15N Nuclear Magnetic Resonance Research Articles

Improved solid-state 13C and 15N NMR reveals fundamental compositional divide between refractory dissolved organic carbon and nitrogen in the sea

Marine dissolved organic matter (DOM) is one of the largest reservoirs of organic carbon and nitrogen in the world. Yet, despite its global importance, most DOM remains molecularly uncharacterized. Solid-state nuclear magnetic resonance (NMR) spectroscopy of isolated DOM fractions represents one of the most powerful techniques to understand overall structural composition. However, it is well known that standard cross polarization magic angle spinning (CP/MAS) NMR, the technique used for almost all past solid-state NMR studies of DOM, is at best “semi-quantitative,” and underestimates fully substituted NMR active nuclei. Additionally, almost all past solid-state NMR work analyzed high molecular weight (HMW) material isolated by ultrafiltration, which is now understood to represent mostly 14C-young, “semi-labile” compounds. In contrast, there is far less information regarding the composition of older, low molecular weight (LMW) DOM, which represents the vast majority of the ocean’s accumulated refractory DOM pool.Here, we applied 13C and 15N solid-state multiCP/MAS NMR, improved NMR methods optimized to more quantitatively resolve fully substituted NMR nuclei, to both HMW and LMW DOM isolated from the surface and deep North Pacific Subtropical Gyre. These methods confirm past work indicating most nitrogen containing HMW DOM as amide compounds, but also demonstrate a modest heterocyclic N component not previously identified. In contrast, we found that LMW DON is almost entirely aromatic heterocyclic N, consistent with the hypothesis that heterocyclic N structures may be largely responsible for the accumulation of the ocean’s refractory DON pool. Surprisingly, however, we find DOC aromatic functionalities still represent only a very minor portion of either the HMW or the LMW refractory carbon pools, in marked contrast to refractory DON composition. Together, these more quantitative solid-state NMR techniques likely represent the most accurate picture of DON and DOC functional and compound-class makeup to date, and so have broad implications for our understanding of marine DOM structure and cycling. Specifically, our new data suggests that while chemical composition likely acts as a key control on DOM lability, the most refractory components of DOC and DON have very different compositions, sources, and cycling, supporting the idea that DOC and DON cycling in the ocean may be largely decoupled.

Molybdenum(VI) Nitrido Complexes with Tripodal Silanolate Ligands. Structure and Electronic Character of an Unsymmetrical Dimolybdenum μ-Nitrido Complex Formed by Incomplete Nitrogen Atom Transfer.

In contrast to a tungsten nitrido complex endowed with a tripodal silanolate ligand framework, which was reported in the literature to be a dimeric species with a metallacyclic core, the corresponding molybdenum nitrides 3 are monomeric entities comprising a regular terminal nitride unit, as proven by single-crystal X-ray diffraction (SC-XRD). Their electronic character is largely determined by the constraints imposed on the metal center by the podand ligand architecture. 95Mo nuclear magnetic resonance (NMR) and, to a lesser extent, 14N NMR spectroscopy allow these effects to be studied, which become particularly apparent upon comparison with the spectral data of related molybdenum nitrides comprising unrestrained silanolate, alkoxide, or amide ligands. Attempted nitrogen atom transfer from these novel terminal nitrides to [(tBuArN)3Mo] (Ar = 3,5-dimethylphenyl) as the potential acceptor stopped at the stage of unsymmetric dimolybdenum μ-nitrido complex 13a as the first intermediate along the reaction pathway. SC-XRD, NMR, electron paramagnetic resonance, and ultraviolet-visible spectroscopy as well as magnetometry in combination with density functional theory allowed a clear picture of the geometric and electronic structure of this mixed-valent species to be drawn. 13a is formally best described as an adduct of the type [(Mo[O])+III-(μN)-III-(Mo[N])+VI], S = 1/2 complex with (Mo[O])+III in the low-spin configuration, whereas related complexes such as [(AdS)3Mo-(μN)-Mo(NtBuAr)3] (19; Ad = 1-adamantyl) have previously been regarded in the literature as mixed-valent Mo+IV/Mo+V species. The spin population at the two Mo centers is uneven and notably larger at the more reduced Mo[O] atom, whereas the only spin present at the (μN) bridge is derived from spin polarization.

1H, 13C and 15N backbone and side-chain resonance assignments of the human oncogenic protein NCYM.

NCYM is a cis-antisense gene of MYCN oncogene and encodes an oncogenic protein that stabilizes MYCN via inhibition of GSK3b. High NCYM expression levels are associated with poor clinical outcomes in human neuroblastomas, and NCYM overexpression promotes distant metastasis in animal models of neuroblastoma. Using vacuum-ultraviolet circular dichroism and small-angle X-ray scattering, we previously showed that NCYM has high flexibility with partially folded structures; however, further structural characterization is required for the design of anti-cancer agents targeting NCYM. Here we report the 1H, 15N and 13C nuclear magnetic resonance assignments of NCYM. Secondary structure prediction using Secondary Chemical Shifts and TALOS-N analysis demonstrates that the structure of NCYM is essentially disordered, even though residues in the central region of the peptide clearly present a propensity to adopt a dynamic helical structure. This preliminary study provides foundations for further analysis of interaction between NCYM and potential partners.

Metal-Mediated Catalytic Polarization Transfer from para Hydrogen to 3,5-Dihalogenated Pyridines.

The neutral catalysts [IrCl(H)2(NHC)(substrate)2] or [IrCl(H)2(NHC)(substrate)(sulfoxide)] are used to transfer polarization from para hydrogen (pH2) to 3,5-dichloropyridine and 3,5-dibromopyridine substrates. This is achieved in a rapid, reversible, and low-cost process that relies on ligand exchange within the active catalyst. Notably, the sulfoxide-containing catalyst systems produced NMR signal enhancements between 1 and 2 orders of magnitude larger than its unmodified counterpart. Consequently, this signal amplification by reversible exchange hyperpolarization method can boost the 1H, 13C, and 15N nuclear magnetic resonance (NMR) signal intensities by factors up to 4350, 1550, and 46,600, respectively (14.0, 1.3, and 15.4% polarization). In this paper, NMR and X-ray crystallography are used to map the evolution of catalytically important species and provide mechanistic rational for catalytic efficiency. Furthermore, applications in spontaneous radiofrequency amplification by stimulated emission and NMR reaction monitoring are also shown.

Effects of structures of lower aliphatic alcohols and concentrations on CO2 chemical absorption and desorption reactions in various alcohol solutions of 1,8-diazabicyclo[5.4.0]undec-7-ene

Alcohol solutions of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) have received considerable interest as chemical absorbers of CO2 and switchable solvents because of their reversible reaction with CO2 and the polarity change triggered by CO2 absorption/desorption. However, there have been only a few systematic studies on the CO2 absorption and desorption behaviors of DBU–alcohol solutions. In this study, we determined the solubility of CO2 in binary solutions of DBU and various lower aliphatic alcohols at different temperatures. Except for the 2-methyl-2-propanol solution, which showed very low reactivity with CO2, all the DBU–alcohol solutions exhibited almost the same solubilities of CO2 at 298.2 K, independent of the alkyl groups present on the alcohols. However, their solubilities varied with DBU concentration. Moreover, we examined the amounts of CO2 recovery from the CO2-saturated solutions at high temperatures up to 393.2 K or the boiling points. The amount of CO2 per mole of DBU desorbed by heating was markedly influenced by both the alkyl group on the alcohols and the DBU concentration, indicating that at the studied concentrations, the temperature dependence of CO2 solubilities is strongly affected by the type of alcohol. To clarify this unique desorption behavior, we measured the 1H, 13C, and 15N nuclear magnetic resonance spectra of the DBU–alcohol solutions with and without CO2 at 298.2 K. In the absence of CO2, the nitrogen atoms at the 8-position of the DBU molecules strongly interact with the hydroxyl hydrogen atoms of the alcohol molecules via hydrogen bonding. As the DBU–alcohol solutions were saturated with CO2, the formation of protonated DBU ([DBUH]+) and alcohol-CO2 adduct (alkyl carbonate, [ROCO2]–) was confirmed. [DBUH]+ is stabilized by the solvation of free alcohol molecules, and the reverse reaction of [DBUH]+ with [ROCO2]– for CO2 release is hindered. Our findings are beneficial for designing and tuning DBU–alcohol systems for CO2 separation.

Continuous Synthesis of Cinnarizine Salt with Malic Acid by Applying Green Chemistry Using Water-Assisted Twin Screw Extrusion.

Organic solvent-free process or green chemistry is needed for manufacturing pharmaceutical salts to avoid various environmental, safety, and manufacturing cost issues involved. In this study, a cinnarizine (CNZ) salt with malic acid at a 1:1 molar ratio was successfully prepared by twin screw extrusion (TSE) with water assistance. The feasibility of salt formation was first evaluated by screening several carboxylic acids by neat grinding (NG) and liquid-assisted grinding (LAG) using a mortar and pestle, which indicated that malic acid and succinic acid could form salts with CNZ. Further studies on salt formation were conducted using malic acid. The examination by hot-stage microscopy revealed that the addition of water could facilitate the formation and crystallization of CNZ-malic acid salt even though CNZ is poorly water-soluble. The feasibility of salt formation was confirmed by determining the pH-solubility relationship between CNZ and malic acid, where a pHmax of 2.7 and a salt solubility of 2.47 mg/mL were observed. Authentic salt crystals were prepared by solution crystallization from organic solvents for examining crystal properties and structure by differential scanning calorimetry (DSC), powder X-ray diffraction (PXRD), Fourier transform infrared (FTIR) spectroscopy, solid-state 13C and 15N nuclear magnetic resonance (NMR), and single-crystal X-ray diffraction (SXD). These techniques also established that a salt, and not a cocrystal, was indeed formed. The CNZ salt crystals were then prepared by TSE of a 1:1 CNZ-malic acid mixture, where the addition of small amounts of water resulted in a complete conversion of the mixture into the salt form. The salts prepared by solvent crystallization and water-assisted TSE had identical properties, and their moisture sorption profiles were also similar, indicating that TSE is a viable method for salt preparation by green chemistry. Since TSE can be conducted in a continuous manner, the results of the present investigation, if combined with other continuous processes, suggest the possibility of continuous manufacturing of drug products from the synthesis of active pharmaceutical ingredients (APIs) to the production of final dosage forms.

Synthesis and Characterization of 15N‐Labeled Poly(sulfur nitride) in Bulk and in Superconductor Composites

Abstract15N‐labeled tetrasulfur tetranitride (S415N4) was synthesized by reacting S2Cl2 with 15NH3. The reaction was finalized with 14NH3. The successful labeling was confirmed by solution 15N nuclear magnetic resonance (NMR) spectroscopy. S415N4 was used for the synthesis of poly(sulfur nitride) S15Nx via the intermediate species of S2N2. It was a topochemical polymerization in the solid state. The isotope ratio in the labeled polymer was obtained by laser deposition ionization time‐of‐flight mass spectroscopy. Solid‐state 15N NMR spectroscopy of S15Nx indicates that at least three different chemical environments for 15N atoms are present in the crystals. Finally, SNx was polymerized in the presence of two other superconductors, MgB2 and yttrium barium copper oxide (YBCO), which demonstrates the capability of SNx for grain boundary engineering.

Liquid-Liquid Phase Separation Modifies the Dynamic Properties of Intrinsically Disordered Proteins.

Liquid-liquid phase separation of flexible biomolecules has been identified as a ubiquitous phenomenon underlying the formation of membraneless organelles that harbor a multitude of essential cellular processes. We use nuclear magnetic resonance (NMR) spectroscopy to compare the dynamic properties of an intrinsically disordered protein (measles virus NTAIL) in the dilute and dense phases at atomic resolution. By measuring 15N NMR relaxation at different magnetic field strengths, we are able to characterize the dynamics of the protein in dilute and crowded conditions and to compare the amplitude and timescale of the different motional modes to those present in the membraneless organelle. Although the local backbone conformational sampling appears to be largely retained, dynamics occurring on all detectable timescales, including librational, backbone dihedral angle dynamics and segmental, chainlike motions, are considerably slowed down. Their relative amplitudes are also drastically modified, with slower, chain-like motions dominating the dynamic profile. In order to provide additional mechanistic insight, we performed extensive molecular dynamics simulations of the protein under self-crowding conditions at concentrations comparable to those found in the dense liquid phase. Simulation broadly reproduces the impact of formation of the condensed phase on both the free energy landscape and the kinetic interconversion between states. In particular, the experimentally observed reduction in the amplitude of the fastest component of backbone dynamics correlates with higher levels of intermolecular contacts or entanglement observed in simulations, reducing the conformational space available to this mode under strongly self-crowding conditions.

Extraction of Nitric Acid and Uranium with DEHiBA under High Loading Conditions.

The mechanism by which high concentrations (1.5 M in n-dodecane) of N,N-di-2-ethylhexyl-isobutyramide (DEHiBA) extracts HNO3 and UO2(NO3)2 is under examination. Most prior studies have examined the extractant and the mechanism at a concentration of 1.0 M in n-dodecane; however, under the higher loading conditions that can be achieved by a higher concentration of extractant, this mechanism could change. Increased extraction of both nitric acid and uranium is observed with an increased concentration of DEHiBA. The mechanisms are examined by thermodynamic modeling of distribution ratios, 15N nuclear magnetic resonance (NMR) spectroscopy, and Fourier transform infrared (FTIR) spectroscopy coupled with principal component analysis (PCA). Speciation diagrams produced through thermodynamic modeling have been qualitatively reproduced through PCA of the FTIR spectra. The predominant extracted species of HNO3(DEHiBA), HNO3(DEHiBA)2, and UO2(NO3)2(DEHiBA)2 are in good agreement with prior literature reports for 1.0 M DEHiBA systems. Evidence for an additional species of either UO2(NO3)2(DEHiBA) or UO2(NO3)2(DEHiBA)2(HNO3) also contributing to the extraction of uranium species is given.

15N CP/MAS NMR as a Tool for the Mechanistic Study of Mechanical Stimuli-Responsive Materials: Evidence for the Conformational Change of an Emissive Dimethylacridane Derivative.

Mechanochromic luminescent molecules are currently attracting considerable attention because of their promising technological applications, but understanding their mechanism of action is challenging and is thus hindering our deeper understanding of these materials. The conformational change of 9,9'-dimethyl-9,10-dihydroacridane derivative 1 was examined using solid-state 15N nuclear magnetic resonance (NMR) spectroscopic techniques without using a specifically 15N-labeled compound. A difference between the two conformers was clearly observed in the measurements and was assigned to the ⟨pl⟩ and ⟨bf⟩ spatial structures. The results were supported by quantum chemical calculations on 15N NMR chemical shifts of each isomer. The technique presented here can clearly identify the structural changes caused by crushing a powder sample. Such structural changes are difficult to determine using X-ray diffraction (XRD) measurements.

Characterization of the hydrochloride salt hemihydrate as a new salt of the antifungal agent tioconazole

Tioconazole is an effective antifungal agent, which has a very low solubility in aqueous media, that limits its bioavailability and efficacy. In an effort to overcome the drug limitations by improving its solubility, the hydrochloride salt was prepared in methanolic 1 M HCl and obtained as the hemihydrate, as demonstrated by elemental analysis. Single crystals were grown by slow evaporation from an aqueous 1 M HCl solution and their structure was determined using single-crystal X-ray diffraction at 302 K. The structures resulting from dehydration and further rehydration were also assessed, at 333 and 283 K, respectively. The morphology of the crystal, which exhibited birefringence under polarized light, was verified by hot stage microscopy. The solid was characterized by additional means, including thermal analysis (melting point, differential scanning calorimetry and thermogravimetry), spectroscopic methods (mid infrared, near infrared, 1H, 13C and 15N nuclear magnetic resonance in solution, as well as 13C and 15N solid state with spinning at the magic angle) and X-ray diffraction techniques. Functional evaluation tests, including the intrinsic dissolution rate and the dissolution of powders were also performed. In the intrinsic dissolution rate test, the salt proved to dissolve over 2000 times faster than tioconazole. The results suggest that the new salt has physicochemical and performance properties which may support its use as a replacement of the free base in certain applications, especially where improved dissolution rate, solubility or bioavailability of the drug would be desired.

Characterization of retinal chromophore and protonated Schiff base in Thermoplasmatales archaeon heliorhodopsin using solid-state NMR spectroscopy

Heliorhodopsin (HeR) is a seven-helical transmembrane protein with a retinal chromophore that corresponds to a new rhodopsin family. HeR from the archaebacterium Thermoplasmatales archaeon (TaHeR) exhibits unique features, such as the inverted protein orientation in the membrane compared to other rhodopsins and a long photocycle. Here, we used solid-state nuclear magnetic resonance (NMR) spectroscopy to investigate the 13C and 15N NMR signals of the retinal chromophore and protonated Schiff base (RPSB) in TaHeR embedded in POPE/POPG membrane. Although the 14- and 20-13C retinal signals indicated 13-trans/15-anti (all-trans) configurations, the 20-13C chemical shift value was different from that of other microbial rhodopsins, indicating weakly steric hinderance between Phe203 and the C20 methyl group. 15N RPSB/λmax plot deviated from the linear correlation based on retinylidene-halide model compounds. Furthermore, 15N chemical shift anisotropy (CSA) suggested that Ser112 and Ser234 polar residues distinguish the electronic environment tendencies of RPSB from those of other microbial rhodopsins. Our NMR results revealed that the retinal chromophore and the RPSB in TaHeR exhibit unique electronic environments.

Relating algal-derived extracellular and intracellular dissolved organic nitrogen with nitrogenous disinfection by-product formation

The dissolved organic nitrogen (DON) pool from algal-derived extracellular and intracellular organic matter (EOM and IOM) comprises proteins, peptides, free amino acids and carbohydrates, of which, proteins can contribute up to 100% of the DON. Previous reports of algal-derived DON character have focused on bulk properties including concentration, molecular weight and hydrophobicity. However, these can be similar between algal species and between the EOM and IOM even when the inherent molecular structures vary. A focus on bulk character presents challenges to the research on algal-derived nitrogenous-disinfection by-product (N-DBP) formation as N-DBP formation is sensitive to the changes in molecular structure. Hence, the main aim of this study was to characterize algal EOM and IOM-derived DON, specifically proteinaceous-DON, using a combination of bulk and molecular characterization techniques to enable a more detailed exploration of the relationship between the character of algal-derived proteins and the N-DBP formation potential. DON from the EOM and IOM of four commonly found algae and cyanobacteria in natural waters were evaluated, namely Chlorella vulgaris, Microcystis aeruginosa, Dolichospermum circinale, and Cylindrospermopsis raciborskii. It was observed that 77-96% of total DON in all EOM and IOM samples was of proteinaceous origin. In the proteins, DON concentrations were highest in the high molecular weight fraction of IOM-derived bulk proteins (0.13–0.75 mg N L−1) and low to medium molecular weight fraction of EOM-derived bulk proteins (0.15–0.63 mg N L−1) in all species. Similar observations were also made via sodium dodecyl sulphate polyacrylamide gel electrophoresis and liquid chromatography-high resolution mass spectrometry. Solid-state 15N nuclear magnetic resonance (NMR) spectroscopy of the EOM and IOM revealed the existence of common aliphatic and heterocyclic N-groups in all samples, including a dominant 2° amide peak. Species dependent variability was also observed in the spectra, particularly in the EOM; e.g. nitro signals were found only in the Cylindrospermopsis raciborskii EOM. Dichloroacetonitrile (DCAN) and N-nitrosamine concentrations from the EOM of the species evaluated in this study were lower than the guideline limits set by regulatory agencies. It is proposed that the dominant 2° amide in all samples decreased N-DBP formation upon chlorination. For chloramination, the presence of nitro groups and aliphatic and heterocyclic N-DBP precursors could cause variable N-nitrosamine formation. Compared to non-algal impacted waters, algae-laden waters are characterised by low organic carbon: organic nitrogen ratios of ∼7–14 and elevated DON and protein concentrations. Hence, relying only on bulk characterization increases the perceived risk of N-DBP formation from algae-laden waters.

Insight into the Molecular Structure, Interaction, and Dynamics of Aqueous Reline Deep Eutectic Solvent: A Nuclear Magnetic Resonance Investigation

Reline, which is composed of choline chloride (ChCl) and urea, is the first and most widely used deep eutectic solvent (DES) described by Abbot and co-workers. Due to the hygroscopic feature, traces of water are unavoidable, which significantly affect the physicochemical properties of reline. At present, the local structure of molecules and the impact from the presence of water are still the most significant questions in this field. Herein, reline and six aqueous dilutions with a controlled amount of water (from 3.2 to 50.0 wt %) were studied mainly by using a combination of nuclear magnetic resonance (NMR) techniques. According to 1D 35Cl NMR, 1D 15N NMR, and 2D 1H-15Cl heteronuclear Overhauser effect spectroscopy, we probed the interactions of urea···Cl- and Ch+···Cl- in pure reline, which gradually dissociated in the presence of water. Moreover, it was revealed that the dissociation rate altered when the water content reached 9.0 wt %, which is ascribed to the higher preference of hydration for Cl- ion compared to other species in the system. Furthermore, selected cross peaks in 1H-1H correlation spectroscopy spectra were analyzed. Accordingly, an enhanced correlation was observed for urea···Ch+ at a lower water fraction within 9.0 wt %. When the water content increased to 24.9 wt %, the water solvation of Ch+ and urea was also observed in COSY spectra. The interaction of H2O···Ch+ got continuously stronger when the water content increased from 24.9 to 50.0 wt %, while H2O···urea got enhanced when the water content reached 33.3 wt % and then diminished gradually from 33.3 to 50.0 wt %. 1H-1H nuclear Overhauser effect spectroscopy and 1H-1H rotating frame Overhauser effect spectroscopy experiments were also conducted for dynamics investigation. The τc value for the species in 9.0 wt % aqueous reline is very close to τccrit of 0.44 ns. For pure reline and the aqueous reline with a water fraction of less than 9.0 wt %, the τc value of the species is longer than 0.44 ns, while for the sample with water of 24.9 wt %, the τc value is much shorter than 0.44 ns. Based on our NMR study, we revealed that with the water amount increasing from 0 to 50.0 wt %, the species involved in the system behaved as the large molecules or molecules in viscous liquids transiting to the medium-sized molecules in nonviscous liquids and finally to small molecules in nonviscous liquids.

Acrylamide derivatives: A dynamic nuclear magnetic resonance study.

Substituted acrylamides have found an extensive application in organic and medical chemistry; therefore, it is very important to get insight into their features such as electronic structure, spectral properties, and stereochemical transformations. A correct interpretation of the chemical behavior and biological activity of these heteroatomic systems is impossible without knowledge of the structure of stereodynamic forms and factors determining their relative stability. The structure and peculiarities of stereodynamic behavior of substituted acrylamides and their model compounds were studied by dynamic and multinuclear 1 H, 13 C, and 15 N nuclear magnetic resonance (NMR) spectroscopy in CDCl3 and DMSO-d6 solution. It has been established that acrylamides in solution are realized as Z- and E-isomers, with the E-rotamer being somewhat predominant. The obtained experimental values of the free activation energy of rotamers vary within 15-17 kcal/mol, depending on the stereochemical structure of the molecule. 15 N NMR spectroscopy is the most reliable and fastest method for determining the structural and stereochemical features of nitrogen-containing compounds.

DMSO-Induced Unfolding of the Antifungal Disulfide Protein PAF and Its Inactive Variant: A Combined NMR and DSC Study.

PAF and related antifungal proteins are promising antimicrobial agents. They have highly stable folds around room temperature due to the presence of 3-4 disulfide bonds. However, unfolded states persist and contribute to the thermal equilibrium in aqueous solution, and low-populated states might influence their biological impact. To explore such equilibria during dimethyl sulfoxide (DMSO)-induced chemical unfolding, we studied PAF and its inactive variant PAFD19S using nuclear magnetic resonance (NMR) and differential scanning calorimetry (DSC). According to the NMR monitoring at 310 K, the folded structures disappear above 80 v/v% DMSO concentration, while the unfolding is completely reversible. Evaluation of a few resolved peaks from viscosity-compensated 15N-1H HSQC spectra of PAF yielded ∆G = 23 ± 7 kJ/M as the average value for NMR unfolding enthalpy. The NMR-based structures of PAF and the mutant in 50 v/v% DMSO/H2O mixtures were more similar in the mixed solvents then they were in water. The 15N NMR relaxation dynamics in the same mixtures verified the rigid backbones of the NMR-visible fractions of the proteins; still, enhanced dynamics around the termini and some loops were observed. DSC monitoring of the Tm melting point showed parabolic dependence on the DMSO molar fraction and suggested that PAF is more stable than the inactive PAFD19S. The DSC experiments were irreversible due to the applied broad temperature range, but still suggestive of the endothermic unfolding of PAF.

Elucidation of Metal Local Environments in Single-Atom Catalysts Based on Carbon Nitrides.

The ability to tailor the properties of metal centers in single-atom heterogeneous catalysts depends on the availability of advanced approaches for characterization of their structure. Except for specific host materials with well-defined metal adsorption sites, determining the local atomic environment remains a crucial challenge, often relying heavily on simulations. This article reports an advanced analysis of platinum atoms stabilized on poly(triazine imide), a nanocrystalline form of carbon nitride. The approach discriminates the distribution of surface coordination sites in the host, the evolution of metal coordination at different stages during the synthesis of the material, and the potential locations of metal atoms within the lattice. Consistent with density functional theory predictions, simultaneous high-resolution imaging in high-angle annular dark field and bright field modes experimentally confirms the preferred localization of platinum in-plane in the corners of the triangular cavities. X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), and dynamic nuclear polarization enhanced 15 N nuclear magnetic resonance (DNP-NMR) spectroscopies coupled with density functional theory (DFT) simulations reveal that the predominant metal species comprise Pt(II) bound to three nitrogen atoms and one chlorine atom inside the coordination sites. The findings, which narrow the gap between experimental and theoretical elucidation, contribute to the improved structural understanding and provide a benchmark for exploring the speciation of single-atom catalysts based on carbon nitrides.

Real-Time High-Sensitivity Reaction Monitoring of Important Nitrogen-Cycle Synthons by 15N Hyperpolarized Nuclear Magnetic Resonance.

Here, we show how signal amplification by reversible exchange hyperpolarization of a range of 15N-containing synthons can be used to enable studies of their reactivity by 15N nuclear magnetic resonance (NO2– (28% polarization), ND3 (3%), PhCH2NH2 (5%), NaN3 (3%), and NO3– (0.1%)). A range of iridium-based spin-polarization transfer catalysts are used, which for NO2– work optimally as an amino-derived carbene-containing complex with a DMAP-d2 coligand. We harness long 15N spin-order lifetimes to probe in situ reactivity out to 3 × T1. In the case of NO2– (T1 17.7 s at 9.4 T), we monitor PhNH2 diazotization in acidic solution. The resulting diazonium salt (15N-T1 38 s) forms within 30 s, and its subsequent reaction with NaN3 leads to the detection of hyperpolarized PhN3 (T1 192 s) in a second step via the formation of an identified cyclic pentazole intermediate. The role of PhN3 and NaN3 in copper-free click chemistry is exemplified for hyperpolarized triazole (T1 < 10 s) formation when they react with a strained alkyne. We also demonstrate simple routes to hyperpolarized N2 in addition to showing how utilization of 15N-polarized PhCH2NH2 enables the probing of amidation, sulfonamidation, and imine formation. Hyperpolarized ND3 is used to probe imine and ND4+ (T1 33.6 s) formation. Furthermore, for NO2–, we also demonstrate how the 15N-magnetic resonance imaging monitoring of biphasic catalysis confirms the successful preparation of an aqueous bolus of hyperpolarized 15NO2– in seconds with 8% polarization. Hence, we create a versatile tool to probe organic transformations that has significant relevance for the synthesis of future hyperpolarized pharmaceuticals.

NMR spectroscopic and theoretical study on the isomerism of dimethyl benzodiazepine(diylidene)diacetates.

The isomerism of dimethyl 2,2'-(7,8-dichloro-1H-benzo[b][1,4]diazepine-2,4-(3H,5H)diylidene)diacetate (1a) and dimethyl 2,2'-(7,8-dichloro-3-methyl-1H-benzo[b][1,4]diazepine-2,4-(3H,5H)diylidene)diacetate (1b) was investigated by 1 H, 13 C and 15 N nuclear magnetic resonance (NMR) spectroscopy. In CDCl3 solution, inversion of the diazepine ring was observed, whereas in (D6 )DMSO and (D7 )DMF solution, besides the ring inversion, a partial cleavage of one chelate ring appeared connected with (E/Z) isomerization about one of the exocyclic C=C bonds. Gibbs free energies (ΔG) and free activation energies (ΔG≠ ) were calculated based on B3PW91-SCRF/ZVP DFT computations. Agreement between NMR data and density functional theory (DFT) computations was found.

Insights into the κ-P,N Coordination of 1,3,5-Triaza-7-phosphaadamantane and Derivatives: κ-P,N-Heterometallic Complexes and a 15N Nuclear Magnetic Resonance Survey.

Complexes {[(PTA)2CpRu-μ-CN-1κC:2κ2N-RuCp(PTA)2-ZnCl3]}·2DMSO (13) {[ZnCl2(H2O)]-(PTA-1κP:2κ2N)(PTA)CpRu-μ-CN-1κC:2κ2N-RuCp(PTA)(PTA-1κP:2κ2N)-[ZnCl2(H2O)]}Cl (14), [RuCp(HdmoPTA)(PPh3)(PTA)](CF3SO3)2 (20), [RuCp(HdmoPTA)(HPTA)(PPh3)](CF3SO3)3 (21), and [RuCp(dmoPTA)(PPh3)(PTA)](CF3SO3) (22) were obtained and characterized, and their crystal structure together with that of the previously published complex 18 is reported. The behavior of the 1,3,5-triaza-7-phosphatricyclo[3.3.1.13,7]decane (PTA) and 3,7-dimethyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane (dmoPTA) ligands against protonation and κN-coordination is discussed, on the basis of 15N nuclear magnetic resonance data collected on 22 different compounds, including PTA (1), HdmoPTA (7H), and some common derivatives as free ligands (2–6 and 8), along with mono- and polymetallic complexes containing PTA and/or HdmoPTA (9–22). 15N detection via 1H–15N heteronuclear multiple bond correlation allowed the construction of a small library of 15N chemical shifts that shed light on important features regarding κN-coordination in PTA and its derivatives.