Search

Pinosylvin monomethyl ether (PsMME) is a natural compound known for its valuable bioactive properties, including antioxidant and anti-inflammatory effects. However, PsMME's susceptibility to photodegradation upon exposure to ultraviolet (UV) radiation poses a significant limitation to its applications in the pharmaceutical field. This study, for the first time, introduces a strategy to enhance the photostability of PsMME by employing various nanoformulations. We utilized mesoporous silica nanoparticles (MSNs) coated with polydopamine via a poly(ethylene imine) layer (PDA-PEI-MSNs), thermally carbonized porous silicon nanoparticles (TCPSi), and pure mesoporous polydopamine nanoparticles (MPDA). All these nanocarriers exhibit unique characteristics, including the potential for shielding the drug from UV light, which makes them promising for enhancing the photostability of loaded drugs. Here, these three nanoparticles were synthesized and their morphological and physicochemical properties, including size and ζ-potential, were characterized. They were subsequently loaded with PsMME, and the release profiles and kinetics of all three nanoformulations were determined. To assess their photoprotection ability, we employed gas chromatography with a flame ionization detector (GC-FID) and gas chromatography-mass spectrometry (GC-MS) to assess the recovery percentage of loaded PsMME before and after UV exposure for each nanoformulation. Our findings reveal that MPDA exhibits the highest protection ability, with a remarkable 90% protection against UV light on average. This positions MPDA as an ideal carrier for PsMME, and by extension, potentially for other photolabile drugs as well. As a final confirmation of its suitability as a drug nanocarrier, we conducted cytotoxicity evaluations of PsMME-loaded MPDA, demonstrating dose-dependent drug toxicity for this formulation.

Introduction: Stilbenoid compounds have been described to have anti-inflammatory properties in animal models in vivo , and have been shown to inhibit Ca2+-influx through the transient receptor potential ankyrin 1 (TrpA1)., Methods: To study how stilbenoid compounds affect inflammatory signaling in vivo , we have utilized the fruit fly, Drosophila melanogaster , as a model system. To induce intestinal inflammation in the fly, we have fed flies with the intestinal irritant dextran sodium sulphate (DSS)., Results: We found that DSS induces severe changes in the bacteriome of the Drosophila intestine, and that this dysbiosis causes activation of the NF-κB transcription factor Relish. We have taken advantage of the DSS-model to study the anti-inflammatory properties of the stilbenoid compounds pinosylvin (PS) and pinosylvin monomethyl ether (PSMME). With the help of in vivo approaches, we have identified PS and PSMME to be transient receptor ankyrin 1 (TrpA1)-dependent antagonists of NF-κB-mediated intestinal immune responses in Drosophila . We have also computationally predicted the putative antagonist binding sites of these compounds at Drosophila TrpA1., Discussion: Taken together, we show that the stilbenoids PS and PSMME have anti-inflammatory properties in vivo in the intestine and can be used to alleviate chemically induced intestinal inflammation in Drosophila ., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2023 Aalto, Saadabadi, Lindholm, Kietz, Himmelroos, Marimuthu, Salo-Ahen, Eklund and Meinander.)

Fabricating bio-latex colloids with core-shell nanostructure is an effective method for obtaining films with enhanced mechanical characteristics. Nano-sized lignin is rising as a class of sustainable nanomaterials that can be incorporated into latex colloids. Fundamental knowledge of the correlation between surface chemistry of lignin nanoparticles (LNPs) and integration efficiency in latex colloids and from it thermally processed latex films are scarce. Here, an approach to integrate self-assembled nanospheres of allylated lignin as the surface-activated cores in a seeded free-radical emulsion copolymerization of butyl acrylate and methyl methacrylate is proposed. The interfacial-modulating function on allylated LNPs regulates the emulsion polymerization and it successfully produces a multi-energy dissipative latex film structure containing a lignin-dominated core (16% dry weight basis). At an optimized allyl-terminated surface functionality of 1.04 mmol g -1 , the LNPs-integrated latex film exhibits extremely high toughness value above 57.7 MJ m -3 . With multiple morphological and microstructural characterizations, the well-ordered packing of latex colloids under the nanoconfinement of LNPs in the latex films is revealed. It is concluded that the surface chemistry metrics of colloidal cores in terms of the abundance of polymerization-modulating anchors and their accessibility have a delicate control over the structural evolution of core-shell latex colloids., (© 2023 Wiley-VCH GmbH.)

Introduction: Data from mHealth apps can provide valuable information on rhinitis control and treatment patterns. However, in MASK-air®, these data have only been analyzed cross-sectionally, without considering the changes of symptoms over time. We analyzed data from MASK-air® longitudinally, clustering weeks according to reported rhinitis symptoms., Methods: We analyzed MASK-air® data, assessing the weeks for which patients had answered a rhinitis daily questionnaire on all 7 days. We firstly used k-means clustering algorithms for longitudinal data to define clusters of weeks according to the trajectories of reported daily rhinitis symptoms. Clustering was applied separately for weeks when medication was reported or not. We compared obtained clusters on symptoms and rhinitis medication patterns. We then used the latent class mixture model to assess the robustness of results., Results: We analyzed 113,239 days (16,177 complete weeks) from 2590 patients (mean age ± SD = 39.1 ± 13.7 years). The first clustering algorithm identified ten clusters among weeks with medication use: seven with low variability in rhinitis control during the week and three with highly-variable control. Clusters with poorly-controlled rhinitis displayed a higher frequency of rhinitis co-medication, a more frequent change of medication schemes and more pronounced seasonal patterns. Six clusters were identified in weeks when no rhinitis medication was used, displaying similar control patterns. The second clustering method provided similar results. Moreover, patients displayed consistent levels of rhinitis control, reporting several weeks with similar levels of control., Conclusions: We identified 16 patterns of weekly rhinitis control. Co-medication and medication change schemes were common in uncontrolled weeks, reinforcing the hypothesis that patients treat themselves according to their symptoms., (© 2022 The Authors. Allergy published by European Academy of Allergy and Clinical Immunology and John Wiley & Sons Ltd.)

Thermal transformations of polyphenols from the lignan and stilbene families were investigated at temperatures ranging from 200 °C to 250 °C, in polyethylene glycol (PEG-400), dimethylformamide (DMF) and in sunflower oil (SO). The polyphenols showed varying degrees of thermal stabilities and in some cases intramolecular transformations were observed. The formed products were isolated and characterized. Oligomerization of the polyphenols at thermo-oxidative conditions was also investigated. Finally, the antioxidative activity of the polyphenols against thermo-oxidative degradation α-linoleic acid was investigated at 200 °C. The results suggested that the studied substrates retained their antioxidative properties at elevated temperatures, with stilbenes showing most efficient protection against thermo-oxidative degradation of polyunsaturated fatty acids., Competing Interests: Declaration of Competing Interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Patrik Runeberg reports financial support was provided by Raisio Research Foundation. Patrik Eklund reports financial support was provided by Academy of Finland. Patrik Runeberg reports financial support was provided by Alfred Kordelin Fundation. The remaining authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

The influence of oxygen (0-50 bar) on the molar mass and composition of hemicelluloses after hydrothermal treatment of spruce chips was studied in a batch reactor setup at 130 °C-160 °C. Purified galactoglucomannan was studied as a reference. The dissolved oxygen enhanced significantly the depolymerization of hemicelluloses from over 15,000 g/mol to 180 g/mol (monomers) as well as promoted acids formation from the monosaccharides. About 2-3 times faster depolymerization was observed already with rather low amounts of oxygen (2-8 bar), while the kinetics of depolymerization was significantly slower in inert atmosphere. The decrease in pH from neutral to as low as 2.5 lead to an autocatalytic effect on the polysaccharide hydrolysis and the consecutive reactions of monosaccharides. The results emphasize the importance of performing hydrothermal treatment under inert atmosphere if large polymeric hemicellulsoses are desired or if monosaccharides are targeted in hydrolysis of hemicelluloses. If autocatalysis begins, it is difficult to stop., (Copyright © 2022. Published by Elsevier Ltd.)

Background: Different treatments exist for allergic rhinitis (AR), including pharmacotherapy and allergen immunotherapy (AIT), but they have not been compared using direct patient data (i.e., "real-world data"). We aimed to compare AR pharmacological treatments on (i) daily symptoms, (ii) frequency of use in co-medication, (iii) visual analogue scales (VASs) on allergy symptom control considering the minimal important difference (MID) and (iv) the effect of AIT., Methods: We assessed the MASK-air® app data (May 2015-December 2020) by users self-reporting AR (16-90 years). We compared eight AR medication schemes on reported VAS of allergy symptoms, clustering data by the patient and controlling for confounding factors. We compared (i) allergy symptoms between patients with and without AIT and (ii) different drug classes used in co-medication., Results: We analysed 269,837 days from 10,860 users. Most days (52.7%) involved medication use. Median VAS levels were significantly higher in co-medication than in monotherapy (including the fixed combination azelastine-fluticasone) schemes. In adjusted models, azelastine-fluticasone was associated with lower average VAS global allergy symptoms than all other medication schemes, while the contrary was observed for oral corticosteroids. AIT was associated with a decrease in allergy symptoms in some medication schemes. A difference larger than the MID compared to no treatment was observed for oral steroids. Azelastine-fluticasone was the drug class with the lowest chance of being used in co-medication (adjusted OR = 0.75; 95% CI = 0.71-0.80)., Conclusion: Median VAS levels were higher in co-medication than in monotherapy. Patients with more severe symptoms report a higher treatment, which is currently not reflected in guidelines., (© 2022 European Academy of Allergy and Clinical Immunology and John Wiley & Sons Ltd.)

Background: Validated combined symptom-medication scores (CSMSs) are needed to investigate the effects of allergic rhinitis treatments. This study aimed to use real-life data from the MASK-air ® app to generate and validate hypothesis- and data-driven CSMSs., Methods: We used MASK-air ® data to assess the concurrent validity, test-retest reliability and responsiveness of one hypothesis-driven CSMS (modified CSMS: mCSMS), one mixed hypothesis- and data-driven score (mixed score), and several data-driven CSMSs. The latter were generated with MASK-air ® data following cluster analysis and regression models or factor analysis. These CSMSs were compared with scales measuring (i) the impact of rhinitis on work productivity (visual analogue scale [VAS] of work of MASK-air ® , and Work Productivity and Activity Impairment: Allergy Specific [WPAI-AS]), (ii) quality-of-life (EQ-5D VAS) and (iii) control of allergic diseases (Control of Allergic Rhinitis and Asthma Test [CARAT])., Results: We assessed 317,176 days of MASK-air ® use from 17,780 users aged 16-90 years, in 25 countries. The mCSMS and the factor analyses-based CSMSs displayed poorer validity and responsiveness compared to the remaining CSMSs. The latter displayed moderate-to-strong correlations with the tested comparators, high test-retest reliability and moderate-to-large responsiveness. Among data-driven CSMSs, a better performance was observed for cluster analyses-based CSMSs. High accuracy (capacity of discriminating different levels of rhinitis control) was observed for the latter (AUC-ROC = 0.904) and for the mixed CSMS (AUC-ROC = 0.820)., Conclusion: The mixed CSMS and the cluster-based CSMSs presented medium-high validity, reliability and accuracy, rendering them as candidates for primary endpoints in future rhinitis trials., (© 2022 The Authors. Allergy published by European Academy of Allergy and Clinical Immunology and John Wiley & Sons Ltd.)

The article describes some of the achievements of the European Innovation Partnership on Active and Healthy Ageing (EIP on AHA), after eight years in operation. These results were achieved thanks to the collaborative work of the action groups (AGs) and reference sites (RSs). RS regional ecosystems include key organisations committed to investing in innovation to foster active and healthy ageing. The AGs are groups of professionals committed to sharing their knowledge and skills in active and healthy ageing. This article reports on the approach used by the EIP on AHA to bring together experts and regions in identifying and addressing these challenges. Synergies between AGs offered substantial support to RSs, allowing regional health and care priorities and challenges to be identified and pursued through AG commitments. Building upon the experiences of the EIP on AHA, the Reference Sites Collaborative Network has set up a number of thematic action groups that bring together multidisciplinary experts from across Europe to address the main health and social care challenges at regional, national and European level., Competing Interests: The authors report no conflicts of interest in this work., (© 2022 Illario et al.)

The current work studies the reductive catalytic depolymerization (RCD) of lignin from a novel semi-industrial process. The aim was to obtain aromatic mono-, di-, tri-, and tetramers for further valorization. The substrate and products were characterized by multiple analytical methods, including high pressure size-exclusion chromatography (HPSEC), gas chromatography-mass spectrometry, GC-flame ionization detector (FID), GC-FID/thermal conductivity detector (TCD), and NMR. The RCD was studied by exploring the influence of different parameters, such as lignin solubility, reaction time, hydrogen pressure, reaction temperature, pH, type and loading of the catalyst, as well as type and composition of the organic/aqueous solvent. The results show that an elevated temperature, a redox catalyst, and a hydrogen atmosphere are essential for the depolymerization and stability of the products, while the reaction medium also plays an important role. The highest obtained mono- to tetramers yield was 98% and mono- to dimers yield over 85% in the liquid phase products. The reaction mechanisms influenced the structure of the aliphatic chain in the monomers, but left the phenolic structure along with the methoxy groups largely unaltered. The current work contributes to the development and debottlenecking of the novel and sustainable overall process, which utilizes efficiently all the fractions of wood, in line with the principles of green engineering and chemistry., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

The chemical composition of extractives in the sapwood (SW), heartwood (HW), knotwood (KW), and branchwood (BW of silver fir ( Abies alba Mill.) was analyzed, and their antifungal and antioxidant properties were studied. In addition, the variability of extractives content in a centripetal direction, i.e., from the periphery of the stem towards the pith, was investigated. The extracts were analyzed chemically with gravimetry, spectrophotometry, and chromatography. The antifungal and antioxidative properties of the extracts were evaluated by the agar well diffusion method and the diphenyl picrylhydrazyl radical scavenging method. Average amounts of hydrophilic extractives were higher in KW (up to 210.4 mg/g) and BW (148.6 mg/g) than in HW (34.1 mg/g) and SW (14.8 mg/g). Extractives identified included lignans (isolariciresinol, lariciresinol, secoisolariciresinol, pinoresinol, matairesinol) phenolic acids (homovanillic acid, coumaric acid, ferulic acid), and flavonoids epicatechin, taxifolin, quercetin). Secoisolariciresinol was confirmed to be the predominant compound in the KW (29.8 mg/g) and BW (37.6 mg/g) extracts. The largest amount of phenolic compounds was extracted from parts of knots (281.7 mg/g) embedded in the sapwood and from parts of branches (258.9 mg/g) adjacent to the stem. HW contained more lignans in its older sections. Hydrophilic extracts from knots and branches inhibited the growth of wood-decaying fungi and molds. KW and BW extracts were better free radical scavengers than HW extracts. The results of the biological activity tests suggest that the protective function of phenolic extracts in silver fir wood can also be explained by their antioxidative properties. The results of this study describe BW as a potential source of phenolic extractives in silver fir.

Background: MASK-air® is an app that supports allergic rhinitis patients in disease control. Users register daily allergy symptoms and their impact on activities using visual analog scales (VASs). We aimed to assess the concurrent validity, reliability, and responsiveness of these daily VASs., Methods: Daily monitoring VAS data were assessed in MASK-air® users with allergic rhinitis. Concurrent validity was assessed by correlating daily VAS values with those of the EuroQol-5 Dimensions (EQ-5D) VAS, the Control of Allergic Rhinitis and Asthma Test (CARAT) score, and the Work Productivity and Activity Impairment Allergic Specific (WPAI-AS) Questionnaire (work and activity impairment scores). Intra-rater reliability was assessed in users providing multiple daily VASs within the same day. Test-retest reliability was tested in clinically stable users, as defined by the EQ-5D VAS, CARAT, or "VAS Work" (i.e., VAS assessing the impact of allergy on work). Responsiveness was determined in users with two consecutive measurements of EQ-5D-VAS or "VAS Work" indicating clinical change., Results: A total of 17,780 MASK-air® users, with 317,176 VAS days, were assessed. Concurrent validity was moderate-high (Spearman correlation coefficient range: 0.437-0.716). Intra-rater reliability intraclass correlation coefficients (ICCs) ranged between 0.870 (VAS assessing global allergy symptoms) and 0.937 (VAS assessing allergy symptoms on sleep). Test-retest reliability ICCs ranged between 0.604 and 0.878-"VAS Work" and "VAS asthma" presented the highest ICCs. Moderate/large responsiveness effect sizes were observed-the sleep VAS was associated with lower responsiveness, while the global allergy symptoms VAS demonstrated higher responsiveness., Conclusion: In MASK-air®, daily monitoring VASs have high intra-rater reliability and moderate-high validity, reliability, and responsiveness, pointing to a reliable measure of symptom loads., Competing Interests: Sinthia Bosnic‐Anticevich reports grants from TEVA and personal fees from TEVA, AstraZeneca, Boehringer Ingelheim, GSK, Sanofi, Mylan. Jean Bousquet reports personal fees from Chiesi, Cipla, Hikma, Menarini, Mundipharma, Mylan, Novartis, Sanofi‐Aventis, Takeda, Teva, Uriach, other from KYomed‐Innov, and personal fees from Purina. Victoria Cardona reports personal fees from ALK, Allergy Therapeutics, LETI, Thermofisher, Merck, Astrazeneca, and GSK. Alvaro A Cruz reports grants and personal fees from GlaxoSmithKline, personal fees from Sanofi, AstraZeneca, Novartis, Chiesi, Boehringer Ingelheim, Mylan, and Eurofarma. Philippe Devillier reports personal fees from Mylan. Bilun Gemicioğlu reports grants from AstraZeneca, MSD, GSK, Deva, Novartis, and Abdi Ibrahim. Tari Haahtela reports personal fees from GSK, Mundipharma, Orion Pharma, Sanofi, Juan Carlos Ivancevich reports personal fees from Sanofi, Faes Farma, Laboratorios Casasco, Abbott, Ludger Klimek reports grants and personal fees from Allergopharma, LETI Pharma, MEDA/Mylan, and Sanofi, personal fees from Allergy Therapeut, Casssela med, and HAL Allergie, grants from ALK Abelló, Stallergenes, Quintiles, ASIT biotech, Lofarma, AstraZeneca, GSK, Inmunotk, and Membership: AeDA, DGHNO, Deutsche Akademie für Allergologie und klinische Immunologie, HNO‐BV, GPA, and EAACI. Piotr Kuna reports personal fees from Adamed, AstraZeneca, Berlin Chemie Menarini, Boehringer Ingelheim, GSK, HAL Allergy, Lekam, Mylan, Novartis, and Teva. Désirée Larenas Linnemann reports personal fees from Allakos, Amstrong, Astrazeneca, DBV Technologies, Grunenthal, GSK, Mylan, Menarini, MSD, Novartis, Pfizer, Sanofi, Siegfried, UCB, Alakos, and Gossamer, grants from Sanofi, Astrazeneca, Novartis, Circassia, UCB, GSK, TEVA, and Purina Institute. Michael Makris reports personal fees from Novartis, AstraZeneca, GSK, Chiesi, Menarini, Sanofi Genzyme, and Pfizer. Joaquin Mullol reports personal fees and other from SANOFI‐GENZYME & REGENERON, Genentech‐Roche & NOVARTIS, grants and personal fees from VIATRIS (MEDA‐MYLAN Pharma) and URIACH Group, and personal fees from Mitsubishi‐Tanabe, Menarini, UCB, AstraZeneca, and GSK. Oliver Pfaar reports grants and personal fees from ALK‐Abelló, Allergopharma, Stallergenes Greer, HAL Allergy Holding B.V./HAL Allergie GmbH, Bencard Allergie GmbH/Allergy Therapeutics, Lofarma, Anergis S.A., ASIT Biotech Tools S.A., Laboratorios LETI/LETI Pharma, and Glaxo Smith Kline, grants from Biomay, Circassia, Pohl‐Boskamp, and Inmunotek S.L., and personal fees from MEDA Pharma/MYLAN, Mobile Chamber Experts (a GA2LEN Partner), Indoor Biotechnologies, Astellas Pharma Global, EUFOREA, ROXALL Medizin, Novartis, Sanofi‐Aventis and Sanofi‐Genzyme, Med Update Europe GmbH, streamedup! GmbH, John Wiley and Sons, AS, and Paul‐Martini‐Stiftung (PMS). Nikolaos G. Papadopoulos reports personal fees from Novartis, Nutricia, HAL, MENARINI/FAES FARMA, SANOFI, MYLAN/MEDA, BIOMAY, AstraZeneca, GSK, MSD, ASIT BIOTECH, and Boehringer Ingelheim and grants from Gerolymatos International SA, and Capricare. Boleslaw Samolinski reports personal fees from Allergopharma, Polpharma, Viatris, TEVA, ADAMED, patient ombudsman, and Polish Allergology Society, grants from AstraZeneca, National Health Programme, and grants and personal fees from AstraZeneca. Ana Todo‐Bom reports grants and personal fees from AstraZeneca, GSK (GlaxoSmithKline), Novartis, Sanofi, Teva, and Mundipharma, personal fees from Bial, and grants from Leti. Torsten Zuberbier reports personal fees from Bayer Health Care, FAES, Novartis, Henkel, Novartis, from Henkel, AstraZeneca, AbbVie Fee for talk, ALK Fee for talk, Almirall Fee for talk, Astellas Fee for talk, Bayer Health Care Fee for talk, Bencard Fee for talk, Berlin Chemie Fee for talk, FAES Fee for talk, HAL Fee for talk, Leti Fee for talk, Meda Fee for talk, Menarini Fee for talk, Merck Fee for talk, MSD Fee for talk, Novartis Fee for talk, Pfizer Fee for talk, Sanofi Fee for talk, Stallergenes Fee for talk, Takeda Fee for talk, Teva Fee for talk, UCB Fee for talk, Henkel Fee for talk, Kryolan Fee for talk, and L'Oréal Fee for talk., (© 2021 The Authors. Clinical and Translational Allergy published by John Wiley and Sons Ltd on behalf of European Academy of Allergy and Clinical Immunology.)

Non-communicable chronic diseases (NCCDs) are the main cause of morbidity and mortality globally. Demographic aging has resulted in older populations with more complex healthcare needs. This necessitates a multilevel rethinking of healthcare policies, health education and community support systems with digitalization of technologies playing a central role. The European Innovation Partnership on Active and Healthy Aging (A3) working group focuses on well-being for older adults, with an emphasis on quality of life and healthy aging. A subgroup of A3, including multidisciplinary stakeholders in health care across Europe, focuses on the palliative care (PC) model as a paradigm to be modified to meet the needs of older persons with NCCDs. This development paper delineates the key parameters we identified as critical in creating a public health model of PC directed to the needs of persons with NCCDs. This paradigm shift should affect horizontal components of public health models. Furthermore, our model includes vertical components often neglected, such as nutrition, resilience, well-being and leisure activities. The main enablers identified are information and communication technologies, education and training programs, communities of compassion, twinning activities, promoting research and increasing awareness amongst policymakers. We also identified key 'bottlenecks': inequity of access, insufficient research, inadequate development of advance care planning and a lack of co-creation of relevant technologies and shared decision-making. Rethinking PC within a public health context must focus on developing policies, training and technologies to enhance person-centered quality life for those with NCCD, while ensuring that they and those important to them experience death with dignity.

Softwood bark is an important by-product of forest industry. Currently, bark is under-utilized and mainly directed for energy production, although it can be extracted with hot water to obtain compounds for value-added use. In Norway spruce ( Picea abies [L.] Karst.) bark, condensed tannins and stilbene glycosides are among the compounds that comprise majority of the antioxidative extractives. For developing feasible production chain for softwood bark extractives, knowledge on raw material quality is critical. This study examined the fate of spruce bark tannins and stilbenes during storage treatment with two seasonal replications (i.e., during winter and summer). In the experiment, mature logs were harvested and stored outside. During six-month-storage periods, samples were periodically collected for chemical analysis from both inner and outer bark layers. Additionally, bark extractives were analyzed for antioxidative activities by FRAP, ORAC, and H 2 O 2 scavenging assays. According to the results, stilbenes rapidly degraded during storage, whereas tannins were more stable: only 5-7% of the original stilbene amount and ca. 30-50% of the original amount of condensed tannins were found after 24-week-storage. Summer conditions led to the faster modification of bark chemistry than winter conditions. Changes in antioxidative activity were less pronounced than those of analyzed chemical compounds, indicating that the derivatives of the compounds contribute to the antioxidative activity. The results of the assays showed that, on average, ca. 27% of the original antioxidative capacity remained 24 weeks after the onset of the storage treatment, while a large variation (2-95% of the original capacity remaining) was found between assays, seasons, and bark layers. Inner bark preserved its activities longer than outer bark, and intact bark attached to timber is expected to maintain its activities longer than a debarked one. Thus, to ensure prolonged quality, no debarking before storage is suggested: outer bark protects the inner bark, and debarking enhances the degradation.

Wastewater-treatment plants (WWTPs) are regarded as one of the main sources of antibiotics in the environment. In the present study, the concentrations of multiple antibiotics and their metabolites belonging to 5 antibiotic classes were determined in 3 major Finnish WWTPs. An online solid phase extraction-liquid chromatography-tandem mass spectrometry method was used for the extraction and analysis of the compounds. The method was fully validated using real and synthetic wastewaters. Seven antibiotics and 3 metabolites were found in the analyzed samples. Sulfonamides were removed most efficiently, whereas macrolides usually showed negative removal efficiency during the treatment, which means that the concentrations for individual antibiotics determined in the effluent samples were higher than in the influent samples. Sulfadiazine was found at concentrations up to 1018 ng/L, which was the highest concentration of any of the detected antibiotics in influent. In the effluent samples, the highest mean concentration was found for trimethoprim (532 ng/L). The measured mass loads of the antibiotics and metabolites to the receiving waters ranged from 2 to 157 mg/d per 1000 population equivalent. The evaluated environmental risk assessment showed that clarithromycin and erythromycin might pose a risk to the environment. The present study further underlines the importance of implementing technology for efficient removal of xenobiotics during wastewater treatment. Environ Toxicol Chem 2020;39:1774-1789. © 2020 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC., (© 2020 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.)

Carbamazepine (CBZ) is a recalcitrant pharmaceutical often detected in wastewater and in the environment. CBZ can be removed from wastewater through advanced oxidation treatment methods such as ozonation. In this study, CBZ and its transformation product 1-(2-benzaldehyde)-(1H,3H)-quinazoline-2,4-dione (BQD) were ozonated, and the formation and transformation of their ozonation products were investigated using liquid chromatography coupled to ion trap mass spectrometry and high-resolution mass spectrometry as well as nuclear magnetic resonance (NMR). The main products, 1-(2-benzaldehyde)-4-hydro-(1H,3H)-quinazoline-2-one (BQM) and BQD were quantified using isolated standards and LC-UV. Of the original CBZ concentration, 74% was transformed into BQM and 83% of BQM was further transformed into BQD. Both products are more stable than CBZ and could still be detected after 240 min of ozonation. Another major product, 2,2'-azanediyldibenzaldehyde (TP225) was for the first time identified using NMR. Twelve further CBZ products were identified.

In this work, ozone has been used to study the transformation of the antibiotic sulfadiazine (SDZ). SDZ and its transformation products was investigated using liquid chromatography coupled to mass spectrometry and using NMR. The results revealed that 6% of SDZ is transformed into 2-aminopyrimidine. A significant amount of SDZ undergoes a rearrangement reaction followed by ring-closing reactions. One of these products, SDZ-P15, is the main product after 240 min of ozonation. Almost 30% of SDZ transforms into SDZ-P15. SDZ was also transformed via the addition of one or more hydroxyl groups, via the oxidation of an amine group to a nitro group as well as via a bond cleavage reaction. Most of the intermediate products presented in this study have not previously been reported as SDZ transformation products formed using ozonation technology., Competing Interests: Declaration of competing interest None., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Epoxidation of the C=C double bond in unsaturated norlignans derived from hydroxymatairesinol was studied. The intermediate epoxides were formed in up to quantitative conversions and were readily further transformed into tetrahydrofuran, aryltetralin, and butyrolactone products-in diastereomeric mixtures-through ring-closing reactions and intramolecular couplings. For epoxidation, the classical Prilezhaev reaction, using stoichiometric amounts of meta -chloroperbenzoic acid ( m CPBA), was used. As an alternative method, a catalytic system using dimeric molybdenum-complexes [MoO 2 L] 2 with ONO- or ONS-tridentate Schiff base ligands and aqueous tert -butyl hydroperoxide (TBHP) as oxidant was used on the same substrates. Although the epoxidation was quantitative when using the Mo-catalysts, the higher temperatures led to more side-products and lower yields. Kinetic studies were also performed on the Mo-catalyzed reactions.

The vast majority of cervical and 75% of oropharyngeal carcinomas are triggered by infection with a type of high-risk oncogenic human papillomavirus (HPV). It is well-known that E6 and E7 oncoproteins are critical for viral-induced cancer, and hence, they represent valuable targets for therapeutic intervention in HPV-mediated cancers. Our earlier research on the cembranoid, anisomelic acid (AA) showed that, AA has the potential to induce apoptosis in HPV cells by the depletion of E6 and E7 oncoproteins. The present study describes the structure-activity relationship and the evaluation of synthetic AA like compounds, i.e simplified cembranoid-like structures, as HPV inhibitors against some papilloma cell lines. Both from experimental and computational results, we observed that these compounds induced apoptosis by the same E6/E7-based mechanism as AA, but at earlier time points, thus being far more effective than AA. Further, the data indicated that only part of the structure of AA is required for the molecular action. Based on these results, we identified some novel and potential compounds for specific treatment of HPV-associated carcinomas.

Aerobic Pd(AcO) 2 /pyridine-catalyzed oxidation of unprotected carbohydrate-based terminal alkenes was studied. In accordance with previous reports, the initial reaction step gave methyl ketones. However, our substrates partially gave subsequent α,β-water elimination and alcohol oxidation to α,β-unsaturated 2,5-diketones. Upon increasing the pressure of O 2 , the reaction was shifted toward formation of α,β-epoxy-2-ketones. The reactions were stereoselective and gave up to quantitative conversions. However, isolated yields were substantially lower because of the complexity of the product mixtures.

In this work we have analyzed the pine and spruce softwood lignin fraction recovered from a novel pressurized hot water extraction pilot process. The lignin structure was characterized using multiple NMR techniques and the thermal properties were analyzed using thermal gravimetric analysis. Acetylated and selectively methylated derivatives were prepared, and their structure and properties were analyzed and compared to the unmodified lignin. The lignin had relatively high molar weight and low PDI values and even less polydisperse fractions could be obtained by fractionation based on solubility in i -PrOH. Condensation, especially at the 5-position, was detected in this sulphur-free technical lignin, which had been enriched with carbon compared to the milled wood lignin (MWL) sample of the same wood chips. An increase in phenolic and carboxylic groups was also detected, which makes the lignin accessible to chemical modification. The lignin was determined to be thermally stable up to (273⁻302 °C) based on its T dst 95% value. Due to the thermal stability, low polydispersity, and possibility to tailor its chemical properties by modification of its hydroxyl groups, possible application areas for the lignin could be in polymeric blends, composites or in resins.

Numerous oxidative transformations of lignan structures have been reported in the literature. In this paper we present an overview on the current findings in the field. The focus is put on transformations targeting a specific structure, a specific reaction, or an interconversion of the lignan skeleton. Oxidative transformations related to biosynthesis, antioxidant measurements, and total syntheses are mostly excluded. Non-metal mediated as well as metal mediated oxidations are reported, and mechanisms based on hydrogen abstractions, epoxidations, hydroxylations, and radical reactions are discussed for the transformation and interconversion of lignan structures. Enzymatic oxidations, photooxidation, and electrochemical oxidations are also briefly reported.

Lignans, neolignans, norlignans and norneolignans constitute a large class of phenolic natural compounds. 9-Norlignans, here defined to contain a β⁻β' bond between the two phenylpropanoid units and to lack carbon number 9 from the parent lignan structure, are the most rarely occurring compounds within this class of natural compounds. We present here an overview of the structure, occurrence and biological activity of thirty-five 9-norlignans reported in the literature to date. In addition, we report the semisynthetic preparation of sixteen 9-norlignans using the natural lignan hydroxymatairesinol obtained from spruce knots, as starting material. 9-Norlignans are shown to exist in different species and to have various biological activities, and they may therefore serve as lead compounds for example for the development of anticancer agents. Hydroxymatairesinol is shown to be a readily available starting material for the preparation of norlignans of the imperanene, vitrofolal and noralashinol family.

The low-molar-mass (LMM) fraction, only, i.e., the GC-eluting compounds, which are mainly lignans, has been characterized in Norway spruce knotwood hydrophilic extracts previously. Of this fraction, many lignans and sesquilignans and all GC peaks supposedly representing dilignans remain unidentified. In this work, dilignans and the GC non-eluting compounds (the high-molar mass fractions, HMM) were characterized in a 7-hydroxymatairesinol-reduced knotwood ethanol extract of Norway spruce by using several fractionation and analytical techniques. A methyl tert-butyl ether (MTBE) insoluble fraction of the extract contained mainly HMM material, of which the main part was shown to consist of lignan oligomers. The oligolignans (with a molar mass up to approximately 3700 Da) seemed to be linked by 55' bonds, some of them containing one or two guaiacylglycerol ether units linked to the lignan by βO4 or β5 bonds. Several oligolignans were identified or tentatively identified. The MTBE soluble fraction, which accounted for the major part (81%) of the extract, contained mainly LMM material (lignans, sesqui- and dilignans). The part of the HMM material in the MTBE soluble fraction that was easily isolable (2%) seemed to contain polymers of fatty acids and alcohols, resin acids, and sterols., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Hypothesis: Polymer constructs are often applied in nanoparticulate systems to expand their applicability. One such common macromolecular modifier is poly(ethylene imine) - poly(ethylene glycol) copolymers. Despite their quite widespread use, and considering that interaction and stabilization mechanisms when combining a polyelectrolyte with a non-charged polymer are not trivial to pinpoint, these systems are generally poorly characterized in literature. Here, we attempt to provide a solid rationale to utilize PEG-PEI copolymers as surface modifiers and stabilizers/dispersion agents in solid colloidal systems with focus on biomedical applicability., Experimental: mPEG grafted PEI copolymers with two different grafting densities and 100 nm sized non-porous silica nanoparticles (SiNP) were synthesized. Detailed physico-chemical characterization of all prepared materials was conducted with spectroscopic methods, while the interaction mechanisms between the produced copolymers and SiNP were investigated by calorimetry. The influence of increased PEG grafting ratio on the attained colloidal stability of copolymer functionalized SiNP was studied by multiple light scattering, and its further implications on the biobehavior of SiNP were evaluated., Findings: The interaction mechanism between SiNP and copolymers was concluded to be mainly directed by electrostatics, whereas an influence of PEG grafting density on the adsorption process was also observed. The implications of the surface modifications on the in vitro biobehavior of SiNP were investigated by combining the knowledge obtained by the detailed characterizations with microscopy evaluation under in vitro conditions., (Copyright © 2013 Elsevier Inc. All rights reserved.)

Galactose units of spruce galactoglucomannan (GGM), guar galactomannan (GM), and tamarind (galacto)xyloglucan (XG) were selectively allylated. Firstly aldehyde functionalities were formed at the C-6 position via enzymatic oxidation by galactose oxidase. The formed aldehydes were further derivatized by an indium mediated Barbier-Grignard type reaction, resulting in the formation of homoallylic alcohols. In addition to allylic halides, the same reaction procedure was also applicable for GGM, when using propargyl bromide as halide. All reaction steps were done in water, thus the polysaccharides were modified in a one-pot reaction. The formation of the allylated, or propargylated, product was identified by MALDI-TOF-MS. All polysaccharide products were isolated and further characterized by GC-MS or NMR spectroscopy. By this chemo-enzymatic process, we have demonstrated a novel method for derivatization of GGM and other galactose-containing polysaccharides. The derivatized polysaccharides are potential platforms for further functionalizations., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

Water-soluble O-acetyl-galactoglucomannans (GGMs) can be obtained from Norway spruce by hot-water-extraction of the wood or as a side product by ultrafiltration of mechanical pulping waters. Cationic and amphiphilic polysaccharides and their derivatives are of interest for a number of applications and thus quaternary nitrogen moieties with cationic charge were grafted onto GGMs in the heterogeneous reaction to render a cationic polyelectrolyte. The degree of substitution was measured by elemental analysis of nitrogen, by quantitative (13)C NMR and interestingly also by polyelectrolyte titration and the results were congruent. NMR, matrix-assisted laser desorption/ionisation mass spectroscopy (MALDI-TOF-MS), and FT-IR analysis were used to characterise the product. THF or DMSO with water enhanced the reaction efficiency and decreased M(w) reduction in comparison to plain water as a reaction media. Cationised GGM was also successfully acetylated. The cationic derivatives of hemicelluloses can potentially be utilised as polyelectrolyte layers in packaging and pharmaceutical applications., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Prostate cancer cells frequently develop resistance toward androgen-deprivation and chemotherapy. To identify new approaches to treat androgen-dependent prostate cancer, we have performed a structure-activity analysis of lignan polyphenols for cancer cell specific sensitization to tumor necrosis factor-related apoptosis-inducing ligand (TRAIL), a death ligand that has ability to induce tumor-specific cell death. In this study, we report that the lignan nortrachelogenin (NTG) is the most efficient of the 27 tested lignan compounds in sensitizing prostate cancer cells to TRAIL-induced apoptosis. Importantly, pretreatment with NTG does not sensitize a non-malignant prostate cell line to TRAIL-induced cell death. The structural comparison of lignans reveals that the dibenzylbutyrolactone skeleton is required for the apoptosis-sensitizing activity, while substitutions at the aromatic rings do not seem to play a critical role in this lignan function. Our study also characterizes the cellular effects and molecular mechanisms involved in NTG anticancer activity. We previously reported that specific lignans inhibit the Akt survival-signaling pathway in concert with TRAIL sensitization. While NTG is also shown to be a effective inhibitor of Akt signaling, in this study we further demonstrate that NTG potently inhibits tyrosine kinase (RTK) activation in response to growth factors, such as insulin and insulin-like growth factor I (IGF-I). Our results identify NTG as a novel agent for prostate cancer therapy with ability to inhibit Akt membrane localization and activity as well as the activation of growth factor receptors (GFRs), thereby efficiently synergizing with TRAIL exposure., (Copyright © 2013 Elsevier Inc. All rights reserved.)

The antimicrobial effects of the wood-associated polyphenolic compounds pinosylvin, pinosylvin monomethyl ether, astringin, piceatannol, isorhapontin, isorhapontigenin, cycloXMe, dHIMP, ArX, and ArXOH were assessed against both Gram-negative (Salmonella) and Gram-positive bacteria (Listeria monocytogenes, Staphylococcus epidermidis, Staphylococcus aureus) and yeasts (Candida tropicalis, Saccharomyces cerevisiae). Particularly the stilbenes pinosylvin, its monomethyl ether and piceatannol demonstrated a clear antimicrobial activity, which in the case of pinosylvin was present also in food matrices like sauerkraut, gravlax and berry jam, but not in milk. The destabilization of the outer membrane of Gram-negative microorganisms, as well as interactions with the cell membrane, as indicated by the NPN uptake and LIVE/DEAD viability staining experiments, can be one of the specific mechanisms behind the antibacterial action. L. monocytogenes was particularly sensitive to pinosylvin, and this effect was also seen in L. monocytogenes internalized in intestinal Caco2 cells at non-cytotoxic pinosylvin concentrations. In general, the antimicrobial effects of pinosylvin were even more prominent than those of a related stilbene, resveratrol, well known for its various bioactivities. According to our results, pinosylvin could have potential as a natural disinfectant or biocide in some targeted applications., (Copyright © 2013 Elsevier B.V. All rights reserved.)

The aim of this study is to establish structured clusters and well-defined ontological entities (nodes) describing ethical values as both ideal and opportunity for ethical manner as perceived by thecaregiver.In this study, we use Bayesian Belief Networks (BBNs) to analyse ethical values (ethos) and ethical manners in daily work with older people. Material is based on questionnaire data collected by the instrument for the self-assessment of individual ethos in the care of older people(ISAEC) in spring 2007 in a municipality in Western Finland. This study is unique in its kind, both concerning the selected approach and methodological questions. BBNs have not been used significantly in nursing research, nor are there any studies that examine the ethical possibilities with focus on the probable effects upon changing conditions.

Galactoglucomannan (GGM) is a polysaccharide mainly consisting of mannose, glucose, and galactose. GGM is the most abundant hemicellulose in the Norway spruce (Picea abies), but is also found in the cell wall of flax seeds, tobacco plants, and kiwifruit. Although several applications for GGM polysaccharides have been developed in pulp and paper manufacturing and the food and medical industries, attempts to synthesize and study distinct fragments of this polysaccharide have not been reported previously. Herein, the synthesis of one of the core trisaccharide units of GGM together with a less-abundant tetrasaccharide fragment is described. In addition, detailed NMR spectroscopic characterization of the model compounds, comparison of the spectral data with natural GGM, investigation of the acetyl-group migration phenomena that takes place in the polysaccharide by using small model compounds, and a binding study between the tetrasaccharide model fragment and a galactose-binding protein (the toxin viscumin) are reported., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

In seed extracts of five oilseed species, in bran extracts of three cereal species, and in seed and/or whole berry extracts of 10 berry species, the concentrations of a large number of lignans and the enantiomeric composition of selected lignans were determined. In the case of sesame and hemp seeds, the lignan content and composition of the whole seeds was compared to that of the hulled seeds. The results showed that cloudberry seeds are the third most lignan-rich food source after linseeds and whole sesame seeds, and that most of the berry species analysed were more lignan-rich than the cereal brans. The lignans are concentrated in the hull of the oilseeds and in the seeds of the berries. In most samples, secoisolarici-, pino-, medio-, and syringaresinol were present as a mixture of two enantiomers., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

Norway spruce O-acetyl-galactoglucomannans (GGM) are water-soluble hemicelluloses that have potential to be produced in large scale as a side product of the mechanical pulping industry or by hot-water extraction of wood. Chemical modification is often needed to tailor such water-soluble polysaccharides into industrially valuable compounds. In this work, treatment of GGM with butyric and benzoic anhydride in pyridine/dimethylformamide rendered GGM derivatives, which were hydrophobic and partially soluble in organic solvents. The degree of substitution can be adjusted by varying the quantity of the reagent and reaction temperature. The dn/dc value for the benzoyl ester of GGM was determined in 0.05 M LiBr DMSO in order to obtain accurate molar mass analysis with SEC-MALLS-RI. Novel substances with adjusted hydrophobicity can thus be prepared on one step synthesis from natural hemicelluloses, which then showed a slight increase in the molar mass upon esterification., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

Molecular dynamics (MD) simulations were performed on sterically hindered α-conidendrin-based chiral 1,4-diols (LIGNOLs) from the naturally occurring lignan hydroxymatairesinol (HMR) using the GROMACS software. The aim of this study was to explore the conformational behaviour of the LIGNOLs in aqueous solution adopting the TIP4P model. The topologies of the LIGNOLs were constructed manually and they were modeled with the OPLS-AA force field implemented in GROMACS. The four most relevant torsional angles in the LIGNOLs were properly analyzed during the simulations. The determining property for the conformation preferred in aqueous solution was found to be the lowest energy in gas phase. The solvation effects on the LIGNOLs were also studied by quantum chemical calculations applying the COnductor-like Screening MOdel (COSMO). The hydration studies of the MD simulations showed that several of these LIGNOLs, produced from a renewable source, have a great potential of acting as chiral catalysts.

Phytoestrogens are plant-derived food ingredients assumed to contribute to the prevention of hormone-dependent cancers, osteoporosis, cardiovascular disease, and menopausal symptoms. Lignans occur in numerous food plants and various structures; they are common constituents of human diet, and estrogen activity has been assessed for lignan metabolites formed in the mammalian intestine. We examined natural lignans and semisynthetic norlignans for estrogen and antiestrogen activity. A transformed yeast strain (Saccharomyces cerevisiae) expressing the estrogen receptor alpha and a reporter system was applied as test system. Some plant lignans showed estrogen activity while others and the semisynthetic norlignans were moderately active antiestrogens. Docking of lignans to protein models of estrogen receptor alpha in the active and inactive form sustained the results of the yeast estrogen assay and supported the concept of plant lignans as phytoestrogens., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

The model complex [(64)Cu((S)-p-NH(2)-Bn-NOTA)](-) ([(64)Cu]1) was used to study the isomerism of [(64)Cu-NOTA-Bn]-labeled radiotracers. Two complex isomers [(64)Cu]1a and [(64)Cu]1b, which were formed at a ratio of 1:9 during the complexation of [(64)Cu]Cu(2+) with (S)-p-NH(2)-Bn-NOTA, were separated using ion pair chromatography. To study the interconversion, the nonradioactive complex isomers Cu1a and Cu1b were separated and thermally treated at 90 °C in both ammonium acetate solution and deionized water. A faster interconversion rate was observed for both isomers with lower concentrations of ammonium ions. At the end of reaction, the thermodynamic Cu1a to Cu1b equilibrium ratio was 6:94. The particular energy barriers of the interconversion for Cu1a and Cu1b were 130 kJ mol(-1) and 140 kJ mol(-1). Spectrophotometric measurements with Cu1a and Cu1b revealed two isomers adopting different geometrical configurations.

The C-6 unit of methyl α-D-galactopyranoside was selectively modified by combining enzymatic oxidation with an indium-mediated allylation reaction. The Barbier-Grignard type reaction, where a carbonyl group reacts with an allyl halide, proceeds in aqueous solution, even with water as the only solvent; thus carbohydrates can be modified without the need for drying or protection-deprotection steps. The corresponding homoallyl alcohols are produced in high yields of >90% in the reactions with allyl bromide and cinnamyl chloride. The main products were isolated and characterized by GC-MS and NMR spectroscopy., (Copyright © 2010 Elsevier Ltd. All rights reserved.)

Background: Multidrug resistance protein 1 (MRP1/ABCC1) is one of the drug efflux pumps mediating multidrug resistance in several cancer types. Efficient nontoxic inhibitors of MRP1-mediated transport are sought to potentially sensitise cancer cells to anticancer drugs. This study examined the potency of a series of plant lignans and norlignans of various structures to inhibit MRP1-mediated transport from human erythrocytes. The occurrence of MRP1 in the human erythrocyte membrane makes this cell a useful model in searching for efficient MRP1inhibitors., Materials and Methods: The inhibition of 2',7'-bis-(carboxypropyl)-5(6)-carboxyfluorescein (BCPCF) transport from human erythrocytes was measured fluorymetrically. In order to study possible membrane-perturbing effects of lignans and norlignans, the potency of these compounds to induce haemolysis, erythrocyte shape change, and phosphatidylserine (PS) exposure in the external layer of the erythrocyte membrane was examined., Results: Nine compounds (six norlignans and three lignans) of the fourteen that were tested inhibited BCPCF transport from human erythrocytes. The most efficient inhibitor, the norlignan coded L1, had IC(50)=50 μM. Structure-activity relationship analysis showed that the strongest inhibitors were found among lignans and norlignans bearing a carbonyl function at position C-9. The highly oxidised structures and the presence of an ionisable group such as the carboxylic acid function enhance activity. All compounds that significantly decreased BCPCF transport were non-haemolytic, did not cause PS exposure and did not have any effect on erythrocyte shapes up to 200 μM., Conclusion: Lignans and norlignans can inhibit MRP1-mediated transport from human erythrocytes and should be further investigated as possible agents reversing multidrug resistance.

A convenient semi-synthesis of (8R,8'R)-matairesinol 4,4'-di-O-beta-d-glucopyranoside (MDG), found in the stems of Trachelospermum asiaticum var. intermedium, is described starting from the readily available starting materials d-glucose and hydroxymatairesinol. By this approach the synthesis of MDG can be accomplished in six steps with an overall yield of 28%. In addition, the first complete NMR-spectroscopic characterization of MDG was accomplished by the combination of standard NMR techniques and spectral simulations performed with the PERCH NMR simulation software.

Acetylated galactoglucomannans (GGMs) are the main hemicellulose type in most softwood species and can be utilized as, for example, bioactive polymers, hydrocolloids, papermaking chemicals, or coating polymers. Acetylation of spruce GGM using acetic anhydride with pyridine as catalyst under different conditions was conducted to obtain different degrees of acetylation on a laboratory scale, whereas, as a classic method, it can be potentially transferred to the industrial scale. The effects of the amount of catalyst and acetic anhydride, reaction time, temperature and pretreatment by acetic acid were investigated. A fully acetylated product was obtained by refluxing GGM for two hours. The structures of the acetylated GGMs were determined by SEC-MALLS/RI, (1)H and (13)C NMR and FTIR spectroscopy. NMR studies also indicated migration of acetyl groups from O-2 or O-3 to O-6 after a heating treatment in a water bath. The thermal stability of the products was investigated by DSC-TGA., (Copyright (c) 2010 Elsevier Ltd. All rights reserved.)

X-ray structures of two compounds isolated from wood knots of coniferous trees, namely dihydrokaempferol (3,5,8,13-tetrahydroxyflavanon) and lariciresinol (3,14-dimetoxy-7,10-epoxylignan-4,15,19-triol), are presented here. Diffraction data for the Dihydrokaempferol crystals were collected on a CAD4 diffractometer and on a synchrotron for the lariciresinol crystal. The investigated compounds inhibit lipid peroxidation and lariciresinol is additionally a good scavenger of superoxide radicals. The structural data presented in this work provide a useful basis for designing more active compounds with potential use as antioxidants.

Highly oxidized lignans produced during the cytochrome P-450 metabolism in the cells show biological activities significantly different from those of their parent natural compounds. Lignans precursors of mammalian enterolignans were treated with a methyltrioxorhenium/hydrogen peroxide catalytic system to afford new compounds oxidized at benzylic as well as in arylic positions. The evaluation of the antioxidant and apoptogenic activity by in vivo protocols of these compounds showed some interesting structure-activity relationships related to the oxidation degree of the molecules.

We report here the first selective de-O-methylation of a large panel of guaiacyl lignans to the corresponding catechol derivatives by using IBX as primary oxidant under green conditions (dimethyl carbonate-H(2)O solvent) through an in situ reduction procedure. The influence of the catechol moiety on the cytotoxicity and genotoxicity of new lignan derivatives has been investigated. The results obtained indicated that the presence of the catechol moiety sharply enhances the clastogenic potential (e.g. induction of chromosomal aberrations), the cytotoxicity and the modulation of cell cycle progression with respect to the parent compounds. Thus, despite the in vitro antioxidant activity usually described for catechol derivatives, our results show for the first time the generation of a clastogenic potential, highly indicative of a long-term genetic and cancer risk.

The fragmentation pattern of 30 compounds belonging to different classes of the lignan family was studied by liquid chromatography-electrospray ionization ion-trap mass spectrometry. On the basis of the observed fragmentation patterns, identification of different types of lignans was achieved. For example, dibenzylbutyrolactone lignans showed a characteristic fragmentation pathway by the loss of 44 Da (CO(2)) from the lactone moiety, whereas dibenzylbutanediols showed a loss of 48 Da by a combined loss of formaldehyde and water from the 1,4-butanediol moiety. Lignan glycosides readily lost the sugar residue to give the parent lignan as their primary product ion. In addition, several compound-specific fragmentations were observed and used for identification of individual compounds.A versatile method for analyses of lignans was developed using LC separation on a C8 column followed by fragmentation and detection of ions produced in the ion trap., (2007 John Wiley & Sons, Ltd)

Twenty-four plant lignans were analyzed by high-performance liquid chromatography-tandem mass spectrometry in bran extracts of 16 cereal species, in four nut species, and in two oilseed species (sesame seeds and linseeds). Eighteen of these were lignans previously unidentified in these species, and of these, 16 were identified in the analyzed samples. Four different extraction methods were applied as follows: alkaline extraction, mild acid extraction, a combination of alkaline and mild acid extraction, or accelerated solvent extraction. The extraction method was of great importance for the lignan yield. 7-Hydroxymatairesinol, which has not previously been detected in cereals because of destructive extraction methods, was the dominant lignan in wheat, triticale, oat, barley, millet, corn bran, and amaranth whole grain. Syringaresinol was the other dominant cereal lignan. Wheat and rye bran had the highest lignan content of all cereals; however, linseeds and sesame seeds were by far the most lignan-rich of the studied species.

The lignans matairesinol (MAT) and secoisolariciresinol (SECO) were fed to Min mice at 0.02% (w/w) in diet to study their effects on intestinal tumor development. The mean number (67 vs. 51, P=0.052) and size (1.4 vs. 1.2 mm, P=0.011) of tumors in the MAT group was elevated when compared with the control group. Tumor formation of the SECO group did not differ from the control group. Intake of MAT increased the level of both MAT and enterolactone in the plasma while SECO feeding increased SECO, enterodiol, and enterolactone (P=0.001). These results showed that MAT or SECO do not prevent intestinal carcinogenesis in Min mice and that MAT may have adverse effects.