DOSY NMR Spectroscopy Research Articles

3D Printable Antimicrobial Polymer Blend

AbstractThree‐dimensional (3D) printing is an innovative manufacturing method for preparing designer materials with complex geometries. However, there are very few studies on the fabrication of antimicrobial polymer materials suitable for use in everyday clinical objects, via 3D printing. In this work, an antibacterial polymer material is prepared by blending polyamide 11 (matrix), a high‐performance engineering thermoplastic, and a styrene maleimide copolymer with pendant quaternary amine moieties, and the blend 3D printed via selective laser sintering. The quaternary amine functionalities confer permanent antimicrobial properties. Blend properties are studied prior to printing via differential scanning calorimetry, powder X‐ray diffraction, and FTIR spectroscopy. Additionally, the mechanical and antimicrobial properties of the polymer blends and printed material are also assessed. The microstructure of the 3D printed polymer materials is further characterized via DOSY NMR spectroscopy. This study indicates that this is a promising approach for preparing nonleaching antimicrobial 3D printable materials.

Host-guest chemistry of tridentate Lewis acids based on tribenzotriquinacene.

Flexible poly-Lewis acids (PLA) based on the tribenzotriquinacene (TBTQ) scaffold have been synthesised. Hydrosilylation of 4b,8b,12b-triallyltribenzotriquinacene and subsequent exchange of the chlorine substituents with weaker coordinating triflate groups afforded a novel triple silyl-functionalised PLA. By regioselective hydroboration of triallyl-TBTQ with various organoboranes, PLAs with different Lewis acidities were obtained. The synthesised PLAs were combined with neutral bases in host-guest experiments. DOSY NMR spectroscopy was performed to elucidate the complexation process in solution. These experiments revealed a highly dynamic interaction between the boron-functionalised PLA and triazine. However, the addition of one equivalent of tris(dimethylphosphino(methyl))phenylsilane led to the formation of a 1 : 1 adduct, which was confirmed by diffusion experiments.

Hexanuclear Ln6 L6 Complex Formation by Using an Unsymmetric Ligand.

Multinuclear, self-assembled lanthanide complexes present clear opportunities as sensors and imaging agents. Despite the widely acknowledged potential of this class of supramolecule, synthetic and characterization challenges continue to limit systematic studies into their self-assembly restricting the number and variety of lanthanide architectures reported relative to their transition metal counterparts. Here we present the first study evaluating the effect of ligand backbone symmetry on multinuclear lanthanide complex self-assembly. Replacement of a symmetric ethylene linker with an unsymmetric amide at the center of a homoditopic ligand governs formation of an unusual Ln6 L6 complex with coordinatively unsaturated metal centers. The choice of triflate as a counterion, and the effect of ionic radii are shown to be critical for formation of the Ln6 L6 complex. The atypical Ln6 L6 architecture is characterized using a combination of mass spectrometry, luminescence, DOSY NMR and EPR spectroscopy measurements. Luminescence experiments support clear differences between comparable Eu6 L6 and Eu2 L3 complexes, with relatively short luminescent lifetimes and low quantum yields observed for the Eu6 L6 structure indicative of non-radiative decay processes. Synthesis of the Gd6 L6 analogue allows three distinct Gd⋯Gd distance measurements to be extracted using homo-RIDME EPR experiments.

Fusing Triphenylbismuth and PnPh3 (Pn = P-Bi): Synthesis, Isolation, and Characterization of 9-Bisma-10-Pnictatriptycenes.

The first series of 9-bisma-10-pnictatriptycenes Bi(C6H4)3Pn (2-Pn, Pn = P-Bi; see graphic) has been synthesized in a two-step procedure via suitable tris(2-bromophenyl)pnictanes 1-Pn and characterized in solution as well as in the solid state. DFT calculations suggest preferential interactions between 2-Pn and soft Lewis acids via the lighter pnictogen donor atom. Experimental studies demonstrate that even the weakest Lewis base in the series of 2-Pn, namely the dibismatriptycene 2-Bi, interacts with Lewis acidic [BiMe2(SbF6)] in solution. Analytical techniques include (VT-)NMR spectroscopy, DOSY NMR spectroscopy, high-resolution mass spectrometry, single-crystal X-ray diffraction analyses, and DFT calculations.

Solution Self‐Assembly of Branched Macromolecules Obtained via Iterative OPE Synthesis and the Passerini Three‐Component Reaction

AbstractIn the last decade, isocyanide‐based multicomponent reactions, like the Passerini three‐component reaction (P‐3CR), have gained significant interest in the synthesis of sequence‐defined macromolecules due to their high efficiency and straightforward one‐pot procedures. The P‐3CR results in unique product structures that are particularly interesting for the synthesis of uniform, branched macromolecules, as they enable the direct introduction of a new branching point into the molecule. In this work, the synthesis of uniform first‐generation dendrons is performed via the P‐3CR using a divergent approach, utilizing three uniform and poorly soluble oligo(phenylene ethynylene)s (OPEs) of varying lengths as a focal moiety. Self‐assembly of the dendrons in cyclohexane solution is confirmed by fluorescence spectroscopy and diffusion‐ordered NMR (DOSY NMR) spectroscopy, highlighting the utility of DOSY NMR spectroscopy for the investigation of solution self‐assembly. Diffusion coefficients for the dendrons and their aggregates are determined and compared for different lengths of the OPE focal moiety. The successful synthesis of the dendrons in good yields and the selective branching introduced on the OPEs by the P‐3CR emphasize the high efficiency and synthetic advantages of multicomponent reactions for the preparation of uniform, branched macromolecules.

Connecting 16- with 4-Membered Rings: Ring-Opening Polymerization of Bio-Based ω-Pentadecalactone with Amino-Alkoxy-Bis(phenolate) Yttrium Initiators and Copolymerization with β-Butyrolactone

Ring-opening polymerization (ROP) of bio-based lactones is an effective way to overcome limited fossil resources. The 16-membered, musk-derived ω-pentadecalactone (PDL) occurs naturally as an ω-hydroxy fatty acid. As PDL is considered a macrolactone, controlled ROP of this transoid lactone is mostly obtained via enzymatic routes. Herein, amino-alkoxy-bis(phenolate) yttrium amido and alkoxide catalysts are reported for controlled metal-catalyzed ROP of PDL. PDL polymerizations are conducted at elevated temperatures from 60 to 100 °C to produce poly(ω-pentadecalactone) (PPDL) with number-average molecular weights of up to 134.5 kg mol−1 and moderate polydispersities (1.5 to 2.1). Utilizing isopropanol as a chain transfer agent (CTA) lead to higher initiator efficiencies and low polydispersities while still showing full monomer conversions with molar masses tunable by the amount of CTA. Block copolymerizations of PDL are performed via sequential addition. Four-membered, cisoid, and rather reluctant, racemic β-butyrolactone (BBL), which can be synthesized from carbon dioxide, is chosen as the second block. After determining that PDL has a lower coordination strength to the yttrium center and has to be added as the first monomer, successful connection between PPDL and poly(3-hydroxybutyrate) (PHB) blocks is shown via SEC and DOSY NMR spectroscopy. Different ratios of PDL and BBL are chosen to obtain PPDL-b-PHB polymers with different block length and molar masses. Powder X-ray diffraction measurements and DSC measurements prove the preservation of crystallinity in the block copolymers.

Catalytic Living ROMP: Synthesis of Degradable Star Polymers.

Star polymers have attracted considerable attention over the past few years due to their distinctive physical and chemical attributes that are different from conventional linear polymers. Here, we present a one-pot synthesis of narrowly dispersed and degradable homoarm and miktoarm star polymers exploiting the catalytic living ring-opening metathesis polymerization (ROMP) mechanism. Several complex polymeric architectures (such as A3-, A4-, A6-, A2B-, A3B-, and AB2-type star polymers) were synthesized quite straightforwardly by using appropriate vinyl ether chain transfer agents. SEC, 1H NMR, and DOSY NMR spectroscopy were employed to analyze and characterize all of the synthesized polymers. We believe that this sustainable and environmentally friendly synthesis of star polymers could become an important synthetic tool for polymer engineers working on supramolecular, industrial or biomedical applications.

Synthesis and Characterization of Dimeric Artesunate Glycerol Monocaprylate Conjugate and Formulation of Nanoemulsion Preconcentrate.

Malaria is one of the major life-threatening health problems worldwide. Artesunate is the most potent antimalarial drug to combat severe malaria. However, development of drug resistance, short plasma half-life, and poor bioavailability limit the efficacy of this drug. Here, we applied the dimerization concept to synthesize dimeric artesunate glycerol monocaprylate conjugate (D-AS-GC) by conjugating artesunate (AS) with glycerol monocaprylate (GC) via esterification reaction. D-AS-GC conjugate, AS, and GC were well characterized by 1H NMR, attached proton test (APT) 13C NMR and 2D NMR spectroscopy. D-AS-GC conjugate was further analyzed by ESI-TOF MS. Finally, a series of nanoemulsion preconcentrate (F1-F6) of D-AS-GC was prepared by mixing different ratios of oil and surfactant/cosurfactant and evaluated after dilution with an aqueous phase. The optimized formulation (F6) exhibits a clear nanoemulsion and the hydrodynamic diameter of the dispersed phase was determined by DLS and DOSY NMR spectroscopy. The morphology of the nanoemulsion droplets of F6 was investigated by AFM, which revealed the formation of tiny nanoemulsion droplets on a hydrophilic mica substrate. Moreover, using a less polar silicon wafer led to the formation of larger droplets with a spherical core shell-like structure. Overall, the rational design of the dimeric artesunate-based nanoemulsion preconcentrate could potentially be used in more efficient drug delivery systems.

Formation, Reactivity, and Catalytic Behavior of a Keggin Polyoxometalate/Bipyridine Hybrid in the Epoxidation of Cyclooctene with H2O2.

The present study further explores the behavior of polyoxometalate-based hybrid compounds as catalysts for liquid-phase cyclooctene epoxidation with H2O2. Precisely, it unveils the nature of the relevant active species derived from the hybrid based on Keggin polyoxometalate (POM) and bipyridines (bpy) of formula (2,2'-Hbpy)3[PW12O40] (1). Whereas (i) it is generally accepted that the catalytic oxidation of organic substrates by H2O2 involving Keggin HPAs proceeds via an oxygen transfer route from a peroxo intermediate and (ii) the catalytically active peroxo species is commonly postulated to be the polyperoxotungstate {PO4[W(O)(O2)2]4}3- complex (PW4), we show that the studied epoxidation reaction seems to be more sophisticated than commonly reported. During the catalytic epoxidation, 1 underwent a partial transformation into two oxidized species, 2 and 3. Compound 3 corresponding to 2,2'-bipyridinium oxodiperoxotungstate of formula [WO(O2)2(2,2'-bpy)] was shown to be the main species responsible for the selective epoxidation of cyclooctene since 2 (in which the POM is associated with a protonated mono-N-oxide derivative of 2,2'-bpy of formula (2,2'-HbpyO)3[PW12O40]) exhibited no activity. The structures of 1, 2, and 3 were solved by single-crystal X-ray diffraction and were independently synthesized. The speciation of 1 was monitored under catalytic conditions by 1H and 1H DOSY NMR spectroscopies, where the formation in situ of 2 and 3 was revealed. A reaction mechanism is proposed that highlights the pivotal, yet often underestimated, role of H2O2 in the reached catalytic performances. The active species responsible for the oxygen transfer to cyclooctene is a hydroperoxide intermediate species that is formed by the interaction between the anionic structure of the catalyst and H2O2. The latter operates as a "conservative agent" whose presence in the catalytic system is required to prevent the catalysts from deactivating irreversibly.

Constitution of the fully supported gold(I)alkynyl (dmpme)·bis[gold(I)ethynyldimethylsilyl]methane in solution

Abstract The dimetallacyclic complex H2C(Me2SiC≡CAuPMe2)2CH2 has been synthesized, in which the two gold centers are bridged by the diphosphine dmpme (= bis(dimethylphosphino)methane) and a diethynyl ligand providing “full support” for the possible transannular Au–Au contact (3). This compound and its “semi-” and “unsupported” analogues (2, 1) have been characterized by NMR spectroscopy and elemental analysis. The monomeric nature of complex 3 in solution has been established using diffusion coefficients measured by DOSY-NMR spectroscopy and comparing the data with those of complexes 1 and 2 as references.

Exploration of Solid-State vs Solution-State Structure in Contact Ion Pair Systems: Synthesis, Characterization, and Solution-State Dynamics of Zinc Diphenyl Phosphate, [Zn{O2P(OPh)2}2], Donor-Base-Supported Complexes.

A family of zinc phosphate complexes supported by nitrogen donor-base ligands have been synthesized, and their molecular structures were identified in both the solid (X-ray crystallography) and solution state (DOSY NMR spectroscopy). [Zn{O2P(OPh)2}2]∞ (1), formed from the reaction of Zn[N(SiMe3)2]2 with HO(O)P(OPh)2 coordinates to donor-base ligands, i.e., pyridine (Py), 4-methylpyridine (4-MePy), 2,2-bipyridine (bipy), tetramethylethylenediamine (TMEDA), pentamethyldiethylenetriamine (PMDETA), and 1,3,5-trimethyl-1,3,5-triazacyclohexane (Me3-TAC), to produce polymeric 1D structures, [(Py)2Zn{O2P(OPh)2}2]∞ (2) and [(4-MePy)2Zn{O2P(OPh)2}2]∞ (3), the bimetalic systems, [(Bipy)Zn{O2P(OPh)2}2]2 (4), [(TMEDA)Zn{O2P(OPh)2}2]2 (5), and [(Me3-TAC)Zn{O2P(OPh)2}2]2 (7), as well as a mono-nuclear zinc bis-diphenylphosphate complex, [(PMDETA)Zn{O2P(OPh)2}2] (6). 1H NMR DOSY has been used to calculate averaged molecular weights of the species. Studies are consistent with the disassembly of polymeric 3 into the bimetallic species [(Me-Py)2·Zn2{O2P(OPh)2}4], where the Me-Py ligand is in rapid exchange with free Me-Py in solution. Further 1H DOSY NMR studies of 4 and 5 reveal that dissolution of the complex results in a monomer dimer equilibrium, i.e., [(Bipy)Zn{O2P(OPh)2}2]2 ⇆ 2[(Bipy)Zn{O2P(OPh)2}2] and [(TMEDA)Zn{O2P(OPh)2}2]2 ⇆ 2[(TMEDA)Zn{O2P(OPh)2}2], respectively, in which the equilibria lie toward formation of the monomer. As part of our studies, variable temperature 1H DOSY experiments (223 to 313 K) were performed upon 5 in d8-tol, which allowed us to approximate the enthalpy [ΔH = -43.2 kJ mol-1 (±3.79)], entropy [ΔS = 109 J mol-1 K-1 (±13.9)], and approximate Gibbs free energy [ΔG = 75.6 kJ mol-1 (±5.62) at 293 K)] of monomer-dimer equilibria. While complex 6 is shown to maintain its monomeric solid-state structure, 1H DOSY experiments of 7 at 298 K reveal two separate normalized diffusion coefficients consistent with the presence of the bimetallic species [(TAC)2-xZn2{O2P(OPh)2}4], (x = 1 or 0) and free TAC ligand.

Synthesis of ONO‐Ligated Tetrylenes Based on 2,6‐bis(2‐Hydroxyphenyl)pyridines: Influence of Ligand Sterics on the Structure of the Products

AbstractA series of novel tetrylenes based on three 2,6‐bis(2‐hydroxyphenyl)pyridines 4 a–4 c have been obtained by the reaction of Lappert's tetrylenes E[N(SiMe3)2]2 (E=Ge, Sn) with corresponding tridentate pyridine‐linked phenol‐based ligands. It was found that the structure of the ligand and the size of the atom of the group 14 element drastically affect the structure of the reaction product. Ligand 4 c with a bulky tert‐butyl group leads to monomeric tetrylenes, while ligands with less bulky groups lead to bis‐ligand derivatives of M(IV) (M=Ge, Sn) and a coordination polymer. Also, derivatives of germanium (IV) and tin (IV) were obtained by the metathesis reaction of MCl4 (M=Ge, Sn) with lithium phenoxides. The compositions and structures of the novel compounds were established by elemental analysis and 1H, 13C, 119Sn (5–7), 1H DOSY (6) NMR spectroscopy, in the solid state by X‐ray diffraction analysis (germylene 10, stannylene 6, Ge4+ compound 8, Sn4+ compound 7) and 119Sn Mössbauer spectrum of tin complex 6. All the synthesized tetrylenes are monomeric. Tetrylenes 6 and 10 were characterized by cyclic voltammetry. A study of the redox behavior of 6, 10 by cyclic voltammetry on a glassy carbon working electrode in acetonitrile solution of 0.1 M Bu4NPF6 as a supporting electrolyte showed that these compounds can be both oxidized and reduced electrochemically in the accessible potential range.

Catalytic living ROMP: block copolymers from macro-chain transfer agents.

Vinyl ether based macro-chain transfer agents (m-CTAs) are used to produce different di or tri-block copolymers under catalytic living ROMP conditions. Polystyrene (PS) vinyl ether m-CTA and polycaprolactone (PCL) or polylactide vinyl ether (PLA) m-CTAs are synthesized straightforwardly via ATRP and ROP respectively. Regioselectivity as well as the high metathesis activity of these m-CTAs enabled us to synthesise a range of metathesis-based A-B diblock copolymers with controlled dispersities (Đ < 1.4). In this manner, PS-ROMP (here, ROMP refers to a poly(MNI-co-DHF) block), PCL-ROMP and PLA-ROMP were synthesized using substoichiometric amounts of ruthenium complex in a living fashion. Also, a more complex PEG-PCL-ROMP tri-block terpolymer was obtained catalytically. All block copolymers were characterized by SEC and DOSY NMR spectroscopy. We believe that this methodology of using macro-chain transfer agents to prepare degradable ROMP polymers under catalytic living ROMP conditions will find applications in biomedicine.

NacNac-zinc-pyridonate mediated ε-caprolactone ROP.

Herein we report the synthesis, isolation and polymerisation activity of two new zinc compounds based on a 2,6-diisopropylphenyl (Dipp) β-diiminate (NacNac) ligand framework with zinc also ligated by an amidate (2-pyridonate or 6-methyl-2-pyridonate) unit. The compounds crystallised as either monomeric (6-Me-2-pyridonate derivative) or dimeric (2-pyridonate) species, although both were found to be monomeric in solution via1H DOSY NMR spectroscopy, which was supported by DFT calculations. These observations suggest that both complexes initiate ring-opening polymerisation (ROP) through a single-site monometallic mechanism. High molecular weight poly ε-caprolactone (PCL) was achieved via exogenous initiator-free ROP conditions with both catalysts. An increase in the 2-pyridonate initiator steric bulk (6-Me- vs. 6-H-) resulted in an improved catalytic activity, facilitating complete monomer conversion within 1 h at 60 °C. Pyridonate end-groups were observed by MALDI-ToF mass spectrometry, contrasting with previous observations for DippNacNac-Zn acetate complexes (where no acetate end groups are observed), instead this more closely resembles the reactivity of DippNacNac-Zn alkoxide complexes in ROP (where RO end groups are observed). Additional major signals in the MALDI-ToF spectra were consistent with cyclic PCL species, which are attributed to back-biting ring-closing termination steps occuring in a process facilitated by the pyridonate unit being an effective leaving group. To the best of our knowledge, these complexes represent the first examples of pyridonate, and indeed amidate, initated ROP.

Silicone-specific identification of trace polydimethylsiloxanes in wines with 2D-diffusion-ordered nuclear magnetic resonance spectroscopy (DOSY-NMR)

Present work stresses a novel analytical approach for increasing the specificity of standard NMR approaches for identifying polydimethylsiloxane (PDMS) and further silicone moieties in wines’ organic extracts, by including a second dimension that correlates chemical shifts with diffusion coefficients by means of pulsed-field gradient diffusion ordered spectroscopy (DOSY-NMR). Each silicone source in wines is unambiguously assigned by correlation of both local chemical environments and by a unique diffusion coefficient value, in turn related to a hydrodynamic radius (RH) that can be obtained with respect proper internal standards. Obtained PDMS diffusion coefficient values and hydrodynamic radii in wines’ extracts, in agreement with expected values, present a selectivity and specificity so far not reported, that positions DOSY-NMR spectroscopy as an alternative in oenology for controlling PDMS limits.

Functionalization of Polylactide with Multiple Tetraphenyethane Inifer Groups to Form PLA Block Copolymers with Vinyl Monomers

In the present contribution, a new strategy for preparing block copolymers of polylactide (PLA), a bio-derived polymer of increasing importance, is described. The method should lead to multiblock copolymers of lactide with vinyl monomers (VM), i.e., monomers that polymerize according to different mechanisms, and is based on the introduction of multiple "inifer" (INItiator/transFER agent) groups into PLA's structure. As an "inifer" group, tetraphenylethane (TPE, known to easily thermally dissociate to radicals) was incorporated into PLA chains using diisocyanate. PLA that contained TPE groups (PLA-PU) was characterized, and its ability to form initiating radicals was demonstrated by ESR measurements. PLA-PU was used as a "macroinifer" for the polymerization of acrylonitrile and styrene upon moderate heating (85 °C) of the PLA-PU in the presence of monomers. The formation of block copolymers PLA/PVM was confirmed by 1H NMR, DOSY NMR, and FTIR spectroscopies and the SEC method. The prepared copolymers showed only one glass transition in DSC curves with Tg values higher than those of PLA-PU.

Macrochain Transfer Agents for Catalytic Ring-Opening Metathesis Polymerization.

A monosubstituted 1,3-diene derivative attached to a polymer is demonstrated to act as a macrochain transfer agent in catalytic ring-opening metathesis polymerization. PEG- and PLA-based macrochain transfer agents were synthesized in a few steps and were characterized using NMR spectroscopy, size exclusion chromatography (SEC) and matrix-assisted laser desorption/ionization-time-of-flight (MALDI-ToF) mass spectrometry. Poly(l-lactide) based diblock copolymer, poly(ethylene glycol)-based diblock, and triblock (ABA type) copolymers of varied chain lengths were prepared catalytically in a one-pot approach via metathesis polymerization. Block copolymers were characterized by SEC and showed monomodal molecular weight distributions. Moreover, DOSY NMR spectroscopy further proved the block microstructures of the synthesized polymers.

Light-driven interconversion of Pd2L4 cage and mononuclear PdL2 mediated by the isomerization of azobenzene ligand

The lantern-shaped cage Pd2L4 and tweezer-like PdL2 can be synthesized from the trans- and cis-isomer of an azobenzene-containing ligand, respectively, which were characterized by 1H, 13C, 1H-1H COSY, DOSY NMR spectroscopies, high-resolution ESI-MS and density function theory (DFT) calculations. The interconversion of Pd2L4 and PdL2 can be achieved via the cis-trans isomerization of the azobenzene unit on the ligand upon alternative irradiation of light 365 nm or 420 nm.

Second Generation Self‐Assembling Dendrimer Combining Supramolecular and Dynamic Covalent Chemistry

AbstractA monodisperse second generation self‐assembled dendrimer has been obtained combining supramolecular chemistry and dynamic covalent chemistry as orthogonal binding moieties. A branching unit 18 and a core 5 were connected via a heteroleptic terpyridine zinc complex exploiting the sterical hindrance of mesitylene units in the 6,6’’‐position of one of the terpyridines as the distinction between the ligands. Solubility problems could be solved by introduction of an ethylhexyl ether. The final sphere of the dendrimer was connected via imines, hydrazones and oximes, whereby the oxime made from O‐methylhydroxylamine (22) led to a complete turnover of all aldehyde functions. Furthermore, no amine signal was left and also no signals for a diffusion constant of the hydroxylamine 22 were observed. The successful formation of the dendrimers was analyzed by 1H NMR and DOSY NMR spectroscopy. Furthermore both, the first and second generation dendrimers could be detected by ESI HRMS.

An AB2 -Type Hyperbranched Supramolecular Polymer Based on Calix[4]Pyrrole Anion Recognition: Construction, Stimuli-Responsiveness, and Morphology Tuning.

An AB2 -type monomer comprised of a calix[4]pyrrole skeleton and alternating bis-carboxylate units is reported and used for the construction of a novel supramolecular hyperbranched polymer based on anion recognition ability of calix[4]pyrrole. 1 H-, DOSY-NMR spectroscopy, viscosity measurements, and dynamic light scatteringtechniques are used for the characterization of the supramolecular hyperbranched polymer exhibiting thermo-, pH-, and chemical responsiveness, as well as concentration dependent morphology tune as inferred from electron microscopy analyses. The present study enriches the field of supramolecular polymers with a new construction motif, building block, and provides a simple approach for the fabrication of smart polymer material with multi-responsiveness and -morphologies.