Umeå University's logo

Introduction: Prostate cancer (PC) diagnosis relies on histopathological examination of prostate biopsies, which is restricted by insufficient sampling of all tumors present. Including samples from non-PC but tumor instructed normal tissues (TINT) may increase the diagnostic power by displaying the adaptive responses in benign tissues near tumors.

Methods: Here, we applied high-resolution magic angle spinning nuclear magnetic resonance (HR MAS NMR) to identify metabolomic biomarkers of possible diagnostic value in benign prostate tissues near low/high-grade tumors.

Results: Benign samples near high-grade tumors (B ISUP 3 + 4) exhibited altered metabolic profiles compared to those close to low-grade tumors (B ISUP 1 + 2). The levels of six metabolites differentiated between the two groups; myo-inositol, lysine, serine and combined signal of lysine/leucine/arginine were increased in benign samples near high-grade tumors (B ISUP 3 + 4) compared to near low-grade tumors (B ISUP 1 + 2), while levels of ethanolamine and lactate were decreased. Additionally, we revealed metabolic differences in non-cancer tissues as a function of their distance to the nearest tumor. Eight metabolites (glutathione, glutamate, combined signal of glutamate/glutamine - glx, glycerol, inosine, ethanolamine, serine and arginine) differentiated between benign tissue located close to the tumor (d ≤ 5 mm) compared to those far away (d ≥ 1 cm).

Conclusion: Our HR MAS NMR-based approach identified metabolic signatures in prostate biopsies that reflect the response of benign tissues to the presence of nearby located tumors in the same prostate and confirmed the power of the TINT concept for improved PC diagnostics and understanding of tumor-tissue interactions.

The perceived flavor of coffee varies depending on the composition of the brewing water, and the influencing mechanisms are poorly understood. To investigate the effect of dissolved divalent cations on the extraction of organic acids in coffee, magnesium and calcium chloride salts were added pre- and post-brew. Citric, malic, lactic and quinic acid were analyzed using gas chromatography – mass spectrometry and nuclear magnetic resonance techniques. At concentrations typically found in drinking water, the salts resulted in limited variation of the acid content, while ten-fold higher salt concentrations produced more pronounced variations. Comparisons between pre- and post-brew additions showed similar acid content in most cases, suggesting that extraction of acids proceeds independent of the water composition. Interactions taking place post-brew may, however, influence the perceived flavor. A scientific basis for water quality recommendations in the coffee industry is long overdue and this work provides experimental and analytical contributions to continued research.

Higher availability of grand granulated blast furnace slag compared to coal fly ash has attributed lots of attention to this supplementary cementitious material in recent years, especially with respect to applications in infrastructure. Therefore, further research on long term performance of slag containing binders in chloride containing environments is promoted. In this article chloride binding in a high slag containing composite binder (70% substitution) with respect to the changes in structure of CSH gel prior and after exposure to chlorides and its effect on chemical and physical chloride binding is accounted for. The changes in the structure of CSH are accounted by NMR analysis and the effect of these changes on chloride binding is addressed through adsorption tests. The results are compared with a ternary binder of cement-silica fume-metakaolin, given the relatively similar chemical composition between these two composite binders, as well as a reference Portland cement binder. The results infer that the slag containing binder exhibits higher chloride binding capacity compared to the metakaolin-silica fume containing. Moreover, a higher share of chemically bound chloride (meaning a lower physical binding) in SCM containing binders is foreseen compared to pure Portland cement system, due to the increased C(-A)-S-H chain length and Al/Si molar ratio in these binders. Furthermore, it is shown that exposure to NaCl causes a higher share of chemically bound chlorides compared to the CaCl2 exposure while the total bound chloride content increases upon exposure to CaCl2.

This paper investigates how the composition of Portland composite cements affects their chloride-binding properties. Hydrated cement pastes prepared with a reference Portland cement and composite Portland cements containing metakaolin and/or silica fume were exposed to NaCl or CaCl₂ solutions. Chloride-binding isotherms were determined and the hydrate assemblage was investigated using TGA, XRD, ²⁷Al NMR, ²⁹Si NMR and thermodynamic modelling. Compared to the reference Portland cement paste, silica fume replacement did not alter the chloride-binding capacity. The metakaolin replacement resulted in the highest chloride-binding capacity. When combining silica fume with metakaolin, the chloride binding is similar to the reference Portland cement. In this study the differences in chloride binding were linked not only to changes in the AFm content, but also to alterations in the Al-uptake and chain length of the C(-A)-S-H.

Herein, we have investigated how pure lignin extracted from birch and spruce via a hybrid organosolv/steam explosion method reacts under hydrothermal carbonization (HTC) to produce hydrochar, a product that has found applications in environmental remediation, energy storage and catalysis. We subjected thirteen lignin samples obtained from birch and spruce under different extraction conditions to HTC at 260 ℃ for four hours. The yield of hydrochar varied between the different extraction conditions and source, although no clear correlation between extraction conditions and yield could be observed. For instance, lignin from birch pretreated in 60%v/v ethanol for 15 min resulted in a hydrochar yield of 39 wt%. Increasing the time to 30 and 60 resulted in a hydrochar yield of 27 wt% and 23 wt%, respectively. This suggested that small changes in the organosolv reaction conditions might produce highly structurally different lignin, resulting in the difference in HTC yield. Thus, we chose a subset of four lignin samples to investigate in-depth, subjecting these samples to a range of hydrothermal reaction temperatures and residence times. Solid State NMR and FTIR analysis indicated that the most significant structural changes occurred below 230 ℃ resulting in the breaking of C-O- linkages. Increasing the temperature or time had minimal impact, with no further C-O- linkages broken and no changes to the ring structure of C-C groups. Size exclusion chromatography indicated that the degree of micro and macromolecules in the liquid product varied significantly with lignin source and HTC reaction conditions. Overall, this study demonstrated that lignin has a large reaction range where it produces a very chemically similar solid product, with the only major difference being the yield of material. This is important for industry, as it indicates that a similar solid product can be easily achieved independently of extraction conditions allowing the HTC reaction to be tuned towards extracting the maximum benefit from products contained in the liquid.

Soil organic matter (SOM) is important in maintaining soil fertility and other ecosystem functions. Yet, land management in intensive agriculture has caused SOM level to decrease, with knock-on effects for soil fertility and quality. Therefore, land management options that ensure that SOM is not depleted and that soil functions are better sustained are of increasing interest. However, there is limited knowledge on how different land managements affect the composition of SOM and associated microbial functional profiles. Twelve long-term field experiments, covering a wide range of climatic zones and soil types, were selected in Sweden. They focused on the role of combining ley in crop rotations with the manure application (livestock farm), as opposed to the management without ley and receiving only inorganic fertilizer (arable farm). In ten out of the 12 study sites, livestock farm management tended to have higher proportions of aliphatic and double bonded C groups, as estimated by mid-infrared spectroscopy. This was further confirmed by 13C NMR analysis, which found greater proportions of O-alkyl and di-O-alkyl groups and less aromatic C in livestock farm than arable farm management in five of the eight sites analyzed. The changes in SOM composition were reflected in microbial functional profiles across many sites: soils from livestock farm management utilized more carbohydrates and amino acids, while polymer and aromatic compounds were associated with arable farm management. Overall, shifts in both microbial functional profiles and SOM composition showed great consistency across geographical and climatic zones. Livestock farm management maintained higher levels of microbial functional diversity and were associated with higher proportions of “reactive” C functional groups. Our investigation demonstrates that livestock farm management could maintain soil fertility over the long-term via the changes in SOM composition and the regulation of microbial functional profiles.

Peatlands store carbon in the form of dead organic residues. Climate change and human impact impose risks on the sustainability of the peatlands carbon balance due to increased peat decomposition. Here, we investigated molecular changes in the upper peat layers (0-40 cm), inferred from high-resolution vertical depth profiles, from a boreal peatland using two-dimensional 1H-13C nuclear magnetic resonance (NMR) spectroscopy, and comparison to δ13C, δ15N, and carbon and nitrogen content. Effects of hydrological conditions were investigated at respective sites: natural moist, drainage ditch, and natural dry. The molecular characterization revealed preferential degradation of specific side-chain linkages of xylan-type hemicelluloses within 0-14 cm at all sites, indicating organic matter losses up to 25%. In contrast, the xylan backbone, galactomannan-type hemicelluloses, and cellulose were more resistant to degradation and accumulated at the natural moist and drainage site. δ13C, δ15N, and carbon and nitrogen content did not correlate with specific hemicellulose structures but reflected changes in total carbohydrates. Our analysis provides novel insights into peat carbohydrate decomposition and indicates substantial organic matter losses in the acrotelm due to the degradation of specific hemicellulose structures. This suggests that variations in hemicellulose content and structure influence peat stability, which may have important implications with respect to climate change.

Sphagnum mosses account for most accumulated dead organic matter in peatlands. Therefore, understanding their responses to increasing atmospheric CO₂ is needed for estimating peatland C balances under climate change. A key process is photorespiration: a major determinant of net photosynthetic C assimilation that depends on the CO₂ to O₂ ratio. We used climate chambers to investigate photorespiratory responses of Sphagnum fuscum hummocks to recent increases in atmospheric CO₂ (from 280 to 400 ppm) under different water table, temperature, and light intensity levels. We tested the photorespiratory variability using a novel method based on deuterium isotopomers (D6^S/D6^R ratio) of photosynthetic glucose. The effect of elevated CO₂ on photorespiration was highly dependent on water table. At low water table (−20 cm), elevated CO₂ suppressed photorespiration relative to C assimilation, thus substantially increasing the net primary production potential. In contrast, a high water table (~0 cm) favored photorespiration and abolished this CO₂ effect. The response was further tested for Sphagnum majus lawns at typical water table levels (~0 and −7 cm), revealing no effect of CO₂ under those conditions. Our results indicate that hummocks, which typically experience low water table levels, benefit from the 20th century's increase in atmospheric CO₂.

Seven different lignin samples, three from Kraft extraction and four from organosolv extraction, were subjected to hydrothermal treatment at 260℃ for four hours to assess the impact of lignin type on the physicochemical properties of the hydrothermal material. The ¹³C Solid state NMR, XPS, FTIR and SEM analysis revealed that the different sources of lignin and the extraction conditions created variations in the degree of syringyl and guaiacyl subunits, inter-unit bonding arrangements, morphology and surface composition. Hydrothermal carbonization appeared to “normalize” the differences between each of the lignin samples, via breaking β-O-4 or α-O-4 linkages, removal of methoxy and syringyl subunits, and creation of C–C and 4-O-5 linkages to polymerization into large 100−200 μm amorphous carbon particles. Overall, this study indicates that the source and extraction type have minimal influence on the physicochemical structure and morphology of the final hydrothermal product.

This work provides the first observations of and insights into the self-generation of carbon microspheres from the supernatant after hydrothermal carbonization of anaerobic digestate has been completed and the hydrochar removed. Solid State NMR and XPS revealed that the carbon microspheres were comprised of decomposed fragments of proteins, carbohydrates and lignin. The carbon microspheres were significantly lower in ash content (3.1%), compared to the hydrothermal solid (41.2%) and precursor (25.2%) and their formation reduced the total organic carbon load of the supernatant. The low ash content allowed them to be easily activated, achieving a surface area of 1711.0 m2 g−1, compared to 51.4 m2 g−1 for the activated hydrothermal solid and 12.8 m2 g−1 for the activated precursor. The microcarbon spheres achieved a specific capacitance from cyclic voltammetry of 86 F g−1 at 100 mV s−1 to 176 F g−1 at 1 mV s−1, while the gravimetric capacitance was 42 F g−1 at 25 A g−1 and 140 F g−1 at 0.5 A g−1 in 0.5 M Li2SO4 and a 1.8V potential window. Overall, this study highlights the importance of exploring this new product and its valorisation potential for the hydrothermal carbonization of ash-rich precursors.