2,5-Dimethyl-3,6-bis[(2,6-diisopropylphenylimino)methyl]- and 2,6-Bis[(2,6-diisopropylphenylimino)methyl]pyrazine: Two New Chelating Ligands for Transition Metal Complexes

The reaction of tetramethylpyrazine with SeO2 yields 2,5-dimethylpyrazine-3,6-dicarboxaldehyde (1) from which the 2,5-dimethyl-3,6-bis[(2,6-diisopropylphenylimino)methyl]pyrazine (2) was synthesized by treatment with 2 equivalents of 2,6-diisopropylaniline. 2,6-Dimethylpyrazine reacts with benzaldehyde to give 2,6-distyrylpyrazine (3). Ozonolysis of 3, followed by treatment with Na2SO3 and 2,6-diisopropylaniline resulted in the formation of 2,6-bis[(2,6-diisopropylphenylimino) methyl]pyrazine (5) together with [(2,6-diisopropylphenylimino)methyl]benzene (6)

Novel properties and potential applications of functional ligand-modified polyoxotitanate cages.

Functional ligand-modified polyoxotitanate (L-POT) cages of the general type [TixOy(OR)z(L)m] (OR = alkoxide, L = functional ligand) can be regarded as molecular fragments of surface-sensitized solid-state TiO2, and are of value as models for studying the interfacial charge and energy transfer between the bound functional ligands and a bulk semiconductor surface. These L-POTs have also had a marked impact in many other research fields, such as single-source precursors for TiO2 deposition, inorganic-organic hybrid material construction, photocatalysis, photoluminescence, asymmetric catalysis and gas adsorption. Their atomically well-defined structures provide the basis for the understanding of structure/property relationships and ultimately for the rational design of new cages targeting specific uses. This highlight focuses on recent advances in L-POTs research, with emphasis on their novel properties and potential applications.EPSRCThis is the final version of the article. It first appeared from Royal Society of Chemistry via https://doi.org/10.1039/C6CC03788G

The influence of halides in polyoxotitanate cages; dipole moment, splitting and expansion of d-orbitals and electron-electron repulsion

Metal-doped polyoxotitanate (M-POT) cages have been shown to be efficient single-source precursors to metal-doped titania [TiO$_2$(M)] (state-of-the-art photocatalytic materials) as well as molecular models for the behaviour of dopant metal ions in bulk titania. Here we report the influence halide ions have on the optical and electronic properties of a series of halide-only, and cobalt halide-‘doped’ POT cages. In this combined experimental and computational study we show that halide ions can have several effects on the band gaps of halide-containing POT cages, influencing the dipole moment (hole–electron separation) and the structure of the valance band edge. Overall, the band gap behaviour stems from the effects of increasing orbital energy moving from F to I down Group 17, as well as crystal-field splitting of the d-orbitals, the potential effects of the Nephelauxetic influence of the halides and electron–electron repulsion.We thank the EPSRC (Doctoral Prize for P. D. M.), A*STAR Singapore (Scholarship for N. L.), the Studienstiftung des deutschen Volkes, Fonds of the Chemical Industry (S. H.) for funding. The authors would like to acknowledge the use of the EPSRC UK National Service for Computational Chemistry Software (NSCCS) at Imperial College London and contributions from its staff in carrying out this work

Real-time counting of single electron tunneling through a T-shaped double quantum dot system

Real-time detection of single electron tunneling through a T-shaped double quantum dot is simulated, based on a Monte Carlo scheme. The double dot is embedded in a dissipative environment and the presence of electrons on the double dot is detected with a nearby quantum point contact. We demonstrate directly the bunching behavior in electron transport, which leads eventually to a super-Poissonian noise. Particularly, in the context of full counting statistics, we investigate the essential difference between the dephasing mechanisms induced by the quantum point contact detection and the coupling to the external phonon bath. A number of intriguing noise features associated with various transport mechanisms are revealed.Comment: 8 pages, 5 figure

ALMA Survey of Orion Planck Galactic Cold Clumps (ALMASOP) : Evidence for a Molecular Jet Launched at an Unprecedented Early Phase of Protostellar Evolution

Protostellar outflows and jets play a vital role in star formation as they carry away excess angular momentum from the inner disk surface, allowing the material to be transferred toward the central protostar. Theoretically, low-velocity and poorly collimated outflows appear from the beginning of the collapse at the first hydrostatic core (FHSC) stage. With growing protostellar core mass, high-density jets are launched, entraininf an outflow from the infalling envelope. Until now, molecular jets have been observed at high velocity (greater than or similar to 100 km s(-1)) in early Class 0 protostars. We, for the first time, detect a dense molecular jet in SiO emission with low velocity (similar to 4.2 km s(-1), deprojected similar to 24 km s(-1)) from source G208.89-20.04Walma (hereafter G208Walma) using ALMA Band 6 observations. This object has some characteristics of FHSCs, such as a small outflow/jet velocity, extended 1.3 mm continuum emission, and N2D+ line emission. Additional characteristics, however, are typical of early protostars: collimated outflow and SiO jet. The full extent of the outflow corresponds to a dynamical timescale of similar to 930(-100)(+200) yr. The spectral energy distribution also suggests a very young source having an upper limit of T-bol similar to 31 K and L-bol similar to 0.8 L-circle dot. We conclude that G208Walma is likely in the transition phase from FHSC to protostar, and the molecular jet has been launched within a few hundred years of initial collapse. Therefore, G208Walma may be the earliest object discovered in the protostellar phase with a molecular jet.Peer reviewe

ALMA Survey of Orion Planck Galactic Cold Clumps (ALMASOP): How Do Dense Core Properties Affect the Multiplicity of Protostars?

During the transition phase from a prestellar to a protostellar cloud core, one or several protostars can form within a single gas core. The detailed physical processes of this transition, however, remain unclear. We present 1.3 mm dust continuum and molecular line observations with the Atacama Large Millimeter/submillimeter Array toward 43 protostellar cores in the Orion molecular cloud complex (λ Orionis, Orion B, and Orion A) with an angular resolution of ∼0.″35 (∼140 au). In total, we detect 13 binary/multiple systems. We derive an overall multiplicity frequency (MF) of 28% ± 4% and a companion star fraction (CSF) of 51% ± 6%, over a separation range of 300-8900 au. The median separation of companions is about 2100 au. The occurrence of stellar multiplicity may depend on the physical characteristics of the dense cores. Notably, those containing binary/multiple systems tend to show a higher gas density and Mach number than cores forming single stars. The integral-shaped filament of the Orion A giant molecular cloud (GMC), which has the highest gas density and hosts high-mass star formation in its central region (the Orion Nebula cluster), shows the highest MF and CSF among the Orion GMCs. In contrast, the λ Orionis GMC has a lower MF and CSF than the Orion B and Orion A GMCs, indicating that feedback from H ii regions may suppress the formation of multiple systems. We also find that the protostars comprising a binary/multiple system are usually at different evolutionary stages.T.L. acknowledges support from the National Natural Science Foundation of China (NSFC) through grants No. 12073061 and No. 12122307, the International Partnership Program of the Chinese Academy of Sciences (CAS) through grant No. 114231KYSB20200009, the Shanghai Pujiang Program (20PJ1415500), and science research grants from the China Manned Space Project with no. CMS-CSST-2021-B06. K.T. was supported by Japan Society for the Promotion of Science (JSPS) KAKENHI (grant No. 20H05645). D.J. and J.d.F. are supported by NRC Canada and by NSERC Discovery Grants. C.-F.L. acknowledge grants from the Ministry of Science and Technology of Taiwan (MoST 107-2119-M-001-040-MY3 and 110-2112-M-001-021-MY3) and Academia Sinica (Investigator Award AS-IA-108-M01). This research was carried out in part at the Jet Propulsion Laboratory, which is operated by the California Institute of Technology under a contract with the National Aeronautics and Space Administration (80NM0018D0004). J.-E.L. was supported by a National Research Foundation of Korea grant funded by the Korean government (MSIT) (grant No. 2021R1A2C1011718). J.H. acknowledges the support of NSFC projects 11873086 and U1631237. This work is sponsored (in part) by the CAS, through a grant to the CAS South America Center for Astronomy in Santiago, Chile. S.-L.Q. is supported by the NSFC with grant No. 12033005. S.Z. acknowledges the support of the China Postdoctoral Science Foundation through grant No. 2021M700248. L.B. gratefully acknowledges support by the ANID BASAL projects ACE210002 and FB210003. P.S. was supported by a Grant-in-Aid for Scientific Research (KAKENHI No. 18H01259) of JSPS. V.-M.P. acknowledges support by the grant PID2020-115892GB-I00 funded by MCIN/AEI/10.13039/501100011033

ALMA Survey of Orion Planck Galactic Cold Clumps (ALMASOP) : Detection of Extremely High-density Compact Structure of Prestellar Cores and Multiple Substructures Within

Prestellar cores are self-gravitating dense and cold structures within molecular clouds where future stars are born. They are expected, at the stage of transitioning to the protostellar phase, to harbor centrally concentrated dense (sub)structures that will seed the formation of a new star or the binary/multiple stellar systems. Characterizing this critical stage of evolution is key to our understanding of star formation. In this work, we report the detection of high-density (sub)structures on the thousand-astronomical-unit (au) scale in a sample of dense prestellar cores. Through our recent ALMA observations toward the Orion Planck Galactic Cold Clumps, we have found five extremely dense prestellar cores, which have centrally concentrated regions of similar to 2000 au in size, and several 10(7) cm(-3) in average density. Masses of these centrally dense regions are in the range of 0.30 to 6.89 M. For the first time, our higher resolution observations (0.8 '' similar to 320 au) further reveal that one of the cores shows clear signatures of fragmentation; such individual substructures/fragments have sizes of 800-1700 au, masses of 0.08 to 0.84 M, densities of 2 - 8 x 10(7) cm(-3), and separations of similar to 1200 au. The substructures are massive enough (greater than or similar to 0.1 M) to form young stellar objects and are likely examples of the earliest stage of stellar embryos that can lead to widely (similar to 1200 au) separated multiple systems.Peer reviewe

Prognostic DNA methylation markers for sporadic colorectal cancer: a systematic review

Background Biomarkers that can predict the prognosis of colorectal cancer (CRC) patients and that can stratify high-risk early stage patients from low-risk early stage patients are urgently needed for better management of CRC. During the last decades, a large variety of prognostic DNA methylation markers has been published in the literature. However, to date, none of these markers are used in clinical practice. Methods To obtain an overview of the number of published prognostic methylation markers for CRC, the number of markers that was validated independently, and the current level of evidence (LoE), we conducted a systematic review of PubMed, EMBASE, and MEDLINE. In addition, we scored studies based on the REMARK guidelines that were established in order to attain more transparency and complete reporting of prognostic biomarker studies. Eighty-three studies reporting on 123 methylation markers fulfilled the study entry criteria and were scored according to REMARK. Results Sixty-three studies investigated single methylation markers, whereas 20 studies reported combinations of methylation markers. We observed substantial variation regarding the reporting of sample sizes and patient characteristics, statistical analyses, and methodology. The median (range) REMARK score for the studies was 10.7 points (4.5 to 17.5) out of a maximum of 20 possible points. The median REMARK score was lower in studies, which reported a p value below 0.05 versus those, which did not (p = 0.005). A borderline statistically significant association was observed between the reported p value of the survival analysis and the size of the study population (p = 0.051). Only 23 out of 123 markers (17%) were investigated in two or more study series. For 12 markers, and two multimarker panels, consistent results were reported in two or more study series. For four markers, the current LoE is level II, for all other markers, the LoE is lower. Conclusion This systematic review reflects that adequate reporting according to REMARK and validation of prognostic methylation markers is absent in the majority of CRC methylation marker studies. However, this systematic review provides a comprehensive overview of published prognostic methylation markers for CRC and highlights the most promising markers that have been published in the last two decades