Identification of volatile compounds from cheek glands of lesser bandicoot rats and assessment of behavioural response for identified compounds

Check gland secretions were collected from sexually mature male and female rats to identify the volatile compounds using gas chromatography linked mass spectroscopy with a modified head space technique. Twenty one volatile fractions including alkanes, aliphatic acids, esters and alcohols were found. Three compounds viz. 3-octen-1-ol (E) (I), cyclopentane undecanoic acid (II) and 2,4,6,8 tetramethyl-l-undecane (III) were present in very high concentrations in both male and female rats. In addition, the estrus female contained another compound, L-alanine, 1,1-dimethyl ethyl ester. On the basis of odour preference tests the compounds I, II and III were found to attract both male and female of the homotypic species. In contrast, the fourth compound present in the female attracts the opposite sex. The results suggest that the volatile fractions have unique function and the level of attraction varies from compound to compound.     

Chemistry of clitoral gland secretions of the laboratory rat: Assessment of behavioural response to identified compounds

The present investigations were carried out to find out the chemical nature of clitoral gland extracts and their involvement in reproductive and social behaviour. Homogenates of clitoral glands of mature estrous female rats were extracted with n-hexane and dichloromethane (1:1 ratio v/v) and analysed by gas chromatography linked mass spectrometry (GC-MS). Three peaks were found to be in higher concentration, which were identified as 6,11-dihydro-dibenz-b,e-oxepin-11-one (I); 2,6,10-dodecatrien-1-ol-3,7,11-trimethyl(Z) (II); and 1,2-benzene-dicarboxylic acid butyl(2-ethylpropyl) ester (III). Odour preference tests demonstrated that the first compound attracted conspecifics of the opposite sex. By contrast, the second and third compounds were found to attract both sexes. The results conclude that the clitoral gland of laboratory rat contains three major chemical compounds which have a unique function in maintaining social and reproductive status.     

Volatile compounds emitted by Triatoma dimidiata,a vector of Chagas disease: chemical analysis and behavioural evaluation

In this study, we evaluated the responses of Triatoma dimidiata Latreille (Hemiptera: Reduviidae) to volatiles emitted by conspecific females, males, mating pairs and metasternal gland (MG) extracts with a Y‐tube olfactometer. The volatile compounds released by mating pairs and MGs of T. dimidiata were identified using solid‐phase microextraction and coupled gas chromatography‐mass spectrometry (GC‐MS). Females were not attracted to volatiles emitted by males or MG extracts; however, they preferred clean air to their own volatiles or those from mating pairs. Males were attracted to volatiles emitted by males, females, mating pairs, pairs in which the male had the MG orifices occluded or MG extracts of both sexes. However, males were not attracted to volatiles emitted by pairs in which the female had the MG orifices occluded. The chemical analyses showed that 14 and 15 compounds were detected in the headspace of mating pairs and MG, respectively. Most of the compounds identified from MG except for isobutyric acid were also detected in the headspace of mating pairs. Both females and males were attracted to octanal and 6‐methyl‐5‐hepten‐2‐one, and males were attracted to 3,5‐dimethyl‐2‐hexanol. Males but not females were attracted to a seven‐compound blend, formulated from compounds identified in attractive MG extracts.     

蝴蝶果根、果仁挥发油化学成分的研究

采用水蒸气蒸馏法从大戟科蝴蝶果的根和果仁中提取挥发油,用气相色谱-质谱联用技术对挥发油化学成分进行分析,并应用面积归一化法测定各成分的相对百分含量。从根中鉴定出23种化合物,占总油量的100%,其主要成分为十六烷酸(18.74%)、(Z,Z)9,12-十八碳二烯酸(12.81%)、1,2-苯二羧酸双(2-甲基丙基)酯(10.59%)、二丁基邻苯二甲酸酯(7.42%)及二十四烷(6.72%)。从果仁中鉴定出17种化合物,占总油量的100%,主要成分为(E-)-9-十八碳烯酸(23.15%)、正十六烷酸(21.20%)、(Z,Z)-9,12-十八碳二烯酸(19.26%)及3-甲基十七烷(6.80%)。     

Characterization of urinary volatiles in Swiss male mice (<Emphasis Type="Italic">Mus musculus</Emphasis>): bioassay of identified compounds

The present study was carried out to investigate the chemical nature of the urine of male mice and to assess its bioactivity. Urine of mature male mice was extracted with dichloromethane (1:1 ratio v/v) and analysed by gas-chromatography linked mass-spectrometry (GC-MS). Ten different compounds such as alkanes, alcohols, etc. were detected in the urine. Among the ten, five compounds are specific to males, namely 3-cyclohexene-1-methanol (I), 3-amino-s-triazole (II), 4-ethyl phenol (III), 3-ethyl-2,7-dimethyl octane (IV) and 1-iodoundecane (V). The compound, 4-ethylphenol, has been previously reported in several strains of male mice. Furthermore, the compounds (II) and (IV) are similar to 2-sec-butylthiazole and dehydro-exo-brevicomin compounds which have already been reported in male mice. Bioassay revealed that compounds (II), (III) and (IV) were responsible for attracting females and in inducing aggression towards males, as compared to the other compounds, i.e. (I) and (V). The results indicate that these three volatiles (II, III and IV) of male mice appear to act as attractants of the opposite sex.     

3-Ethyl-2,7-dimethyl octane, a testosterone dependent unique urinary sex pheromone in male mouse (Mus musculus)

A previous investigation revealed that urine from normal male mice contained five unique volatile constituents; namely: 3-cyclohexene-1-methanol (I); 3-amino triazole (II); 4-ethyl phenol (III); 3-ethyl-2,7-dimethyl octane (IV); 1-iodoundecane (V). The present study was designed to find out whether the production of these male specific urinary compounds was androgen-dependent. Urine of castrated and castrated plus testosterone-treated male mice was analyzed using gas chromatography linked mass spectrometry (GC-MS). Even though castrated male urine contained 10 detectable compounds, the five male specific compounds present in intact males were absent in castrated male mice urine. Only 3-ethyl-2,7-dimethyl octane (IV) reappeared following testosterone treatment into castrated males. Our earlier bioassay revealed that this compound was involved in attracting females. The present study concluded that this compound was a male specific volatile cue that acted as a releaser pheromone and its production was under the control of androgen.     

Behavioural effects of minor sex pheromone components in Brazilian apple leafroller Bonagota cranaodes (Lep., Tortricidae)

Abstract:  The behavioural response of Brazilian apple leafroller males, Bonagota cranaodes (Meyrick), to natural and synthetic sex pheromone was studied in a wind tunnel. Calling females elicited upwind flights followed by landing and wingfanning at the source in 72% of the males tested. Female gland extracts, with the main compound ( E , Z )3,5dodecadienyl acetate released at 100 pg/min, attracted 57% of the males to the source. Few males (1%) were attracted to the main compound alone, released at the same rate. Even a synthetic blend of all five gland compounds eliciting an antennal response, formulated according to their proportion in female gland extracts, was barely attractive (7%). Comparison of this synthetic blend and female gland extracts indicates a behavioural role of other gland compounds. Male attraction was significantly increased (34%) in response to a 100 : 5 : 5 : 5-blend of the main compound and three minor gland compounds, ( Z )-5-dodecenyl acetate, ( E , Z )-3,5-tetradecadienyl acetate, and ( Z )-9-hexadecenyl acetate.     

Putative chemosignals of the ferret (Mustela furo) associated with individual and gender recognition

Quantitative stir bar sorptive extraction methods, both in the aqueous and headspace modes, followed by thermal desorption gas chromatography-mass spectrometry were used to investigate individual variations in the volatile components of male and female ferret (Mustela furo) urine. The urinary profiles were further compared with volatile profiles of anal gland secretions of breeding male and female ferrets. Thirty volatile compounds were quantified in male and female urine. Among them, 2-methylquinoline was unique to male urine. Four ketones (4-heptanone, 2-heptanone, o-aminoacetophenone, and a dimethoxyacetophenone) and several nitrogen compounds (e.g., 2,5-dimethylpyrazine, quinoline, 4-methylquinazoline) and low levels of three unidentified nonsulfur compounds were significantly more abundant in males than in females. Quantitative comparison of 30 volatile urinary compounds showed several statistically significant differences between the sexes and individuals of the same sex. These findings suggest that ferrets may use urine marking for sex and individual recognitions. Ten of the 26 compounds identified in anal gland secretions from females and males were also found in urine. However, most of the major compounds (thietanes, dithiolanes, and indole) in anal glands were not present in urine. This suggests that urine may convey specific signals that differ from those of anal glands. Additionally, 10 volatiles (two aldehydes, five ketones, benzothiazole, 2-methylquinoline, and 4-methylquinazoline), not previously identified, were found in ferret anal gland secretions. Among the new compounds, o-aminoacetophenone was found only in males, while only traces of this compound were found in females. Similar results were previously obtained in anal glands of three other Mustela species. These findings provide new information about the constituents of urine and volatile components of anal gland secretions in ferrets.     

花生茎叶酚性成分研究

运用大孔树脂对花生茎叶提取液进行富集,不同浓度乙醇洗脱,硅胶、RP-18、Sephadex LH-20等多种材料进一步分离纯化,研究花生茎叶化学成分,并通过理化方法和光谱分析对化合物进行结构鉴定。结果表明:从花生茎叶大孔树脂10%乙醇洗脱部位中分离并鉴定了10个化合物,分别为邻苯二甲酸二异丁酯(1)、水杨酸(2)、儿茶酚(3)、对羟基苯甲酸(4)、(反)-3,4-二羟基苯丙烯酸(5)、对羟基苯酚(6)、邻苯二甲酸二丁酯(7)、3,4-二羟基苯乙醇(8)、对羟基苯乙醇(9)、3,4-二羟基苯甲酸(10)。除化合物1、2和4外,其余均为首次从该植物中分离得到。     

Disruption of sexual communication in the mirid bug Lygocoris pabulinus by hexyl butanoate

1 The metathoracic scent gland in Lygocoris pabulinus contains mostly hexyl butanoate. As secretions of this gland in Heteroptera may serve as an alarm pheromone, we determined whether hexyl butanoate is released by disturbed bugs, and whether this compound disrupts sexual attraction of L. pabulinus males towards females. 2 Undisturbed males and females, and disturbed males released less than 100 ng/h hexyl butanoate, whereas disturbed females released a highly variable amount, ranging from 25 ng/h to more than 1 μg/h. 3 In the field, traps with virgin females and rubber septa containing 20 mg hexyl butanoate, caught a total of one male in a month. In control traps without hexyl butanoate, 36 males were caught in the same period. 4 In Y‐track olfactometer tests, males were not attracted to virgin females when a dispenser with 20 mg hexyl butanoate was placed in the bottle with females. Males were attracted to females when the dispenser was placed downwind from the females, but upwind from the point of male release. 5 These results suggest that males are not repelled by hexyl butanoate, but that this compound inhibits sex pheromone release in females. Application possibilities for pest management are discussed.     

粉红粘帚霉菌丝体化学成分研究*

用柱层析色谱进行分离,光谱和化学方法进行结构鉴定,从一种明显促进花叶开唇兰Anoectochilus roxburghii (Wall.)Lindl.生长的粘帚霉属真菌——粉红粘帚霉Gliocladium roseum (Link) Bani.的菌丝体分离鉴定了1,3-二棕榈酰基-2-(4,4-二甲基庚二酸单酰基) 甘油酯(I),4,4-二甲基庚二酸(II)等4个化合物。其中,I为新化合物, II 为首次从本属分离得到的天然产物。     

粉红粘帚霉菌丝体化学成分研究

用柱层析色谱进行分离,光谱和化学方法进行结构鉴定,从一种明显促进花叶开唇兰Anoectochilus roxburghii (Wall.)Lindl.生长的粘帚霉属真菌——粉红粘帚霉Gliocladium roseum (Link) Bani.的菌丝体分离鉴定了1,3-二棕榈酰基-2-(4,4-二甲基庚二酸单酰基) 甘油酯(I),4,4-二甲基庚二酸(II)等4个化合物。其中,I为新化合物, II 为首次从本属分离得到的天然产物。     

Lipophilic compounds in femoral secretions of males and females of the El Hierro giant lizard Gallotia simonyi (Lacertidae)

Many lizards use femoral gland secretions in reliable intraspecific communication. Based on mass spectra, obtained by GC–MS, we found 57 lipophilic compounds in femoral secretions of males and females of El Hierro giant lizards, Gallotia simonyi (fam. Lacertidae). Compounds included steroids (mainly cholesterol) and fatty acids ranging between n-C₁₆ and n-C₂₂ (mainly hexadecanoic and octadecanoic acids), followed by aldehydes, alcohols, ketones, squalene and waxy esters. There were important intersexual differences in the presence, abundance and number of compounds (more numerous in males). Males had higher proportions of the most odoriferous compounds (fatty acids and aldehydes), while females had higher proportions of more stable compounds (steroids, waxy alcohols, waxy esters and terpenoids). This suggests sexual differences in function of femoral secretions. In addition, some compounds could reflect the physiological state, allowing monitoring health of lizards from secretions samples, which is especially important given the critical conservation status of this lizard.     

大叶桉叶水浸提液成分分析

为进一步明确大叶桉的化学成分,对大叶桉叶水浸提液分别用不同极性的有机溶剂石油醚、乙酸乙酯和正丁醇进行萃取,对各萃取相进行GC-MS分析。结果表明:大叶桉叶水浸提液共含有37种化合物,其中,石油醚萃取相中含有20种,主成分为草酸丁基异己酯(37.24%);乙酸乙酯萃取相中含有16种,主成分为2,2-二亚甲基双[6-(1,1-二甲基乙基-4-甲基)]-苯酚(50.05%);正丁醇萃取相中含有5种,主成分为丙基-2-甲基丁酸酯(54.57%)。在所有成分中,酯类物质居多,也有少量的烯、酮、醇、苯和烷烃。1-甲基,4-(1-甲基乙基)-1,4环己二烯、2,2-二亚甲基[6-(1,1-二甲基乙基)-4-甲基]苯酚、1-十八烯和二十烷为石油醚和乙酸乙酯的共有成分;1、2-苯二甲酸单(2-乙基己基)酯为乙酸乙酯和正丁醇的共有成分。该研究进一步明确了大叶桉的化学成分,为其在医药、化工和化感方面的应用研究奠定了基础。     

Synthesis and characterization of 3,13- and 2,13-octadecadienyl compounds for identification of the sex pheromone secreted by a clearwing moth, Nokona pernix

Several geometrical isomers of 3,13- and 2,13-octadecadien-1-ols and their acetates were synthesized starting from 1,8-octanediol or 1,9-nonanediol utilizing acetylene coupling reactions. In addition to commercially available compounds, all geometrical isomers of each dienyl compound were analyzed by NMR and GC-MS to accumulate chemical data for studies of sex pheromones secreted from clearwing moths classified into the family Sesiidae of Lepidoptera. Although acetoxy derivatives of the 3,13- and 2,13-dienes showed almost the same mass spectra, the alcohols were distinguished by comparing the relative intensities of [M-18](+) at m/z 248, indicating direct differentiation of the two positional isomers without derivatization. Furthermore, each geometrical isomer eluted from a high-polar GC column with a different retention time. Base on these data, a pheromone gland extract of a sesiid moth, Nokona pernix, was analyzed by GC-EAD and GC-MS, and two EAG-active components were identified, viz., the (3E,13Z)- and (3Z,13Z)-isomers of 3,13-octadecadien-1-ol in a ratio of 9:1. In the field, the synthetic compounds mixed in 9:1 ratio attracted N. pernix males well, while a single component scarcely attracted the males. The number of attracted males peaked in the middle of June, and a small second peak was observed in August.     

Responses to Femoral Gland Secretions by Visually Adept Male and Female Collared Lizards

Although visually transmitted social signals are well documented in many diurnal iguanians, including collared lizards, secretory femoral glands also suggest a role of chemical signals in intraspecific communication. We conducted laboratory trials to test the extent to which male and female collared lizards responded by tongue‐flicking femoral gland secretions, neutral (water), and odoriferous (cologne) control substances, males distinguished self‐secretions from those produced by unfamiliar rival males, and females distinguish secretions from unfamiliar vs. familiar males. Both males and females spent similar amounts of time in four arena quadrants each with a Petri dish treated with one of the four test compounds. Males gave more tongue flicks/trial to secretions produced by unfamiliar rivals and cologne than they tongue‐flicked their own secretions and water. By contrast, the number of tongue flicks by females on control substances and familiar and unfamiliar males was similar. Results support the hypothesis that femoral gland secretions function in intrasexual signaling among male collared lizards, perhaps allowing them to distinguish unfamiliar rivals. Females tongue‐flicked secretions from familiar and unfamiliar males with similar frequency that was high relative to that of males, suggesting a possible role of secretions in assessment of males. Ours is the first evidence of a signaling role of femoral gland secretions in collared lizards and adds to a growing body of evidence that chemical signaling has evolved in diurnal lizards that also have highly developed visual‐based signaling.     

Mutagenicity of the anticancer drug, caracemide, and related compounds for salmonella

Caracemide, MeCON(CONHMe)(OCONHMe) (I), is a novel anticancer drug. Since it was derived from acetohydroxamic acid (II), a known mutagen, its potential metabolites and related compounds were synthesized and tested for mutagenicities in S. typhimurium TA98 and TA100. These compounds were: MeNHCONH(OCONHMe) (III), MeCONH(OCONHMe) (IV), MeCONOH(CONHMe) (V), MeNHCOONH2 X HCl (VI), MeNHCONHOH (VII), MeNHCOON(CONHMe)2 (VIII), and NOH(CONHMe)2 (IX). The mutagenicities in the absence of rat liver homogenate were: (VI) much greater than (IV) greater than (II), (III), (V). The other compounds were not mutagenic. (I) was mutagenic only in the presence of rat liver homogenate. The doses required to demonstrate mutagenicities of these compounds were from 0.05 to 5 mumoles/plate. The major hydrolytic products at 25 degrees C, pH 7, were (III), (IV), and (V) from (I); (II) and (III) from (IV); and (II), (III), (VII) and MeNHCONH(OCOMe) (X) from (V). (III) was stable at pH 7. Treatment of (IV) with HCl yielded (VI). Hydrolysis of (III) or (V) with ammonia yielded (VII). These results suggest that caracemide may be activated enzymatically or nonenzymatically by deacetylation or decarbamoylation, and its anticancer activity may be related to the reactivity of its metabolites with DNA. The synthetic procedures and characterizations of new compounds (IV), (V) and (X) are described.     

Inhibitory effect of sulfur-containing compounds in Scorodocarpus borneensis Becc. on the aggregation of rabbit platelets

The inhibitory effects of three pure compounds isolated from wood garlic, 2,4,5-trithiahexane (I), 2,4,5,7-tetrathiaoctane (II), and 2,4,5,7-tetrathiaoctane 2,2-dioxide (III), on rabbit platelet aggregation induced by collagen, arachidonic acid, U46619, ADP (adenosine 5'-diphosphate), PAF (platelet aggregating factor), and thrombin were studied in vitro. The anti-aggregating activity of 2,4,5,7-tetrathiaoctane 4,4-dioxide (IV) was also measured with collagen and arachidonic acid. I, II, III, and IV inhibited the platelet aggregation induced by all tested agonists. I, II, and III exhibited a stronger inhibitory effect against the thrombin-induced aggregation of GFP (gel-filtered platelets) than against the aggregation induced by the other agonists. Notably, the IC50 value for III was 4 microM, which is approximately 2.5 times stronger than MATS (methyl allyl trisulfide), a major anti-platelet compound isolated from garlic. In inhibiting collagen-induced aggregation, II was as potent as MATS and aspirin, with a marked disaggregation effect on the secondary aggregation by arachidonic acid, at the rate of 47.05%/min at a concentration of 10(-4) M. I, II, and III also suppressed U46619-induced aggregation. These results suggest that sulfur-containing compounds in wood garlic not only inhibit arachidonic acid metabolism but also suppress aggregation in association with the function of the platelet plasma membrane.     

发酵无花果香料的挥发性成分分析

利用微生物发酵无花果开发特色香料,并采用同时蒸馏萃取装置收集挥发性成分并用气相色谱一质谱仪对生物技术制备的无花果香料挥发性成分进行分离和鉴定,经毛细管色谱分离出47种组分,确认了其中的45种成分,并用面积归一化法测定了各种成分的百分含量,其主要成分为：9,12-十八碳二烯酸乙酯(27．34％)、十六酸乙酯(23．99％)、邻苯二甲酸二丁酯(6．18％)、邻苯二甲酸二异丁酯(5．52％)、9,12-十八碳二烯酸甲酯(4．72％)、十六酸甲酯(4．67％)、9,12,15-十八碳三烯酸乙酯(4．48％)、9-十八碳烯酸乙酯(3．80％)、糠醛(2．53％)、9,12,15-十八碳三烯酸甲酯(1．85％)、十八酸乙酯(1．42％)、9-十八碳烯酸甲酯(1．26％)等。     

Histochemical analysis of accessory genital gland secretions in female Pimpla turionellae L. (Hymenoptera: Ichneumonidae)

The secretions produced by the 3 accessory glands of the female genital tract of Pimpla turionellae were investigated histochemically. The uterus gland secretion was identified as a mixture of hyaluronic acid and lipoprotein, that of the poison gland as a neutral mucoprotein. The product of the alkaline gland (Dufour's gland) consists of lecithin and a cholesterol ester. Pimpla females, as parasites of Lepidoptera pupae, inject these secretions into the host hemocoel during oviposition, thus preventing hemocytic encapsulation of their eggs. The physiological functions of the secretions are briefly discussed.