Design of Cell-Adhesive Shellac Derivatives and Endowment of Photoswitchable Cell-Adhesion Properties.

The emergence of new biodegradable cell-adhesion materials is an attractive topic in biomaterial chemistry, particularly for the development of cell incubation scaffolds and drug encapsulation materials used in in situ regenerative therapy. Shellac is a natural resin with unique film-forming properties and high miscibility with various chemicals, in addition to being biodegradable and nontoxic to biological systems. However, since native shellac does not adhere to mammalian cells, there have been no reports of using shellac to develop cell-adhesive biomaterials. In this study, we report on the development of cell-adhesive shellac derivatives through slight chemical modification. Shellac is a mixture of oligoesters that consists of hydroxyl fatty acids and resin acids, and therefore, all oligomers have one carboxylic acid group at the terminal. We discovered that a simple modification of hydrophobic chemical groups, particularly those containing aromatic groups in the ester form, could dramatically improve cell-adhesion properties for mammalian cells. Furthermore, by using photocleavable esters containing aromatic groups, we successfully endowed photoswitchable properties in cell adhesion. Given that shellac is a low-cost, biodegradable, and nontoxic natural resin, the modified shellacs have the potential to become new and attractive biomaterials applicable to in situ regenerative therapy.

Guayule (Parthenium argentatum A. Gray), a Renewable Resource for Natural Polyisoprene and Resin: Composition, Processes and Applications.

Natural rubber is an essential material, especially for plane and truck tyres but also for medical gloves. Asia ranks first in the production of natural rubber, of which the Hevea tree is currently the sole source. However, it is anticipated that this source alone will not be able to fulfill the growing demand. Guayule, a shrub native to northern Mexico and southern United States, may also contribute. This plant not only contains polyisoprene, but also resin, a mixture of lipids and terpenoids. This review summarizes various aspects of this plant, from the usage history, botanical description, geographical distribution and cultivation practices, down to polyisoprene and resin biosynthesis including their distribution within the plant and molecular composition. Finally, the main processes yielding dry rubber or latex are depicted, as well as the properties of the various extracts along with economic considerations. The aim is to provide a wide picture of current knowledge available about this promising crop, a good feedstock candidate for a multiple-product biorefinery.

Gambogic acid: A shining natural compound to nanomedicine for cancer therapeutics.

The United States Food and Drug Administration has permitted number of therapeutic agents for cancer treatment. Most of them are expensive and have some degree of systemic toxicity which makes overbearing in clinical settings. Although advanced research continuously applied in cancer therapeutics, but drug resistance, metastasis, and recurrence remain unanswerable. These accounts to an urgent clinical need to discover natural compounds with precisely safe and highly efficient for the cancer prevention and cancer therapy. Gambogic acid (GA) is the principle bioactive and caged xanthone component, a brownish gamboge resin secreted from the of Garcinia hanburyi tree. This molecule showed a spectrum of biological and clinical benefits against various cancers. In this review, we document distinct biological characteristics of GA as a novel anti-cancer agent. This review also delineates specific molecular mechanism(s) of GA that are involved in anti-cancer, anti-metastasis, anti-angiogenesis, and chemo-/radiation sensitizer activities. Furthermore, recent evidence, development, and implementation of various nanoformulations of gambogic acid (nanomedicine) have been described.

Increasing potency and price of cannabis in Europe, 2006-16.

AIMS: To quantify changes in (i) potency (concentration of Δ9 -tetrahydrocannabinol; %THC), (ii) price (euros/g of cannabis) and (iii) value (mg THC/euro) of cannabis resin and herbal cannabis in Europe. DESIGN: Repeated cross-sectional study. SETTING AND PARTICIPANTS: Data collected from 28 European Union (EU) member states, Norway and Turkey by the European Monitoring Centre for Drugs and Drug Addiction. MEASUREMENTS: Outcome variables were potency, price and value for cannabis resin and herbal cannabis in Europe, 2006-16. Inflation was estimated using the Harmonised Indices of Consumer Prices. Mixed-effects linear regression models were used to estimate linear and quadratic time trends, with a random intercept and slope fitted to account for variation across countries. FINDINGS: Resin potency increased from a mean [95% confidence interval (CI)] of 8.14% THC (6.89, 9.49) in 2006 to 17.22 (15.23, 19.25) in 2016. Resin price increased from 8.21 euros/g (7.54, 8.97) to 12.27 (10.62, 14.16). Resin increased in value, from 11.00 mg THC per euro (8.60, 13.62) to 16.39 (13.68, 19.05). Quadratic time trends for resin potency and value indicated minimal change from 2006 to 2011, followed by marked increases from 2011 to 2016. Herbal cannabis potency increased from 5.00% THC (3.91, 6.23) to 10.22 (9.01, 11.47). Herbal price increased from 7.36 euros/g (6.22, 8.53) to 12.22 (10.59, 14.03). The value of herbal cannabis did not change from 12.65 mg of THC per euro (10.18, 15.34) to 12.72 (10.73, 14.73). All price trends persisted after adjusting for inflation. CONCLUSIONS: European cannabis resin and herbal cannabis increased in potency and price from 2006 to 2016. Cannabis resin (but not herbal cannabis) increased in the quantity of Δ9 -tetrahydrocannabinol per euro spent. Marked increases in resin potency and value from 2011 to 2016 are consistent with the emergence of new resin production techniques in European and neighbouring drug markets.

Ecological conditions alter cooperative behaviour and its costs in a chemically defended sawfly.

The evolution of cooperation and social behaviour is often studied in isolation from the ecology of organisms. Yet, the selective environment under which individuals evolve is much more complex in nature, consisting of ecological and abiotic interactions in addition to social ones. Here, we measured the life-history costs of cooperative chemical defence in a gregarious social herbivore, Diprion pini pine sawfly larvae, and how these costs vary under different ecological conditions. We ran a rearing experiment where we manipulated diet (resin content) and attack intensity by repeatedly harassing larvae to produce a chemical defence. We show that forcing individuals to allocate more to cooperative defence (high attack intensity) incurred a clear cost by decreasing individual survival and potency of chemical defence. Cooperative behaviour and the magnitude of its costs were further shaped by host plant quality. The number of individuals participating in group defence, immune responses and female growth decreased on a high resin diet under high attack intensity. We also found some benefits of cheating: non-defending males had higher growth rates across treatments. Taken together, these results suggest that ecological interactions can shape the adaptive value of cooperative behaviour and maintain variation in the frequency of cooperation and cheating.

TLC Fingerprinting and Pattern Recognition Methods in the Assessment of Authenticity of Poplar-Type Propolis.

Propolis is a "natural" remedy with prominent biological activity, which is used as dietary supplement. In the absence of clinical studies that would substantiate these claims, information on the biological activity of propolis is valuable. This study comprises chromatographic, image processing and chemometric approach for phenolic profiling of Serbian, Croatian and Slovenian propolis test solutions. Modern thin-layer chromatography equipment in combination with software for image processing was applied for fingerprinting and data acquisition, whereas the principal component analysis was used as pattern recognition method. Characterization of phenolic profile was performed along with the determination of the botanical and geographical origin of propolis. High-performance thin-layer chromatograms reveal that Central and Southeastern European propolis samples are rich in flavonoids. In addition, phenolic compounds proved to be suitable markers for the determination of European propolis authenticity.

Antimicrobial Assessment of Resins from Calophyllum Antillanum and Calophyllum Inophyllum.

The Calophyllum genus is well-known for its antimicrobial and cytotoxic activities, and therefore, we analyzed these biological activities for resins of Calophyllum antillanum and Calophyllum inophyllum growing in Cuba. C. antillanum resins showed a potent activity against Plasmodium falciparum (IC50 = 0.3 ± 0.1 µg/mL), while its cytotoxicity against MRC-5 cells was much lower (IC50 = 21.6 ± 1.1 µg/mL). In contrary, the resin of C. inophyllum showed an unspecific activity. The presence of apetalic acid, isoapetalic acid, calolongic acid, pinetoric acid I, pinetoric acid II, isocalolongic acid, pinetoric acid III, and isopinetoric acid III in C. antillanum resins was also confirmed. These results demonstrated for the first time the potential activity of C. antillanum resins against P. falciparum.

Bioconversion of lignocellulosic residues by Agrocybe cylindracea and Pleurotus ostreatus mushroom fungi--assessment of their effect on the final product and spent substrate properties.

Nine agro-industrial and forestry by-products were subjected to solid-state fermentation by Agrocybe cylindracea and Pleurotus ostreatus, and the process and end-products were comparatively evaluated. Grape marc waste plus cotton gin trash was the best performing medium for both fungi, while substrate composition had a marked effect on most cultivation parameters. Biological efficiency was positively correlated with nitrogen, lignin and ash, and negatively with hemicelluloses and carbohydrate content of substrates. Spent substrates demonstrated high reductions in hemicelluloses and cellulose in contrast to lignin; fibre fractions were correlated with nitrogen, fat and ash content of initial materials, while residual mycelial biomass was affected by mushroom productivity. Mushroom proximate analysis revealed significant variations of constituents depending on the substrate. Crude protein and fat were correlated with substrates nitrogen for both species. Alternative cultivation substrates of high potential are proposed, while spent material could be exploited as animal feed due to its upgraded properties.

Assessment of ferula Gummosa gum as a binding agent in tablet formulations.

Ferula gummosa Boiss. (Apiaceae) is one of the natural plants of Iran. The whole plant, but especially the root, contains the gum resin "galbanum". A study of the comparative effects of galbanum gum and two standard binding agents--polyvinylpyrolidone and acacia--on characteristics of acetaminophen and calcium carbonate compacts was made. The Ferula gummosa gum was extracted and its swelling index was determined. Acetaminophen and calcium carbonate granules were prepared using the wet granulation method and were evaluated for their micromeritics and flow properties, while the compacts were evaluated for mechanical properties using the hardness, tensile strength and friability. The drug release from acetaminophen compacts were assessed using dissolution studies. The dry powder of Ferula gummosa gum resin (galbanum) yielded 14% w/w of gum using distilled water as extraction solvent. The swelling index indicates that galbanum gum swelled to about 190% of initial volume in distilled water. Thus galbanum gum has the ability to hydrate and swells in cold water. The bulk and tapped densities and the interspace porosity (void porosity) percent of the granules prepared with different binders showed significant difference. The hardness and tensile strength of acetaminophen and calcium carbonate compacts containing various binders was of the rank order PVP > acacia > galbanum gum (p < 0.05) and the friability percent was of the reverse order (p < 0.05). The ranking for the dissolution rate of tablets containing the different binders was PVP> galbanum gum > acacia. The results of mechanical properties of acetaminophen and calcium carbonate compacts indicate that galbanum gum could be useful to produce tablets with desired mechanical characteristics for specific purposes, and could be used as an alternative substitute binder in pharmaceutical industries.

Chemical composition of South American Burseraceae non-volatile oleoresins and preliminary solubility assessment of their commercial blend.

INTRODUCTION: Non-volatile oleoresins from neotropical Burseraceae are traditionally used for craft, technological and medicinal purposes. The crude resin is usually sold in popular markets of the forest communities. Adding value to this rainforest raw material requires establishing its composition. OBJECTIVE: To analyse the resin composition from different Burseraceae species and establish a minimally reproducible profile by gas chromatography, in order to parameterise its quality control. METHODOLOGY: Crude oleoresin samples of 10 Protium and Trattinnickia species and a commercial blend were subjected to hydrodistillation to remove volatile compounds. The chloroform-soluble residues were methylated, analysed by GC-FID (flame ionisation detection), and individual components were identified by analysing their mass fragmentation pattern in GC-MS and comparison with data from the literature. The blend solubility was assayed in 30 non-chlorinated solvents at three different proportions. RESULTS: The resins consisted exclusively of triterpenes, showing a common predominance of four major compounds in all the samples, corresponding to α-amyrin, ß-amyrin, α-amyrenone and ß-amyrenone. This profile was complemented with minor amounts of the tetracyclic ß-elemolic and α-elemolic acids, maniladiol, brein and other oxidised trace compounds. The better solvents for the resin were those chemically bearing more than four carbon atoms, as n-butyl acetate, 2-ethoxyethanol and isopropanol. The crude resin blend sold contained around 10% of insoluble material that was constituted by up to 70% inorganic residues mixed with humic acid derivatives, as attested by ash analysis and IR spectroscopy, respectively. CONCLUSION: The experimental results, complemented by a general inspection of the literature, demonstrated a systematically reproducible triterpene profile in Protium and Trattinnickia species.

Application of plant-based antimicrobials for the growth inhibition of clostridia in pressed beet pulp silage.

BACKGROUND: In this study the inhibition of hop beta acids on the growth of clostridia in soil-contaminated pressed sugar beet pulp silages was investigated. Hop beta acids are natural substances which display their effect at low concentrations. Fresh pressed beet pulp material was mixed with soil to artificially contaminate it with clostridia. Laboratory silos were filled with the substrate, stored at 25 °C and opened for sampling at 0, 2, 8, 15, 30, 60, and 90 days. The impact on clostridial growth during silage fermentation was monitored by determination of the pH value and dry matter content, as well as chemical analysis of the fermentation products. Throughout the experiments, the effect of a commercial silage inoculant based on lactic acid bacteria (LAB) and hop-resistant LAB were examined with and without the combination of plant-based antimicrobials. RESULTS: Results indicate that in contaminated silage samples without any additives high butyric acid contents occurred due to clostridial growth. This spoilage could not be suppressed by the application of LAB, whereas the combined application of LAB and hop beta acids significantly improved silage quality, which was reflected by favourable organic acid composition (P < 0.05). CONCLUSION: The experimental data indicate that the application of hop beta acids improves the preservation effect of LAB in suppressing clostridial growth in silages and thus demonstrates some potential for the combined use of plant-based antimicrobials and LAB.

Assessment of the ageing of triterpenoid paint varnishes using fluorescence, Raman and FTIR spectroscopy.

The assessment of the influence of natural and artificial ageing on the spectrofluorescence of triterpenoid varnishes dammar and mastic is the focus of this work. Both Fourier transform infrared (FTIR) microscopy using attenuated total reflectance and Raman spectroscopy have been employed for complementary molecular analysis of samples. Synchronous fluorescence spectroscopy, excitation emission spectroscopy, and statistical analysis of data have been used to monitor changes in the optical properties of varnish samples. Assessment of naturally and artificially aged samples using excitation emission spectroscopy suggests that extensive exposure to visible light does not lead to easily appreciable differences in the fluorescence of mastic and dammar; cluster analysis has been used to assess changes, which occur with artificial ageing under visible light, indicating that differences in the fluorescence spectra of aged triterpenoids may be insufficient for their discrimination. The results highlight significant differences between the initial fluorescence of films of dammar and mastic and the fluorescence, which develops with ageing and oxidation, and specific markers, which change with ageing in FTIR and Raman spectra, have been identified.

Evaluation of resin and fatty acid concentration levels by online sample enrichment followed by atmospheric pressure chemical ionization-mass spectrometry (APCI-MS).

BACKGROUND, AIM, AND SCOPE: In papermaking, there is a continuous interest both to minimize fresh water consumption and to reduce discharges into the environment. These general trends mean an increase in the amounts of detrimental substances, such as resin and fatty acids, in papermaking process waters. Resin acids, in particular, are responsible for much of the toxicity typically present in paper mill effluents and, for this reason, the routine and rapid monitoring of these compounds in various process streams is necessary. This also means that there is a continuous need to develop straightforward offline and online techniques to clarify problems occurring, for example, as a result of the introduction of more intensively closed systems of water circulation. In the present study, we describe the use of a novel, online, sample enrichment technique followed by atmospheric pressure chemical ionization-mass spectrometry (APCI-MS) suitable for monitoring the concentration levels of common resin and fatty acids in papermaking process waters. MATERIALS AND METHODS: The representative process water samples were taken from the grinding zone of a thermomechanical pulping mill. The samples were first preconcentrated in a precolumn C18, and the analytes were transferred online to MS. The high intensive [M-H](-) ion was used for the identification of each analyte since, according to the present ionization method, no other fragmentation was observed. Laboratory-scale, online measurements with an online sample feed were carried out by connecting a centrifugal pump and a ceramic filter to the APCI-MS. RESULTS: Quality parameters, such as repeatability, linearity, and limit of detection (LOD), were determined by using dehydroabietic acid (DHAA) in order to evaluate the suitability of the method for the rapid screening of concentration levels. This method provided satisfactory linearity and a good correlation between analyte concentration and peak area. The suitability of the system for the continuous analysis of the same acids was evaluated in laboratory-scale, online experiments. In all cases, the response to changes in the analyte concentration was linear, and the repeatability of the system was also satisfactory. DISCUSSION: Only a few studies have been published on the analysis of resin and fatty acids with MS techniques. The present method was applied to the monitoring of dehydroabietic, oleic, and stearic acids. The quality parameters were highly comparable with those reported earlier, and the LOD values of the DHAA were below the levels usually encountered in process waters. The quality parameters were only slightly higher than those obtained by the traditional methods of analysis, probably due to the absence of an effective sample clean-up before analysis. CONCLUSIONS: The results of the laboratory-scale, online experiments indicated that the online enrichment APCI-MS system is a suitable alternative for monitoring the concentration levels of selected resin and fatty acids in papermaking process waters. The method can be used, for example, to provide useful information about the concentration levels of these acids in different stages of the process, thus signaling possibly impending problems. In general, faster and simpler measurements are needed to meet the requirements for a reduction in fresh water usage in papermaking. RECOMMENDATIONS AND PERSPECTIVES: Compared to the conventional methods used for this purpose, the main benefits of the method are rapidity of measurement, simplicity of use, and absence of the need for multistage sample treatments (short analysis time). For this reason, this online method is more suitable for the control of papermaking by analyzing the concentration levels of interfering substances (i.e., selected resin and fatty acids) than an offline analysis detailing all the individual extractives-based compounds in process streams. It is also obvious that the technique can easily be modified for other environmental pollutants as well.

Myrrh: medical marvel or myth of the Magi?

Since antiquity, the genus Commiphora is composed of more than 200 species, and has been exploited as a natural drug to treat pain, skin infections, inflammatory conditions, diarrhea, and periodontal diseases. In more recent history, products derived from Commiphora myrrha and various other species of Commiphora are becoming recognized to possess significant antiseptic, anesthetic, and antitumor properties. Traditional practice and evidence-based research have supported that these properties are directly attributable to terpenoids (especially furanosesquiterpenes), the active compounds present in myrrh essential oil. More recently, current studies have focused on applying clinical trial methodologies to validate its use as an antineoplastic, an antiparasitic agent, and as an adjunct in healing wounds.

Exudate gums: occurrence, production, and applications.

This paper presents a review of the industrially most relevant exudate gums: gum arabic, gum karya, and gum tragacanth. Exudate gums are obtained as the natural exudates of different tree species and exhibit unique properties in a wide variety of applications. This review covers the chemical structure, occurrence and production of the different gums. It also deals with the size and relative importance of the various players on the world market. Furthermore, it gives an overview of the main application fields of the different gums, both food and non-food.

Peptomers: a versatile approach for the preparation of diverse combinatorial peptidomimetic bead libraries.

This report describes a versatile approach in the generation of peptidomimetic bead libraries. The method is based on the preparation of peptide-peptoid hybrids using the portioning-mixing procedure, which gives diverse peptidomimetic bead libraries composed of peptides, peptoids and peptide-peptoid hybrids. We term these peptomers, from peptide-peptoid hybrid polymers. The synthesis of the peptomers is easily accomplished by adapting the peptoid synthesis strategy, in which a primary amine reacts with bromoacetic acid, and we combine this methodology with conventional peptide synthesis. The sequence of the active compound is deduced by conventional microsequencing using Edman degradation chemistry, thus avoiding the synthesis of a coding structure or the addition of molecular tags. We demonstrate the utility of the peptomer approach by the synthesis of a bead library together with the identification of novel peptidomimetic ligands binding to the macromolecular targets streptavidin and the insulin receptor.