Antioxidative and Antimicrobial Evaluation of Bark Extracts from Common European Trees in Light of Dermal Applications.

Plant species have developed effective defense strategies for colonizing diverse habitats and protecting themselves from numerous attacks from a wide range of organisms, including insects, vertebrates, fungi, and bacteria. The bark of trees in particular constitutes a number of components that protect against unwanted intruders. This review focuses on the antioxidative, dermal immunomodulatory, and antimicrobial properties of bark extracts from European common temperate trees in light of various skin pathogens, wound healing, and the maintenance of skin health. The sustainability aspect, achieved by utilizing the bark, which is considered a byproduct in the forest industry, is addressed, as are various extraction methods applied to retrieve extracts from bark.

Lead-binding biogenic polyelectrolyte multilayer coating for lead retention in perovskite solar cells.

Perovskite solar cells promise to deliver high efficiencies at low manufacturing costs. Yet on their way towards commercialization, they have to face the associated risk of potential lead leakage into the environment after damage to the cell's encapsulation. Here we present a new approach to generate a lead binding coating, based on a layer-by-layer deposition of biopolymers. A lead-adsorbing functionality was shown after subsequent crosslinking, demonstrating a high binding capacity. The lead binding capabilities could be further enhanced by increasing the thickness of the coatings, analyzed both in the supernatant and on the surface of the coated material. The thin-layered coating had a thickness of less than one micrometer, was stable even under low pH conditions and could successfully be transferred onto different substrates, ranging from silicon, gold and glass substrates to polymeric nonwoven materials with high surface areas, further increasing its lead binding capacity. This newly described coating was applied within perovskite solar cell stacks without impeding the overall efficiency but strongly reducing the amount of lead released after simulated rain tests on devices with damaged encapsulation. Accordingly, incorporation of lead-binding polyelectrolyte multilayers inside the encapsulation of perovskite solar cells shows great potential to limit the perovskite solar cells inherent risk of lead leakage in a sustainable manner.

Microwave-Assisted Lignin Extraction-Utilizing Deep Eutectic Solvents to Their Full Potential.

The current research intended to investigate the suitability of different choline-chloride-based deep eutectic solvents for their role in microwave lignin extraction. Lignin, a widely spread biopolymer in plants and woody structures, is a valuable replacement for fossil-fuel-based materials. While some promising applications have been trialled already, the extraction of this material from its matrix still causes problems. Here, we highlight an efficient and fast method to extract lignin from untreated larch bark with deep eutectic solvents in a standard domestic microwave. We developed a straightforward, green methodology, which can be used on various reaction scales, with materials available to many researchers. Lignin was extracted within only 30 min of microwave irradiation in yields of up to 96%. Compared to traditional deep eutectic extraction by conventional heating, the reaction time was cut by 87% and the energy costs were reduced by 93.5%. The hydrogen bond donors were exchanged and different types, namely acid-based, hydroxyl-based and amide-based donor systems, were evaluated for their suitability concerning microwave lignin extraction. This study presents a novel approach towards energy-efficient and green lignin valorisation, without the inherent need for costly equipment.

Antimicrobial Activity and Wound-Healing Capacity of Birch, Beech and Larch Bark Extracts.

Bark is a major by-product of woodworking industries. The contents of several wood species are known to harbor antimicrobial, antiviral, anti-inflammatory and wound-healing capacities. The aim of this work was to identify beneficial properties of Austrian larch, birch and beech bark extracts for their potential usage as additives or active ingredients in dermatological applications. Bacterial agar diffusion assay and resazurin-based broth microdilution assay were used to evaluate anti-bacterial activity. To gain more insight into the cellular response to bark extracts, viability-, scratch-assays and ELISAs were performed. Birch and beech extracts showed strong antimicrobial activities against Gram-positive bacteria, including Cutibacterium acnes, Staphylococcus epidermidis and MRSA. Wound closure was enhanced with birch and beech extracts as compared to controls in the scratch-assays. Whereas beneficial properties of birch bark components have previously been described, the similar effects of beech extracts are novel. The combined positive effect on wound-healing and antimicrobial activity has great potential for the treatment of various skin diseases, including acne in future dermal applications.

Organosolv Lignin from European Tree Bark: Influence of Bark Pretreatment.

As lignin is becoming more and more attractive to industry and the circular economy continues to grow, the utilization of a byproduct that, to date, has been underrated by the wood industry is investigated as an abundantly available source of lignin. Bark from spruce, larch and beech tress is extracted using the organosolv process with and without prior hot water extraction. The influence of the treatment on chemical properties of the lignin was determined by spectrophotometric, chromatographic, and vibrational spectroscopy. It was found that hot water extraction prior to organosolv extraction influences the chemical composition, antioxidative properties and molecular weight distribution of the obtained extracts. While hot water extracts are rich in flavonoids, organosolv fractions can contain high amounts of organic acids depending on whether they are from a hardwood or softwood source. This investigation lays the foundation for further research into the utilization of byproducts to generate high-value resources.

Production and Physical-Mechanical Characterization of Peat Moss (Sphagnum) Insulation Panels.

Peat moss (sphagnum) is a commonly used sealant, fill, and insulation material in the past. During the efforts to rewet drained moors due to ecological considerations, the technical use of peat moss (sphagnum farming) again became the focus of attention. In the framework of this investigation, insulation panels consisting of peat moss, bound with urea formaldehyde, were produced. Panels manufactured in a wet process and mats bound with textiles were also fabricated. The specimens' thermal conductivity, water vapor diffusion resistance, modulus of rupture, modulus of elasticity, internal bond, compression resistance, water absorption, and thickness swelling were measured. Physical-mechanical properties were adequate with the resin-bound panels, but not with wet process panels. Moss mats had good characteristics for cavity insulation purposes. The thermal conductivity of the moss panels and mats was found to be lowest with a density of 50 kg/m3, accounting for 0.04 W/m·K. The results show that peat moss is a promising resource for production insulation panels, because their thermal conductivity and mechanical stability are comparable to other insulation materials.

Chemical constitution of polyfurfuryl alcohol investigated by FTIR and Resonant Raman spectroscopy.

The actual chemical structure of polyfurfuryl alcohol (PFA) is still uncertain in spite of several studies on the topic, variations during the polymerization processes being one reason that must be addressed. The use of a limited set of analytical techniques is often insufficient to provide an exhaustive chemical characterization. Moreover, it is still not possible to exactly determine presence and amount of each specific functional group in the polymeric structure. We employed both Fourier Transform Infrared Spectroscopy (FTIR) and Resonant Raman spectroscopy (RR), corroborated by quantum mechanically aided analysis of the experimental spectra, to infer about the chemical structure of two samples of PFAs, synthetized in different ways and appearing macroscopically different, the first one being a liquid and viscous commercial sample, the second one being a self-prepared solid and rigid sample produced following a thermosetting procedure. The vibrational spectroscopic analysis confirms the presence of differences in their chemical structures. The viscous form of PFA is mainly composed by short polymeric chains, and is characterized by the presence of isolated furfuryl alcohol and furfural residues similar to 5-hydroxymethylfurfural; the thermosetted PFA is formed by more cross-linked structures, characterized by several ketones and alkene double bonds, as well as a significant presence of Diels-Alder structures. In summary, the present study evidences how the use of both FTIR and RR spectroscopy, the latter carried out at several laser excitation wavelengths, indicates an accurate way to spectroscopically investigate complex polymers enabling to satisfactorily infer about their peculiar chemical structure.

Changing in Larch Sapwood Extractives Due to Distinct Ionizing Radiation Sources.

Wood extractives have an influence on different material properties. This study deals with the changes in wood extractives of larch sapwood due to two different low doses of energy irradiations. Electron beam irradiation (EBI) and γ-ray irradiation treatments were done by using two industrial processes. After the different modifications the extractions were performed with an accelerated solvent extractor (ASE) using hexane and acetone/water. The qualitative and quantitative chemical differences of irradiated larch sapwood samples were analysed using gas chromatography-mass spectrometry (GC-MS) and Fourier-transform infrared spectroscopy (FT-IR) vibrational spectroscopy methods. The yields of the quantitative extractions decreased due to the two different irradiation processes. While the compounds extracted with nonpolar solvent from wood were reduced, the number of compounds with polar functionalities increased based on the oxidation process. Quantitatively, resin acids and polyphenols were highly affected when exposed to the two irradiation sources, leading to significant changes (up, down) in their relative amount. Furthermore, two new substances were found in the extracts of larch sapwood samples after EBI or γ-ray treatments. New insight into the different effects of larch sapwood and wood extractives by EBI and γ-ray was gained in this study.

Bio-Based Polymers for Engineered Green Materials.

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Synthesis and Characterization of High-Performing Sulfur-Free Tannin Foams.

Tannin foams are green lightweight materials that have attracted industrial interest for the manufacturing of sandwich panels for insulation purposes. However, the dimensions of the cells and the presence of sulfur in the formulation developed until now have discouraged their upscaling. In this work, we present the synthesis and the characterization of the more promising small cell and sulfur-free materials. It was observed that, with respect to standard ones, foams catalyzed with nitric acid present similar physical properties and more phenolic character, which favors the absorption of ionic pollutants. Conversely, the foams blown with aliphatic solvents and surfactants present smaller pores, and higher mechanical and insulating properties, without affecting the chemical properties or the heating value. The combined foam produced with nitric acid as a catalyst and petroleum ether as a blowing agent result in sulfur-free and small cell material with overall improved features. These foams have been produced at 30 × 30 × 3 cm3, with high homogeneity and, to date, they represent the most suitable formulation for industrial upscaling.

Larch Wood Residues Valorization through Extraction and Utilization of High Value-Added Products.

Many of current bio-based materials are not fully or partly used for material utilization, as the composition of their raw materials and/or possible applications are unknown. This study deals with the analysis of the wood extractives from three different tissue of larch wood: Sapwood mainly from outer part of the log, and sound knotwood as well as dead knotwood. The extractions were performed with an accelerated solvent extractor (ASE) using hexane and acetone/water. The obtained extracts were analyzed by gas chromatography coupled to mass spectrometry (GC-MS). Three various vibrational spectroscopy (FT-RAMAN, FT-IR and FT-NIR) methods reflect the information from the extracts to the chemical composition of the types of wood before the extraction processes. Multivariate data analysis of the spectra was used to obtain a better insight into possible classification methods. Taxifolin and kaempferol were found in larger amount in sound knotwood samples compared to larch wood with high percentage of sapwood and dead knotwood samples. While the extractions of dead knotwood samples yielded more larixol and resin acids than the other larch wood samples used. Based on the chemical composition, three lead compounds were defined for the classification of the different wood raw materials. The vibrational spectroscopy methods were applied to show their potential for a possible distinction of the three types of larch wood tissue. This new insight into the different larch wood extracts will help in the current efforts to use more environmentally friendly raw materials for innovative applications. The connection between the raw materials and extraction yields of the target values is important to transform the results from the laboratory to industry and consumer applications.

Understanding the Polymerization of Polyfurfuryl Alcohol: Ring Opening and Diels-Alder Reactions.

Polyfurfuryl alcohol (PFA) is one of the most intriguing polymers because, despite its easy polymerization in acid environment, its molecular structure is definitely not obvious. Many studies have been performed in recent decades, and every time, surprising aspects came out. With the present study, we aim to take advantage of all of the findings of previous investigations and exploit them for the interpretation of the completely cured PFA spectra registered with three of the most powerful techniques for the characterization of solid, insoluble polymers: Solid-State 13C-NMR, Attenuated Total Reflectance (ATR), Fourier Transform Infrared (FTIR) spectroscopy, and UV-resonant Raman spectroscopy at different excitation wavelengths, using both an UV laser source and UV synchrotron radiation. In addition, the foreseen structures were modeled and the corresponding 13C-NMR and FTIR spectra were simulated with first-principles and semi-empiric methods to evaluate their matching with experimental ones. Thanks to this multi-technique approach, based on complementary analytical tools and computational support, it was possible to conclude that, in addition to the major linear unconjugated polymerization, the PFA structure consists of Diels-Alder rearrangements occurring after the opening of some furanic units, while the terminal moieties of the chain involves γ-lactone arrangements. The occurrence of head-head methylene ether bridges and free hydroxyl groups (from unreacted furfuryl alcohol, FA, or terminal chains) could be excluded, while the conjugated systems could be considered rather limited.

REQUITE: A prospective multicentre cohort study of patients undergoing radiotherapy for breast, lung or prostate cancer.

PURPOSE: REQUITE aimed to establish a resource for multi-national validation of models and biomarkers that predict risk of late toxicity following radiotherapy. The purpose of this article is to provide summary descriptive data. METHODS: An international, prospective cohort study recruited cancer patients in 26 hospitals in eight countries between April 2014 and March 2017. Target recruitment was 5300 patients. Eligible patients had breast, prostate or lung cancer and planned potentially curable radiotherapy. Radiotherapy was prescribed according to local regimens, but centres used standardised data collection forms. Pre-treatment blood samples were collected. Patients were followed for a minimum of 12 (lung) or 24 (breast/prostate) months and summary descriptive statistics were generated. RESULTS: The study recruited 2069 breast (99% of target), 1808 prostate (86%) and 561 lung (51%) cancer patients. The centralised, accessible database includes: physician- (47,025 forms) and patient- (54,901) reported outcomes; 11,563 breast photos; 17,107 DICOMs and 12,684 DVHs. Imputed genotype data are available for 4223 patients with European ancestry (1948 breast, 1728 prostate, 547 lung). Radiation-induced lymphocyte apoptosis (RILA) assay data are available for 1319 patients. DNA (n = 4409) and PAXgene tubes (n = 3039) are stored in the centralised biobank. Example prevalences of 2-year (1-year for lung) grade ≥2 CTCAE toxicities are 13% atrophy (breast), 3% rectal bleeding (prostate) and 27% dyspnoea (lung). CONCLUSION: The comprehensive centralised database and linked biobank is a valuable resource for the radiotherapy community for validating predictive models and biomarkers. PATIENT SUMMARY: Up to half of cancer patients undergo radiation therapy and irradiation of surrounding healthy tissue is unavoidable. Damage to healthy tissue can affect short- and long-term quality-of-life. Not all patients are equally sensitive to radiation "damage" but it is not possible at the moment to identify those who are. REQUITE was established with the aim of trying to understand more about how we could predict radiation sensitivity. The purpose of this paper is to provide an overview and summary of the data and material available. In the REQUITE study 4400 breast, prostate and lung cancer patients filled out questionnaires and donated blood. A large amount of data was collected in the same way. With all these data and samples a database and biobank were created that showed it is possible to collect this kind of information in a standardised way across countries. In the future, our database and linked biobank will be a resource for research and validation of clinical predictors and models of radiation sensitivity. REQUITE will also enable a better understanding of how many people suffer with radiotherapy toxicity.

Pollutant Absorption as a Possible End-Of-Life Solution for Polyphenolic Polymers.

Tannin- and lignin-furanic foams are natural porous materials that have attracted high interest in the scientific and industrial communities for their high thermal and fire-resistant properties. However, no interesting solutions have been proposed for the management of their end-life as yet. In this study, the phenolic-furanic powders derived from the foams were analyzed for their capacity to remove different pollutants like neutral, cationic, and anionic organic molecules from wastewater. It was observed that the macromolecules produced from initially bigger fractions were more suitable to remove methylene blue and sodium dodecyl sulfate (SDS) while contained absorptions were observed for riboflavin. Acidified tannin powders were also prepared to understand the role of the flavonoid in the absorption mechanism. The latter showed outstanding absorption capacity against all of the tested pollutants, highlighting the key-role of the flavonoid fraction and suggesting the limited contribution of the furanic part. All adsorbents were investigated through FT-IR and solid state 13C-NMR. Finally, the powders were successfully regenerated by simple ethanol washing, showing almost complete absorption recovery.

Modifications of the CZTSe/Mo back-contact interface by plasma treatments.

Molybdenum (Mo) is the most commonly used back-contact material for copper zinc tin selenide (CZTSe)-based thin-film solar cells. For most fabrication methods, an interfacial molybdenum diselenide (MoSe2) layer with an uncontrolled thickness is formed, ranging from a few tens of nm up to ≈1 µm. In order to improve the control of the back-contact interface in CZTSe solar cells, the formation of a MoSe2 layer with a homogeneous and defined thickness is necessary. In this study, we use plasma treatments on the as-grown Mo surface prior to the CZTSe absorber formation, which consists of the deposition of stacked metallic layers and the annealing in selenium (Se) atmosphere. The plasma treatments include the application of a pure argon (Ar) plasma and a mixed argon-nitrogen (Ar-N2) plasma. We observe a clear impact of the Ar plasma treatment on the MoSe2 thickness and interfacial morphology. With the Ar-N2 plasma treatment, a nitrided Mo surface can be obtained. Furthermore, we combine the Ar plasma treatment with the application of titanium nitride (TiN) as back-contact barrier and discuss the obtained results in terms of MoSe2 formation and solar cell performance, thus showing possible directions of back-contact engineering for CZTSe solar cells.

XRCC1 Polymorphism Associated With Late Toxicity After Radiation Therapy in Breast Cancer Patients.

PURPOSE: To identify single-nucleotide polymorphisms (SNPs) in oxidative stress-related genes associated with risk of late toxicities in breast cancer patients receiving radiation therapy. METHODS AND MATERIALS: Using a 2-stage design, 305 SNPs in 59 candidate genes were investigated in the discovery phase in 753 breast cancer patients from 2 prospective cohorts from Germany. The 10 most promising SNPs in 4 genes were evaluated in the replication phase in up to 1883 breast cancer patients from 6 cohorts identified through the Radiogenomics Consortium. Outcomes of interest were late skin toxicity and fibrosis of the breast, as well as an overall toxicity score (Standardized Total Average Toxicity). Multivariable logistic and linear regression models were used to assess associations between SNPs and late toxicity. A meta-analysis approach was used to summarize evidence. RESULTS: The association of a genetic variant in the base excision repair gene XRCC1, rs2682585, with normal tissue late radiation toxicity was replicated in all tested studies. In the combined analysis of discovery and replication cohorts, carrying the rare allele was associated with a significantly lower risk of skin toxicities (multivariate odds ratio 0.77, 95% confidence interval 0.61-0.96, P=.02) and a decrease in Standardized Total Average Toxicity scores (-0.08, 95% confidence interval -0.15 to -0.02, P=.016). CONCLUSIONS: Using a stage design with replication, we identified a variant allele in the base excision repair gene XRCC1 that could be used in combination with additional variants for developing a test to predict late toxicities after radiation therapy in breast cancer patients.

Univariate and multivariate analysis of tannin-impregnated wood species using vibrational spectroscopy.

Vibrational spectroscopy is one of the most powerful tools in polymer science. Three main techniques--Fourier transform infrared spectroscopy (FT-IR), FT-Raman spectroscopy, and FT near-infrared (NIR) spectroscopy--can also be applied to wood science. Here, these three techniques were used to investigate the chemical modification occurring in wood after impregnation with tannin-hexamine preservatives. These spectroscopic techniques have the capacity to detect the externally added tannin. FT-IR has very strong sensitivity to the aromatic peak at around 1610 cm(-1) in the tannin-treated samples, whereas FT-Raman reflects the peak at around 1600 cm(-1) for the externally added tannin. This high efficacy in distinguishing chemical features was demonstrated in univariate analysis and confirmed via cluster analysis. Conversely, the results of the NIR measurements show noticeable sensitivity for small differences. For this technique, multivariate analysis is required and with this chemometric tool, it is also possible to predict the concentration of tannin on the surface.

Reactions of carbon monoxide with free palladium oxide clusters: strongly size dependent competition between adsorption and combustion.

The gas phase reactions of carbon monoxide with small mass-selected clusters of palladium, Pd(x)(+) (x = 2-7), and their oxides, Pd(x)O(+) (x = 2-7) and Pd(x)O(2)(+) (x = 4-6), have been investigated in a radio frequency ion trap operated under multi-collision conditions. The bare palladium clusters were found to readily adsorb CO yielding a highly size dependent product pattern. Most interestingly, the reactions of the pre-oxidized palladium clusters with CO lead to very similar product distributions of Pd(x)(CO)(z)(+) complexes as in the case of the corresponding pure Pd(x)(+) clusters. Consequently, it has been concluded that the investigated palladium oxide clusters efficiently oxidize CO under formation of the bare clusters, which further adsorb CO molecules yielding the previously observed Pd(x)(CO)(z)(+) product complex distributions. This CO combustion reaction has been observed even at temperatures as low as 100 K. However, for Pd(2)O(+), Pd(6)O(+), Pd(6)O(2)(+), and Pd(7)O(+) a competing reaction channel yielding palladium oxide carbonyls Pd(x)O(CO)(z)(+) could be detected. The latter adsorption reaction may even hamper the CO combustion under certain reaction conditions and indicates enhanced activation barriers involved in the CO oxidation and/or the CO(2) elimination process on these clusters.

Reirradiation for recurrent neck metastases of head-and-neck tumors using CT-guided interstitial 192Ir HDR brachytherapy.

PURPOSE: To report the therapeutic results obtained with CT-guided interstitial high-dose-rate brachytherapy (HDR-BRT) as exclusive treatment for recurrent neck metastases of head-and-neck tumors. PATIENTS AND METHODS: Between 1995 and 1999, 49 patients with prior radiation therapy (RT) with or without surgery for primary head-and-neck tumors were treated for recurrent neck metastases located within previously irradiated volumes. All patients had fixed lymphadenopathy with a mean tumor volume of 96 cm(3) (range, 15-452 cm(3)). There were 38 males and eleven females with a mean age of 60 years (range, 28-79 years). All patients had previously received RT as primary or adjuvant treatment with a mean dose of 54 Gy (range, 45-80 Gy). 36 patients (73%) underwent surgery, and 26 (53%) received adjuvant or palliative chemotherapy. The accelerated hyperfractionated interstitial HDR-BRT (2 x 3.0 Gy/day) delivered 30 Gy in 37/49 (75%) and 36 Gy in 12/49 implants (25%). RESULTS: At a minimum 6-week follow-up, the response rate was 83% (41/49) with complete remission in 20% (10/49) and partial remission in 63% (31/49) of the implanted tumor sites. 8/49 patients (17%) did not respond to the treatment. After 19 months of median follow-up, the local control rate was 69% and a total of 15/49 patients (30%) experienced local disease progression. Of these, nine (18%) had locoregional progression and six (12%) progression within the treated volume. The median post-BRT survival was 14 months. The overall survival rate was 52% at 1 year, 31% at 2 years, and 6% at 3 years. CONCLUSION: In patients with recurrent cervical lymphadenopathy of head-and-neck tumors, exclusive interstitial HDR-BRT can provide palliation and tumor control.

Usefulness of tumor volumetry as a prognostic factor of survival in head and neck cancer.

BACKGROUND: The TNM classification system of tumor stage does not always reflect the actual tumor mass present at diagnosis. This study aimed at evaluating the prognostic value of volumetric data regarding survival in head and neck cancer patients being treated with either cisplatin or carboplatin administered concomitantly with radiotherapy. PATIENTS AND METHODS: We retrospectively analyzed 107 patients suffering from squamous cell carcinoma of the head and neck in a Greek-German cooperative study (see Table 1). All patients were treated by radiotherapy and concomitant chemotherapy. 65 patients received chemotherapy with carboplatin and 42 with cisplatin. More than 6,200 CT scans were analyzed by digitalization of contours which subsequently led to the computation of the tumor volume (primary and macroscopic lymph node metastases). RESULTS: Median follow-up was 43 months and median survival 30 months. Median initial tumor volume was 32.5 ml (range 2.1-220.1 ml) in the carboplatin and 44.4 ml (range 3.2-202.5 ml) in the cisplatin group (see Figure 1). After treatment, tumor volumes did not differ significantly (median of 3.1 ml [range 0.0-167.1 ml] and 3.5 ml [range 0.0-166.0 ml], respectively). 41 patients (63.1%) died in the carboplatin group and 22 patients (52.4%) in the cisplatin group (see Figure 2). Pretherapeutic tumor volume was prognostic with respect to survival while TNM classification and age were not. Pretherapeutic tumor volume was negatively and percent decrease in tumor volume positively associated with survival (see Tables 2 and 3). CONCLUSION: Knowledge of the initial tumor volume adds valuable information in terms of prognosis. Initial tumor volume should be included in all future clinical trials regarding head and neck cancer patients.