Differences among Epilobium and Hypericum species revealed by four IR spectroscopy modes: transmission, KBr tablet, diffuse reflectance and ATR.

INTRODUCTION: Quality control of dried plant material in assessments of suitability of herbal medicinal products is of extreme importance. Commonly used procedures for identification of species are time consuming and expensive. The development of multivariate statistical methods has enabled application of vibrational spectroscopy for establishing plant species membership. OBJECTIVE: To determine which infrared spectroscopy mode gives most informative spectra for plant species identification. METHODOLOGY: Different modes of infrared spectroscopy were applied for investigation of differences among Epilobium and Hypericum species: diffuse reflectance (DR), attenuated total reflectance (ATR), direct transmission of whole leaves and KBr tablet transmission with comminuted leaves. The same chemometrical methods were applied to all spectra. The informative wave numbers were chosen by one-way analysis of variance. Afterwards the colinearity was reduced with principal component analysis. In the final step the species identification was determined with discriminant analysis. RESULTS: Transmission and diffuse reflectance mode did not give satisfactory results. Best results for discrimination among Epilobium species were obtained with ATR mode (98%), while best results for Hypericum species were obtained with KBr transmission mode (97%). This might be explained by the morphological properties of the two genera. Epilobium species differ in distribution and morphology of trichomes on the surface of the leaves. Hypericum species differ in structures and secondary metabolites in the interior of the leaves. CONCLUSION: For best results in using infrared spectroscopy for plant species identification in quality control, the morphological properties of plant material should be taken into consideration.

Potentiometric and ³¹P NMR studies on inositol phosphates and their interaction with iron(III) ions.

Potentiometric, conductometric and ³¹P NMR titrations have been applied to study interactions between myo-inositol hexakisphosphate (phytic acid), (±)-myo-inositol 1,2,3,5-tetrakisphosphate and (±)-myo-inositol 1,2,3-trisphosphate with iron(III) ions. Potentiometric and conductometric titrations of myo-inositol phosphates show that addition of iron increases acidity and consumption of hydroxide titrant. By increasing the Fe(III)/InsP(6) ratio (from 0.5 to 4) 3 mol of protons are released per 2 mol of iron(III). At first, phytates coordinate iron octahedrally between P2 and P1,3. The second coordination site represents P5 and neighbouring P4,6 phosphate groups. Complexation is accompanied with the deprotonation of P1,3 and P4,6 phosphate oxygens. At higher concentration of iron(III) intermolecular P-O-Fe-O-P bonds trigger formation of a polymeric network and precipitation of the amorphous Fe(III)-InsP(6) aggregates. (31)P NMR titration data complement the above results and display the largest chemical shift changes at pD values between 5 and 10 in agreement with strong interactions between iron and myo-inositol phosphates. The differences in T(1) relaxation times of phosphorous atoms have shown that phosphate groups at positions 1, 2 and 3 are complexated with iron(III). The interactions between iron(III) ions and inositol phosphates depend significantly on the metal to ligand ratio and an attempt to coordinate more than two irons per InsP(6) molecule results in an unstable heterogeneous system.

Non-destructive characterisation of iron gall ink drawings: not such a galling problem.

Iron gall inks are of extraordinary historical significance considering their widespread use for over a millennium. Due to their corrosiveness, which is a consequence of their acidity and content of transition metals, iron gall inks accelerate the degradation of the writing or drawing support, which in this study is rag paper. Characterisation of acidity (pH) and degree of polymerisation (DP) of cellulose in paper is thus of high interest as it enables the estimation of material stability and assessment of risks associated with its handling. Based on a well-characterised set of samples with iron gall ink from the 18th and 19th centuries, we developed a near infrared spectroscopic method with partial least squares calibration for non-destructive determination of pH and DP of both inked areas and paper. Using this method, 27 18th and 19th century iron gall ink drawings from the British Museum collection were analysed and in all cases, inked areas turned out to be more acidic and degraded than the surrounding paper. Based on the obtained DP data, we were able to estimate the time needed for the inked areas to degrade to the point when they become at risk of damage due to handling. Using the average uncertainty of the calculated lifetime, we propose a quantitative stability classification method which could contribute to the curatorial and conservation decision-making process.

Material degradomics: on the smell of old books.

We successfully transferred and applied -omics concepts to the study of material degradation, in particular historic paper. The main volatile degradation products of paper, constituting the particular "smell of old books", were determined using headspace analysis after a 24 h predegradation procedure. Using supervised and unsupervised methods of multivariate data analysis, we were able to quantitatively correlate volatile degradation products with properties important for the preservation of historic paper: rosin, lignin and carbonyl group content, degree of polymerization of cellulose, and paper acidity. On the basis of volatile degradic footprinting, we identified degradation markers for rosin and lignin in paper and investigated their effect on degradation. Apart from the known volatile paper degradation products acetic acid and furfural, we also put forward a number of other compounds of potential interest, most notably lipid peroxidation products. The nondestructive approach can be used for rapid identification of degraded historic objects on the basis of the volatile degradation products emitted by degrading paper.

Imidazolium-based ionic liquids for the efficient treatment of iron gall inked papers.

Iron gall inks have been known since Roman times, were widely used in the Medieval Age, and became the most used ink in the Renaissance period. They were still officially used by the German Government as recently as 1973. The two main constituents of the ink are tannic acid and ferrous sulfate (vitriol). The vitriol normally used was not very pure and likely contained a mixture of iron sulfate with traces of other metals, in particular, copper. Certain transition-metal ions contained in iron gall inks and their acidity are known to deteriorate paper. Therefore, stabilization treatments consist of deacidification and the addition of antioxidants. To this end, the use of tetraalkylammonium bromides was recently proposed. Here, it is shown that 1-butyl-2,3-dimethylimidazolium bromide both in aqueous and in alcoholic solution can prevent the oxidative deterioration of cellulose. Furthermore, it does not lead to the yellowing of paper nor does it significantly affect the colour of the ink.

Nondestructive analysis and dating of historical paper based on IR spectroscopy and chemometric data evaluation.

Sampling restrictions in analysis of cultural heritage materials narrow the choice of appropriate analytical methods considerably. In this work, near- and mid-FT-IR reflectance data were related to paper properties determined with classical analytical methods using partial least-squares. Nondestructive determination of properties, which are of importance for evaluation of the long-term stability of historical paper, i.e., ash content, lignin content, degree of polymerization of cellulose, pH, and aluminum content, is possible. With the use of a considerable sample set, satisfactory reliability was achieved for all properties but aluminum content. Considering that with age, chemical properties of paper change, dating of historical documents was attempted for the first time, also with success.

Non-Destructive Evaluation of Historical Paper Based on pH Estimation from VOC Emissions.

Volatile organic compounds (VOCs) emitted from materials during degradationcan be a valuable source of information. In this work, the emissions of furfural and aceticacid from cellulose were studied using solid-phase micro-extraction (SPME) incombination with gas chromatography-mass spectrometry. Two sampling techniques wereemployed: static headspace sampling using SPME for 1 h at 40 oC after 18-h samplepreparation at 80 oC in a closed glass vial, and contact SPME in a stack of paper (or abook). While a number of VOCs are emitted from paper under conditions of natural oraccelerated degradation, two compounds were confirmed to be of particular diagnosticvalue: acetic acid and furfural. The emissions of furfural are shown to correlate with pH ofthe cellulosic environment. Since pH is one of the most important parameters regardingdurability of this material, the developed method could be used for non-destructiveevaluation of historical paper.

Insight into the short-range structure of amorphous iron inositol hexaphosphate as provided by (31)P NMR and Fe X-ray absorption spectroscopy.

Short-range structure and formation of amorphous aggregates of iron inositol hexaphosphate (iron phytate) were studied by broadline solid-state 31P NMR and Fe X-ray absorption spectroscopy. It was shown that bonds P-O-Fe with strong covalent character exist in solid substances. Iron in these substances is octahedrally coordinated by six oxygen atoms and further monodentatly bonded to three or four phosphorus atoms. In this way, iron generates -P-O-Fe-O-P- intermolecular connections. An insight into the formation of the network was obtained by studying structural changes in iron phytates with increasing concentrations of iron. It was shown that the solid network builds when at least four out of six phosphate groups per one phytic molecule bond to iron atoms and thus participate in the intermolecular connections. This leads to iron phytate with approximately two iron atoms per one molecule of phytate. When the concentration of iron in aggregates increases, the number of P-O-Fe bonds, and thus the number of phosphate groups that are bonded to iron, increases. Solid iron phytate with approximately four iron atoms per one molecule of phytate is almost saturated with iron. Its short-range structural properties can be explained well by a structure that is approaching an idealized model, in which each phosphate group is bonded to two iron atoms and each iron atom is bonded to three phosphorus atoms and is shared between two phytic molecules.

Synthesis of myo-inositol 1,2,3-tris- and 1,2,3,5-tetrakis(dihydrogen phosphate)s as a tool for the inhibition of iron-gall-ink corrosion.

Two myo-inositol phosphates, myo-inositol 1,2,3-tris(dihydrogen phosphate) and myo-inositol 1,2,3,5-tetrakis(dihydrogen phosphate), have been synthesised in several steps from myo-inositol (in Chem. Abstr.: d-myo-inositol) in the form of their sodium salts. They were shown to prevent iron-gall-ink decay in cellulose items at the same level as phytic acid dodecasodium salt.

Size exclusion chromatography of cellulose in LiCl/N,N-dimethylacetamide.

Size exclusion of cellulose in LiCl/N,N-dimethylacetamide has been used for the past 15 years, yet much of the current research is still devoted to fundamental studies, as many issues regarding column calibration, separation mechanisms and solution behavior have not been resolved yet. The paper reviews practical aspects of sample preparation and it is demonstrated that sample heating and several techniques to aid solvent exchange call for reevaluation. It is further shown that the use of internal standard may introduce minor improvements in repeatability. The commonly used column calibration procedures, chromatographic conditions and applications are also reviewed. Further research is needed to understand the mechanisms of separation, to optimize column calibration and to facilitate and optimize sample preparation.

Anti- and prooxidative properties of gallic acid in fenton-type systems.

The anti- and prooxidative properties of gallic acid in Fenton-type systems containing H(2)O(2) and Fe(III) were examined in pH 3-10 reaction media and at reaction temperatures of 20-50 degrees C. Although it is a free radical scavenger, gallic acid may exhibit prooxidative properties, as it promotes the production of hydroxyl radicals due to iron chelation. The overall effect is prooxidative if the ratio of the concentrations of gallic acid and Fe(III) in the reaction medium is smaller than 2. If the ratio is greater than 2, the overall effect of gallic acid presence is antioxidative due to free radical scavenging properties. The dependence of rates and of apparent activation energies of gallic acid consumption on pH in Fenton-type systems was also examined, and it is concluded that the rate-determining steps in acidic and alkaline media are different, the overall rate of gallic acid consumption being lowest at pH 7.

Enthalpic interactions in size exclusion chromatography of pullulan and cellulose in LiCL-N,N-dimethylacetamide.

Enthalpic phenomena were shown to contribute to the size exclusion separation mechanisms during chromatographic analysis of solutions of pullulan and cellulose in LiCl-N,N-dimethylacetamide (LiCl-DMAc) solvent and eluent. The effect of LiCl concentration in the sample solutions and the effect of temperature were of the same order of magnitude for both pullulan and cellulose samples. This led to systematic errors in the determination of mean molecular mass in the range of tens of percent, depending on the chromatographic conditions and on the molecular mass of the analyte. The systematic error is much higher than the random errors; the typical values of the latter being up to a few percent (RSD). Low column temperature and a higher content of LiCl in the sample solution led to lower determined mean molecular mass values. This can be explained by a decrease in the interactions between dissolved macromolecules, although polymer-stationary phase interactions should also be taken into account. Furthermore, the cellulose stability in solution was determined: the zero order random degradation constant being k = 6.9 x 10(-8) mol mol-1 monomer day-1.