pinecone/core-2020-05-10-deduplication huggingface dataset:
Electron transfer and hydride transfer pathways in the Stoltz-Grubbs reducing system (KOtBu-Et3SiH)

Recent studies by Stoltz, Grubbs et al. have shown that triethylsilane and potassium tert-butoxide react to form a highly attractive and versatile system that shows (reversible) silylation of arenes and heteroarenes as well as reductive cleavage of C-O bonds in aryl ethers and C-S bonds in aryl thioethers. Their extensive mechanistic studies indicate a complex network of reactions with a number of possible intermediates and mechanisms, but their reactions likely feature silyl radicals undergoing addition reactions and SH2 reactions. This paper focuses on the same system, but through computational and experimental studies, reports complementary facets of its chemistry based on (a) single electron transfer (SET), and (b) hydride delivery reactions to arenes
Gold(III) Alkyne Complexes: Bonding and Reaction Pathways

The synthesis and characterization of hitherto hypothetical AuIII π-alkyne complexes is reported. Bonding and stability depend strongly on the trans effect and steric factors. Bonding characteristics shed light on the reasons for the very different stabilities between the classical alkyne complexes of PtII and their drastically more reactive AuIII congeners. Lack of back-bonding facilitates alkyne slippage, which is energetically less costly for gold than for platinum and explains the propensity of gold to facilitate C−C bond formation. Cycloaddition followed by aryl migration and reductive deprotonation is presented as a new reaction sequence in gold chemistry
Control of luminescence by tuning of crystal symmetry and local structure in Mn4+-activated narrow band fluoride phosphors

This work was supported by the Ministry of Science and Technology of Taiwan (Contract Nos. MOST 104-2113-M-002-012-MY3 and MOST 104-2923-M-002-007-MY3) and National Center for Research and Development Poland Grant (No. PL-TW2/8/2015). Y Jin thanks the National Nature Science Foundation of China (No. 11104366), Chongqing Research Program of Basic Research and Frontier Technology (No. cstc2014jcyjA50018), and the Scientific and Technological Research Program of Chongqing Municipal Education Commission (No. KJ1500913). T. Lesniewski would like to acknowledge the support of University of Gdansk Research Grant 538-5200-B468-17.Mn4+-doped fluoride phosphors have been widely used in wide-gamut backlighting devices because of their extremely narrow emission band. In this study, solid solutions of Na2(SixGe1-x)F6:Mn4+ and Na2(GeyTigros)F6:Mn4+ have been successfully synthesized to elucidate the behavior of zero-phonon line (ZPL) in different structures because of the sensitivity of ZPL intensity to the local coordinated environment. The structures of the products are examined by X-ray diffraction and Rietveld refinement. The ratio between ZPL and the highest emission intensity υ6 phonon sideband exhibits a strong relationship with luminescent decay rate. First-principles calculations are conducted to model the variation in the structural and electronic properties of the prepared solid solutions as a function of the composition. The calculated results are consistent with the experimentally determined structural parameters. To compensate for the limitations of Rietveld refinement, electron paramagnetic resonance and high-resolution steady-state emission spectra are used to prove the diverse local environment for Mn4+ in the structure. Finally, the spectral luminous efficacy of radiation (LER) is used to reveal the important role of ZPL in practical application.PostprintPeer reviewe
Exploring Tetrathiafulvalene-Carbon Nanodots Conjugates in\ud
Charge Transfer Reactions

Carbon nanodots (CNDs) have been synthesized using low-cost and biocompatible starting materials such as citric acid/urea, under microwave irradiation and constant pressure conditions. The obtained pressure synthesized CNDs (pCND) were covalently modified with photo- and electro-active π-extended tetrathiafulvalene (exTTF) by means of a two-step esterification reaction affording pCND-exTTF. The electronic interactions between the CNDs and exTTF were investigated in the ground and excited states. Ultrafast pump-probe experiments assisted in corroborating that charge separation governs the deactivation of photoexcited pCND-exTTF. These size-regular structures, as revealed by AFM, are stable electron donor-acceptor conjugates of interest for a better understanding of basic processes such as artificial photosynthesis, catalysis and photovoltaics, involving readily available fluorescent nanodots
Encapsulation of Crabtree's catalyst in sulfonated MIL-101(Cr): enhancement of stability and selectivity between competing reaction pathways by the MOF chemical microenvironment

Crabtree's catalyst was encapsulated inside the pores of the sulfonated MIL-101(Cr) metal-organic framework (MOF) by cation exchange. This hybrid catalyst is active for the heterogeneous hydrogenation of non-functionalized alkenes either in solution or in the gas phase. Moreover, encapsulation inside a well-defined hydrophilic microenvironment enhances catalyst stability and selectivity to hydrogenation over isomerization for substrates bearing ligating functionalities. Accordingly, the encapsulated catalyst significantly outperforms its homogeneous counterpart in the hydrogenation of olefinic alcohols in terms of overall conversion and selectivity, with the chemical microenvironment of the MOF host favouring one out of two competing reaction pathways
Designed long lived emission from CdSe quantum dots by reversible electronic energy transfer with a surface bound chromophore

The size-tunable emission of luminescent quantum dots (QDs) makes them highly interesting for applications that range from bioimaging to optoelectronics. For the same applications, engineering their luminescence lifetime – in particular, making it longer – would be as important; however, no rational methodology to reach this goal is available to date. Here we describe a strategy to prolong the emission lifetime of QDs by electronic energy shuttling to the triplet excited state of a surface-bound molecular chromophore. To implement this idea we made CdSe QDs of different sizes, and we self-assembled them with a pyrene derivative. We observed that the conjugates exhibit delayed luminescence, with emission decays that are prolonged by more than 3 orders of magnitude compared to the parent CdSe QDs (lifetimes up to 330 s). The mechanism invokes unprecedented reversible quantum dot-to-organic chromophore electronic energy transfer
RuBisCO-Inspired CO2 Activation and Transformation by an Iridium(I) Complex

The synthesis of a new iridium(I) complex containing an enamido phosphine anion (dbuP(-)) and its unique reactivity with CO2 is reported. The complex binds two equivalents of CO2 and initiates a highly selective reaction cascade. The reaction leads to the reversible cleavage of CO2 and the enamido ligand as well. Computational analysis points to the existence of a relatively stable Ir-CO2 complex as a reaction intermediate prior to CO2 cleavage, which was confirmed experimentally. The observed transformation resembles several aspects of enzymatic CO2 fixation by RuBisCO
Higher acenes by on‐surfacedehydrogenation : from heptacene to undecacene

A unified approach to the synthesis of the series of higher acenes up to previously unreported undecacene has been developed through the on‐surface dehydrogenation of partially saturated precursors. These molecules could be converted into the parent acenes by both atomic manipulation with the tip of a scanning tunneling and atomic force microscope (STM/AFM) as well as by on‐surface annealing. The structure of the generated acenes has been visualized by high‐resolution non‐contact AFM imaging and the evolution of the transport gap with the increase of the number of fused benzene rings has been determined on the basis of scanning tunneling spectroscopy (STS) measurements
Undoped Layered Perovskite Oxynitride Li₂LaTa₂O₆N for Photocatalytic CO₂Reduction with Visible Light

Oxynitrides are promising visible‐light‐responsive photocatalysts, but their structures are almost confined with three‐dimensional (3D) structures such as perovskites. A phase‐pure Li₂LaTa₂O₆N with a layered perovskite structure was successfully prepared by thermal ammonolysis of a lithium‐rich oxide precursor. Li₂LaTa₂O₆N exhibited high crystallinity and visible‐light absorption up to 500 nm. As opposed to well‐known 3D oxynitride perovskites, Li₂LaTa₂O₆N supported by a binuclear Ruᴵᴵ complex was capable of stably and selectively converting CO₂ into formate under visible light (λ>400 nm). Transient absorption spectroscopy indicated that, as compared to 3D oxynitrides, Li₂LaTa₂O₆N possesses a lower density of mid‐gap states that work as recombination centers of photogenerated electron/hole pairs, but a higher density of reactive electrons, which is responsible for the higher photocatalytic performance of this layered oxynitride
Stabilising peptoid helices using non-chiral fluoro-alkyl monomers.

Stability towards protease degradation combined with modular synthesis has made peptoids of considerable interest in the fields of chemical biology, medicine, and biomaterials. Given their tertiary amide backbone, peptoids lack the capacity to hydrogen‐bond, and as such, controlling secondary structure can be challenging. The incorporation of bulky, charged, or chiral aromatic monomers can be used to control conformation but such building blocks limit applications in many areas. Through NMR and X‐ray analysis we demonstrate that non‐chiral neutral fluoroalkyl monomers can be used to influence the Kcis/trans equilibria of peptoid amide bonds in model systems. The cis‐isomer preference displayed is highly unprecedented given that neither chirality nor charge is used to control the peptoid amide conformation. The application of our fluoroalkyl monomers in the design of a series of linear peptoid oligomers that exhibit stable helical structures is also reported
Superflexible Multifunctional Polyvinylpolydimethylsiloxane-Based Aerogels as Efficient Absorbents, Thermal Superinsulators, and Strain Sensors

超柔軟性エアロゲルの開発 --有機ポリマーと無機ポリマーの精緻な架橋構造がもたらす可能性--. 京都大学プレスリリース. 2018-07-05.Aerogels are attractive porous materials but usually show poor mechanical properties and limited functionality, which significantly restrict their practical applications. Preparation of highly bendable and machinable aerogels with multifunctionality still remains a difficult challenge. Here we report unprecedented superflexible aerogels based on polyvinylpolydimethylsiloxane (PVPDMS) network, PVPDMS/polyvinylpolymethylsiloxane (PVPMS) copolymer network, and PVPDMS/PVPMS/graphene nanocomposite via a facile radical polymerization/hydrolytic polycondensation strategy followed by low-cost ambient pressure drying or freeze drying. The resulting aerogels possess a doubly cross-linked organic-inorganic network structure consisting of flexible polydimethylsiloxanes and hydrocarbon chains with tunable crosslinking density, and exhibit tunable pore size and bulk density, high hydrophobicity, excellent machinability, and superflexibility against both compression and bending. More importantly, they show multifunctionality combining selective absorption, efficient separation of oil and water, thermal superinsulation, and strain sensing. This study is expected to provide new concepts to synthesize multifunctional materials with a wide range of potential applications in absorbents, superinsulators, sensors, wearable electronics, etc
'I will not leave my baby behind': A Cook Island Maori family's experience of New Zealand Maori traditional healing

Traditional healers in many parts of the world have used family focused understandings and interventions well before the emergence of western family therapy theory and practice. This paper gives a detailed account of New Zealand.

Māori traditional healing work with a Cook Island Māori family in which the eldest daughter was in considerable distress as were her family, who believed that she had become maki tūpāpaku (possessed). This account is told from the perspectives of the child psychiatrist, the traditional healer and the mother of the family. While the intervention bears a superficial resemblance to western family therapy approaches, the theoretical foundation reflects the traditional healer’s New Zealand Māori world views in which spiritual understandings are paramount, and concepts of mana, tapu and mauri guide him in the family healing process. The single session described here can be viewed as an indigenous family therapy intervention involving six generations of family members, both living and deceased, in the one room. 

Conclusions: Indigenous communities have called for traditional healers to be employed alongside child mental health workers and family therapists who work with their communities. Close and sincere collaboration between an indigenous traditional healer and a health professional can offer a family in distress healing possibilities that may not be available to them in conventional child mental health or other family therapy settings
"So I Feel Like I’m Getting It and Then Sometimes I Think OK, No I’m Not": couple and family therapists learning an evidence-based practice

This research concerns itself with the experiences of couple and family therapists (CFT) learning about and using an evidence-based practice.  The engagement with evidence-based practice is growing across many aspects of the mental health and health care systems. The evidence-based practice model is now being applied in a broad range of health and human service systems, including mental and behavioral health care, social work, education, and criminal justice (Hunsley, 2007).  The dialogue about the role of evidence-based approaches in the practice of couple and family therapy and research literature about same is also evolving (Sexton et al., 2011; Sprenkle 2012).  Interestingly, while the research delves into what are the best approaches with different populations and presenting issues, little research has explored the experience of CFTs themselves, particularly while learning and adopting an evidence-based practice.  \ud
Using a phenomenological approach called interpretive phenomenological analysis (Smith, Flowers, & Larking, 2009), this research explored the experiences of CFTs learning and using an evidence-based practice.  The paper reports key issues, challenges, and areas for CFTs, educators, and supervisors. As researchers, educators, administrators, policy makers, and CFTs struggle with what works best with which populations and when, how best to allocate resources, how best to educate and support CFTs, and the complexity of doing research in real-life settings, this research has the potential to contribute to those varied dialogues
Lanthanide borohydrido complexes for MMA polymerization: syndio- vs iso- stereocontrol

This paper presents an extensive study of the polymerization of MMA with borohydrido lanthanide complexes for the first time. Catalytic systems are made from a lanthanide derivative bearing zero one, or two bulky ligands: substituted cyclopentadienyl (Cp*' = C5Me4nPr, Cp4i = C5HiPr4, CpPh3 = H2C5Ph3-1,2,4), and/or diketiminate ([(p-tol)NN] = [(p-CH3C6H4)N(CH3)C]2CH), in the presence of variable quantities of alkylating agent. With BuLi in apolar medium, highly isotactic polymer (up to 95.6%) is formed. In THF, syndiotactic-rich PMMA is obtained whatever the nature of the cocatalyst (BuLi or MgnBu2). The presence of an electron-withdrawing ligand such as CpPh3 allows high syndioregularity, up to 81.8% at 0 ◦C, together with the highest conversion. There is quite good concordance between calculated and experimental molecular data in THF. Divalent Cp*'2SmII(THF) and (CpPh3)2SmII(THF) are active as single-component initiators; the former affords PMMA 88% syndiotactic at 0 ◦C
Catalysis and mechanistic studies of ruthenium and osmium on synthesis of anthranilic acids

Ruthenium, osmium and ruthenium + osmium catalyzed synthetic methodology was developed for the synthesis of anthranilic acids from indoles in good to excellent yields using bromamine-B in alkaline acetonitrile-water (1 : 1) at 313 K. Detailed catalysis studies of ruthenium, osmium and the mixture of both were carried out for the synthetic reactions. The positive synergistic catalytic activity of Ru(III) + Os(VIII) was observed to a large extent with the activity greater than the sum of their separate catalytic activities. Detailed kinetic and mechanistic investigations for each catalyzed reactions were carried out. The kinetic pattern and mechanistic picture of each catalyzed reaction were found to be different for each catalyst and to obey the underlying rate laws
Green conditions for the Suzuki reaction using microwave irradiation and a new HNT- supported ionic liquid-like phase (HNT-SILLP) catalyst

A new catalytic system based on modified halloysite nanotubes was employed in the Suzuki reaction under microwave irradi- ation. A set of solvents, times and bases was screened and the best experimental conditions were obtained when the reactions were carried out for 10 min in water–ethanol at 120 °C in presence of K2CO3 as base. Good recyclability was observed. The new catalytic system was employed using either 1 mol% or 0.1 mol%. The palladium catalyst displayed good activity, allowing the synthesis of several biphenyl compounds in high yield working with only 0.1 mol% palladium loading. The application of mi- crowave irradiation decreased the reaction time and also improved conversion with respect to traditional heating
Organotin(IV) complexes derived from proteinogenic amino acid: synthesis, structure and evaluation of larvicidal efficacy on Anopheles stephensi mosquito larvae

Five new organotin(IV) complexes of composition [Bz2SnL1]n (), [Bz3SnL1H⋅H2O] (), [Me2SnL2⋅H2O] (), [Me2SnL3] () and [Bz3SnL3H]n () (where L1 = (2S)-2-{[(E)-(4-hydroxypentan-2-ylidene)]amino}-4-methylpentanoate, L2 = (rac)-2-{[(E)-1-(2-hydroxyphenyl)methylidene]amino}-4-methylpentanoate and L3 = (2S)- or (rac)-2-{[(E)-1-(2-hydroxyphenyl)ethylidene]amino}-4-methylpentanoate) were synthesized and characterized using 1H NMR, 13C NMR, 119Sn NMR and infrared spectroscopic techniques. The crystal structure of reveals a distorted trigonal-bipyramidal geometry around the tin atom where the oxygen atoms of the carboxylate ligand and a water ligand occupy the axial positions, while the three benzyl ligands are located at the equatorial positions. On the other hand, the analogous derivative of enantiopure L3H () consists of polymeric chains, in which the ligand-bridged tin atoms adopt the same trans-Bz3SnO2 trigonal-bipyramidal configuration and are now coordinated to a phenolic oxygen atom instead of H2O. In , the OH hydrogen of the ketoimine substituent has moved to the nearby nitrogen atom while in the salicylidene derivative , the OH is located almost midway between the phenolic oxygen atom and the nitrogen atom of the C[DOUBLE BOND]N group. For the dibenzyltin derivative , a polymeric chain structure is observed as a result of a long intermolecular Sn⋅⋅⋅O bond involving the exocyclic carbonyl oxygen atom from the tridentate ligand of a neighbouring tin-complex unit. The tin atom in this complex has distorted octahedral coordination geometry. In contrast, the racemic dimethyltin(IV) complexes and display discrete monomeric structures with a distorted octahedral- and trigonal-bipyramidal geometry, respectively. The structures show that the coordination mode of the Schiff base ligand depends primarily on the number of bulky benzyl ligands (R) at the tin atom, as indeed found in the structures of related complexes where R = phenyl. With three bulky R groups, the tridentate chelating O,N,O coordination mode is preferred, whereas with fewer or less bulky R ligands, only the carboxylate and hydroxy groups are involved, which leads to polymers. Larvicidal efficacies of two of the new tribenzyltin(IV) complexes ( and ) were assessed on the second larval instar of Anopheles stephensi mosquito larvae and compared with two triphenyltin(IV) analogues, [Ph3SnL1H]n and [Ph3SnL3H]n. The results demonstrate that the compounds containing Sn–Ph ligands are more effective than those with Sn–Bz ligands. Copyright © 2016 John Wiley & Sons, Ltd
Atmospheric Pressure Chemical Vapour Deposition of Fluorine-doped Tin(IV) Oxide from Fluoroalkyltin Precursors

Perfluoroalkytin compounds R(4-n)Sn(Rf)n (R = Me, Et, Bu, Rf = C4F9, n = 1; R = Bu, Rf =\ud
C4F9, n = 2, 3; R = Bu, Rf = C6F13, n = 1) have been synthesised, characterised by 1H, 13C,\ud
19F and 119Sn NMR and evaluated a precursors for the atmospheric pressure CVD\ud
(APCVD) of F-doped SnO2 thin films. All precursors were sufficiently volatile at in the\ud
range 84 – 136oC and glass substrate temperatures of ca. 550oC to yield high quality\ud
films with ca. 0.79 – 2.02% fluorine incorporation, save for Bu3SnC6F13 which\ud
incorporated < 0.05% fluorine. Films were characterised by XRD, SEM, thickness, haze,\ud
emissivity, sheet resistance. The fastest growth rates and highest quality films were\ud
obtained from Et3SnC4F9. An electron diffraction study of Me3SnC4F9 revealed four\ud
conformations of which only the two of lowest abundance showed close F…Sn\ud
contacts which could plausibly be associated with halogen transfer to tin and in each\ud
case it was fluorine attached to either the γ- or δ-carbon atoms of the Rf chain
Atmospheric Pressure Deposition of Fluorinedoped SnO2 Thin Films from Organotin Fluorocarboxylate Precursors.

Nine organotin fluorocarboxylates RnSnO2CRf (n = 3, R = Bu, Rf = CF3, C2F5, C3F7, C7F15; R = Et,\ud
Rf = CF3, C2F5; R = Me, Rf = C2F5; n = 2, R =Me, Rf = CF3) have been synthesised; key examples\ud
have been used to deposit F-doped SnO2 thin films by atmospheric pressure CVD.\ud
Et3SnO2CC2F5, in particular, gives high quality films with fast deposition rates despite adopting\ud
a polymeric, carboxylate-bridged structure in the solid state, as determined by x-ray\ud
crystallography. Gas phase electron diffraction on the model compound Me3SnO2CC2F5 shows\ud
that accessible conformations do not allow contact between tin and fluorine, and that direct\ud
transfer is therefore unlikely to be part of the mechanism for fluorine incorporation in SnO2\ud
films. The structure of Me2Sn(O2CCF3)2(H2O) has also been determined and adopts a trans-\ud
Me2SnO3 coordination sphere about tin in which each carboxylate group is monodentat
Overall gas-liquid mass transfer from Taylor bubbles flowing upwards in a circular capillary

Overall liquid side volumetric mass transfer coefficient kLa was determined experimentally for co-current Taylor flow moving upwards in a glass tube of internal diameter 3mm. Experiments were performed for physical absorption of oxygen in 20% aqueous solution of ethanol. Shadowgraph technique was deployed for precise measurements of bubble lengths and velocities. Experimental values of volumetric mass transfer coefficient kLa were evaluated by use of oxygen sensor and contributions of two possible mass transfer mechanisms: bubble to liquid slug and bubble to liquid film, were discussed. Effects of various hydrodynamic parameters like superficial velocity, length of bubble and slug, etc. on kLa have also been presented. A correlation has been proposed for the estimation of kLa for a wide range of bubble to slug lengths ratio and superficial velocities of gas and liquids