, 2010, Kaltenrieder et al., 2010 and Valsecchi et al., 2010). For the first time the high values of the indicators for anthropogenic activity no buy Vorinostat longer coincided with high fire frequencies ( Conedera and Tinner, 2000). During the Middle Ages the approach to fire by the Alpine population reveals contrasting aspects. As a general rule, fire use was banished from the landscape being a threat to buildings, protection

forests ( Brang et al., 2006), timber plantations and crops, as deducible from the numerous local bylaws dating back to the 13th century ( Conedera and Krebs, 2010). On the other hand, no prohibition or even obligation of pastoral burning in selected common pastures existed in many local communities ( Conedera et al., 2007). Besides a number of bylaws, evidence remaining of the second fire epoch can be found

in the many place names referring to the use of fire to clear brushwood to improve pasture-land or to eliminate trees (Italian brüsada; old French arsis, arsin, arselle; old German swenden and riuten; or present Swiss German schwendi) ( Sereni, 1981 and Conedera et al., 2007), as well as in the historical literature, e.g., Schmitthenner (1923), Schneiter (1970), Sereni (1981), Lutz (2002), Bürgi and Stuber (2003), Goldammer and Bruce (2004), Forni (2011). As a consequence, charcoal influx records slightly increase during the Middle Ages at the majority of sites investigated ( Gobet et al., 2003, Rolziracetam Blarquez et al., 2010, Kaltenrieder et al., 2010 and Valsecchi et al., 2010). Later, in the 18th and 19th MAPK Inhibitor Library centuries, the shortage of timber resources, forest privatization and development of the timber industry required increased fire control, and the prohibition of agro-pastoral use of fire (Conedera et al., 2004a and Conedera and Krebs, 2010), similarly to what Pyne (2001) reported for other areas. As a consequence, charcoal influx records decreased in Modern Times reaching

constant lower values in the 20th century in comparison with previous periods, excluding Roman Times (Tinner et al., 1999, Carcaillet et al., 2009, Blarquez et al., 2010, Colombaroli et al., 2010, Kaltenrieder et al., 2010 and Valsecchi et al., 2010). Similarly to other geographical areas, fire control policies have been strengthened during the second half of the 20th century also in the Alps, determining an overall decrease in the area burnt in the Alpine region (Conedera et al., 2004b, Zumbrunnen et al., 2010 and Pezzatti et al., 2013). Fig. 4 shows the decrease in yearly burnt area from the end of the 20th century which characterized most Alpine areas. This is particular evident in sub-regions with the highest burnt area such as Piemonte, Ticino and Friuli Venezia Giulia in Western, Central and Eastern Alps, respectively (Fig. 5). The current fire regime is characterized mainly by autumn-winter and early-spring slope-driven anthropogenic surface fires (Pezzatti et al.

The flexibility of the system to handle multiple sample types and process one to seven samples per run expands the capability of the system to be used for processing crime scene evidence for lead investigation, disaster victim identification and hit confirmation as examples. Protocols are being developed to support future applications on the RapidHIT System. The authors have no financial interests to disclose regarding this work. The buccal samples were collected in accordance with methods approved by the

Institutional Review Boards for IntegenX. The authors would like Transmembrane Transproters inhibitor to thank Jacklyn Buscaino, Sayali Salodkar, and Francesca Pearson for technical assistance with this work. The authors also extend their gratitude to Dennis Wang (ThermoFisher Scientific) for providing the DNA sample containing the SE33 microvariant. “
“According to demographic data from the register in 2002 the population of the Republic of Macedonia is 2,022,547 with 64.2% ethnical Macedonian, 25.2% ethnical Albanians, 3.9% ethnical Turks, 2.7% ethnical Romanies and a small percentage of other ethnic groups. People from different ethnic communities rarely have marriages between each other due to their national Dolutegravir and religious determination. Whether or not this has an effect on the distribution of mitochondrial lineages has yet not been studied for Macedonia. An earlier study described mitochondrial (mt)DNA control region variation

for ethnical Loperamide Macedonians, which brought a similar haplogroup distribution to other West-Eurasian populations [1]. Here, we describe mtDNA control region variation in carefully selected samples of the three other major ethnic groups (148 Albanians, 150 Turks and 146 Romanies) and thus add a total of 444 high quality mtDNA lineages to the body of world-wide mtDNA database. The data will also be made available for forensic searches via EMPOP [2] under accession numbers EMP00644 (Albanians), EMP00645 (Romanies), and EMP00646 (Turks). This study was reviewed and approved by the ethics commission of the University “St.Cyril and Methodius”

(study classification number 03-5904/2 from 01.02.13, session number XXVI). All participants (N = 444) gave their written consent before a buccal swab was taken. Study participants were sampled from different geographic locations in the Republic of Macedonia (Fig. S1), Albanians derived mostly from the western part, Turks originated from the eastern, western and southern parts and Romanies derived from the central and northern parts of the country. DNA was extracted using the QIAamp mini kit (Qiagen, Hilden, Germany) following the manufacturer’s recommendations. PCR amplification and mtDNA control region sequencing were carried out following the EMPOP protocol [3] updated in [4]. Nucleotide sequences were analysed and interpreted using Sequencher (Version 5.1, Gene Codes Corporation) and aligned relative to the rCRS [5] following phylogenetic alignment rules defined in [6].

We sequenced the two lower bands, Band-A and Band-B, derived from different cultivars showing different genotypes for each of the five markers. Two representative cultivars, Chunpoong and Yunpoong, were sequenced for all five markers and other cultivars were also sequenced, including Sunpoong for the gm47n marker, Sunun for the gm129 marker, Sunone for the gm175 marker, and Sunpoong, Sunone, and Gopoong for the gm184 marker. A total of 34 high-quality sequences derived from individual bands was obtained. Multiple sequence comparison allowed us to classify the multiple bands as representing different loci in the same cultivar (paralogs) or allelic forms of the same locus in different

cultivars (alleles; Fig. 2). The bands close to the expected size (Band-B of gm45n, gm47n, and gm175 and Band-A of gm129 and gm184) were derived SCH 900776 datasheet from same locus as the reported EST. The other bands (Band-B of gm45n, gm47n, and gm175 and Band-A of gm129 and gm184) http://www.selleckchem.com/products/CAL-101.html amplified from a paralogous locus showed relatively different sizes from those expected. The paralogous sequences

were characterized by SNP or InDel variations as well as much larger variations in SSR unit number. For example, the gm175 marker showed polymorphism for both loci among cultivars. Each of the two bands showed one or two copy differences of the AGG SSR motif among cultivars. There was a maximum copy number difference of four for the AGG SSR motif as well as a 21 bp InDel variation between Band-A and Band-B (Table 1). The Band-B sequence of Chunpoong corresponded to the EST, indicating that the EST is derived from the locus of Band-B (Fig. 2A). The gm45n marker showed a maximum copy number difference of five for the TGG SSR motif, (TGG)5 and (TGG)10, as well as two SNPs between Band-A and Band-B. The allelic form of Band-B showed only a two-copy difference for the TGG SSR motif, (TGG)8 and (TGG)10, in Chunpoong and Yunpoong

cultivars, respectively (Table 1). By contrast, Band-A showed no variation Thiamet G among the different cultivars. Similarly, only one of the two bands, Band-B, was polymorphic among cultivars, except for the gm175 marker. Among the five markers, four had SNPs and the other had an InDel between Band-A and Band-B that served as a signature to distinguish paralogous sequences (Fig. 2, Table 1). We next tried to develop locus-unique markers to amplify selectively single bands derived from one of two paralogous regions. We focused on the SNP regions between paralogous sequences. The gm47n marker showed a more than four SSR unit difference as well as one SNP between Band-A and Band-B (Fig. 2B). The SNP was identified at the position 51 bp as “C” and “T” for Band-A and Band-B, respectively (Table 1). For the polymorphic Band-B-specific primer, we designed an additional left primer, 5′-CTCTGTTTTCTTCCCTTTTCTCTGT-3′, which has the Band-B specific nucleotide “T” at the end and an additional modified nucleotide “G” ( Fig. 2B).

Likewise, Tiessen et al. (2010) reported that conversion to conservation tillage increased P concentrations and exports, mostly as soluble P, especially during snowmelt. Kleinman et al. (2011) showed that while PP decreased by 37% in a no-till vs. conventional-till watershed, TP increased by 12%, with that increase

attributed to dissolved P mediated by high concentrations of surface soil P. BMPs that lower the accumulation of P at the soil surface should be considered in areas where DRP is a major concern (Tiessen et al., 2010). A summary of BMPs that focused on controlling DRP (Crumrine, 2011) outlines their potential effectiveness, costs, and likelihood of use. Bosch et al. (2013) explored the impacts of expanding the current use of filter Selleckchem Sunitinib strips, cover crops, and no-till BMPs in controlling runoff. When implemented singly and in combinations at levels currently considered feasible by farm experts, these BMPs reduced sediment and nutrient yields by only

0–11% relative to current values ( Fig. 15). Yield reduction was greater for sediments and the greatest reduction was found when all three BMPs were implemented simultaneously. They also found that targeting BMPs in high source locations (see above), rather than randomly, decreased nutrient yields more; whereas, reduction in sediment yields was greatest when BMPs were located near the river outlet. A more detailed analysis of increased BMP Thiamine-diphosphate kinase implementation strategies for the Maumee watershed ( Fig. 16) pointed to the need for more aggressive implementation of multiple BMPs to reduce loads substantially. For example, a 20% reduction in TP or DRP find more load requires implementing the BMPs on more than 50% of the agricultural land. Meteorological conditions, including both temperature and precipitation, have changed appreciably during the past century in the Great Lakes basin, with increased temperature and winter/spring precipitation expected into the future (Hayhoe et al., 2010 and Kling et al., 2003). Thus, establishing loading targets to control Lake Erie hypoxia should consider

how potential climate change might impact loads, processes that lead to hypoxia formation, fish, and BMP effectiveness. While uncertainty surrounding the projected future regional precipitation is greater than for temperatures, confidence is increasing that future precipitation patterns will continue to trend toward more intense late-winter and early spring precipitation events (Hayhoe et al., 2010). Such intense events could lead to higher nutrient runoff, and in the absence of dramatic changes in land use, could increase overall nutrient loads because 60–75% of P inputs are delivered during precipitation-driven river discharge events (Baker and Richards, 2002, Dolan and McGunagle, 2005 and Richards et al., 2001). A preliminary study of the impact of climate change on the Maumee River (DeMarchi et al.

10). Of the 404 sequence of dams, 73% are closer than 100 km to each other. Results show that the 512 km

between the Garrison and Oahe Dam is not enough distance to consider these dams separately. We propose a conceptual model of how a sequence of interacting dams might impact river geomorphology (Fig. 11) based on our results. We call this morphologic sequence the Inter-Dam Sequence, and we present a simplified model based on the Upper Missouri River that could be easily adapted to other river reaches. Although the morphologic sequence is a useful conceptualization, there are clear limitations to these results. buy Staurosporine This model is likely only applies to large Trichostatin A dams on alluvial rivers. Dams on rivers that are controlled by bedrock or where morphologic adjustment is limited by vegetation or cohesive banks may respond completely different than the model presented here. Similarly, the downstream effects of small dams will likely attenuate

over much shorter distances. However, this framework is a helpful advancement in our understanding of longitudinal responses to multiple dams. One of the greatest influences that humans have had on the fluvial landscape is the construction of dams. Despite significant advancements in the study of the downstream and upstream impacts of dams, they are often considered separately from each other. The Garrison and Oahe Dama on the Missouri River are used to demonstrate Ribose-5-phosphate isomerase that the effects of an upstream dam maintains significant geomorphic control over river morphology as the backwater effects of downstream reservoir begin to occur. The upstream–downstream interaction of multiple dams overlap to create a distinct morphologic sequence.

Five unique geomorphic gradational reaches were identified for the Garrison Reach, two of which are controlled solely by the upstream dam and three of which are controlled by the dam interaction termed: Dam Proximal, Dam-Attenuating, River-Dominated Interaction, Reservoir-Dominated Interaction, and Reservoir. A conceptual model was developed of a morphologic sequence of downstream dam impacts and dam interaction which can be adapted to other rivers. The current distribution of dams on the major rivers in the U.S. indicates that more than 80% of large rivers may have interacting between their dams. Given this widespread occurrence, we describe a generalized morphologic sequence termed the Inter-Dam Sequence and suggest it should be the focus of additional research. We would like to acknowledge project funding from the following sources: U.S. Army Corps of Engineers, ND State Water Commission, ND Department of Transportation, ND Game and Fish Department, ND Department of Health, City of Bismark, City of Mandan, Burleigh County WRB, Morton County WRB, and Lower Hart WRB.

, 2011, Steffen et al., 2011, Zalasiewicz et al., 2011a and Zalasiewicz

et al., 2011b). Rather Venetoclax chemical structure than constituting a formal chronostratatgraphic definition of the Anthropocene epoch, this consensus adopts, as a practical measure, a beginning date in the past 50–250 years: In this paper, we put forward the case for formally recognizing the Anthropocene as a new epoch in Earth history, arguing that the advent of the Industrial Revolution around 1800 provides a logical start date for the new epoch. (Steffen et al., 2011, p. 842) Steffen et al. (2011) follow the lead of Crutzen and Stoermer (2000) in identifying the rapid and substantial global increase in greenhouse gasses associated with the Industrial Revolution as marking the onset of the Anthropocene, while also documenting a wide range of other rapid increases in human activity since 1750, from the growth of McDonald’s restaurants to expanded

fertilizer use (Steffen et al., 2011, p. 851). In identifying massive and rapid evidence for human impact on the earth’s atmosphere as necessary for defining the Holocene–Anthropocene transition, and requiring such impact to be global in scale, Steffen et al. (2011) are guided by the formal criteria employed by the International Commission on Stratigraphy (ICS) in designating geological time TGF-beta inhibitor units. Such formal geologic criteria also play a central role the analysis of Zalasiewicz et al. (2011b) in their comprehensive consideration of potential and observed stratigraphic markers of the Anthropocene: “Thus, if the Anthropocene is to take it’s Adenosine triphosphate place alongside other temporal divisions of the Phanerozoic, it should be expressed in the rock record with unequivocal and characteristic stratigraphic signals.” (Zalasiewicz et al., 2011b, p.

1038). Ellis et al. (2011) also looks for rapid and massive change on a global scale of assessment in his consideration of human transformation of the terrestrial biosphere over the past 8000 years, and employs a standard of “intense novel anthropogenic changes …across at least 20 per cent of Earth’s ice-free land surface” as his criteria for “delimiting the threshold between the wild biosphere of the Holocene and the anthropogenic biosphere of the Anthropocene” (2011, p. 1027). A quite different, and we think worthwhile, approach to defining the onset of an Anthropocene epoch avoids focusing exclusively and narrowly on when human alteration of the earth systems reached “levels of equal consequence to that of past biospheric changes that have justified major divisions of geological time” (Ellis, 2011, p. 1027). We argue that the focus should be on cause rather than effect, on human behavior: “the driving force for the component global change” (Zalasiewicz et al., 2011a, p.

The extremely limited accumulation of NH4+ on ionic resins in the spruce-Cladina forest could be a function of the high rate of NO3− formation in these same soils which could lead to N losses due to leaching and or denitrification ultimately reducing the amount of mineralizable N. The combined effect of the loss of N2 fixing feathermosses and loss of juniper from the understory likely led to a reduction in success of germination and growth of pine or birch seedlings. Juniper has previously been reported to increase the surface concentrations of available P and create a microhabitat for feathermoss growth (DeLuca

and Zackrisson, 2007). It is suspected that the juniper also this website serves as a nurse crop for the growth of pine and spruce seedlings

as it serves to protect young saplings from trampling and browse by reindeer (Castro et al., 2004). In comparing pine seedling survival and growth in open bare ground compared to under spiny shrubs and under juniper, Castro et al. (2004) found the highest rate of survival under juniper shrubs. Juniper is highly flammable and readily eliminated from sites exposed to selleck inhibitor frequent, recurrent fire (Thomas et al., 2007). Accordingly, the loss of juniper from the spruce, pine forests of northern Sweden as a result of recurrent burning, would have likely led to a decline in the presence of fertile microsites associated with juniper (DeLuca and Zackrisson, 2007) and loss of the protective cover created by juniper shrubs. Loss of these two components of the plant community would build upon itself ultimately resulting in a reduction in the presence of pine and birch in the soil seed bank. The development of an open spruce canopy with a forest floor dominated by lichen and partial dwarf shrub cover would provide limited protection against erosion and result in limited accumulation of organic matter. Cladina spp. harbor green algae as a photobiont rather than cyanobacteria and therefore do not

exhibit the capacity for N2 fixation observed in cyanolichens ( Yahr et al., 2006). And in spite of the fact that Cladina may harbor bacteria with nif genes ( Grube et al., 2009), attempts to Sodium butyrate measure nitrogenase activity in Cladina have been negative (Zackrisson, unpublished data). Stereocaulon, a lichen capable of relatively high rates of N fixation per unit biomass ( Crittenden and Kershaw, 1978), accounts for 10–20% of the ground cover in the Cladina-lichen forests, the total N contribution is likely to be extremely small given the limited biomass per unit area ( Gavazov et al., 2010). In the undisturbed Scots pine, Norway spruce reference forest, the feathermoss P. schreberi alone accounts for over 70% ground cover. Nitrogen fixation in P.

In the spring, the Al saturations tended to increase with the deepening layers. The Al saturations at 0–5 cm and 5–10 cm depths increased obviously in the summer and autumn. The highest Al saturation of all the beds at all three depths was found in the transplanted

2-yr-old ginseng beds. To better understand the potential soil damage caused by the artificial plastic canopy during ginseng cultivation, an annual cycle investigation was conducted to inspect the seasonal dynamics of soil acidity and related parameters in the albic ginseng bed soils. The results showed that ginseng planting resulted in soil acidification (Fig. 3A–E), decreased concentrations of Ex-Ca2+ (Fig. 1K–O), NH4+ (Fig. 2A–E), TOC (Fig. 3K–O), and Alp (Fig. 3P–T), and increased bulk density (Fig. 2P–T) of soils originating AT13387 research buy from albic luvisols. There were also marked seasonal changes in the Ex-Al3+ and NO3− concentrations and spatial variation of water content (Fig. 2 and Fig. 3F–J). The soil conditions were analyzed further as described in the following text. Generally,

soil acidification results from proton sources such as nitrification, acidic deposition, dissociation of organic anions and carbonic acid, and excessive uptake of cations over anions by vegetation [19]. In this study, the plastic canopy minimized the influence of rainfall, and thus acid deposition can be ignored. The form of nitrogen ( NH4+ or NO3−) has a prominent influence on the cation–anion balance in plants and the net production or consumption of H+ in roots, which accounts for a corresponding decrease or increase click here in the substrate pH [20]. The remarkable decrease in NH4+ concentrations and the surface increase in NO3− concentrations in the summer and autumn might mean that NH4+ is the major nitrogen source for ginseng uptake. It is difficult for ginseng to uptake the surface accumulation of NO3− due to spatial limitations. The for remarkable decrease in NH4+ concentrations within a 1-yr investigation cycle (Fig. 2A–E) might be

the result of two factors: (1) NH4+ uptake by plants; and (2) the nitrification transformation of NH4+ to NO3−. Either uptake by ginseng or transformation to NO3− will release protons and result in soil acidification. This is consistent with the finding that pH is positively correlated with NH4+ concentration (r = 0.463, p < 0.01, n = 60; Fig. 3A–E). The active nitrification process in ginseng garden soils might result in significant NO3− accumulation, especially in the summer and autumn (Fig. 2F–J). The clear seasonality of NO3− distribution in ginseng garden soils might also be driven by water movement (Fig. 2K–O), which was demonstrated in the variation in soil moisture in ginseng beds under plastic shades (Fig. 2K–O). In the summer and autumn, the potential difference in the amount of water between the layers might have resulted in upward water capillary action (Fig. 2K–O). The following spring, the snow melted and leaching occurred again (Fig. 2K–O).

Although these archeological sites are all very large, they also had unusually long use-lives, so the human communities living there at any given time were not nearly so large as the archeological sites we now see. The size and longevity of the sites themselves does, however, indicate that they were situated in near-optimal settings that kept people coming back over centuries. Sannai Maruyama was occupied over some 1600 years (5900–4300 cal BP) and more than 600 pit-dwellings are known to exist there, along with many large raised-floor buildings and other structures, some of

them surely storage depots for locally abundant and durable foods such as chestnuts and acorns (Habu, 2008). Extensive paleoethnobotanical research into the flourishing forest economy of Neolithic-era Japan has generated a clear picture of Jomon people engaged in anthropogenic modification of their GSK2118436 in vivo landscape as they engineered their distinctive ecological niche over a long period. Crawford, 2011a and Crawford, 2011b provides a very extensive

accounting of species identified from Jomon sites, a number of which he characterizes as “potential domesticates/tended plants.” Plants probably domesticated were barnyard grass (Echinochloa crus-galli) and soybean; cultivated plants included bottle gourd (Lagenaria siceraria), hemp (Cannabis sativa), and possibly beefsteak plant and azuki bean. People encouraged certain valuable plants, and probably exercised some form of management of

the lacquer tree (Toxicodendron verniciflua), as well as nut-bearing chestnut (Castanea crenata) and horse chestnut (Aesculus Bortezomib mw turbinata) trees. Crawford (2011b) concludes that “these characteristics place the Jomon in a middle ground that is neither hunting and gathering nor traditionally conceptualized agriculture” and suggests that “plant husbandry” would be an appropriate term for the subsistence system. The Jomon culture continued to flourish through Middle Jomon (5000–4000 cal BP) and Late Jomon times (4000–3000 cal BP), and in central Honshu this interval is well known for its many large communities of mainly, if not exclusively, single-family pit houses organized around a defining Amine dehydrogenase central open space. Excavations here have yielded spectacularly elaborated pottery vessels as well as anthropomorphic figurines, drums, and other items that bespeak a significant degree of social display and status differentiation, probably acted out in the context of communal feasting. Kidder (1968) provides a useful and attractive photographic catalog of illustrative Jomon specimens from this and other areas. East and south of the mountains in the Tokyo Bay region, large numbers of both year-round villages and seasonally important mass harvesting sites are also documented (Aikens, 2004, Akazawa, 1981, Akazawa, 1982, Akazawa, 1986, Habu, 2001 and Koike, 1986).

Before the inclusion complex was investigated by ESI–MS, the β-CD and drug molecules: propiconazole (PCZ) and propiconazole nitrate (NO3PCZ) were analyzed individually CX-5461 price to check their purity in order to contrast the relative CID energies between β-CD and its complex. The formation of the molecular ion by ESI–MS occurs only in positive mode and therefore only positive ions were analyzed. It is most likely that the proton will be retained onto the nitrogen atom of the 1,2,4-triazole heterocycle of PCZ molecule. The ESI–MS spectrum for PCZ in methanol

solutions is shown in Fig. 5, and the zoom isotope peaks of PCZ isomers are also shown as an inset in the figure. Specifically for PCZ molecules (mixture of four stereoisomers) there is an observation PD0332991 price that the isomers arise

at m/z 342 and 344. Besides the formation of the propiconazole species one may observe the low intensity peaks at m/z 364 and 707, which can be attributed to sodium PCZ adduct and later to the sodium adduct of the two associated PCZ molecule. The ESI–MS analysis of NO3PCZ in water methanol mixture (1:1 v/v) (Fig. 6) revealed the formation of proton charged propiconazole nitrate at m/z=405, which confirms that the nitration reaction of PCZ was successfully carried out and click here can be observed by this technique. Fig. 7 shows ESI-MS spectrum of β-CD–NO3PCZ inclusion complex in water methanol mixture (1:1 v/v), where the most abundant peak at m/z 1157 corresponds to β-CD sodium adduct, while a peak at 1199m/z can be attributed to NO3CD. The peak at m/z 1540 corresponds to [β-CD–NO3PCZ+H+]+

which directly confirmed the 1:1 complex formation between β-CD and NO3PCZ. In order to obtain information on the binding strength of the non-covalent complex, MS/MS experiments on β-CD, PCZ, NO3PCZ and their inclusion complexes were performed. The tandem mass spectra in the positive ion mode for the PCZ ions at the collision energy of 30 eV (Fig. 8) revealed a major peak at m/z 158 which can be attributed to C7H5Cl2 fragment from PCZ and the other small peaks, resulting solely, from PCZ fragmentation ( Fig. 9). The tandem mass spectra in the positive ion mode for the NO3PCZ ions at the collision energy of 30 eV are shown in Fig. 10. The peaks resulting from NO3PCZ fragmentation are observed at m/z 219, 259, 306 and 319, assigned to the structures from Fig. 11. A confirmatory experiment of the formation of [β-CD–NO3PCZ+H+]+ complex, made using different relative collision energies (10–50 eV), put out its specific peak at m/z 1540 ( Fig. 12). The peak at m/z 1197 observed on MS spectrum in Fig.