochemical activities

"Particle Informatics": Advancing Our Understanding of Particle Properties through Digital Design

We introduce a combination of existing and novel approaches to the assessment and prediction of particle properties intrinsic to the formulation and manufacture of pharmaceuticals. Naturally following on from established solid form informatics methods, we return to the drug lamotrigine, re-evaluating its context in the Cambridge Structural Database (CSD). We then apply predictive digital design tools built around the CSD-System suite of software, including Synthonic Engineering methods that focus on intermolecular interaction energies, to analyze and understand important particle properties and their effects on several key stages of pharmaceutical manufacturing. We present a new, robust workflow that brings these approaches together to build on the knowledge gained from each step and explain how this knowledge can be combined to provide resolutions at decision points encountered during formulation design and manufacturing processes

Curves on Heisenberg invariant quartic surfaces in projective 3-space

This paper is about the family of smooth quartic surfaces $X \subset \mathbb{P}^3$ that are invariant under the Heisenberg group $H_{2,2}$. For a very general such surface $X$, we show that the Picard number of $X$ is 16 and determine its Picard group. It turns out that the general Heisenberg invariant quartic contains 320 smooth conics and that in the very general case, this collection of conics generates the Picard group.Comment: Updated references, corrected typo

Chemiluminescence studies on comparison of antioxidant effectiveness on multiextruded polyethylenes

Several polyethylene resins; high density polyethylene (Ph-HDPE, Phillips metal oxide catalyst) and linear low density polyethytlenes (LLDPE, formed using Ziegler–Natta catalyst and metallocene catalyst technology, m-LLDPE) were used in order to acquire an insight in to the effect of different polymerization catalyst systems on the melt stabilization performance of single AO. Chemiluminescence (CL) and melt flow rate (MFR) were used to analyze the degradation as a function of the number of passes through a twin-screw extruder. A good correlation was obtained, and the additives resulting with the best melt flow stability in the polymer were the same as those that promote the best CL results

Marshalin, a microtubule minus-end binding protein, regulates cytoskeletal structure in the organ of Corti

Dramatic structural changes in microtubules (MT) and the assembly of complicated intercellular connections are seen during the development of the cellular matrix of the sense organ for hearing, the organ of Corti. This report examines the expression of marshalin, a minus-end binding protein, during this process of cochlear development. We discovered that marshalin is abundantly expressed in both sensory hair cells and supporting cells. In the adult, prominent marshalin expression is observed in the cuticular plates of hair cells and in the noncentrosomal MT organization centers (MTOC) of Deiters' and pillar cells. Based upon differences in marshalin expression patterns seen in the organ of Corti, we identified eight isoforms ranging from 863 to 1280 amino acids. mRNAs/proteins associated with marshalin's isoforms are detected at different times during development. These isoforms carry various protein-protein interacting domains, including coiled-coil (CC), calponin homology (CH), proline-rich (PR), and MT-binding domains, referred to as CKK. We, therefore, examined membranous organelles and structural changes in the cytoskeleton induced by expressing two of these marshalin isoforms in vitro. Long forms containing CC and PR domains induce thick, spindle-shaped bundles, whereas short isoforms lacking CC and PR induce more slender variants that develop into densely woven networks. Together, these data suggest that marshalin is closely associated with noncentrosomal MTOCs, and may be involved in MT bundle formation in supporting cells. As a scaffolding protein with multiple isoforms, marshalin is capable of modifying cytoskeletal networks, and consequently organelle positioning, through interactions with various protein partners present in different cells

Gene and protein expression of glucose transporter 1 and glucose transporter 3 in human laryngeal cancer—the relationship with regulatory hypoxia-inducible factor-1α expression, tumor invasiveness, and patient prognosis

Increased glucose uptake mediated by glucose transporters and reliance on glycolysis are common features of malignant cells. Hypoxia-inducible factor-1α supports the adaptation of hypoxic cells by inducing genes related to glucose metabolism. The contribution of glucose transporter (GLUT) and hypoxia-inducible factor-1α (HIF-1α) activity to tumor behavior and their prognostic value in head and neck cancers remains unclear. The aim of this study was to examine the predictive value of GLUT1, GLUT3, and HIF-1α messenger RNA (mRNA)/protein expression as markers of tumor aggressiveness and prognosis in laryngeal cancer. The level of hypoxia/metabolic marker genes was determined in 106 squamous cell laryngeal cancer (SCC) and 73 noncancerous matched mucosa (NCM) controls using quantitative realtime PCR. The related protein levels were analyzed by Western blot. Positive expression of SLC2A1, SLC2A3, and HIF-1α genes was noted in 83.9, 82.1, and 71.7 % of SCC specimens and in 34.4, 59.4, and 62.5 % of laryngeal cancer samples. Higher levels of mRNA/protein for GLUT1 and HIF-1α were noted in SCC compared to NCM (p<0.05). SLC2A1 was found to have a positive relationship with grade, tumor front grading (TFG) score, and depth and mode of invasion (p<0.05). SLC2A3 was related to grade and invasion type (p<0.05). There were also relationships of HIF-1α with pTNM, TFG scale, invasion depth and mode, tumor recurrences, and overall survival (p<0.05). In addition, more advanced tumors were found to be more likely to demonstrate positive expression of these proteins. In conclusion, the hypoxia/metabolic markers studied could be used as molecular markers of tumor invasiveness in laryngeal cancer.This work was supported, in part, by the statutory fund of the Department of Cytobiochemistry, University of Łódź, Poland (506/811), and by grant fromtheNational Science Council, Poland (N403 043 32/2326)

Quasar feedback survey: molecular gas affected by central outflows and by ∼10-kpc radio lobes reveal dual feedback effects in \u27radio quiet\u27 quasars

\ua9 The Author(s) 2023. Published by Oxford University Press on behalf of Royal Astronomical Society. We present a study of molecular gas, traced via CO (3–2) from Atacama Large Millimeter/submillimeter Array data, of four z &lt; 0.2, ‘radio quiet’, type 2 quasars (Lbol ∼ 1045.3–1046.2 erg s−1; L1.4 GHz ∼ 1023.7–1024.3 WHz−1). Targets were selected to have extended radio lobes (≥ 10 kpc), and compact, moderate-power jets (1–10 kpc; Pjet ∼ 1043.2–1043.7 erg s−1). All targets show evidence of central molecular outflows, or injected turbulence, within the gas discs (traced via high-velocity wing components in CO emission-line profiles). The inferred velocities (Vout = 250–440 km s−1) and spatial scales (0.6–1.6 kpc), are consistent with those of other samples of luminous low-redshift active galactic nuclei. In two targets, we observe extended molecular gas structures beyond the central discs, containing 9–53 per cent of the total molecular gas mass. These structures tend to be elongated, extending from the core, and wrap-around (or along) the radio lobes. Their properties are similar to the molecular gas filaments observed around radio lobes of, mostly ‘radio loud’, brightest cluster galaxies. They have the following: projected distances of 5–13 kpc; bulk velocities of 100–340 km s−1; velocity dispersion of 30–130 km s−1; inferred mass outflow rates of 4–20 M⊙ yr−1; and estimated kinetic powers of 1040.3–1041.7 erg s−1. Our observations are consistent with simulations that suggest moderate-power jets can have a direct (but modest) impact on molecular gas on small scales, through direct jet–cloud interactions. Then, on larger scales, jet-cocoons can push gas aside. Both processes could contribute to the long-term regulation of star formation

The quasar feedback survey: discovering hidden Radio-AGN and their connection to the host galaxy ionized gas

We present the first results from the Quasar Feedback Survey, a sample of 42 z 1042.1 ergs s−1) with moderate radio luminosities (i.e. L1.4GHz > 1023.4 W Hz−1; median L1.4GHz = 5.9 × 1023 W Hz−1). Using high spatial resolution (∼0.3–1 arcsec), 1.5–6 GHz radio images from the Very Large Array, we find that 67 per cent of the sample have spatially extended radio features on ∼1–60 kpc scales. The radio sizes and morphologies suggest that these may be lower radio luminosity versions of compact, radio-loud AGNs. By combining the radio-to-infrared excess parameter, spectral index, radio morphology, and brightness temperature, we find radio emission in at least 57 per cent of the sample that is associated with AGN-related processes (e.g. jets, quasar-driven winds, or coronal emission). This is despite only 9.5–21 per cent being classified as radio-loud using traditional criteria. The origin of the radio emission in the remainder of the sample is unclear. We find that both the established anticorrelation between radio size and the width of the [O III] line, and the known trend for the most [O III] luminous AGNs to be associated with spatially extended radio emission, also hold for our sample of moderate radio luminosity quasars. These observations add to the growing evidence of a connection between the radio emission and ionized gas in quasar host galaxies. This work lays the foundation for deeper investigations into the drivers and impact of feedback in this unique sample

Pretreatment Serum Concentrations of 25-Hydroxyvitamin D and Breast Cancer Prognostic Characteristics: A Case-Control and a Case-Series Study

Results from epidemiologic studies on the relationship between vitamin D and breast cancer risk are inconclusive. It is possible that vitamin D may be effective in reducing risk only of specific subtypes due to disease heterogeneity.In case-control and case-series analyses, we examined serum concentrations of 25-hydroxyvitamin D (25OHD) in relation to breast cancer prognostic characteristics, including histologic grade, estrogen receptor (ER), and molecular subtypes defined by ER, progesterone receptor (PR) and HER2, among 579 women with incident breast cancer and 574 controls matched on age and time of blood draw enrolled in the Roswell Park Cancer Institute from 2003 to 2008. We found that breast cancer cases had significantly lower 25OHD concentrations than controls (adjusted mean, 22.8 versus 26.2 ng/mL, p<0.001). Among premenopausal women, 25OHD concentrations were lower in those with high- versus low-grade tumors, and ER negative versus ER positive tumors (p≤0.03). Levels were lowest among women with triple-negative cancer (17.5 ng/mL), significantly different from those with luminal A cancer (24.5 ng/mL, p = 0.002). In case-control analyses, premenopausal women with 25OHD concentrations above the median had significantly lower odds of having triple-negative cancer (OR = 0.21, 95% CI = 0.08-0.53) than those with levels below the median; and every 10 ng/mL increase in serum 25OHD concentrations was associated with a 64% lower odds of having triple-negative cancer (OR = 0.36, 95% CI = 0.22-0.56). The differential associations by tumor subtypes among premenopausal women were confirmed in case-series analyses.In our analyses, higher serum levels of 25OHD were associated with reduced risk of breast cancer, with associations strongest for high grade, ER negative or triple negative cancers in premenopausal women. With further confirmation in large prospective studies, these findings could warrant vitamin D supplementation for reducing breast cancer risk, particularly those with poor prognostic characteristics among premenopausal women

A striking relationship between dust extinction and radio detection in DESI QSOs: evidence for a dusty blow-out phase in red QSOs

We present the first eight months of data from our secondary target programme within the ongoing Dark Energy Spectroscopic Instrument (DESI) survey. Our programme uses a mid-infrared and optical colour selection to preferentially target dust-reddened quasi-stellar objects (QSOs) that would have otherwise been missed by the nominal DESI QSO selection. So far, we have obtained optical spectra for 3038 candidates, of which ∼70 per cent of the high-quality objects (those with robust redshifts) are visually confirmed to be Type 1 QSOs, consistent with the expected fraction from the main DESI QSO survey. By fitting a dust-reddened blue QSO composite to the QSO spectra, we find they are well-fitted by a normal QSO with up to AV ∼4 mag of line-of-sight dust extinction. Utilizing radio data from the LOFAR Two-metre Sky Survey (LoTSS) DR2, we identify a striking positive relationship between the amount of line-of-sight dust extinction towards a QSO and the radio detection fraction, that is not driven by radio-loud systems, redshift and/or luminosity effects. This demonstrates an intrinsic connection between dust reddening and the production of radio emission in QSOs, whereby the radio emission is most likely due to low-powered jets or winds/outflows causing shocks in a dusty environment. On the basis of this evidence, we suggest that red QSOs may represent a transitional 'blow-out' phase in the evolution of QSOs, where winds and outflows evacuate the dust and gas to reveal an unobscured blue QSO