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[GeCl2(dioxane)] reacts with the neutral aza-macrocyclic ligands L, L = Me3tacn (1,4,7-trimethyl-1,4,7-triazacyclononane), Me4cyclen (1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane) or Me4cyclam (1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) and two mol. equiv. of Me3SiO3SCF3 in thf solution to yield the unusual and hydrolytically very sensitive [Ge(L)][O3SCF3]2 as white solids in moderate yield. Using shorter reaction times [Ge(Me3tacn)]Cl2 and [Ge(Me3tacn)]Cl[O3SCF3] were also isolated; the preparation of [Ge(Me4cyclen)][GeCl3]2 is also described. The structures of the Me3tacn complexes show kappa3-coordination of the macrocycle, with the anions interacting only weakly to produce very distorted five- or six-coordination at germanium. In contrast, the structure of [Ge(Me4cyclen)][O3SCF3]2 shows no anion interactions, and a distorted square planar geometry at germanium from coordination to the tetra-aza macrocycle. Crystal structures of the Si(iv) complexes, [SiCl3(Me3tacn)]Y (Y = O3SCF3, BArF; [B{3,5-(CF3)2C6H3}4]) and [SiHCl2(Me3tacn)][BArF], obtained from reaction of SiCl4 or SiHCl3 with Me3tacn, followed by addition of either Me3SiO3SCF3 or Na[BArF], contain distorted octahedral cations, with facial kappa3-coordinated Me3tacn. The open-chain triamine, Me2NCH2CH2N(Me)CH2CH2NMe2 (pmdta), forms [SiCl3(pmdta)][BArF] and [SiBr3(pmdta)][BArF] under similar conditions, containing mer-octahedral cations.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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The design and fabrication of safe and highly efficient nonviral vectors is the key scientific issue for the achievement of clinical gene therapy. Supramolecular cationic polymers have unique structures and specific functions compared to covalent cationic polymers, such as low cytotoxicity, excellent biodegradability, and smart environmental responsiveness, thereby showing great application prospect for gene therapy. However, supramolecular gene vectors are facile to be degraded under physiological conditions, leading to a significant reduction of gene transfection efficiency. In order to achieve highly efficient gene expression, it is necessary for supramolecular gene vectors being provided with appropriate biostability to overcome various cell obstacles. To this end, a novel cationic supramolecular block copolymer composed of a conventional polymer and a noncovalent polymer was constructed through robust beta-cyclodextrin/ferrocene host-guest recognition. The resultant supramolecular block copolymer perfectly combines the advantages of both conventional polymers and supramolecular polymers ranging from structures to functions. This supramolecular copolymer not only has the ability to effectively condense pDNA for enhanced cell uptake, but also releases pDNA inside cancer cells triggered by H2O2, which can be utilized as a prospective nonviral delivery vehicle for gene delivery. The block polymer exhibited low cytotoxicity, good biostability, excellent biodegradability, and intelligent responsiveness, ascribing to the dynamic/reversible nature of noncovalent linkages. In vitro studies further illustrated that the supramolecular block polymer exhibited greatly improved gene transfection efficiency in cancer cells. This work offers an alternative platform for the exploitation of smart nonviral vehicles for specific cancer gene therapy in the future.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Negatively charged polystyrene latex was synthesized, and a copolymer shell of 2-(methyl-2?-chloropropionato)ethyl acrylate (HEA-Cl) and styrene was added, from which poly(N,N-dimethylacrylamide) (PDMA) was polymerized by atom transfer radical polymerization in aqueous suspension at room temperature. Increasing monomer concentration in the presence of CuCl or CuBr and one of three ligands (N,N,N?,N?,N?-pentamethyldiethylenetriamine (PMDETA),1,1,4,7,10,10-hexamethyltriethylenetetramine (HMTETA), and tris[2-(dimethylamino)ethyl]amine (Me6TREN)) produced grafts whose molecular weight increased to over 600 000 and polydispersities in the range of 1.3-1.8, determined from chains recovered following cleavage by base. Hydrodynamic brush thickness were 70-80 nm, and average chain separations, calculated from Mn and the mass of polymer recovered per particle, varied from 4.0 to 1.1 nm. Very high grafting densities were achieved with good molecular weight control, the highest densities yet reported for high molecular weight polymer chains grown from a surface. Control of the polymerization was improved by addition of Cu(II) to enhance deactivation of free radicals, by including a low concentration of exogenous hydrophobic initiator at high monomer concentration and by reducing latex concentration. Increasing the concentration of exogenous initiator reduced graft thickness but eliminated control over the polydispersity. The unusual conditions required for optimization of the reaction and the observation of decreasing chain separation as Mn increased were explained by invoking a model of the particle surface that took into account the finite depth and high copolymer concentration of the region in which chains were initiated and particularly the fixed charges due to the sulfate initiator of shell copolymerization.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Fluoroaromatic scaffolds pose a challenge to lithiation due to low stability of lithiated intermediates. Here we apply trans-metal-trapping (TMT) to a series of key fluorinated aromatics. In TMT, LiTMP performs the metalation, while an organometallic trap intercepts the emergent carbanion. This study contrasts the trapping abilities of iBu2AlTMP and Ga(CH2SiMe3)3, structurally mapping their TMT reactions and probing relative stabilities of metalated fluoroaromatic intermediates by NMR studies. Results show the installed Al?C(aryl) bonds are more prone to decomposition by benzyne formation and Li-F liberation, than the Ga?C(aryl) species. The latter are thus better for onward reactivity as demonstrated in cross-coupling reactions with benzoyl chloride that produce ketones.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Bark and alkaline extracts of bark were oxypropylated to produce bio-polyols. It was found that bark had a much higher yield (79%) than the alkaline extracts (32%). Solvent extraction and thermo-gravimetric analysis showed that the homopolymer helped reduce viscosity and that the co-polymer showed evidence of grafting. As a result, the bark derived bio-polyols had a very low viscosity, especially compared to reported values for other types of biomass that produced prohibitively highly viscous liquids. GPC analysis showed that high molecular weight compounds from bark were made highly soluble by the grafting of PO chains. This resulted in a molecular weight average of 6800. Da for the oxypropylated bark, and 7100. Da for the alkaline extract of bark. The hydroxyl value and high concentration of secondary alcohols in the bio-polyols was consistent with typical commercial polyols used for rigid foam formulations. Finally, when foamed, the oxypropylated bark-based foam showed superior compressive behavior to previous work done on liquefied bark-based PUFs and a control foam.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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In homogeneous catalysis, the catalyst is in the same phase as the reactant. The number of collisions between reactants and catalyst is at a maximum.In a patent, 3030-47-5, name is N1-(2-(Dimethylamino)ethyl)-N1,N2,N2-trimethylethane-1,2-diamine, introducing its new discovery. COA of Formula: C9H23N3

N-lithio-N,N’,N”,N”-tetramethyldiethylenetriamine (I-Li) is formed from 2,5,8,11-tetramethyl-2,5,8,11-tetraazadodecane (III) or from 2,5,8,11,14,17- hexamethyl-2,5,8,11,14,17-hexaazaoctadecane (IV) with n-BuLi or sec-BuLi, respectively, its isomer N’-lithio-N,N,N”,N”,-tetramethyldiethylene- triamine (II-Li) from tris(2-dimethylaminoethyl)amine (V) with n-BuLi. IV results from treatment of N-lithiomethyl-N,N’,N”,N”- tetramethyldiethylenetriamine (PMDTA-Li) with 1,2-dibromoethane.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Research interest in electrochemical redox stimulus has grown considerably due to its easy trigger mode, in which the linkers have played important roles, such as the beta-cyclodextrin-ferrocene (beta-CD-Fc) linker. Star amphiphilic copolymers with well-defined and flexible structures are considered to be excellent choices for drug delivery systems (DDSs). Driven by the idea that using star polymers to improve the biocompatibility and efficiency of the beta-CD-Fc-based DDS, we designed and synthesized star polymer 4 arm-poly(epsilon-caprolactone)-beta-CD (4A PCL-CD) and linear polymer polyethylene glycol-Fc (PEG-Fc). They can form supramolecular block copolymer 4A PCL-CD/Fc-PEG and self-assemble to micelles, which are electrochemical responsive and can be applied as drug carriers for potential controlled release, with higher efficiency and better biocompatibility compared with their linear analogues.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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A pressure-sensitive adhesive polymeric composition comprising the blend or reaction product of butyl rubber, an olefinic polymer component, filler that includes titanium dioxide, and an unfunctionalized phenolic resin, where the composition is devoid of isocyanate or isocyanate residue.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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A commonly used deprotonation agent is the combination of n-butyllithium and N,N,N?,N?,N?-pentamethyldiethylenetriamine (PMDTA). The highly reactive aggregate [{(nBuLi)2-PMDTA}2] crystallizes out of a 2:1 mixture of nBuLi and PMDTA. The molecular structure provides insight into the significant influence of the nBuLi/PMDTA ratio on the course of some deprotonation reactions.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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The POSS supported (S)-alpha,alpha-diphenylprolinol trimethylsilyl ether catalyst was synthesized and applied in the asymmetric Michael addition reactions of aldehydes and arylnitroalkenes, providing the products in good yields with excellent enantioselectivities and good diastereoselectivities. The POSS supported catalyst can be readily recycled and reused for further transformations at least eight cycles without observing significant decrease in yield and stereoselectivity.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI