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The crystallinity of cellulose has a strong impact on various material properties. Over the years, many methods have become available to estimate the crystallinity. The purpose of this work was to revise existing NMR-based methods and to introduce a complementary NMR method related to the 13 C T 1 relaxation time. The 13 C T 1 differs by an order of magnitude for amorphous and crystalline polymers among them cellulose. We have utilized the signal boost of 1 H– 13 C cross polarization and the difference in 13 C T 1 as a filter to calculate the degree of crystallinity. The evaluation of the method is based on the difference in peak integrals, which is fed into a simple equation. The method was applied to five cellulosic samples of different nature and compared the obtained degree of crystallinity with the degree estimated from deconvoluted X-ray scattering patterns. Furthermore, an attempt has been made to give a basic understanding on the origin of CP enhancement in order to validate various proposed NMR methods. With the recent progress of NMR equipment, the presented method can be automatized and applied to a series of samples using a sample changer.

Results of the high-level computational study of 12 bisindole alkaloids of the Strychnos-Strychnos type are reported in addition of that of five retuline-like monomers frequently encountered in moieties constituting dimeric alkaloids. Based on the comparison of theoretical and experimental NMR chemical shifts, a detailed conformational survey of these stereochemically rich natural products containing multiple asymmetric centers was performed. Our original methodology is based on searching multiple conformational states, geometry optimization, and high-level NMR calculations at the DFT level. Taking into account all known experimental chemical shifts together with their calculated values in the natural products under study, a correlation estimate of NMR chemical shifts was performed by using statistical descriptors. In general, a good agreement of the performed calculations with experiment was achieved, which is manifested by the Corrected Mean Absolute Error of about 0.2 ppm for 1H and 1.9 ppm for 13C NMR chemical shifts in this series.

Brain development is a highly orchestrated complex process. The developing brain utilizes many substrates including glucose, ketone bodies, lactate, fatty acids and amino acids for energy, cell division and the biosynthesis of nucleotides, proteins and lipids. Metabolism is crucial to provide energy for all cellular processes required for brain development and function including ATP formation, synaptogenesis, synthesis, release and uptake of neurotransmitters, maintaining ionic gradients and redox status, and myelination. The rapidly growing population of infants and children with neurodevelopmental and cognitive impairments and life-long disability resulting from developmental brain injury is a significant public health concern. Brain injury in infants and children can have devastating effects because the injury is superimposed on the high metabolic demands of the developing brain. Acute injury in the pediatric brain can derail, halt or lead to dysregulation of the complex and highly regulated normal developmental processes. This paper provides a brief review of metabolism in developing brain and alterations found clinically and in animal models of developmental brain injury. The metabolic changes observed in three major categories of injury that can result in life-long cognitive and neurological disabilities, including neonatal hypoxia–ischemia, pediatric traumatic brain injury, and brain injury secondary to prematurity are reviewed.

Several spectroscopic techniques have been optimized to check extra-virgin olive oil quality and authenticity, as well as to detect eventual adulterations. These methods are usually complementary and can give information about different olive oil chemical components with bioactive and antioxidant properties. In the present work, a well-characterized set of extra-virgin olive oil (cultivar Frantoio) samples from a specific area of Tuscany (Italy) were investigated by combining near UV-Vis absorption spectroscopy, 1H and 13C nuclear magnetic resonance (NMR) to identify and quantify different chemical components, such as pigments, secoiridoids and squalene, related to the nutritional and quality properties of olive oils. Moreover, the pigmentation index of olives, organoleptic and sensory properties, total phenolic compound contents and the lipidic fractions of olive oils were investigated. The results obtained are, finally, compared and discussed in order to correlate several properties of both olives and olive oils with specific features of the cultivation area.

PURPOSE: Fire in mountainous areas can lead to increased variability of their soil organic matter (SOM) due to spatial inhomogeneity and pre-fire fuel distribution. Here, we elucidated if this was the case in our study area and how this affected the reliability of solid-state ¹³C NMR spectroscopy applied for the study of the medium-term impact of fire on SOM MATERIALS AND METHODS: The study occurred in the Sierra de Aznalcóllar, Southern Spain, which experienced their last intense fire 7 years before sampling. In a first approach (method 1), the corners and the center of a randomly chosen square with a side length of 15 m were sampled and analyzed separately. For comparison, composite samples (method 2) were obtained from three soils. We characterized material from unburnt, burnt, and double burnt regions. Data describing the physical and chemical properties of the soils together with the NMR spectroscopic characterization were analyzed using ANOVA. RESULTS AND DISCUSSION: Both sampling methods yielded comparable results with comparable standard errors. No major differences between the fire-affected and unburnt soils were observed with respect to physical and chemical properties and C and N contents, but solid-state ¹³C NMR spectroscopy indicated a small but significant elevation of aromaticity in the soils with fire history. CONCLUSIONS: The analysis showed that sampling with reduced replicates (method 1) can still lead to representative NMR data. The more complex sampling of comparing three composite samples (method 2) did not decrease the standard error. Our results also indicate that in the study area typical properties of the soil and its SOM induced by former burnings will not persist beyond a few decades.

Recent findings demonstrate that concentrated sulfuric acid supports rich organic chemistry, including the stability of the canonical DNA bases adenine, thymine, guanine and cytosine. Yet, due to full protonation in concentrated sulfuric acid, these bases may not pair as effectively as they do in water. We are therefore motivated to study nucleic acid bases that pair via hydrophobic and van der Waals interactions instead of canonical hydrogen bonding. Here, we investigate the stability of 14 selected, commercially available alternative nucleobases in concentrated sulfuric acid to evaluate their potential for forming DNA-like polymers in this solvent. The reactivity of compounds 1–14 have not been previously investigated in concentrated sulfuric acid. We incubate the selected compounds in 98% and 81% w/w sulfuric acid and monitor their stability using 1H and 13C NMR spectroscopy over 3 weeks at room temperature. In 98% w/w sulfuric acid, six bases—benzo[c][1,2,5]thiadiazole (1), 2,2′-bipyridine (2), 1,1′-biphenyl (3), 1-methoxy-3-methylbenzene (MMO2) (7) and 1-chloro-3-methoxybenzene (ClMO) (13), and 2,4-difluorotoluene (14)—remain soluble and stable with no detectable degradation. A few compounds show non-destructive reactivity, like sulfonation (compound 3) or H/D exchange (compounds 7, 13, 14). The other compounds react rapidly or are insoluble in 98% w/w sulfuric acid. In 81% w/w sulfuric acid, only compounds 1 and 2 remain stable and soluble, while other selected compounds are insoluble or unstable. Our findings identify a subset of alternative bases stable in concentrated sulfuric acid, advancing efforts towards the design of an example genetic-like polymer in this unusual solvent. Our work further highlights sulfuric acid’s potential for supporting complex organic chemistry, with implications for astrobiology, planetary science of Venus and synthetic biology.

There are varieties of methods available for the exploration of solids using nuclear magnetic resonance (NMR) spectroscopy. Some of these methods are quite sophisticated, others require specialized equipment. This review is addressed to those for whom NMR is not the main research method. It discusses simple methods that can be applied to solids with little or no adaptation to a specific system. Despite their technical simplicity and ease of use, these methods are powerful analytical tools that provide unique insights into the structure, dynamics, and noncovalent interactions in homo- and heterogeneous systems. Particular attention is paid to the characterization of porous materials and solids containing phosphorus. 31P NMR of organometallic compounds has been used as an example of how theoretical calculations can help in deeper analysis of experimental data.

Life as we know it depends on peptide and nucleic acid polymers built from a limited set of backbone residues, yet planetary environments beyond Earth motivate consideration of alternative chemical frameworks for genetic- and protein-like polymers. In this context, we synthesize four azatide dipeptide analogs (Alaa-Glya (1), Glya-Alaa (2), Glya-Glya (3), and Alaa-Alaa (4)) as candidate backbone motifs for non-standard biologically relevant polymers. We then systematically assess their stability and reactivity in 98% w/w sulfuric acid, a solvent relevant to Venusian cloud chemistry. We assess the stability of the azatides via 1H and 13C NMR spectroscopy supported with ELSD-LCMS. We monitor the stability of the compounds over periods from hours to two weeks at room temperature and at elevated temperatures (50–80 °C). All four azatides readily dissolve in 98% w/w D2SO4 and are generally stable at room temperature. Glya-Alaa (2) shows no detectable degradation over a two-week incubation in 98% w/w sulfuric acid. The other three azatide analogs display only minor decomposition. ELSD-LCMS measurements qualitatively confirm the NMR results, revealing only minor-to-moderate loss of parent compounds after two weeks at room temperature. At higher temperatures, representative of the lower Venusian cloud deck, the stability of the azatides decreases dramatically. All four compounds undergo significant decomposition at 50 °C and completely degrade within one to two weeks at 80 °C. Our findings indicate that azatides, despite being generally stable in concentrated sulfuric acid at room temperature, lack the thermal stability that might be required to serve as viable backbone motifs for biological polymers in environments spanning the full temperature range of Venusian clouds.

In this study, the importance of hemicellulose content and structure in chemical pulps on the property relationships in compression molded wood pulp biocomposites is examined. Three different softwood pulps are compared; an acid sulfite dissolving grade pulp with high cellulose purity, an acid sulfite paper grade pulp and a paper grade kraft pulp, the latter two both containing higher amounts of hemicelluloses. Biocomposites based the acid sulfite pulps exhibit twice as high Young’s modulus as the composite based on paper grade kraft pulp, 11–12 and 6 GPa, respectively, and the explanation is most likely the difference in beating response of the pulps. Also the water retention value (WRV) is similarly low for the two molded sulfite pulps (0.5 g/g) as compared to the molded kraft pulp (0.9 g/g). The carbohydrate composition is determined by neutral sugar analysis and average molar masses by SEC. The cellulose supramolecular structure (cellulose fibril aggregation) is studied by solid state CP/MAS 13 C-NMR and two forms of hemicellulose are assigned. During compression molding, cellulose fibril aggregation occurs to higher extent in the acid sulfite pulps as compared to the kraft pulp. In conclusion, the most important observation from this study is that the difference in hemicellulose content and structure seems to affect the aggregation behaviour and WRV of the investigated biocomposites.

Physical separation of soil into different soil organic matter (SOM) fractions is widely used to identify organic carbon pools that are differently stabilized and have distinct chemical composition. However, the mechanisms underlying these differences in stability and chemical composition are only partly understood. To provide new insights into the stabilization of different chemical compound classes in physically-separated SOM fractions, we assessed shifts in the biomolecular composition of bulk soils and individual particle size fractions that were incubated in the laboratory for 345 days. After the incubation, also the incubated bulk soil was fractionated. The chemical composition of organic matter in bulk soils and fractions was characterized by ¹³C-CPMAS nuclear magnetic resonance spectroscopy and sequential chemical extraction followed by GC/MS measurements. Plant-derived lipids and lignin were abundant in particulate organic matter (POM) fractions of sand-, silt-, and clay-size and the mineral-bound, clay-sized organic matter. These results indicate that recent conceptualizations of SOM stabilization probably understate the contribution of plant-derived organic matter to stable SOM pools. Although our data indicate that inherent recalcitrance could be important in soils with limited aggregation, organomineral interactions and aggregation were responsible for long-term SOM stabilization. In particular, we observed consistently higher concentrations of plant-derived lipids in POM fractions that were incubated individually, where aggregates were disrupted, as compared to those incubated as bulk soil, where aggregates stayed intact. This finding emphasizes the importance of aggregation for the stabilization of less ‘recalcitrant’ biomolecules in the POM fractions. Because also the abundance of lipids and lignin in clay-sized, mineral-associated SOM was substantially influenced by aggregation, the bioavailability of mineral-associated SOM likely increases after the destruction of intact soil structures.