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A new method is proposed to measure the linear coefficient of thermal expansion (CTE) of solid metals and ceramics of micron-sized dimensions. This approach uses a focused ion beam (FIB) to extract and transfer a slab of the sample, typically (15-20) ×10 × (3-5) µm onto a Micro-Electro-Mechanical Systems (MEMS) in situ heating holder inside a scanning electron microscope (SEM). CTE is thereafter calculated by image correlating the change of length (ΔL) between the fiducial marks on the slab as a function of temperature, taking advantage of the temperature calibration of the MEMS heating holder and nanometre resolution of the scanning electron microscope. The CTE results are validated to be consistent with standard copper and silicon. We further demonstrate the method on a graphene platelet reinforced copper composite and a graphite filler phase isolated from a bulk sample, these represent materials that cannot be practically synthesised or isolated at the macro-scale. Errors associated with the measurement are discussed.
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Catalytic reduction of a representative set of imines, both aldimines and ketimines, to amines has been studied using transfer hydrogenation from 1,4-dicyclohexadiene. Unusually, this has been achieved using s-block pre-catalysts, namely 1-metallo-2-tert-butyl-1,2-dihydropyridines, 2-tBuC5 H5 NM, M(tBuDHP), where M=Li-Cs. Reactions have been monitored in C6 D6 and tetrahydrofuran-d8 (THF-d8 ). A definite trend is observed in catalyst efficiency with the heavier alkali metal tBuDHPs outperforming the lighter congeners. In general, Cs(tBuDHP) is the optimal pre-catalyst with, in the best cases, reactions producing quantitative yields of amines in minutes at room temperature using 5â mol % catalyst. Supporting the experimental study, Density Functional Theory (DFT) calculations have also been carried out which reveal that Cs has a pathway with a significantly lower rate determining step than the Li congener. In the postulated initiation pathways DHP can act as either a base or as a surrogate hydride.
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We explore the suitability of operando attenuated total reflection infrared (ATR-IR) spectroscopy methodologies for the study of organoaluminate electrolytes for Mg battery applications. The "all-phenyl complex" in tetrahydrofuran (THF), with the molecular structure [Mg2Cl3·6THF]+[AlPh4]-, is used as an exemplar electrolyte to compare two different spectroelectrochemical cell configurations. In one case, a Pt gauze is used as a working electrode, while in the second case, a thin (â¼10 nm) Pt film working electrode is deposited directly on the surface of the ATR crystal. Spectroscopic measurements indicate substantial differences in the ATR-IR response for the two configurations, reflecting the different spatial arrangements of the working electrode with respect to the ATR sampling volume. The relative merits and potential pitfalls associated with the two approaches are discussed.
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Arylmethyl anions allow alkali-metals to bind in a σ-fashion to the lateral carbanionic centre or a π-fashion to the aryl ring or in between these extremities, with the trend towards π bonding increasing on descending group 1. Here we review known alkali metal structures of diphenylmethane, fluorene, 2-benzylpyridine and 4-benzylpyridine. Next, we synthesise Li, Na, K monomers of these diarylmethyls using polydentate donors PMDETA or Me6 TREN to remove competing oligomerizing interactions, studying the effect that two aromatic rings has on negative charge (de)localisation via NMR, X-ray crystallographic and DFT studies. Diphenylmethyl and fluorenyl anions maintain C(H)-M interactions regardless of alkali-metal, although the adjacent arene carbons engage in interactions with larger alkali-metals. Introducing a nitrogen atom into the ring (at the 2- or 4-position) encourages relocalisation of negative charge away from the deprotonated carbon and onto nitrogen. Phenyl(2-pyridyl)methyl moves from an enamide formation at one extremity (lithium) to an aza-allyl formation at the other extremity (potassium), while C- or N-coordination modes become energetically viable for Na and K phenyl(4-pyridyl)methyl complexes.
Assuntos
Metais Alcalinos , Álcalis , Ânions/química , Cátions/química , Metais Alcalinos/química , Modelos MolecularesRESUMO
A series of groupâ 1 hydrocarbon-soluble donor free aluminates [AM(t BuDHP)(TMP)Al(i Bu)2 ] (AM=Li, Na, K, Rb) have been synthesised by combining an alkali metal dihydropyridyl unit [(2-t BuC5 H5 N)AM)] containing a surrogate hydride (sp3 C-H) with [(i Bu)2 Al(TMP)]. These aluminates have been characterised by X-ray crystallography and NMR spectroscopy. While the lithium aluminate forms a monomer, the heavier alkali metal aluminates exist as polymeric chains propagated by non-covalent interactions between the alkali metal cations and the alkyldihydropyridyl units. Solvates [(THF)Li(t BuDHP)(TMP)Al(i Bu)2 ] and [(TMEDA)Na(t BuDHP)(TMP)Al(i Bu)2 ] have also been crystallographically characterised. Theoretical calculations show how the dispersion forces tend to increase on moving from Li to Rb, as opposed to the electrostatic forces of stabilization, which are orders of magnitude more significant. Having unique structural features, these bimetallic compounds can be considered as starting points for exploring unique reactivity trends as alkali-metal-aluminium hydride surrog[ATES].
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The development of synthetic chemistry since the early 1900s owes much to the service of organolithium reagents. Brilliant bases (e.g., deprotonating C-H bonds), nucleophiles (e.g., adding to unsaturated molecules), and transfer agents (e.g., delivering ligands to other metals), these versatile virtuosi and to a lesser extent the organic derivatives of the other common alkali metals sodium and potassium have proved indispensable in both academia and technology. Today these monometallic compounds are still utilized widely in synthetic campaigns, but in recent years they have been joined by an assortment of bimetallic formulations that also contain an alkali metal but in company with another metal. These bimetallic formulations often exhibit unique chemistry that can be interpreted in terms of synergistic effects, for which the alkali metal is essential, though it is often the second metal that performs the synthetic transformation. Here, this "alkali-metal-mediated" chemistry is surveyed focusing mainly on bimetallic formulations containing two alkali metals or an alkali metal paired with magnesium, calcium, zinc, aluminum, or gallium. In this International Year of the Periodic Table (IYPT), we ponder whether a Pairiodic Table of Element Pairs will emerge in the future.
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A site-specific xenon plasma focused ion beam preparation technique for microcantilever samples (1-20 µm width and 1:10 aspect ratio) is presented. The novelty of the methodology is the use of a chunk lift-out onto a clean silicon wafer to facilitate easy access of a low-cost probe type indenter which provides bending force measurement. The lift-out method allows sufficient room for the indenter and a line of sight for the electron beam to enable displacement measurement. An electroplated nanotwinned copper (NTC) was cut to a 3 × 3 × 25 µm microbeam and in situ mechanically tested using the developed technique. It demonstrated measured values of Youngs modulus of 78.7 ± 11 GPa and flow stress of 0.80 ± 0.05 GPa, which is within the ranges reported in the literature. LAY DESCRIPTION: In this paper a site specific method is present for making particularly small mechanical tests samples, of the order of 100th the size of a human hair. These small samples can then be used to determine the mechanical properties of the bulk material. Copper with a nano twinned grain structure is used as a test medium. Ion milling was used to cut the sample to shape and a micro probe was used for mechanical testing. Ion milling can cut away very small volumes of material as it accelerates ions at the surface of the sample, atomically machining the sample. Micro probes are a cost-effective small-scale load measurement devices, however, they require a large area for accessing the sample. The indenter requirements are a problem when making you samples with ion milling as ion millers are best at making small cuts. Our aim was to design a cutting strategy which reduces the amount of cutting required while allowing samples to be fabricated anywhere on the sample. We used a chunk lift out technique to remove a piece of material which is then welded to a wafer of silicon this gives sufficient space around the sample for ion milling and testing. The additional space allowed easy access for the probe. A 3 × 3 × 10 µm micro cantilever beam was cut out from copper, this beam was then bent. The force from bending and distance bent was measured and converted into Youngs modulus which is a measure of flexibility. The modulus value measured was comparable to the values reported in other papers.
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A microbial fuel cell (MFC) based on a new wild-type strain of Salinivibrio sp. allowed the self-sustained treatment of hypersaline solutions (100â g L-1 , 1.71 m NaCl), reaching a removal of (87±11) % of the initial chemical oxygen demand after five days of operation, being the highest value achieved for hypersaline MFC. The degradation process and the evolution of the open circuit potential of the MFCs were correlated, opening the possibility for online monitoring of the treatment. The use of alginate capsules to trap bacterial cells, increasing cell density and stability, resulted in an eightfold higher power output, together with a more stable system, allowing operation up to five months with no maintenance required. The reported results are of critical importance to efforts to develop a sustainable and cost-effective system that treats hypersaline waste streams and reduces the quantity of polluting compounds released.
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A series of heteroleptic monoamido-monohydrido-dialkylaluminate complexes of general formula [iBu2 AlTMPHLiâ donor] were synthesized and characterised in solution and in the solid state. Applying these complexes in catalytic hydroboration reactions with representative aldehydes and ketones reveals that all are competent, however a definite donor substituent effect is discernible. The bifunctional nature of the complexes is also probed by assessing their performance in metallation of a triazole and phenylacetylene and addition across pyrazine. These results lead to an example of phenylacetylene hydroboration, which likely proceeds via deprotonation, rather than insertion as observed with the aldehydes and ketones. Collectively, the results emphasise that reactivity is strongly influenced by both the mixed-metal constitution and mixed-ligand constitution of the new aluminates.
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Equipped with excellent hydrocarbon solubility, the lithium hydride surrogate 1-lithium-2-tert-butyl-1,2-dihydropyridine (1tLi) functions as a precatalyst to convert Me2 NHâ BH3 to [NMe2 BH2 ]2 (89 % conversion) under competitive conditions (2.5â mol %, 60â h, 80 °C, toluene solvent) to that of previously reported LiN(SiMe3 )2 . Sodium and potassium dihydropyridine congeners produce similar high yields of [NMe2 BH2 ]2 but require longer times. Switching the solvent to pyridine induces a remarkable change in the dehydrocoupling product ratio, with (NMe2 )2 BH favoured over [NMe2 BH2 ]2 (e.g., 94 %:2 % for 1tLi). Demonstrating its versatility, precatalyst 1tLi was also successful in promoting hydroboration reactions between pinacolborane and a selection of aldehydes and ketones. Most reactions gave near quantitative conversion to the hydroborated products in 15â minutes, though sterically demanding carbonyl substrates require longer times. The mechanisms of these rare examples of Groupâ 1 metal-catalysed processes are discussed.
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In reactions restricted previously to a ruthenium catalyst, a 1-lithium-2-alkyl-1,2-dihydropyridine complex is shown to be a competitive alternative dehydrogenation catalyst for the transformation of diamine boranes into cyclic 1,3,2-diazaborolidines, which can in turn be smoothly arylated in good yields. This study established the conditions and solvent dependence of the catalysis through NMR monitoring, with mechanistic insight provided by NMR (including DOSY) experiments and X-ray crystallographic studies of several model lithio intermediates.
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PURPOSE: Radical surgery for neoplasms of the tongue can endanger at least 1 lingual artery, threatening the survival of the remaining tissue and the recovery of speech and swallowing. Although there is little anastomosis in the substance of the tongue, this study investigated whether arterial anastomoses outside the tongue could provide collateral circulation to protect the surviving tissue. MATERIALS AND METHODS: Parts of 9 embalmed cadaver heads were examined. In 2 specimens, the arteries had been previously injected with latex and India ink. In the remaining, a mixture of latex and India ink was injected into the lingual artery at its origin on 1 side. Five injections were successful. RESULTS: There was considerable variation in the course and distribution of the lingual arteries. Arteries did not cross the midline of the tongue, but actual or potential anastomoses could be seen round the base of the tongue, in the floor of the mouth, and with facial artery branches. After the experimental injections, the mass filled the lingual artery and its branches on the injected side, but also reached the trunk and main branches of the opposite side. CONCLUSION: A mass injected into the lingual artery of 1 side can reach the trunk and territory of the lingual artery of the opposite side. In life, it is likely that a similar collateral circulation would exist. Some clinical literature supports this conclusion, but preoperative arteriography might be a reasonable precaution.
Assuntos
Artérias/cirurgia , Língua/cirurgia , Anastomose Cirúrgica/métodos , Humanos , Fluxo Sanguíneo Regional , Língua/irrigação sanguíneaRESUMO
Organometallic bases are becoming increasingly complex, because mixing components can lead to bases superior to single-component bases. To better understand this superiority, it is useful to study metalated intermediate structures prior to quenching. This study is on 1-phenyl-1H-benzotriazole, which was previously deprotonated by an in situ ZnCl2 â TMEDA/LiTMP (TMEDA=N,N,N',N'-tetramethylethylenediamine; TMP=2,2,6,6-tetramethylpiperidide) mixture and then iodinated. Herein, reaction with LiTMP exposes the deficiency of the single-component base as the crystalline product obtained was [{4-R-1-(2-lithiophenyl)-1H-benzotriazoleâ 3THF}2 ], [R=2-C6 H4 (Ph)NLi], in which ring opening of benzotriazole and N2 extrusion had occurred. Supporting lithiation by adding iBu2 Al(TMP) induces trans-metal trapping, in which C-Li bonds transform into C-Al bonds to stabilise the metalated intermediate. X-ray diffraction studies revealed homodimeric [(4-R'-1-phenyl-1H-benzotriazole)2 ], [R'=(iBu)2 Al(µ-TMP)Li], and its heterodimeric isomer [(4-R'-1-phenyl-1H-benzotriazole){2-R'-1-phenyl-1H-benzotriazole}], whose structure and slow conformational dynamics were probed by solution NMR spectroscopy.
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Generally considered kinetic intermediates in addition reactions of alkyllithiums to pyridine, 1-lithio-2-alkyl-1,2-dihydropyridines have been rarely isolated or characterized. This study develops their "isolated" chemistry. By a unique stoichiometric (that is, 1:1, alkyllithium/pyridine ratios) synthetic approach using tridentate donors we show it is possible to stabilize and hence crystallize monomeric complexes where alkyl is tert-butyl. Theoretical calculations probing the donor-free parent tert-butyl species reveal 12 energetically similar stereoisomers in two distinct cyclotrimeric (LiN)3 conformations. NMR spectroscopy studies (including DOSY spectra) and thermal volatility analysis compare new sec-butyl and iso-butyl isomers showing the former is a hexane soluble efficient hydrolithiation agent converting benzophenone to lithium diphenylmethoxide. Emphasizing the criticalness of stoichiometry, reaction of nBuLi/Me6 TREN with two equivalents of pyridine results in non-alkylated 1-lithio-1,4-dihydropyridineâ Me6 TREN and 2-n-butylpyridine, implying mechanistically the kinetic 1,2-n-butyl intermediate hydrolithiates the second pyridine.
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Laryngomalacia is a dynamic airway condition characterised by inward collapse of flaccid supraglottic structures during inspiration. Although the most common cause of stridor in the paediatric population, adult-onset laryngomalacia remains a rare entity and its management, challenging. Two cases of adult-onset laryngomalacia are reported. A review of the English literature is performed and additional publications identified by hand-searching relevant papers; 13 case reports/series comprising 28 cases of adult-onset laryngomalacia were identified, divided into two main groups: idiopathic (6/28) and acquired (22/28). The aetiology of the acquired form includes neurological, traumatic and iatrogenic. Reported therapeutic measures used are laser supraglottoplasty, epiglottopexy, partial epiglottidectomy, defunctioning tracheostomy and intubation whilst correcting the underlying cause. The majority of patients only required one therapeutic procedure (follow-up of 2-24 months). A strong index of suspicion is required to diagnose adult-onset laryngomalacia aided by in-office laryngoscopy. The rarity of this condition prevents management-based randomised controlled trials.
Assuntos
Laringomalácia , Laringoplastia/métodos , Laringoscopia/métodos , Traqueostomia/métodos , Gerenciamento Clínico , Epiglote/fisiopatologia , Epiglote/cirurgia , Feminino , Humanos , Laringomalácia/diagnóstico , Laringomalácia/etiologia , Laringomalácia/fisiopatologia , Laringomalácia/cirurgia , Pessoa de Meia-Idade , Sons Respiratórios/etiologiaRESUMO
Rubidium and cesium are the least studied naturally occurring s-block metals in organometallic chemistry but are in plentiful supply from a sustainability viewpoint as highlighted in the periodic table of natural elements published by the European Chemical Society. This underdevelopment reflects the phenomenal success of organometallic compounds of lithium, sodium, and potassium, but interest in heavier congeners has started to grow. Here, the synthesis and structures of rubidium and cesium bis(amido)alkyl magnesiates [(AM)MgN'2alkyl]∞, where N' is the simple heteroamide -N(SiMe3)(Dipp), and alkyl is nBu or CH2SiMe3, are reported. More stable than their nBu analogues, the reactivities of the CH2SiMe3 magnesiates toward 1,4-cyclohexadiene are revealed. Though both reactions produce target hydrido-magnesiates [(AM)MgN'2H]2 in crystalline form amenable to X-ray diffraction study, the cesium compound could only be formed in a trace quantity. These studies showed that the bulk of the -N(SiMe3)(Dipp) ligand was sufficient to restrict both compounds to dimeric structures. Bearing some resemblance to inverse crown complexes, each structure has [(AM)(N)(Mg)(N)]2 ring cores but differ in having no AM-N bonds, instead Rb and Cs complete the rings by engaging in multihapto interactions with Dipp π-clouds. Moreover, their hydride ions occupy µ3-(AM)2Mg environments, compared to µ2-Mg2 environments in inverse crowns.
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Recently main group compounds have stepped into the territory of precious transition metal compounds with respect to utility in the homogeneous catalysis of fundamentally important organic transformations. Inspired by the need to promote more sustainability in chemistry because of their greater abundance in nature, this change of direction is surprising since main group metals generally do not possess the same breadth of reactivity as precious transition metals. Here, we introduce the dihydropyridylsodium compound, Na-1,2-tBu-DH(DMAP), and its monomeric variant [Na-1,2-tBu-DH(DMAP)]·Me6TREN, and demonstrate their effectiveness in transfer hydrogenation catalysis of the representative alkene 1,1-diphenylethylene to the alkane 1,1-diphenylethane using 1,4-cyclohexadiene as hydrogen source [DMAP = 4-dimethylaminopyridine; Me6TREN = tris(N,N-dimethyl-2-aminoethyl)amine]. Sodium is appealing because of its high abundance in the earth's crust and oceans, but organosodium compounds have been rarely used in homogeneous catalysis. The success of the dihydropyridylsodium compounds can be attributed to their high solubility and reactivity in organic solvents.
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Lithium 2,2,6,6-tetramethylpiperidide (LiTMP), one of the most important polar organometallic reagents both in its own right and as a key component of ate compositions, has long been known for its classic cyclotetrameric (LiTMP)4 solid-state structure. Made by a new approach through transmetalation of Zn(TMP)2 with tBuLi in n-hexane solution, a crystalline polymorph of LiTMP has been uncovered. X-ray crystallographic studies at 123(2)â K revealed this polymorph crystallises in the hexagonal space group P63 /m and exhibited a discrete cyclotrimeric (C3h ) structure with a strictly planar (LiN)3 ring containing three symmetrically equivalent TMP chair-shaped ligands. The molecular structure of (LiTMP)4 was redetermined at 123(2)â K, because its original crystallographic characterisation was done at ambient temperature. This improved redetermination confirmed a monoclinic C2/c space group with the planar (LiN)4 ring possessing pseudo (non-crystallographic) C4h symmetry. Investigation of both metalation and transmetalation routes to LiTMP under different conditions established that polymorph formation did not depend on the route employed but rather the temperature of crystallisation. Low-temperature (freezer at -35 °C) cooling of the reaction solution favoured (LiTMP)3 ; whereas high-temperature (bench) storage favoured (LiTMP)4 . Routine (1) H and (13) Câ NMR spectroscopic studies in a variety of solvents showed that (LiTMP)3 and (LiTMP)4 exist in equilibrium, whereas (1) Hâ DOSY NMR studies gave diffusion coefficient results consistent with their relative sizes.
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The series of alkali-metal (Li, Na, K) complexes of the substituted benzyl anion 3,5-dimethylbenzyl (Me2C6H3CH2(-)) derived from 1,3,5-trimethylbenzene (mesitylene) have been coerced into monomeric forms by supporting them with the tripodal tetradentate Lewis donor tris(N,N-dimethyl-2-aminoethyl)amine, [N(CH2CH2NMe2)3, Me6TREN]. Molecular structure analysis by X-ray crystallography establishes that the cation-anion interaction varies as a function of the alkali-metal, with the carbanion binding to lithium mainly in a σ fashion, to potassium mainly in a π fashion, with the interaction toward sodium being intermediate between these two extremes. This distinction is due to the heavier alkali-metal forcing and using the delocalization of negative charge into the aromatic ring to gain a higher coordination number in accordance with its size. Me6TREN binds the metal in a η(4) mode at all times. This coordination isomerism is shown by multinuclear NMR spectroscopy to also extend to the structures in solution and is further supported by density functional theory (DFT) calculations on model systems. A Me6TREN stabilized benzyl potassium complex has been used to prepare a mixed-metal ate complex by a cocomplexation reaction with tBu2Zn, with the benzyl ligand acting as an unusual ditopic σ/π bridging ligand between the two metals, and with the small zinc atom relocalizing the negative charge back on to the lateral CH2 arm to give a complex best described as a contacted ion pair potassium zincate.
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Most synthetic chemists will have at some point utilized a sterically demanding secondary amide (R2 N(-) ). The three most important examples, lithium 1,1,1,3,3,3-hexamethyldisilazide (LiHMDS), lithium diisopropylamide (LiDA), and lithium 2,2,6,6-tetramethylpiperidide (LiTMP)-the "utility amides"-have long been indispensible particularly for lithiation (Li-H exchange) reactions. Like organolithium compounds, they exhibit aggregation phenomena and strong Lewis acidity, and thus appear in distinct forms depending on the solvents employed. The structural chemistry of these compounds as well as their sodium and potassium congeners are described in the absence or in the presence of the most synthetically significant donor solvents tetrahydrofuran (THF) and N,N,N',N'-tetramethylethylenediamine (TMEDA) or closely related solvents. Examples of hetero-alkali-metal amides, an increasingly important composition because of the recent escalation of interest in mixed-metal synergic effects, are also included.