Resin Pinaceae

Pine resin, namely rosin or colophony, is one of the most widespread diterpenoid resins and has been used for waterproofing, for treating wood and paper, as varnish, as incense and as an ingredient in scented ointments. The main compounds present in fresh Pinaceae resins... 

However, in many archaeological samples pimarane diterpenoids are often absent, and of the abietane compounds only dehydroabietic acid remains. In fact, dehydroabietic acid is present as a minor component in the fresh resins, but its abundance increases on ageing at the expense of the abietadienic acids since the latter undergo oxidative dehydrogenation to the more stable aromatic triene, dehydroabietic acid [2,18]. If oxygen is available, dehydroabietic acid can be oxidized to 7-oxodehydroabietic acid and 15-hydroxy-7-oxodehydroabietic acid. Since these diterpenoid compounds are often the dominant components in archaeological samples [95,97], they are considered characteristic for the presence of Pinaceae resins. 

In Roman times tar and pitch from Pinaceae resinous wood were used to treat the inner surface of amphorae to store fluids such as wine [ 145,149] and to seal ship planks [89,144], Heating treatments applied to natural resins and resinous wood profoundly modify the chemical composition of the original material. Diterpenoid compounds undergo aromati-zation, demethylation and decarboxylation reactions, with the formation of new compounds of a lower molecular weight that show a high degree of aromatisation [87,88]. In tar and pitch produced from Pinaceae resin and woods, retene is considered as a stable end product of these reaction pathways and nor-abietatrienes, simonellite and tetrahydroretene represent the intermediates of these reactions [87,89,150]. 

Pyrolysis in the presence of tetramethylammonium hydroxide (THM)-GC/MS allowed the identification of high- and low-molecular weight components in manila Copal and sandarac fresh and artificially aged samples. The pyrograms showed signals due to the polymer fraction and to free diterpenoids [43]. THM-GC/MS has also been used to determine the molecular composition of Pinaceae resins, allowing the study of fresh, naturally and artificially aged samples [16, 44 46]. 

Py-GC/MS characterisation of diterpenoid resins using online trimethilsilylation with HMDS has been performed on fresh Pinaceae resins, manila Copal, sandarac, and Copaiba... 

In Pinaceae resins, for instance, fully trimethylsilylated derivatives of 7-hydroxy-DHA, 15-hydroxy-DHA and 15-hydroxy-7-oxo-DHA have been identified, as well as all the other abietadiene and pimaranediene acids present in these resins. The derivatization was ineffective on some labdane alcohols such as larixyl acetate, a marker compound for Venice turpentine, but in general labdane compounds have been identified in their trimethylsilylated form. Labdane acids, such as communic, agathic, agathalic, agatholic and acetoxy agatholic acids, that are among the most important constituents of sandarac... 

Abietic acid (abietane diterpenoid) Widespread in Pinaceae [resin] Pirns insularis, Pinus kesiya, Pirns strobes, Pinus sylvestris (pinaceae) CDPK, PKA... 

Abietic acid Pinus spp. (Pinaceae) [resin] 17(31 ISOR (10 20) (5-LOX)... 

Coniferales Pinaceae Pinus (pine resin, colophony) Abies (Strasbourg turpentine) Larix (Venice turpentine) Abietadienic acids, pimaradienic acids Abietadienic acids, pimaradienic acids, cis abienol Abietadienic acids, pimaradienic acids, epimanool, larixol, larixyl acetate... 

Figure 1.1 Characteristic diterpenoid compounds of Pinaceae and Cupressaceae resins...

The plants that exude diterpenoid resins belong to the order of conifers. Pine resins (from the Firms genus), Strasburg turpentine (from the Abies genus), Venice turpentine (from Larix decidua) were extracted from Pinaceae. Sandarac, juniper and cypress resins were extracted from trees of the Cupressaceae family Tetraclinis articulata, Juniperus spp. and Cupressus semprevirens, respectively. Moreover, labdanum resin from the Cistaceae family (Cistus spp.) also belongs to the diterpenoid resins. 

Figure 3.17 shows the mass profile of the resinous material collected from the Roman amphora. It shows the presence of abietane skeleton diterpenoids due to the occurrence of the peaks at m/z 315, 299, 285, 253 and 239. Furthermore, a high degree of oxidation of the resin was ascertained by the abundance of peaks at m/z 315 and 253, deriving from 7-oxo-dehydroabietic acid, and those at m/z 331 and 329, from highly oxidised tricyclic diterpenoid molecules. Finally, the presence of retene was evidenced by the peaks at m/z 234 and 219. The results showed that a pitch from Pinaceae had been in the amphora. 

Turpentine oil Pinus palustris and other Pinus species (Pinaceae) distillation of the resin (turpentine) secreted from bark ... 

Cyclohexane monoterpenes are a chemically diverse group of monoterpenoids that occur in the plant kingdom mainly as hydrocarbons, alcohols, ketones, aromatic hydrocarbons, and phenols (Fig. 5). The saturated hydrocarbon trans-p-menthme (El) is a constituent of the oil of turpentine and the resin of pine (Pinaceae) trees. Its unsaturated analogs, namely (i )-(- -)-limonene (E2) [present in oil of orange (Citrus aurantium) and mandarin (Citrus reticulata, Rutaceae) peel oil] a-terpinene (E3) and terpinolene (E4) in some Citrus, Juniperus, Mentha and Pinus species (i )-(-)-a-phellandrene (E5) in Eucalyptus phellandra (Myrtaceae) and (5)-(- -)-3-phellandrene (E6) in water feimel (Phel-landrium aquaticum, Umbelliferae), are components of many plant volatile oils. The rich chemical diversity of cyclohexane monoterpene alcohols is apparent from the natural occurrence of all four pairs of / -menthan-3-ol enantiomers, for... 

Diterpene resin acids are abundantly produced in conifers of the pine family (Pinaceae) and in other plant species (Fig. 6). They are produced in the epithelial cells that surround the resin ducts that are found constitutively, or they are induced in the xylem upon wounding and are important for the physical and chemical plant defenses against herbivores and pathogens (18, 40). Industrially, diterpene resin acids are important chemicals for the naval stores industry, in printing inks, as potential antimicrobials and pharmaceuticals, and are byproducts of wood pulping processes. 

Pinacea Conifercs) or Pine Family.—Trees or shrubs with resinous juice whose wood is characterized by being composed largely of tracheids with bordered pits. Leaves entire, awl- or needle-shaped frequently fascicled, exstipulate, usually evergreen. Flowers, monoecious or rarely dioecious, achlamydeous, in cones. Staminate... 

Pinus wallichiana Kail Pinaceae Tree Resin Arthritis... 

Amber. Succinite Baltic amber Bernstein. A fossil resin from the extinct pine tree Pfnries succtnifera (Goepp.) Conway, Pinaceae. Found along the Baltic coast, also mined in Samland (East Prussia). Baltic amber contains C 79%. H 10.5%, O 10,5% succinic acid 3-8% a-amyrin 20-30%. Refi Plonait, Angew. Chem. 48, 184... 

Balsam Canada, Canada turpentine balsam of fir. Improperly Bairn a/ Gilead". Liquid oleoresin from Abies belsameo (L.), Mill., Pinaceae. Habit. Canada and Northern U.S. to Va. west to Minnesota- Constil, 27.5% Volatiles (pinene, nopinene, S-phellandrene), 44.5% resin acid (13% abietic, 8% neoabietic). 27% neutral resinous compounds. Ref Lombard et al, Peintures, Pigments, Vemis 34, 106 (1958), CL 52, 12420 (1958). 

Sandarac. Resin from Callitris quadrivatvis Vent.. Pinaceae. Habit. Morocco. Constit. About 80% pimaric acid, about 10% callitrolic acid sandaricinic acid. 

White Pine. Deal pine Northern pine Weymouth pine, The dried inner bark of Pinus strobus L, Pinaceae. Constit. Conifer in glycoside, couiferyl alcohol, tannin, oleo-resin, volatile oils. 

NAGY, N.E., FRANCESCHI, V.R., SOLHEIM, H., KREKLING, T., CHRISTIANSEN, E., Wound-induced traumatic resin duct development in stems of Norway spruce (Pinaceae) anatomy and cytochemical traits., Amer. J. Bot., 2000, 87,302-313. 

The tenn terpenes originates from turpentine lat. balsamum terebinthinae). Turpentine, the so-called "resin of pine trees", is the viseous pleasantly smelling balsam which flows upon cutting or carving the bark and the new wood of several pine tree species (Pinaceae). Turpentine contains the "resin acids" and some hydrocarbons, which were originally referred to as terpenes. Traditionally, all natural compounds built up from isoprene subunits and for the most part originating from plants are denoted as terpenes (section 1.2). 

Benzenoid (-)-(75, 105)-calamenene is isolated from Ulmus thomasii (Uhnaceae), and (-l-)-3,8-calamenenediol from Heterotheca subaxillaris. The naphthalene sesquiterpene cadalene oeeurs in eonifers, for example in flie resin of fir Abies sibirica (Pinaceae). The wood of several trees contains 3-cadalenol. Cadalen-2,3-qutnone, also known as mansonone C, is a constituent of Mansonia altissima and Ulmus lactinata (Table 3). 

The bicyclic labdanoid diterpenes are characteristic of the bark and needle resins of the Pinaceae, whereas tricyclic types (especially the abietanes and pimaranes) dominate in the wood resin (Croteau and Johnson, 1985) (Fig. 22.10). Highly oxygenated derivatives of the labdane series are widespread in the Asteraceae, Lamiaceae, Verbenaceae, and in the genus Croton of the Euphorbiaceae. 

Pinaceae, usually are diterpenes with a 5a,10p-configura-tion. Many plants serve as commerical sources of resins the genera Hymenaea and Copaifera (Fabaceae) and Pinus and Agatha (gymnosperms) are probably the best known producers. Resins are used as feedstocks for products such as insecticides, incense, varnishes, rosin, and adhesives, and as components of drugs and polishes. Fossilized deposits of diterpenes are known as amber (Langenheim, 1990). 

Pine and Spruce are the common names used for hundreds of species of conifers belonging to the genus Pinus and Piceay members of the Pinaceae family. Principally, most of these timbers are found in the northern hemisphere. Pine and Spruce species are the source of wood balsam which, after separation of the volatile part (turpentine), yields rosin (colophony). Rosin consists of 90% resin acids an 10% neutral components. 

While classifying individual resins is difficult, they are sometimes classified as mixtures with other plant constituents, for example gum-resins, oleo-gum-resins, glycoresins. One of the most well known resins comes from the Finns genus (Pinaceae) and is known as rosin. This amber-coloured resin is mainly used in varnishes and other industrial products. 

Plants rich in essential oils are mainly found in species of the families Apiaceae, Asteraceae, Cupressaceae, Lamiaceae, Lauraceae, Myrtaceae, Pinaceae, Piperaceae, Rutaceae, Santalaceae, and Zingiberaceae. As lipophilic compoimds, essential oils are accumulated in particular structures as oil cells, secretory ducts, or glandular hairs. Frequently, the essential oils are associated with resins or gums. 

In many species of Pinaceae oleoresin biosynthesis may occtur as a constitutive pattern of growth and development (primary or preformed resin), or its formation... 

A range of modem resin samples from the Dipterocarpaceae, Pinaceae and Burseraceae families (Table I), encompassing both diterpenoid and triterpenoid resins, have been examined using GC and GC-MS to act as reference materials against which to compare results from the archaeological samples. Wherever possible, the higher terpenoid peaks have been identified by comparison with previously published data. 

The diterpenoid constituents of resins analysed are usually seen as a group of peaks eluting at around 20 minutes retention time. All of the diterpenoid resins in Table I are coniferous and come from the Pinaceae and Araucariaceae families. To date, no evidence for the use of diterpenoid resins in association with archaeological ceramics has been found. 

Other durable timbers, notably those of the family Cupressaceae, have been used for buildings in many countries and for other purposes, such as boats and coffins, and have survived microbiological and insect attack for centuries (18). The stave churches remaining in good condition in Norway after more than 800 years were built from logs of resinous Scots pine Pinus sylvestris, Pinaceae) (2). 

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