835 research outputs found
Quantifying the pathway and predicting spontaneous emulsification during material exchange in a two phase liquid system
Kinetic restriction of a thermodynamically favourable equilibrium is a common theme in materials processing. The interfacial instability in systems where rate of material exchange is far greater than the mass transfer through respective bulk phases is of specific interest when tracking the transient interfacial area, a parameter integral to short processing times for productivity streamlining in all manufacturing where interfacial reaction occurs. This is even more pertinent in high-temperature systems for energy and cost savings. Here the quantified physical pathway of interfacial area change due to material exchange in liquid metal-molten oxide systems is presented. In addition the predicted growth regime and emulsification behaviour in relation to interfacial tension as modelled using phase-field methodology is shown. The observed in-situ emulsification behaviour links quantitatively the geometry of perturbations as a validation method for the development of simulating the phenomena. Thus a method is presented to both predict and engineer the formation of micro emulsions to a desired specification
Aesthetics of immanence in the digital world
This project is an Exp-workshop for the DRS conference to further explore the aesthetics and the role of both creator and user of āVirtual Craftā in the digital world. Expworkshop was work for the conference was designated as half-experience and half-workshop, to make the audience perceive, imagine, and trigger acts of consciousness through experiential guidance. The objective is to stimulate experimentations, a new network, and a new thinking about practice in Art and Design. Today, the rise of the smartphone and social media filters have promoted temporary virtual-reality body adornments and the creation of virtual artefacts. We plan to initiate debates and panel discussions to explore the function and meaning of ācraftā in the digital world
Aesthetics of immanence in the digital world
This project is an Exp-workshop for the DRS conference to further explore the aesthetics and the role of both creator and user of āVirtual Craftā in the digital world. Expworkshop was work for the conference was designated as half-experience and half-workshop, to make the audience perceive, imagine, and trigger acts of consciousness through experiential guidance. The objective is to stimulate experimentations, a new network, and a new thinking about practice in Art and Design. Today, the rise of the smartphone and social media filters have promoted temporary virtual-reality body adornments and the creation of virtual artefacts. We plan to initiate debates and panel discussions to explore the function and meaning of ācraftā in the digital world
Reactions of <i>m</i>- and <i>p</i>-DivinylbenzeneāDiiron Hexacarbonyl with Aryllithium Reagents. Crystal Structures of [(CO)<sub>3</sub>Fe(<i>m</i>-C<sub>10</sub>H<sub>10</sub>)(CO)<sub>2</sub>FeC(OC<sub>2</sub>H<sub>5</sub>)C<sub>6</sub>H<sub>4</sub>CH<sub>3</sub>-<i>o</i>] and [(CO)<sub>3</sub>Fe(<i>p</i>-C<sub>10</sub>H<sub>10</sub>)(CO)<sub>2</sub>FeC(OC<sub>2</sub>H<sub>5</sub>)C<sub>6</sub>H<sub>4</sub>CF<sub>3</sub>-<i>p</i>]<sup>ā </sup>
The reactions of m-divinylbenzeneādiiron hexacarbonyl
(1) with aryllithium reagents, ArLi
(Ar = C6H5, o-, m-,
p-CH3C6H4,
p-CH3OC6H4,
p-CF3C6H4,
m-ClC6H4), in ether at
low
temperature gave acylmetalate intermediates followed by alkylation with
Et3OBF4 in aqueous
solution at 0 °C to afford the isomerized divinylbenzene-coordinated
alkoxycarbene complexes
[(CO)3Fe(m-C10H10)(CO)2FeC(OC2H5)Ar]
(3, Ar = C6H5; 4, Ar
= o-CH3C6H4;
5, Ar =
m-CH3C6H4; 6,
Ar = p-CH3C6H4;
7, Ar =
p-CH3OC6H4;
8, Ar =
p-CF3C6H4; 9,
Ar = m-ClC6H4)
with two types of structures. The
p-divinylbenzene-diiron hexacarbonyl (2) also
reacted with
the aryllithium reagents under the same conditions to give the
corresponding isomerized
alkoxycarbene complexes
[(CO)3Fe(p-C10H10)(CO)2FeC(OC2H5)Ar]
(10, Ar = C6H5; 11, Ar
=
o-CH3C6H4;
12, Ar =
m-CH3C6H4;
13, Ar =
p-CH3C6H4;
14, Ar =
p-CH3OC6H4;
15, Ar =
p-CF3C6H4;
16, Ar = m-ClC6H4).
The structures of complexes 4 and 15 have
been determined
by single-crystal X-ray diffraction studies
Fluoro-Substituted 2,6-Bis(imino)pyridyl Iron and Cobalt Complexes:ā High-Activity Ethylene Oligomerization Catalysts
Six five-coordinate difluoro-substituted 2,6-bis(imino)pyridyl iron and cobalt complexes,
[{2,6-(2,X-F2C6H3Nī»CCH3)2C5H3N}MCl2] (X = 6, M = Fe (1), Co (2); X = 5, M = Fe (3), Co
(4)); X = 4, M = Fe (5), Co (6)), were synthesized by reactions of the corresponding bis(imino)pyridyl ligands with FeCl2Ā·4H2O or CoCl2 in tetrahydrofuran (THF). However, a
reaction between 2,6-diacetylpyridinebis(2,6-difluoroanil) and FeCl2Ā·4H2O in CH3CN provided
the ion-pair complex [Fe{2,6-(2,6-F2C6H3Nī»CCH3)2C5H3N}2]2+[FeCl4]2- (7) instead of a five-coordinate complex. The molecular structures of complexes 3 and 6 were determined by
X-ray diffraction. The catalytic activities of complexes 1ā7 for ethylene oligomerization were
studied using modified methylaluminoxane (MMAO) as cocatalyst. At 60 °C and 10 atm of
ethylene pressure, the iron complexes 1, 3, and 5 show very high activities:ā 4.07 Ć 107,
9.33 Ć 107, and 11.1 Ć 107 g/((mol of cat.) h), respectively. The oligomers formed consist
mainly of dimer, trimer, and tetramer, with approximately 90% of the products being in the
range of C4āC8. The complexes 1, 3, and 5 also exhibit high selectivity for linear α-olefins:ā
>98% (complex 1) and >93% (complexes 3 and 5). The cobalt complexes 2, 4, and 6 and the
ion-pair iron complex 7 are inactive for ethylene oligomerization
Metabolic Regulation of Trisporic Acid on <em>Blakeslea trispora</em> Revealed by a GC-MS-Based Metabolomic Approach
<div><p>The zygomycete <em>Blakeslea trispora</em> is used commercially as natural source of Ć¢-carotene. Trisporic acid (TA) is secreted from the mycelium of <em>B. trispora</em> during mating between heterothallic strains and is considered as a mediator of the regulation of mating processes and an enhancer of carotene biosynthesis. Gas chromatography-mass spectrometry and multivariate analysis were employed to investigate TA-associated intracellular biochemical changes in <em>B. trispora</em>. By principal component analysis, the differential metabolites discriminating the control groups from the TA-treated groups were found, which were also confirmed by the subsequent hierarchical cluster analysis. The results indicate that TA is a global regulator and its main effects at the metabolic level are reflected on the content changes in several fatty acids, carbohydrates, and amino acids. The carbon metabolism and fatty acids synthesis are sensitive to TA addition. Glycerol, glutamine, and Ć£-aminobutyrate might play important roles in the regulation of TA. Complemented by two-dimensional electrophoresis, the results indicate that the actions of TA at the metabolic level involve multiple metabolic processes, such as glycolysis and the bypass of the classical tricarboxylic acid cycle. These results reveal that the metabolomics strategy is a powerful tool to gain insight into the mechanism of a microorganismās cellular response to signal inducers at the metabolic level.</p> </div
Novel Reactions of Cationic Carbyne Complexes of Manganese and Rhenium with (Ph<sub>3</sub>P)<sub>2</sub>NW(CO)<sub>5</sub>NCO, (Ph<sub>3</sub>P)<sub>2</sub>NW(CO)<sub>5</sub>SCN, and NaW(CO)<sub>5</sub>CN
The reaction of a cationic carbyne complex of manganese, [Ī·-C5H5(CO)2Mnā®CC6H5]BBr4
(1), with (Ph3P)2NW(CO)5NCO (3) in THF at low temperature gave the novel chelated carbene
complex [Ī·-C5H4(CO)2Mnī»C(NHCī»O)C6H5] (6). The analogous reaction of a cationic carbyne
complex of rhenium, [Ī·-C5H5(CO)2Reā®CC6H5]BBr4 (2), with 3 afforded the azametallacyclic
complex [Ī·-C5H5(CO)2ReC(C6H5)(Cī»O)NW(CO)5] (7). The reaction between 1 and (Ph3P)2NW(CO)5SCN (4) led to the loss of a sulfur atom to give the phenyl(pentacarbonylisocyanotungsten)carbeneāmanganese complex [Ī·-C5H5(CO)2Mnī»C(C6H5)CNW(CO)5] (8). However,
the reaction of 2 with 4 afforded the (isothiocyanato)phenylcarbeneārhenium complex
[Ī·-C5H5(CO)2Reī»C(C6H5)SCN] (9). Complexes 1 and 2 react with NaW(CO)5CN (5) to produce
novel phenyl(pentacarbonylcyanotungsten)carbeneāmanganese and ārhenium complexes,
[Ī·-C5H5(CO)2Mnī»C(C6H5)NCW(CO)5] (10) and [Ī·-C5H5(CO)2Reī»C(C6H5)NCW(CO)5] (11),
respectively. The structures of 6, 7, 8, and 11 have been established by X-ray diffraction
studies
<i>C</i><i><sub>s</sub></i>-Symmetric <i>a</i><i>nsa</i>-Lanthanocenes Designed for Stereospecific Polymerization of Methyl Methacrylate. Synthesis and Structural Characterization of Silylene-Bridged Fluorenyl Cyclopentadienyl Lanthanide Halides, Amides, and Hydrocarbyls
A series of new Cs-symmetric organolanthanocene chlorides, [R2Si(Flu)(RāCp)Ln(μ-Cl)]2
(Flu = C13H8, fluorenyl; Cp = C5H3) (R = Me, Rā = H, Ln = Y (1), Lu (2), Dy (3), Er (4);
R = Ph, Rā = tBu, Ln = Y (5), Dy (6)), has been synthesized by the reaction of anhydrous
lanthanide chloride with the dilithium salt of the ligand Me2Si(FluH)(CpH). Treatment of
the resulting chlorides with ME(TMS)2 (M = Li or K, E = N, CH) gave the amide and
hydrocarbyl derivatives Me2Si(Flu)(Cp)LnE(TMS)2 (E = N, Ln = Dy (7), Er (9); E = CH,
Ln = Dy (8), Er (10)). X-ray structures of chloride compounds reveal unusual CpāSiMe2āCp bridging dimeric coordination. All of the amide and hydrocarbyl complexes show normal
chelating structure and exhibit apparently intramolecular γ-agostic LnāMeāSi interaction.
These complexes are active for the polymerization of methyl methacrylate
Additional file 1: of Cost-effectiveness of nivolumab plus ipilimumab as first-line therapy in advanced renal-cell carcinoma
Calibration curve: progression-free and overall survival. Predicted data (dotted line) were plotted along with the observed data from CheckMate 214 trial (solid line). (PDF 38ĆĀ kb
Remarkable Reactions of Cationic Carbyne Complexes of Manganese and Rhenium with Na[Fe(CO)<sub>4</sub>CN] and Et<sub>4</sub>N[Mn(CO)<sub>4</sub>(CN)<sub>2</sub>]
The reaction of a cationic carbyne complex of manganese, [(Ī·-C5H5)(CO)2Mnā®CC6H5]BBr4
(1), with Na[Fe(CO)4CN] (3) in THF at low temperature gives the phenyl(tetracarbonylcyanoiron)carbeneāmanganese complex [(Ī·-C5H5)(CO)2Mnī»C(C6H5)NCFe(CO)4] (5). The analogous reaction of a cationic carbyne complex of rhenium, [(Ī·-C5H5)(CO)2Reā®CC6H5]BBr4 (2),
with 3 affords the corresponding carbeneārhenium complex [(Ī·-C5H5)(CO)2Reī»C(C6H5)NCFe(CO)4] (6). Complex 1 reacts with Et4N[Mn(CO)4(CN)2] (4) to yield the novel trinuclear metal
dicarbeneāmanganese complex [{(Ī·-C5H5)(CO)2Mnī»C(C6H5)NC}2Mn(CO)3CN] (7) and the
novel tetranuclear metal dicarbeneāmanganese complex [{(Ī·-C5H5)(CO)2Mnī»C(C6H5)NC}2Mn(CO)3CNMn(CO)2(Ī·-C5H5)] (8). Complex 2 reacts similarly with 4 to afford the corresponding trinuclear dicarbeneārhenium complex [{(Ī·-C5H5)(CO)2Reī»C(C6H5)NC}2Mn(CO)3CN] (9). The structures of complexes 5ā9 have been established by X-ray crystallography
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