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While syringyl units are the most abundant monolignols in hardwood lignin, their phenolic (i.e. hydroxyl) end group concentration has not been measured. In two uniformly 13C-enriched young hardwoods, from beech and oak, the syringyl units were quantitatively investigated by advanced solid-state 13C NMR. Small signals of OH-terminated syringyl units were resolved in spectrally edited two-dimensional 13C-13C NMR spectra of the two hardwoods. Their distinct peak positions predicted based on literature data were validated via the abundant OH-terminated syringyl units in hydrolyzed 13C-beechwood. In a two-dimensional 13C-13C exchange spectrum with diagonal-ridge suppression, a well-resolved peak of phenolic syringyl units was observed at the characteristic C-H peak position of syringyl rings, without significant overlap from guaiacyl peaks. Accurate 13C chemical shifts of regular and end-group syringyl units were obtained. Through spectrally edited 2D NMR after 1H inversion recovery, phenols of condensed tannin complexed with arginine were carefully analyzed and shown to overlap minimally with signals from phenolic syringyl units. The local structure and resulting spin dynamics of ether (chain) and hydroxyl (end-group) syringyl units are nearly the same, enabling quantification by peak integration or deconvolution, which shows that phenolic syringyl end groups account for 2 ± 1 % of syringyl units in beechwood and 5 ± 2 % in oakwood. The observed low end-group concentration needs to be taken into account in realistic molecular models of hardwood lignin structure.
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Conventional topochemical photopolymerization reactions occur exclusively in precisely-engineered photoactive crystalline states, which often produces high-insoluble polymers. To mitigate this, here, we report the mechanoactivation of photostable styryldipyrylium-based monomers, which results in their amorphization-enabled solid-state photopolymerization and produces soluble and processable amorphous polymers. A combination of solid-state nuclear magnetic resonance, X-ray diffraction, and absorption/fluorescence spectroscopy reveals the crucial role of a mechanically-disordered monomer phase in yielding polymers via photo-induced [2 + 2] cycloaddition reaction. Hence, mechanoactivation and amorphization can expand the scope of topochemical polymerization conditions to open up opportunities for generating polymers that are otherwise difficult to synthesize and analyze.
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Patiromer (Veltassa®) is a crosslinked, insoluble co-polymer drug used as a nonabsorbent potassium binder, approved for treatment of hyperkalemia. Quantitative solid-state 13C nuclear magnetic resonance (NMR) analysis with comprehensive peak assignment, component quantification, and calculation of mole and weight fractions of monomer units was performed on three doses of patiromer. The workflow is documented in detail. Spectrally edited solid-state 13C NMR spectra of patiromer show =CHn peaks of matching intensity at 116 and 141â¯ppm, characteristic of -CH=CH2 vinyl groups. Similar spectral features can be observed in earlier studies but were previously ignored. In this study, the vinyl signals are well-resolved in a 2-s direct polarization (DP) spectrum without and with dipolar dephasing, which confirms that these sp2-hybridized carbons are bonded to hydrogen and partially mobile, consistent with vinyl side groups from incompletely reacted divinyl crosslinkers. The vinyl groups account for 1.6% of all carbon, 3% of the monomer units, and nearly 1/3 of the crosslinkers. Furthermore, an unexpected OCH3 moiety accounting for â¼1.2% of all carbons was identified by spectral editing; its chemical shift of 54â¯ppm is more consistent with a methyl ester than with a methyl ether. It can originate from incomplete hydrolysis of â¼6% of methyl-2-fluoroacrylate, the main monomer of patiromer. Characteristic cross peaks in two-dimensional 1H-13C heteronuclear correlation NMR confirm the presence of the vinyl and OCH3 groups. Trace amounts of xanthan gum are also detected. The quantitative 13C NMR spectrum of patiromer has been matched in a simulation using a model with five monomer units.
Asunto(s)
Ésteres , Espectroscopía de Resonancia Magnética , Polímeros , Polímeros/química , Ésteres/química , Espectroscopía de Resonancia Magnética/métodos , Compuestos de Vinilo/química , Solubilidad , Espectroscopía de Resonancia Magnética con Carbono-13/métodosRESUMEN
Boron trifluoride (BF3 ) is a highly corrosive gas widely used in industry. Confining BF3 in porous materials ensures safe and convenient handling and prevents its degradation. Hence, it is highly desired to develop porous materials with high adsorption capacity, high stability, and resistance to BF3 corrosion. Herein, we designed and synthesized a Lewis basic single-crystalline hydrogen-bond crosslinked organic framework (HC OF-50) for BF3 storage and its application in catalysis. Specifically, we introduced self-complementary ortho-alkoxy-benzamide hydrogen-bonding moieties to direct the formation of highly organized hydrogen-bonded networks, which were subsequently photo-crosslinked to generate HC OFs. The HC OF-50 features Lewis basic thioether linkages and electron-rich pore surfaces for BF3 uptake. As a result, HC OF-50 shows a record-high 14.2â mmol/g BF3 uptake capacity. The BF3 uptake in HC OF-50 is reversible, leading to the slow release of BF3 . We leveraged this property to reduce the undesirable chain transfer and termination in the cationic polymerization of vinyl ethers. Polymers with higher molecular weights and lower polydispersity were generated compared to those synthesized using BF3 â Et2 O. The elucidation of the structure-property relationship, as provided by the single-crystal X-ray structures, combined with the high BF3 uptake capacity and controlled sorption, highlights the molecular understanding of framework-guest interactions in addressing contemporary challenges.
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Hydroxypropyl methylcellulose acetyl succinate (HPMCAS) is widely used as a pharmaceutical excipient, making a detailed understanding of its tunable structure important for formulation design. Several recently reported peak assignments in the solid-state 13 C NMR spectrum of HPMCAS have been corrected here using peak integrals in quantitative spectra, spectral editing, empirical chemical-shift predictions based on solution NMR, and full spectrum simulation analogous to deconvolution. Unlike in cellulose, the strong peak at 84 ppm must be assigned to C2 and C3 methyl ethers, instead of regular C4 of cellulose. The proposed assignment of signals at <65 ppm to OCH sites, including C5 of cellulose, could not be confirmed. CH2 spectral editing showed two resolved OCH2 bands, a more intense one from O-CH2 ethers of C6 at >69 ppm and a smaller one from its esters and possibly residual CH2 -OH groups, near 63 ppm. The strong intensities of resolved signals of acetyl, succinoyl, and oxypropyl substituents indicated the substitution of >85% of the OH groups in HPMCAS. The side-group concentrations in three different grades of HPMCAS were quantified.
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We address a critical challenge of recovering and recycling homogeneous organocatalysts by designing photoswitchable catalyst structures that display a reversible solubility change in response to light. Initially insoluble catalysts are UV-switched to a soluble isomeric state, which catalyzes the reaction, then back-isomerizes to the insoluble state upon completion of the reaction to be filtered and recycled. The molecular design principles that allow for the drastic solubility change over 10 times between the isomeric states, 87 % recovery by the light-induced precipitation, and multiple rounds of catalyst recycling are revealed. This proof of concept will open up opportunities to develop highly recyclable homogeneous catalysts that are important for the synthesis of critical compounds in various industries, which is anticipated to significantly reduce environmental impact and costs.
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Citrate is a critical metabolic substrate and key regulator of energy metabolism in mammalian cells. It has been known for decades that the skeleton contains most (>85%) of the body's citrate, but the question of why and how this metabolite should be partitioned in bone has received singularly little attention. Here, we show that osteoblasts use a specialized metabolic pathway to regulate uptake, endogenous production, and the deposition of citrate into bone. Osteoblasts express high levels of the membranous Na+-dependent citrate transporter solute carrier family 13 member 5 (Slc13a5) gene. Inhibition or genetic disruption of Slc13a5 reduced osteogenic citrate uptake and disrupted mineral nodule formation. Bones from mice lacking Slc13a5 globally, or selectively in osteoblasts, showed equivalent reductions in cortical thickness, with similarly compromised mechanical strength. Surprisingly, citrate content in mineral from Slc13a5-/- osteoblasts was increased fourfold relative to controls, suggesting the engagement of compensatory mechanisms to augment endogenous citrate production. Indeed, through the coordinated functioning of the apical membrane citrate transporter SLC13A5 and a mitochondrial zinc transporter protein (ZIP1; encoded by Slc39a1), a mediator of citrate efflux from the tricarboxylic acid cycle, SLC13A5 mediates citrate entry from blood and its activity exerts homeostatic control of cytoplasmic citrate. Intriguingly, Slc13a5-deficient mice also exhibited defective tooth enamel and dentin formation, a clinical feature, which we show is recapitulated in primary teeth from children with SLC13A5 mutations. Together, our results reveal the components of an osteoblast metabolic pathway, which affects bone strength by regulating citrate deposition into mineral hydroxyapatite.
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Ácido Cítrico , Simportadores , Animales , Ratones , Ácido Cítrico/metabolismo , Simportadores/metabolismo , Durapatita/metabolismo , Citratos , Ciclo del Ácido Cítrico , Osteoblastos/metabolismo , Mamíferos/metabolismo , Transportadores de Ácidos Dicarboxílicos/metabolismoRESUMEN
Selective binding of organic compounds is the cornerstone of many important industrial and pharmaceutical applications. Here, we achieved highly selective binding of aromatic compounds in aqueous solution and gas phase by oxygen-enriched graphene oxide (GO) nanosheets via a previously unknown mechanism based on size matching and polarity matching. Oxygen-containing functional groups (predominately epoxies and hydroxyls) on the nongraphitized aliphatic carbons of the basal plane of GO formed highly polar regions that encompass graphitic regions slightly larger than the benzene ring. This facilitated size match-based interactions between small apolar compounds and the isolated aromatic region of GO, resulting in high binding selectivity relative to larger apolar compounds. The interactions between the functional group(s) of polar aromatics and the epoxy/hydroxyl groups around the isolated aromatic region of GO enhanced binding selectivity relative to similar-sized apolar aromatics. These findings provide opportunities for precision separations and molecular recognition enabled by size/polarity match-based selectivity.
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The energetics of photosynthesis in plants have been re-analyzed in a framework that represents the relatively high energy of O2 correctly. Starting with the photon energy exciting P680 and "loosening an electron", the energy transfer and electron transport are represented in a comprehensive, self-explanatory sequence of redox energy transfer and release diagrams. The resulting expanded Z-scheme explicitly shows charge separation as well as important high-energy species such as O2, TyrZË, and P680+Ë, whose energies are not apparent in the classical Z-scheme of photosynthesis. Crucially, the energetics of the three important forms of P680 and of P700 are clarified. The relative free energies of oxidized and reduced species are shown explicitly in kJ/mol, not encrypted in volts. Of the chemical energy produced in photosynthesis, more is stored in O2 than in glucose. The expanded Z-scheme introduced here provides explanatory power lacking in the classical scheme. It shows that P680* is energetically boosted to P680+Ë by the favorable electron affinity of pheophytin and that Photosystem I (PSI) has insufficient energy to split H2O and produce O2 because P700* is too easily ionized. It also avoids the Z-scheme's bewildering implication, according to the "electron waterfall" concept, that H2O gives off electrons that spontaneously flow to chlorophyll while releasing energy. The new analysis explains convincingly why plants need two different photosystems in tandem: (i) PSII mostly extracts hydrogen from H2O, producing PQH2 (plastoquinol), and generates the energetically expensive product O2; this step provides little energy directly to the plant; (ii) PSI produces chemical energy for the organism, by pumping protons against a concentration gradient and producing less reluctant hydrogen donors. It also documents that electron transport and energy transfer occur in opposite directions and do not involve redox voltages. The analysis makes it clear that the high-energy species in photosynthesis are unstable, electron-deficient species such as P680+Ë and TyrZË, not putative high-energy electrons.
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This study examined conditions that mimic oxidative processes of biomass chars during formation and weathering in the environment. A maple char prepared at the single heat treatment temperature of 500 °C for 2 h was exposed to different thermal oxidation conditions or accelerated oxidative aging conditions prior to sorption of naphthalene or the dication paraquat. Strong chemical oxidation (SCO) was included for comparison. Thermal oxidation caused micropore reaming, with ambient oxidation and SCO much less so. All oxidative treatments incorporated O, acidity, and cation exchange capacity (CEC). Thermal incorporation of O was a function of headspace O2 concentration and reached a maximum at 350 °C due to the opposing process of burn-off. The CEC was linearly correlated with O/C, but the positive intercept together with nuclear magnetic resonance data signifies that, compared to O groups derived by anoxic pyrolysis, O acquired through oxidation by thermal or ambient routes contributes more to the CEC. Thermal oxidation increased the naphthalene sorption coefficient, the characteristic energy of sorption, and the uptake rate due to pore reaming. By contrast, ambient oxidation (and SCO) suppressed naphthalene sorption by creating a more hydrophilic surface. Paraquat sorption capacity was predicted by an equation that includes a CEC2 term due to bidentate interaction with pairs of charges, predominating over monodentate interaction, plus a term for the capacity of naphthalene as a reference representing nonspecific driving forces.
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Carbón Orgánico , Adsorción , Biomasa , Cationes , Oxidación-Reducción , TemperaturaRESUMEN
The molecular structure of nanothreads produced by the slow compression of 13C4-furan was studied by advanced solid-state NMR. Spectral editing showed that >95% of carbon atoms were bonded to one hydrogen (C-H) and that there were 2-4% CH2, 0.6% CâO, and <0.3% CH3 groups. Alkenes accounted for 18% of the CH moieties, while trapped, unreacted furan made up 7%. Two-dimensional (2D) 13C-13C and 1H-13C NMR identified 12% of all carbon in asymmetric O-CHâCH-CH-CH- and 24% in symmetric O-CH-CHâCH-CH- rings. While the former represented defects or chain ends, some of the latter appeared to form repeating thread segments. Around 10% of carbon atoms were found in highly ordered, fully saturated nanothread segments. Unusually slow 13C spin-exchange with sites outside the perfect thread segments documented a length of at least 14 bonds; the small width of the perfect-thread signals also implied a fairly long, regular structure. Carbons in the perfect threads underwent relatively slow spin-lattice relaxation, indicating slow spin exchange with other threads and smaller amplitude motions. Through partial inversion recovery, the signals of the perfect threads were observed and analyzed selectively. Previously considered syn-threads with four different C-H bond orientations were ruled out by centerband-only detection of exchange NMR, which was, on the contrary, consistent with anti-threads. The observed 13C chemical shifts were matched well by quantum-chemical calculations for anti-threads but not for more complex structures like syn/anti-threads. These observations represent the first direct determination of the atomic-level structure of fully saturated nanothreads.
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Relationships between dissolved organic matter (DOM) reactivity and chemical composition in a groundwater plume containing petroleum-derived DOM (DOMHC) were examined by quantitative and qualitative measurements to determine the source and chemical composition of the compounds that persist downgradient. Samples were collected from a transect down the core of the plume in the direction of groundwater flow. An exponential decrease in dissolved organic carbon concentration resulting from biodegradation along the transect correlated with a continuous shift in fluorescent DOMHC from shorter to longer wavelengths. Moreover, ultrahigh resolution mass spectrometry showed a shift from low molecular weight (MW) aliphatic, reduced compounds to high MW, unsaturated (alicyclic/aromatic), high oxygen compounds that are consistent with carboxyl-rich alicyclic molecules. The degree of condensed aromaticity increased downgradient, indicating that compounds with larger, conjugated aromatic core structures were less susceptible to biodegradation. Nuclear magnetic resonance spectroscopy showed a decrease in alkyl (particularly methyl) and an increase in aromatic/olefinic structural motifs. Collectively, data obtained from the combination of these complementary analytical techniques indicated that changes in the DOMHC composition of a groundwater plume are gradual, as relatively low molecular weight (MW), reduced, aliphatic compounds from the oil source were selectively degraded and high MW, alicyclic/aromatic, oxidized compounds persisted.
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Agua Subterránea , Petróleo , Contaminantes Químicos del Agua , Biodegradación Ambiental , Hidrocarburos , Contaminantes Químicos del Agua/análisisRESUMEN
A comprehensive 13C nuclear magnetic resonance (NMR) approach for characterizing the location of chain ends of polyethers and polyesters, at the crystallite surface or in the amorphous layers, is presented. The OH chain ends of polyoxymethylene are labeled with 13COO-acetyl groups and their dynamics probed by 13C NMR with chemical shift anisotropy (CSA) recoupling. At least three-quarters of the chain ends are not mobile dangling cilia but are immobilized, exhibiting a powder pattern characteristic of the crystalline environment and fast CSA dephasing. The location and clustering of the immobilized chain ends are analyzed by spin diffusion. Fast 1H spin diffusion from the amorphous regions shows confinement of chain ends to the crystallite surface, corroborated by fast 13C spin exchange between chain ends. These observations confirm the principle of avoidance of density anomalies, which requires that chains terminate at the crystallite surface to stay out of the crowded interfacial layer.
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Molecular miscibility and homogeneity of amorphous solid dispersions (ASDs) are critical attributes that impact physicochemical stability, bioavailability, and processability. Observation of a single glass transition is utilized as a criterion for good mixing of drug substance and polymeric components but can be misleading and cannot quantitatively analyze the domain size at high resolution. While imaging techniques, on the other hand, can characterize phase separation on the particle surface at the nanometer scale, they often require customized sample preparation and handling. Moreover, a mixed system is not necessarily homogeneous. Compared to the numerous studies that have evaluated the mixing of drug substance and polymer in ASDs, inhomogeneity in the phase compositions has remained significantly underexplored. To overcome the analytical challenge, we have developed a 1H spin diffusion NMR technique to quantify molecular mixing of bulk ASDs at sub-100 nm resolution. It combines relaxation filtering (T2H and T1ρ) that leaves the active pharmaceutical ingredient (API) as the main source of 1H magnetization at the start of spin diffusion to the polymer matrix. A spray-dried nifedipine-poly(vinylpyrrolidone) (Nif-PVP) ASD at a 5 wt % drug loading was a homogeneous reference system that exhibited equilibration of magnetization transfer from API to polymer within a short spin diffusion time of â¼3 ms. While fast initial magnetization transfer proving mixing on the 1 nm scale was also observed in Nif-PVP ASDs prepared by hot-melt extrusion (HME) at 186 °C at a 40 wt % drug loading, incomplete equilibration of peak intensities documented inhomogeneity on the ≥30 nm scale. The nonuniformity was confirmed by the partial inversion of the Nif magnetization in the filter that resulted in an even more pronounced deviation from equilibration and by 1H-13C heteronuclear correlation (HETCOR) NMR. It is consistent with the observed differential 1H spin-lattice relaxation of Nif and PVP as well as a domain structure on the 20 nm scale observed in atomic force microscopy (AFM) images. The incomplete equilibration and differential relaxation were consistently reproduced in a model of two mixed phases of different compositions, e.g., 40 wt % of the ASD with a 15 wt % drug loading and the remaining 60 wt % with a 56 wt % drug loading. Hot-melt extrusion produced more inhomogeneous samples than spray drying for the samples examined in our study. To the best of our knowledge, this spin diffusion NMR method provides currently the highest-resolution quantification of inhomogeneous molecular mixing and phase composition in bulk samples of pharmaceutical dispersions produced with equipment, procedures, and drug loadings that are relevant to industrial drug development.
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Preparaciones Farmacéuticas/química , Rastreo Diferencial de Calorimetría/métodos , Difusión , Espectroscopía de Resonancia Magnética/métodos , Nifedipino/química , Polímeros/química , Polivinilos/química , Pirrolidinas/química , Solubilidad/efectos de los fármacosRESUMEN
The molecular connectivity of polymer-metal-organic framework (polyMOF) hybrid materials was investigated using density functional theory calculations and solid-state NMR spectroscopy. The architectural constraints that dictate the formation of polyMOFs were assessed by examining poly(1,4-benzenedicarboxylic acid) (pbdc) polymers in two archetypical MOF lattices (UiO-66 and IRMOF-1). Modeling of the polyMOFs showed that in the IRMOF-1-type lattice, six, seven, and eight methylene (-CH2-) groups between 1,4-benzenedicarboxylate (terephthalate, bdc2-) units can be accommodated without significant distortions, while in the UiO-66-type lattice, an optimal spacing of seven methylene groups between bdc2- units is needed to minimize strain. Solid-state NMR supports these predictions and reveals pronounced spectral differences for the same polymer in the two polyMOF lattices. With seven methylene groups, polyUiO-66-7a shows 7 ± 3% of uncoordinated terephthalate linkers, while these are undetectable (<4%) in the corresponding polyIRMOF-1-7a. In addition, NMR-detected backbone mobility is significantly higher in the polyIRMOF-1-7a than in the corresponding polyUiO-66-7a, again indicative of taut chains in the latter.
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Efficient cellulose depolymerization is a major bottleneck for economical production of second-generation biofuels. In this work, crystalline cellulose was subjected to sequential ball milling and ethanolysis as a mild and selective depolymerization approach. Ball milling and ethanolysis resulted in 38±1 % cellulose conversion, with 24 % ethyl-glucopyranoside as the main identified and quantified product and negligible side reaction of the ethanol solvent to form diethyl ether. In comparison, ethanolysis of the original cellulose resulted in only 3±1 % conversion. Additional soluble products from cellulose ethanolysis included carbohydrate isomers and oligomers, differing from the products obtained from hydrolysis. X-ray diffraction and nuclear magnetic resonance spectroscopy revealed increased crystallinity post-reaction, retarding further depolymerization. Hot liquid water extracted soluble oligomers from the ethanolyzed cellulose, suggesting formation of a nanoscale barrier of crystalline cellulose that traps soluble products during ethanolysis. Use of cellulose-swelling co-solvents and repeated mechanical decrystallization both proved effective at increasing cellulose conversion and soluble product yields. Repeated ball milling and ethanolysis resulted in 62±1 % cellulose conversion. Ethanolysis of decrystallized cellulose has potential for rapid (<2â h) de-polymerization at mild conditions.
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The molecular structure of a crosslinked nitrogen-rich resin made from melamine, urea, and aldehydes, and of microcapsules made from the reactive resin with multiple polymeric components in aqueous dispersion, has been analyzed by 13C, 13C{1H}, 1H-13C, 1H, 13C{14N}, and 15N solid-state NMR without isotopic enrichment. Quantitative 13C NMR spectra of the microcapsules and three precursor materials enable determination of the fractions of different components. Spectral editing of non-protonated carbons by recoupled dipolar dephasing, of CH by dipolar DEPT, and of C-N by 13C{14N} SPIDER resolves peak overlap and helps with peak assignment. It reveals that the N- and O-rich resin "imitates" the spectrum of polysaccharides such as chitin, cellulose, or Ambergum to an astonishing degree. 15N NMR can distinguish melamine from urea and guanazole, NC=O from COO, and primary from secondary amines. Such a comprehensive and quantitative analysis enables prediction of the elemental composition of the resin, to be compared with combustion analysis for validation. It also provides a reliable reference for iterative simulations of 13C NMR spectra from structural models. The conversion from quantitative NMR peak areas of structural components to the weight fractions of interest in industrial practice is derived and demonstrated. Upon microcapsule formation, 15N and 13C NMR consistently show loss of urea and aldehyde and an increase in primary amines while melamine is retained. NMR also made unexpected findings, such as imbedded crystallites in one of the resins, as well as persistent radicals in the microcapsules. The crystallites produce distinct sharp lines and are distinguished from liquid-like components by their strong dipolar couplings, resulting in fast dipolar dephasing. Fast 1H spin-lattice relaxation on the 35-ms time scale and characteristically non-exponential 13C spin-lattice relaxation indicate persistent radicals, confirmed by EPR. Through 1H spin diffusion, the mixing of components on the 5-nm scale was documented.
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Nitrógeno/química , Resonancia Magnética Nuclear Biomolecular , Polímeros/química , Aldehídos/química , Cápsulas , Radicales Libres/química , Triazinas/química , Urea/químicaRESUMEN
Fused-ring aromatics, important skeletal components of black carbon (BC), contribute to long-term carbon (C) sequestration in nature. They have previously been thought to be primarily formed by incomplete combustion of organic materials, whereas the nonpyrogenic origins are negligible. Using advanced solid-state 13C nuclear magnetic resonance (NMR), including recoupled long-range C-H dipolar dephasing, exchange with protonated and nonprotonated spectral editing (EXPANSE), and dipolar-dephased double-quantum/single-quantum (DQ/SQ) spectroscopy, we for the first time identify fused-ring aromatics that formed during the decomposition of wheat (Triticum sp.) straw in soil under aerobic, but not anaerobic conditions. The observed formation of polyaromatic units as plant litter decomposes provides direct evidence for humification. Moreover, the estimation of the annual flux of such nonpyrogenic BC could be equivalent to 3-12% of pyrogenic BC added to soils from all other sources. Our findings significantly extend the understanding of potential sources of fused-ring aromatic C and BC in soils as well as the global C cycle.
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Triticum/química , Aerobiosis , Bacterias/metabolismo , Biodegradación Ambiental , Tallos de la Planta/química , Tallos de la Planta/microbiología , Microbiología del Suelo , Triticum/microbiologíaRESUMEN
A fundamental re-assessment of the overall energetics of biochemical electron transfer chains and cycles is presented, highlighting the crucial role of the highest-energy molecule involved, O2. The chemical energy utilized by most complex multicellular organisms is not predominantly stored in glucose or fat, but rather in O2 with its relatively weak (i.e., high-energy) double bond. Accordingly, reactions of O2 with organic molecules are highly exergonic, while other reactions of glucose, fat, NAD(P)H, or ubiquinol (QH2) are not, as demonstrated in anaerobic respiration with its meager energy output. The notion that "reduced molecules" such as alkanes or fatty acids are energy-rich is shown to be incorrect; they only unlock the energy of more O2, compared to O-containing molecules of similar mass. Glucose contains a moderate amount of chemical energy per bond (<20% compared to O2), as confirmed by the relatively small energy output in glycolysis and the Krebs cycle converting glucose to CO2 and NADH. Only in the "terminal" aerobic respiration reaction with O2 does a large free energy change occur due to the release of oxygen's stored chemical energy. The actual reaction of O2 in complex IV of the inner mitochondrial membrane does not even involve any organic fuel molecule and yet releases >1 MJ when 6 mol of O2 reacts. The traditional presentation that relegated O2 to the role of a low-energy terminal acceptor for depleted electrons has not explained these salient observations and must be abandoned. Its central notion that electrons release energy because they move from a high-energy donor to a low-energy acceptor is demonstrably false. The energies of (at least) two donor and two acceptor species come into play, and the low "terminal" negative reduction potential in aerobic respiration can be attributed to the unusually high energy of O2, the crucial reactant. This is confirmed by comparison with the corresponding half-reaction without O2, which is endergonic. In addition, the electrons are mostly not accepted by oxygen but by hydrogen. Redox energy transfer and release diagrams are introduced to provide a superior representation of the energetics of the various species in coupled half-reactions. Electron transport by movement of reduced molecules in the electron transfer chain is shown to run counter to the energy flow, which is carried by oxidized species. O2, rather than glucose, NAD(P)H, or ATP, is the molecule that provides the most energy to animals and plants and is crucial for sustaining large complex life forms. The analysis also highlights a significant discrepancy in the proposed energetics of reactions of aerobic respiration, which should be re-evaluated.
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The composition of fluorescent polymer nanoparticles, commonly referred to as carbon dots, synthesized by microwave-assisted reaction of citric acid and ethylenediamine was investigated by 13 C, 13 C{1 H}, 1 Hâ13 C, 13 C{14 N}, and 15 N solid-state nuclear magnetic resonance (NMR) experiments. 13 C NMR with spectral editing provided no evidence for significant condensed aromatic or diamondoid carbon phases. 15 N NMR showed that the nanoparticle matrix has been polymerized by amide and some imide formation. Five small, resolved 13 C NMR peaks, including an unusual âCH signal at 84 ppm (1 H chemical shift of 5.8 ppm) and âCN2 at 155 ppm, and two distinctive 15 N NMR resonances near 80 and 160 ppm proved the presence of 5-oxo-1,2,3,5-tetrahydroimidazo[1,2-a]pyridine-7-carboxylic acid (IPCA) or its derivatives. This molecular fluorophore with conjugated double bonds, formed by a double cyclization reaction of citric acid and ethylenediamine as first shown by Y. Song, B. Yang, and coworkers in 2015, accounts for the fluorescence of the carbon dots. Cross-peaks in a 1 Hâ13 C HETCOR spectrum with brief 1 H spin diffusion proved that IPCA is finely dispersed in the polyamide matrix. From quantitative 13 C and 15 N NMR spectra, a high concentration (18 ± 2 wt%) of IPCA in the carbon dots was determined. A pronounced gradient in 13 C chemical-shift perturbations and peak widths, with the broadest lines near the COO group of IPCA, indicated at least partial transformation of the carboxylic acid of IPCA by amide or ester formation.