ChemWiki - User contributions [en]

It:knots

2006-12-08T01:19:52Z

Dswl05: Synthetic Route Diagram

===knots===

[[Image:knots.jpg|thumb|left|300|reference1]]
The simplest knotted molecule so far.

Reference
1. http://plus.maths.org/issue15/features/knots/index.html

= Introduction =

Knots are objects with no loose ends and can be tied together to create complicated knots or links. Do such objects exist at a molecular scale and if possible, how can such objects be explained by theory and investigated experimentally? A set of methods is needed for the synthesis of molecular knots.
<table border="0" cellpadding=10>
<tr>

<td>
{| border="1" style="fix: right; clear: left; margin: 1 1 1em 1em; border-collapse: collapse;"
! [[Image:Knots.gif|thumb|200px|center|Types of knots]]
|-
! ''[http://www.rsc.org/delivery/_ArticleLinking/DisplayHTMLArticleforfree.cfm?JournalCode=NJ&Year=2006&ManuscriptID=b601895e&Iss=6]''
|}
</td>

<td>
<div align=justify>

= Knot Theory =

The mathematical theory, the knot theory, of knots and links came from physics. W. Thromson (later known as Lord Kelvin) started studying knots as a potential model for atoms in the last third of the 19th century. He prepared tabulations of knots with crossing number n, prime knots n<sub>k</sub>, where k is a counting index for prime knots and n ranges from 3 to 7 (as shown in the figure of knots above). The prime knots can be combined to create more complex knots, called composite knots n<sub>k</sub>m<sub>l</sub> or l-component links, n<sup>l</sup><sub>k</sub>.
Today the knot theory is mostly used to classify knots and to find knot invariants. These invariants allow us to decide whether 2 given knots are identical or interconvertible.
</div>
</td>

</tr>
</table>

<table border="0" cellpadding=10>
<tr>

<td>
A universal invariant has not been discovered but many different levels of invariants are already well-studied. The knot theory is a well established part of topology, and from such a viewpoint, representing a particular knot or link with a rope, or necklace-like string with beads has become entirely unimportant(shown on the right).
Today, different types of knotted molecules can be successfully synthesised under controlled conditions. They depend on self-assembly and 3D template effects, the effect in metal-ligand complexes, the directional nature of hyderogen bonds ,the pi-pi stacking interaction in aromatic systems and the self-assemply of amide groups.
</td>

<td>
<div align=justify>

{| border="1" style="fix: right; clear: left; margin: 1 1 1em 1em; border-collapse: collapse;"
! [[Image:Knots2.gif|thumb|100px|center]]
|-
! ''[http://www.rsc.org/delivery/_ArticleLinking/DisplayHTMLArticleforfree.cfm?JournalCode=NJ&Year=2006&ManuscriptID=b601895e&Iss=6]''
|}
</div>
</td>

</tr>
</table>

The following figure shows molecules that can only be understood theoretically: hydrogenated sections of single-walled carbon nanotubes, new forms of P and S, and a [2]-catenane created from 2 cycloalkanethiole molecules.
{| border="1" style="fix: right; clear: left; margin: 1 1 1em 1em; border-collapse: collapse;"
! [[Image:Knots3.gif|thumb|300px|center]]
|-
! ''[http://www.rsc.org/delivery/_ArticleLinking/DisplayHTMLArticleforfree.cfm?JournalCode=NJ&Year=2006&ManuscriptID=b601895e&Iss=6]''
|}

= Synthesis of Knots and Links =

Many synthetic routes have been suggested. One suggested route involves covering surface regularly with linker groups. The arrangement of these groups then offers a template for the systematic directed and controlled synthesis of knots at a molecular scale. This technique is known as the surface template technique.

Prior to employment of this technique requires the matery of sophisticated chemical experimental skills, some of which have already been established, while some are still under development in the field of nanotechnology. The application of surface template can only be performed at ease with further development of these skills.

Protection group, tunneling microscope and single-molecule detection and manipulation techniques are also required. Only now can it be possible to use a range of both organic and inorganic monomers to form homo- and hetero-oligomeric states of knots and links.

The figure below displays the surface technique with 4 exmaples of the generation of molecular knots: trivial 0<sub>1</sub>, trefoil 3<sub>1</sub>, Hopf link 2<sup>2</sup><sub>1</sub> and "fabric in plain weave"-like knot. In each synthesis, 4 steps of the techniques are shown.
{| border="1" style="fix: right; clear: left; margin: 1 1 1em 1em; border-collapse: collapse;"
! [[Image:Knots4.gif|thumb|400px|center|Assumption: Groups on the surface are in a square lattice]]
|-
! ''[http://www.rsc.org/delivery/_ArticleLinking/DisplayHTMLArticleforfree.cfm?JournalCode=NJ&Year=2006&ManuscriptID=b601895e&Iss=6]''
|}

= Tying a Molecular Knot =
[[Image:Knots5.GIF]]

= Synthetic Scheme for a Chiral Trefoil Knot =

The simplest knot synthesised to date was reported by Reuter et al. in 2000<sup>1</sup>. By combining the acid dichloride and diamine reactants in highly diluted conditions, without auxiliary components (a method of self organisation known as 'self-templating), a three-component mixture comprising a large cyclic tetra-amide, a rotaxane and the trefoil knot in 20% yield was obtained.

[[Image:Syntheticschememolecularknots.JPG]]

Reuters et al.

Recently, Fenlen et al.<sup>2</sup> have claimed to have created an even simpler trefoil knot. The group's target molecule is a hydrocarbon with 63 carbon atoms in its backbone (the simplest knot theorised has 50 carbon atoms in its backbone) and would be the first hydrocarbon molecular knot and if successfully characterised, would be the simplest knot synthesised.

= Applications =

Tying a molecular knot is more than an esoteric experiment in theory. It is believed that the curvature in molecular knotting directs the interaction of intracellular filaments and their associated proteins and ligands. It has been noted that RNA polymerase dissociates from DNA when the strand of DNA is straightened.<sup>3</sup> Further quantitative analysis of association constants at varying curvatures will be useful in the understanding the interaction between proteins and cytoskeletal filaments.

Knotting can also be used as a tool to probe the mechanics of biological phenomena on the molecular level. Suggestions have included using molecular knots to mimic cytokinesis or artificial compartmentalisation by looping them around cells, or using natural strands such as actin filaments to bundle DNA.<sup>4</sup>

= Conclusion =

The synthesis of molecular knots relies on complicated mathematical calculations. Molecular knots are believed to represent the local minima on potential energy hypersurfaces.

= Acknowledgement =
[http://http://www.rsc.org/delivery/_ArticleLinking/DisplayHTMLArticleforfree.cfm?JournalCode=NJ&Year=2006&ManuscriptID=b601895e&Iss=6 Molecular knots, links, and fabrics: prediction of existence and suggestion of a synthetic route by Dirk Andrae]

Pictures of tying a molecular knot can be found in the following link:
[http://www.nature.com/nature/journal/v399/n6735/full/399446a0.html Tying a molecular knot with optical tweezers]

and [http://www.lps.ens.fr/~vincent/smb/PDF/kino-knot.pdf Journal on Tying a molecular knot with optical tweezers]

= References =

1. C Reuter, R Schmieder, F Vogtle. From rotaxanes to knots. Templating, hydrogen bond patterns and cyclochirality. Pure Appl. Chem., 2000, 72, 2233-41

2. [http://www.fandm.edu/x13247.xml Franklin & Marshall News: Chemistry Professor Ties World's Smallest Knot]

3. Harada, Y.et al. Single-molecule imaging of RNA polymerase-DNA interactions in real time. Biophys. J. 1999, 76, 709–715

4. Yasuharu Arai1, Ryohei Yasuda, Ken-ichirou Akashi, Yoshie Harada, Hidetake Miyata1, Kazuhiko Kinosita, Jr and Hiroyasu Itoh. Tying a Molecular Knot with Optical Tweezers. Nature 399, 446-448 (3 June 1999)

2006-10-23T15:04:36Z

Dswl05:

It:Gossypol

2006-10-23T14:56:23Z

Dswl05:

== Abstract ==

Gossypol is a polyphenol extracted from plants of the genus Gossypium, Malvaceae (commonly known as cottonseed plant). Gossypol is believed to act as an inhibitor of dehydrogenases and thus destroys cellular energy. One of the main applications of Gossypol in the industry is as a male contraceptive, most widely manufactured in China.

Chemical name: 2,2'-bis-(Formyl-1,6,7-trihydroxy-5-isopropyl-3-methylnaphthalene)

The (-) isomer of acts as a contraceptive whereas the (+) isomer is a toxin.

== Structure ==
{| class="toccolours" border="1" style="fix: right; clear: left; margin: 1 1 1em 1em; border-collapse: collapse;"
|+ '''Gossypol'''
! [[Image:Wiki_gosspol.gif]]!! <jmol>
<jmolApplet>
<size>300</size>
<color>black</color>
<script>zoom 80; bns on;frame 1; move 10 -20 10 0 0 0 0 0 3; delay 1;</script>
<inlineContents>water.mol
title1
title2
71 70 0 0 0 0 0 0 0 0 0 0
0.7498 0.7380 0.5973 C 0 0 0 0 0 0 0 0 0 0 0 0
0.2538 -0.5230 0.3153 C 0 0 0 0 0 0 0 0 0 0 0 0
0.7008 -1.6210 1.0873 C 0 0 0 0 0 0 0 0 0 0 0 0
1.6328 -1.4230 2.0673 C 0 0 0 0 0 0 0 0 0 0 0 0
3.2158 -0.0000 3.3443 C 0 0 0 0 0 0 0 0 0 0 0 0
3.6718 1.2570 3.5933 C 0 0 0 0 0 0 0 0 0 0 0 0
3.1688 2.3950 2.9433 C 0 0 0 0 0 0 0 0 0 0 0 0
2.2128 2.3060 1.9403 C 0 0 0 0 0 0 0 0 0 0 0 0
1.6918 0.9850 1.6193 C 0 0 0 0 0 0 0 0 0 0 0 0
2.1768 -0.1500 2.3483 C 0 0 0 0 0 0 0 0 0 0 0 0
-0.1712 -0.9620 -2.0767 C 0 0 0 0 0 0 0 0 0 0 0 0
-0.6912 -0.7180 -0.8287 C 0 0 0 0 0 0 0 0 0 0 0 0
-2.0982 -0.6810 -0.6647 C 0 0 0 0 0 0 0 0 0 0 0 0
-2.8902 -0.9380 -1.7477 C 0 0 0 0 0 0 0 0 0 0 0 0
-3.2422 -1.4910 -4.1577 C 0 0 0 0 0 0 0 0 0 0 0 0
-2.6942 -1.6870 -5.3787 C 0 0 0 0 0 0 0 0 0 0 0 0
-1.3042 -1.5370 -5.6077 C 0 0 0 0 0 0 0 0 0 0 0 0
-0.4272 -1.2510 -4.5697 C 0 0 0 0 0 0 0 0 0 0 0 0
-0.9672 -1.1180 -3.2377 C 0 0 0 0 0 0 0 0 0 0 0 0
-2.3732 -1.1800 -3.0437 C 0 0 0 0 0 0 0 0 0 0 0 0
0.1358 -3.0140 0.8133 C 0 0 0 0 0 0 0 0 0 0 0 0
1.7938 3.5600 1.3443 C 0 0 0 0 0 0 0 0 0 0 0 0
3.8168 -1.1790 4.0863 C 0 0 0 0 0 0 0 0 0 0 0 0
5.2908 -1.3470 3.8143 C 0 0 0 0 0 0 0 0 0 0 0 0
3.5188 -1.1650 5.5613 C 0 0 0 0 0 0 0 0 0 0 0 0
-2.7042 -0.3820 0.7003 C 0 0 0 0 0 0 0 0 0 0 0 0
0.9438 -0.9780 -4.9517 C 0 0 0 0 0 0 0 0 0 0 0 0
-4.7402 -1.6550 -3.9647 C 0 0 0 0 0 0 0 0 0 0 0 0
-5.5372 -0.6900 -4.7897 C 0 0 0 0 0 0 0 0 0 0 0 0
-5.1692 -3.0650 -4.1717 C 0 0 0 0 0 0 0 0 0 0 0 0
0.3338 1.8200 -0.1267 O 0 0 0 0 0 0 0 0 0 0 0 0
2.2348 4.6650 1.6713 O 0 0 0 0 0 0 0 0 0 0 0 0
3.6998 3.5580 3.3573 O 0 0 0 0 0 0 0 0 0 0 0 0
4.6318 1.4810 4.5573 O 0 0 0 0 0 0 0 0 0 0 0 0
1.1938 -1.1050 -2.2307 O 0 0 0 0 0 0 0 0 0 0 0 0
1.3808 -1.1380 -6.0917 O 0 0 0 0 0 0 0 0 0 0 0 0
-0.9042 -1.6750 -6.8807 O 0 0 0 0 0 0 0 0 0 0 0 0
-3.4602 -2.0440 -6.4577 O 0 0 0 0 0 0 0 0 0 0 0 0
1.9638 -2.2670 2.6513 H 0 0 0 0 0 0 0 0 0 0 0 0
-3.9612 -0.9580 -1.6057 H 0 0 0 0 0 0 0 0 0 0 0 0
-0.9002 -3.0690 1.0983 H 0 0 0 0 0 0 0 0 0 0 0 0
0.6968 -3.7660 1.3393 H 0 0 0 0 0 0 0 0 0 0 0 0
0.2498 -3.1330 -0.2807 H 0 0 0 0 0 0 0 0 0 0 0 0
1.0488 3.5230 0.5623 H 0 0 0 0 0 0 0 0 0 0 0 0
3.3968 -2.0370 3.7753 H 0 0 0 0 0 0 0 0 0 0 0 0
5.3518 -1.4990 2.7583 H 0 0 0 0 0 0 0 0 0 0 0 0
5.6928 -2.2640 4.2303 H 0 0 0 0 0 0 0 0 0 0 0 0
5.7998 -0.4280 4.1903 H 0 0 0 0 0 0 0 0 0 0 0 0
2.5358 -0.9760 5.7973 H 0 0 0 0 0 0 0 0 0 0 0 0
4.0508 -0.2240 5.8903 H 0 0 0 0 0 0 0 0 0 0 0 0
3.8668 -2.0240 6.0913 H 0 0 0 0 0 0 0 0 0 0 0 0
-3.6592 -0.3550 0.6033 H 0 0 0 0 0 0 0 0 0 0 0 0
-2.4422 0.6230 0.9773 H 0 0 0 0 0 0 0 0 0 0 0 0
-2.3242 -1.1830 1.2853 H 0 0 0 0 0 0 0 0 0 0 0 0
1.6208 -0.6090 -4.1897 H 0 0 0 0 0 0 0 0 0 0 0 0
-4.9462 -1.4070 -2.9317 H 0 0 0 0 0 0 0 0 0 0 0 0
-5.2242 0.2920 -4.3637 H 0 0 0 0 0 0 0 0 0 0 0 0
-6.5322 -0.7500 -4.4837 H 0 0 0 0 0 0 0 0 0 0 0 0
-5.4112 -0.7890 -5.9167 H 0 0 0 0 0 0 0 0 0 0 0 0
-4.6452 -3.7870 -3.6137 H 0 0 0 0 0 0 0 0 0 0 0 0
-4.9552 -3.3100 -5.2607 H 0 0 0 0 0 0 0 0 0 0 0 0
-6.1692 -3.1490 -3.9887 H 0 0 0 0 0 0 0 0 0 0 0 0
-0.1652 1.5730 -0.8157 H 0 0 0 0 0 0 0 0 0 0 0 0
3.1858 4.2730 2.7443 H 0 0 0 0 0 0 0 0 0 0 0 0
5.0608 2.4590 4.4183 H 0 0 0 0 0 0 0 0 0 0 0 0
1.5708 -0.9000 -1.5387 H 0 0 0 0 0 0 0 0 0 0 0 0
0.0858 -1.4660 -6.9737 H 0 0 0 0 0 0 0 0 0 0 0 0
-2.8932 -1.8450 -7.1217 H 0 0 0 0 0 0 0 0 0 0 0 0
-5.4154 -0.8438 -5.8415 H 0 0 0 0 0 0 0 0 0 0 0 0
-4.9355 -3.2804 -5.1934 H 0 0 0 0 0 0 0 0 0 0 0 0
4.9775 0.6403 4.8661 H 0 0 0 0 0 0 0 0 0 0 0 0
1 2 2 0 0 0 0
1 9 4 0 0 0 0
1 31 1 0 0 0 0
2 3 4 0 0 0 0
2 12 1 0 0 0 0
3 4 2 0 0 0 0
3 21 1 0 0 0 0
4 10 4 0 0 0 0
4 39 1 0 0 0 0
5 6 2 0 0 0 0
5 10 4 0 0 0 0
5 23 1 0 0 0 0
6 7 4 0 0 0 0
6 34 1 0 0 0 0
7 8 4 0 0 0 0
7 33 4 0 0 0 0
8 9 1 0 0 0 0
8 22 1 0 0 0 0
9 10 4 0 0 0 0
11 12 2 0 0 0 0
11 19 4 0 0 0 0
11 35 1 0 0 0 0
12 13 4 0 0 0 0
13 14 2 0 0 0 0
13 26 1 0 0 0 0
14 20 4 0 0 0 0
14 40 1 0 0 0 0
15 16 2 0 0 0 0
15 20 4 0 0 0 0
15 28 1 0 0 0 0
16 17 4 0 0 0 0
16 38 1 0 0 0 0
17 18 4 0 0 0 0
17 37 4 0 0 0 0
18 19 4 0 0 0 0
18 27 1 0 0 0 0
19 20 4 0 0 0 0
21 41 1 0 0 0 0
21 42 1 0 0 0 0
21 43 1 0 0 0 0
22 32 2 0 0 0 0
22 44 1 0 0 0 0
23 24 1 0 0 0 0
23 25 1 0 0 0 0
23 45 1 0 0 0 0
24 46 1 0 0 0 0
24 47 1 0 0 0 0
24 48 1 0 0 0 0
25 49 1 0 0 0 0
25 50 1 0 0 0 0
25 51 1 0 0 0 0
26 52 1 0 0 0 0
26 53 1 0 0 0 0
26 54 1 0 0 0 0
27 36 2 0 0 0 0
27 55 1 0 0 0 0
28 29 1 0 0 0 0
28 30 1 0 0 0 0
28 56 1 0 0 0 0
29 57 1 0 0 0 0
29 58 1 0 0 0 0
29 69 1 0 0 0 0
30 60 1 0 0 0 0
30 62 1 0 0 0 0
30 70 1 0 0 0 0
31 63 1 0 0 0 0
34 71 1 0 0 0 0
35 66 1 0 0 0 0
37 67 1 0 0 0 0
38 68 1 0 0 0 0
M END</inlineContents>
</jmolApplet>
</jmol>
|- align="center"
| '''2D Structure'''
| '''3D Structure'''
|}

Molecular Weight: 518.5634<br />
Molecular Formula: C<sub>30</sub>H<sub>30</sub>O<sub>8</sub><br />
Melting Point: 177 - 182 C

== How Gossypol Works ==
<table border="0" cellpadding=10>
<tr>

<td>
{| border="1" style="fix: right; clear: left; margin: 1 1 1em 1em; border-collapse: collapse;"
! [[Image:CLBphoto5.jpg|thumb|150px|center|Gossypol Expression in Cotton]]
|-
! ''[http://www.anbg.gov.au anbg.gov.au]''
|}
</td>

<td>
<div align=justify>
'''Gossypol suppresses P24Ag in semen.'''<br />

Appropriate quantities of Gossypol acetate (gp) suppress P24Ag in semen of HIV(+) men. Gp has shown its role as an inhibitor on the replication of HIV. It has been found that 15 out of 18 test subjects have shown P24Ag (-) in their semen and it remained consistent while taking gp. However this test was discontinued when AIDs symptoms was found in 10 of the 18 patients and 5 developed infections including PCP, pulmonary tuberculosis, cryptosporidium and CMV enteritis, esophageal candida.
</div>
</td>

</tr>
</table>

== Uses and Dosage ==

The amount of Gossypol to intake depends on the strength of the medicine and the reason for intake. Follow the instructions on the medicine bottle if not advised by a caregiver or doctor.

Heat or moisture might lead to breakdown of the medicine and it might not function as normal. Keep the medicine locked and beyond the reach of children.
Do not take Gossypol without a doctor's advice if you are taking:
* Digoxin
* Water Pills
* Iron
* Isoproterenol
* Medicine for pain or swelling
* Potassium
* Alcohol / Breastfeeding

Possible Side Effects:
* Breathing problems or chest pains
* Hives, rash and swollen skin
* Muscle Weakness
* Hair Loss, nausea, or bowel problems.

== Synthetic Studies ==

Various studies have undertaken the task of the total synthesis of Gossypol. In 1937 Adams and Geissman<sup>1</sup> proposed the following scheme which synthesises Gossypol via its derivative Desapogossypolone tetramethyl ether.

[[Image:gossypolsynthesis1.gif]]

== References ==

1. R. Adams, T. A. Geissman; Structure of Gossypol. XXIII. Attempts to Prepare Desapogossypolone Tetramethyl Ether. Condensation of Hexadiene-2,4 with Dibenzoethylene; J. Am Chem Soc, 1939, 2038

It:Gossypol

2006-10-23T14:51:29Z

Dswl05:

== Abstract ==

Gossypol is a polyphenol extracted from plants of the genus Gossypium, Malvaceae (commonly known as cottonseed plant). Gossypol is believed to act as an inhibitor of dehydrogenases and thus destroys cellular energy. One of the main applications of Gossypol in the industry is as a male contraceptive, most widely manufactured in China.

Chemical name: 2,2'-bis-(Formyl-1,6,7-trihydroxy-5-isopropyl-3-methylnaphthalene)

The (-) isomer of acts as a contraceptive whereas the (+) isomer is a toxin.

== Structure ==
{| class="toccolours" border="1" style="fix: right; clear: left; margin: 1 1 1em 1em; border-collapse: collapse;"
|+ '''Gossypol'''
! [[Image:Wiki_gosspol.gif]]!! <jmol>
<jmolApplet>
<size>300</size>
<color>black</color>
<script>zoom 80; bns on;frame 1; move 10 -20 10 0 0 0 0 0 3; delay 1;</script>
<inlineContents>water.mol
title1
title2
71 70 0 0 0 0 0 0 0 0 0 0
0.7498 0.7380 0.5973 C 0 0 0 0 0 0 0 0 0 0 0 0
0.2538 -0.5230 0.3153 C 0 0 0 0 0 0 0 0 0 0 0 0
0.7008 -1.6210 1.0873 C 0 0 0 0 0 0 0 0 0 0 0 0
1.6328 -1.4230 2.0673 C 0 0 0 0 0 0 0 0 0 0 0 0
3.2158 -0.0000 3.3443 C 0 0 0 0 0 0 0 0 0 0 0 0
3.6718 1.2570 3.5933 C 0 0 0 0 0 0 0 0 0 0 0 0
3.1688 2.3950 2.9433 C 0 0 0 0 0 0 0 0 0 0 0 0
2.2128 2.3060 1.9403 C 0 0 0 0 0 0 0 0 0 0 0 0
1.6918 0.9850 1.6193 C 0 0 0 0 0 0 0 0 0 0 0 0
2.1768 -0.1500 2.3483 C 0 0 0 0 0 0 0 0 0 0 0 0
-0.1712 -0.9620 -2.0767 C 0 0 0 0 0 0 0 0 0 0 0 0
-0.6912 -0.7180 -0.8287 C 0 0 0 0 0 0 0 0 0 0 0 0
-2.0982 -0.6810 -0.6647 C 0 0 0 0 0 0 0 0 0 0 0 0
-2.8902 -0.9380 -1.7477 C 0 0 0 0 0 0 0 0 0 0 0 0
-3.2422 -1.4910 -4.1577 C 0 0 0 0 0 0 0 0 0 0 0 0
-2.6942 -1.6870 -5.3787 C 0 0 0 0 0 0 0 0 0 0 0 0
-1.3042 -1.5370 -5.6077 C 0 0 0 0 0 0 0 0 0 0 0 0
-0.4272 -1.2510 -4.5697 C 0 0 0 0 0 0 0 0 0 0 0 0
-0.9672 -1.1180 -3.2377 C 0 0 0 0 0 0 0 0 0 0 0 0
-2.3732 -1.1800 -3.0437 C 0 0 0 0 0 0 0 0 0 0 0 0
0.1358 -3.0140 0.8133 C 0 0 0 0 0 0 0 0 0 0 0 0
1.7938 3.5600 1.3443 C 0 0 0 0 0 0 0 0 0 0 0 0
3.8168 -1.1790 4.0863 C 0 0 0 0 0 0 0 0 0 0 0 0
5.2908 -1.3470 3.8143 C 0 0 0 0 0 0 0 0 0 0 0 0
3.5188 -1.1650 5.5613 C 0 0 0 0 0 0 0 0 0 0 0 0
-2.7042 -0.3820 0.7003 C 0 0 0 0 0 0 0 0 0 0 0 0
0.9438 -0.9780 -4.9517 C 0 0 0 0 0 0 0 0 0 0 0 0
-4.7402 -1.6550 -3.9647 C 0 0 0 0 0 0 0 0 0 0 0 0
-5.5372 -0.6900 -4.7897 C 0 0 0 0 0 0 0 0 0 0 0 0
-5.1692 -3.0650 -4.1717 C 0 0 0 0 0 0 0 0 0 0 0 0
0.3338 1.8200 -0.1267 O 0 0 0 0 0 0 0 0 0 0 0 0
2.2348 4.6650 1.6713 O 0 0 0 0 0 0 0 0 0 0 0 0
3.6998 3.5580 3.3573 O 0 0 0 0 0 0 0 0 0 0 0 0
4.6318 1.4810 4.5573 O 0 0 0 0 0 0 0 0 0 0 0 0
1.1938 -1.1050 -2.2307 O 0 0 0 0 0 0 0 0 0 0 0 0
1.3808 -1.1380 -6.0917 O 0 0 0 0 0 0 0 0 0 0 0 0
-0.9042 -1.6750 -6.8807 O 0 0 0 0 0 0 0 0 0 0 0 0
-3.4602 -2.0440 -6.4577 O 0 0 0 0 0 0 0 0 0 0 0 0
1.9638 -2.2670 2.6513 H 0 0 0 0 0 0 0 0 0 0 0 0
-3.9612 -0.9580 -1.6057 H 0 0 0 0 0 0 0 0 0 0 0 0
-0.9002 -3.0690 1.0983 H 0 0 0 0 0 0 0 0 0 0 0 0
0.6968 -3.7660 1.3393 H 0 0 0 0 0 0 0 0 0 0 0 0
0.2498 -3.1330 -0.2807 H 0 0 0 0 0 0 0 0 0 0 0 0
1.0488 3.5230 0.5623 H 0 0 0 0 0 0 0 0 0 0 0 0
3.3968 -2.0370 3.7753 H 0 0 0 0 0 0 0 0 0 0 0 0
5.3518 -1.4990 2.7583 H 0 0 0 0 0 0 0 0 0 0 0 0
5.6928 -2.2640 4.2303 H 0 0 0 0 0 0 0 0 0 0 0 0
5.7998 -0.4280 4.1903 H 0 0 0 0 0 0 0 0 0 0 0 0
2.5358 -0.9760 5.7973 H 0 0 0 0 0 0 0 0 0 0 0 0
4.0508 -0.2240 5.8903 H 0 0 0 0 0 0 0 0 0 0 0 0
3.8668 -2.0240 6.0913 H 0 0 0 0 0 0 0 0 0 0 0 0
-3.6592 -0.3550 0.6033 H 0 0 0 0 0 0 0 0 0 0 0 0
-2.4422 0.6230 0.9773 H 0 0 0 0 0 0 0 0 0 0 0 0
-2.3242 -1.1830 1.2853 H 0 0 0 0 0 0 0 0 0 0 0 0
1.6208 -0.6090 -4.1897 H 0 0 0 0 0 0 0 0 0 0 0 0
-4.9462 -1.4070 -2.9317 H 0 0 0 0 0 0 0 0 0 0 0 0
-5.2242 0.2920 -4.3637 H 0 0 0 0 0 0 0 0 0 0 0 0
-6.5322 -0.7500 -4.4837 H 0 0 0 0 0 0 0 0 0 0 0 0
-5.4112 -0.7890 -5.9167 H 0 0 0 0 0 0 0 0 0 0 0 0
-4.6452 -3.7870 -3.6137 H 0 0 0 0 0 0 0 0 0 0 0 0
-4.9552 -3.3100 -5.2607 H 0 0 0 0 0 0 0 0 0 0 0 0
-6.1692 -3.1490 -3.9887 H 0 0 0 0 0 0 0 0 0 0 0 0
-0.1652 1.5730 -0.8157 H 0 0 0 0 0 0 0 0 0 0 0 0
3.1858 4.2730 2.7443 H 0 0 0 0 0 0 0 0 0 0 0 0
5.0608 2.4590 4.4183 H 0 0 0 0 0 0 0 0 0 0 0 0
1.5708 -0.9000 -1.5387 H 0 0 0 0 0 0 0 0 0 0 0 0
0.0858 -1.4660 -6.9737 H 0 0 0 0 0 0 0 0 0 0 0 0
-2.8932 -1.8450 -7.1217 H 0 0 0 0 0 0 0 0 0 0 0 0
-5.4154 -0.8438 -5.8415 H 0 0 0 0 0 0 0 0 0 0 0 0
-4.9355 -3.2804 -5.1934 H 0 0 0 0 0 0 0 0 0 0 0 0
4.9775 0.6403 4.8661 H 0 0 0 0 0 0 0 0 0 0 0 0
1 2 2 0 0 0 0
1 9 4 0 0 0 0
1 31 1 0 0 0 0
2 3 4 0 0 0 0
2 12 1 0 0 0 0
3 4 2 0 0 0 0
3 21 1 0 0 0 0
4 10 4 0 0 0 0
4 39 1 0 0 0 0
5 6 2 0 0 0 0
5 10 4 0 0 0 0
5 23 1 0 0 0 0
6 7 4 0 0 0 0
6 34 1 0 0 0 0
7 8 4 0 0 0 0
7 33 4 0 0 0 0
8 9 1 0 0 0 0
8 22 1 0 0 0 0
9 10 4 0 0 0 0
11 12 2 0 0 0 0
11 19 4 0 0 0 0
11 35 1 0 0 0 0
12 13 4 0 0 0 0
13 14 2 0 0 0 0
13 26 1 0 0 0 0
14 20 4 0 0 0 0
14 40 1 0 0 0 0
15 16 2 0 0 0 0
15 20 4 0 0 0 0
15 28 1 0 0 0 0
16 17 4 0 0 0 0
16 38 1 0 0 0 0
17 18 4 0 0 0 0
17 37 4 0 0 0 0
18 19 4 0 0 0 0
18 27 1 0 0 0 0
19 20 4 0 0 0 0
21 41 1 0 0 0 0
21 42 1 0 0 0 0
21 43 1 0 0 0 0
22 32 2 0 0 0 0
22 44 1 0 0 0 0
23 24 1 0 0 0 0
23 25 1 0 0 0 0
23 45 1 0 0 0 0
24 46 1 0 0 0 0
24 47 1 0 0 0 0
24 48 1 0 0 0 0
25 49 1 0 0 0 0
25 50 1 0 0 0 0
25 51 1 0 0 0 0
26 52 1 0 0 0 0
26 53 1 0 0 0 0
26 54 1 0 0 0 0
27 36 2 0 0 0 0
27 55 1 0 0 0 0
28 29 1 0 0 0 0
28 30 1 0 0 0 0
28 56 1 0 0 0 0
29 57 1 0 0 0 0
29 58 1 0 0 0 0
29 69 1 0 0 0 0
30 60 1 0 0 0 0
30 62 1 0 0 0 0
30 70 1 0 0 0 0
31 63 1 0 0 0 0
34 71 1 0 0 0 0
35 66 1 0 0 0 0
37 67 1 0 0 0 0
38 68 1 0 0 0 0
M END</inlineContents>
</jmolApplet>
</jmol>
|- align="center"
| '''2D Structure'''
| '''3D Structure'''
|}

Molecular Weight: 518.5634<br />
Molecular Formula: C<sub>30</sub>H<sub>30</sub>O<sub>8</sub><br />
Melting Point: 177 - 182 C

== How Gossypol Works ==
<table border="0" cellpadding=10>
<tr>

<td>
{| border="1" style="fix: right; clear: left; margin: 1 1 1em 1em; border-collapse: collapse;"
! [[Image:CLBphoto5.jpg|thumb|150px|center|Gossypol Expression in Cotton]]
|-
! ''[http://www.anbg.gov.au anbg.gov.au]''
|}
</td>

<td>
<div align=justify>
'''Gossypol suppresses P24Ag in semen.'''<br />

Appropriate quantities of Gossypol acetate (gp) suppress P24Ag in semen of HIV(+) men. Gp has shown its role as an inhibitor on the replication of HIV. It has been found that 15 out of 18 test subjects have shown P24Ag (-) in their semen and it remained consistent while taking gp. However this test was discontinued when AIDs symptoms was found in 10 of the 18 patients and 5 developed infections including PCP, pulmonary tuberculosis, cryptosporidium and CMV enteritis, esophageal candida.
</div>
</td>

</tr>
</table>

== Uses and Dosage ==

The amount of Gossypol to intake depends on the strength of the medicine and the reason for intake. Follow the instructions on the medicine bottle if not advised by a caregiver or doctor.

Heat or moisture might lead to breakdown of the medicine and it might not function as normal. Keep the medicine locked and beyond the reach of children.
Do not take Gossypol without a doctor's advice if you are taking:
* Digoxin
* Water Pills
* Iron
* Isoproterenol
* Medicine for pain or swelling
* Potassium
* Alcohol / Breastfeeding

Possible Side Effects:
* Breathing problems or chest pains
* Hives, rash and swollen skin
* Muscle Weakness
* Hair Loss, nausea, or bowel problems.

== Synthetic Studies ==

Various studies have undertaken the task of the total synthesis of Gossypol. In 1937 Adams and Geissman proposed the following scheme which synthesises Gossypol via its derivative Desapogossypolone tetramethyl ether.

[[Image:gossypolsynthesis1.gif]]

File:Gossypolsynthesis1.gif

2006-10-23T14:47:26Z

Dswl05: Synthethetic Scheme via Desapogossypolone Tetramethyl Ether

Synthethetic Scheme via Desapogossypolone Tetramethyl Ether

It:Gossypol

2006-10-23T14:46:29Z

Dswl05:

== Abstract ==

Gossypol is a polyphenol extracted from plants of the genus Gossypium, Malvaceae (commonly known as cottonseed plant). Gossypol is believed to act as an inhibitor of dehydrogenases and thus destroys cellular energy. One of the main applications of Gossypol in the industry is as a male contraceptive, most widely manufactured in China.

Chemical name: 2,2'-bis-(Formyl-1,6,7-trihydroxy-5-isopropyl-3-methylnaphthalene)

The (-) isomer of acts as a contraceptive whereas the (+) isomer is a toxin.

== Structure ==
{| class="toccolours" border="1" style="fix: right; clear: left; margin: 1 1 1em 1em; border-collapse: collapse;"
|+ '''Gossypol'''
! [[Image:Wiki_gosspol.gif]]!! <jmol>
<jmolApplet>
<size>300</size>
<color>black</color>
<script>zoom 80; bns on;frame 1; move 10 -20 10 0 0 0 0 0 3; delay 1;</script>
<inlineContents>water.mol
title1
title2
71 70 0 0 0 0 0 0 0 0 0 0
0.7498 0.7380 0.5973 C 0 0 0 0 0 0 0 0 0 0 0 0
0.2538 -0.5230 0.3153 C 0 0 0 0 0 0 0 0 0 0 0 0
0.7008 -1.6210 1.0873 C 0 0 0 0 0 0 0 0 0 0 0 0
1.6328 -1.4230 2.0673 C 0 0 0 0 0 0 0 0 0 0 0 0
3.2158 -0.0000 3.3443 C 0 0 0 0 0 0 0 0 0 0 0 0
3.6718 1.2570 3.5933 C 0 0 0 0 0 0 0 0 0 0 0 0
3.1688 2.3950 2.9433 C 0 0 0 0 0 0 0 0 0 0 0 0
2.2128 2.3060 1.9403 C 0 0 0 0 0 0 0 0 0 0 0 0
1.6918 0.9850 1.6193 C 0 0 0 0 0 0 0 0 0 0 0 0
2.1768 -0.1500 2.3483 C 0 0 0 0 0 0 0 0 0 0 0 0
-0.1712 -0.9620 -2.0767 C 0 0 0 0 0 0 0 0 0 0 0 0
-0.6912 -0.7180 -0.8287 C 0 0 0 0 0 0 0 0 0 0 0 0
-2.0982 -0.6810 -0.6647 C 0 0 0 0 0 0 0 0 0 0 0 0
-2.8902 -0.9380 -1.7477 C 0 0 0 0 0 0 0 0 0 0 0 0
-3.2422 -1.4910 -4.1577 C 0 0 0 0 0 0 0 0 0 0 0 0
-2.6942 -1.6870 -5.3787 C 0 0 0 0 0 0 0 0 0 0 0 0
-1.3042 -1.5370 -5.6077 C 0 0 0 0 0 0 0 0 0 0 0 0
-0.4272 -1.2510 -4.5697 C 0 0 0 0 0 0 0 0 0 0 0 0
-0.9672 -1.1180 -3.2377 C 0 0 0 0 0 0 0 0 0 0 0 0
-2.3732 -1.1800 -3.0437 C 0 0 0 0 0 0 0 0 0 0 0 0
0.1358 -3.0140 0.8133 C 0 0 0 0 0 0 0 0 0 0 0 0
1.7938 3.5600 1.3443 C 0 0 0 0 0 0 0 0 0 0 0 0
3.8168 -1.1790 4.0863 C 0 0 0 0 0 0 0 0 0 0 0 0
5.2908 -1.3470 3.8143 C 0 0 0 0 0 0 0 0 0 0 0 0
3.5188 -1.1650 5.5613 C 0 0 0 0 0 0 0 0 0 0 0 0
-2.7042 -0.3820 0.7003 C 0 0 0 0 0 0 0 0 0 0 0 0
0.9438 -0.9780 -4.9517 C 0 0 0 0 0 0 0 0 0 0 0 0
-4.7402 -1.6550 -3.9647 C 0 0 0 0 0 0 0 0 0 0 0 0
-5.5372 -0.6900 -4.7897 C 0 0 0 0 0 0 0 0 0 0 0 0
-5.1692 -3.0650 -4.1717 C 0 0 0 0 0 0 0 0 0 0 0 0
0.3338 1.8200 -0.1267 O 0 0 0 0 0 0 0 0 0 0 0 0
2.2348 4.6650 1.6713 O 0 0 0 0 0 0 0 0 0 0 0 0
3.6998 3.5580 3.3573 O 0 0 0 0 0 0 0 0 0 0 0 0
4.6318 1.4810 4.5573 O 0 0 0 0 0 0 0 0 0 0 0 0
1.1938 -1.1050 -2.2307 O 0 0 0 0 0 0 0 0 0 0 0 0
1.3808 -1.1380 -6.0917 O 0 0 0 0 0 0 0 0 0 0 0 0
-0.9042 -1.6750 -6.8807 O 0 0 0 0 0 0 0 0 0 0 0 0
-3.4602 -2.0440 -6.4577 O 0 0 0 0 0 0 0 0 0 0 0 0
1.9638 -2.2670 2.6513 H 0 0 0 0 0 0 0 0 0 0 0 0
-3.9612 -0.9580 -1.6057 H 0 0 0 0 0 0 0 0 0 0 0 0
-0.9002 -3.0690 1.0983 H 0 0 0 0 0 0 0 0 0 0 0 0
0.6968 -3.7660 1.3393 H 0 0 0 0 0 0 0 0 0 0 0 0
0.2498 -3.1330 -0.2807 H 0 0 0 0 0 0 0 0 0 0 0 0
1.0488 3.5230 0.5623 H 0 0 0 0 0 0 0 0 0 0 0 0
3.3968 -2.0370 3.7753 H 0 0 0 0 0 0 0 0 0 0 0 0
5.3518 -1.4990 2.7583 H 0 0 0 0 0 0 0 0 0 0 0 0
5.6928 -2.2640 4.2303 H 0 0 0 0 0 0 0 0 0 0 0 0
5.7998 -0.4280 4.1903 H 0 0 0 0 0 0 0 0 0 0 0 0
2.5358 -0.9760 5.7973 H 0 0 0 0 0 0 0 0 0 0 0 0
4.0508 -0.2240 5.8903 H 0 0 0 0 0 0 0 0 0 0 0 0
3.8668 -2.0240 6.0913 H 0 0 0 0 0 0 0 0 0 0 0 0
-3.6592 -0.3550 0.6033 H 0 0 0 0 0 0 0 0 0 0 0 0
-2.4422 0.6230 0.9773 H 0 0 0 0 0 0 0 0 0 0 0 0
-2.3242 -1.1830 1.2853 H 0 0 0 0 0 0 0 0 0 0 0 0
1.6208 -0.6090 -4.1897 H 0 0 0 0 0 0 0 0 0 0 0 0
-4.9462 -1.4070 -2.9317 H 0 0 0 0 0 0 0 0 0 0 0 0
-5.2242 0.2920 -4.3637 H 0 0 0 0 0 0 0 0 0 0 0 0
-6.5322 -0.7500 -4.4837 H 0 0 0 0 0 0 0 0 0 0 0 0
-5.4112 -0.7890 -5.9167 H 0 0 0 0 0 0 0 0 0 0 0 0
-4.6452 -3.7870 -3.6137 H 0 0 0 0 0 0 0 0 0 0 0 0
-4.9552 -3.3100 -5.2607 H 0 0 0 0 0 0 0 0 0 0 0 0
-6.1692 -3.1490 -3.9887 H 0 0 0 0 0 0 0 0 0 0 0 0
-0.1652 1.5730 -0.8157 H 0 0 0 0 0 0 0 0 0 0 0 0
3.1858 4.2730 2.7443 H 0 0 0 0 0 0 0 0 0 0 0 0
5.0608 2.4590 4.4183 H 0 0 0 0 0 0 0 0 0 0 0 0
1.5708 -0.9000 -1.5387 H 0 0 0 0 0 0 0 0 0 0 0 0
0.0858 -1.4660 -6.9737 H 0 0 0 0 0 0 0 0 0 0 0 0
-2.8932 -1.8450 -7.1217 H 0 0 0 0 0 0 0 0 0 0 0 0
-5.4154 -0.8438 -5.8415 H 0 0 0 0 0 0 0 0 0 0 0 0
-4.9355 -3.2804 -5.1934 H 0 0 0 0 0 0 0 0 0 0 0 0
4.9775 0.6403 4.8661 H 0 0 0 0 0 0 0 0 0 0 0 0
1 2 2 0 0 0 0
1 9 4 0 0 0 0
1 31 1 0 0 0 0
2 3 4 0 0 0 0
2 12 1 0 0 0 0
3 4 2 0 0 0 0
3 21 1 0 0 0 0
4 10 4 0 0 0 0
4 39 1 0 0 0 0
5 6 2 0 0 0 0
5 10 4 0 0 0 0
5 23 1 0 0 0 0
6 7 4 0 0 0 0
6 34 1 0 0 0 0
7 8 4 0 0 0 0
7 33 4 0 0 0 0
8 9 1 0 0 0 0
8 22 1 0 0 0 0
9 10 4 0 0 0 0
11 12 2 0 0 0 0
11 19 4 0 0 0 0
11 35 1 0 0 0 0
12 13 4 0 0 0 0
13 14 2 0 0 0 0
13 26 1 0 0 0 0
14 20 4 0 0 0 0
14 40 1 0 0 0 0
15 16 2 0 0 0 0
15 20 4 0 0 0 0
15 28 1 0 0 0 0
16 17 4 0 0 0 0
16 38 1 0 0 0 0
17 18 4 0 0 0 0
17 37 4 0 0 0 0
18 19 4 0 0 0 0
18 27 1 0 0 0 0
19 20 4 0 0 0 0
21 41 1 0 0 0 0
21 42 1 0 0 0 0
21 43 1 0 0 0 0
22 32 2 0 0 0 0
22 44 1 0 0 0 0
23 24 1 0 0 0 0
23 25 1 0 0 0 0
23 45 1 0 0 0 0
24 46 1 0 0 0 0
24 47 1 0 0 0 0
24 48 1 0 0 0 0
25 49 1 0 0 0 0
25 50 1 0 0 0 0
25 51 1 0 0 0 0
26 52 1 0 0 0 0
26 53 1 0 0 0 0
26 54 1 0 0 0 0
27 36 2 0 0 0 0
27 55 1 0 0 0 0
28 29 1 0 0 0 0
28 30 1 0 0 0 0
28 56 1 0 0 0 0
29 57 1 0 0 0 0
29 58 1 0 0 0 0
29 69 1 0 0 0 0
30 60 1 0 0 0 0
30 62 1 0 0 0 0
30 70 1 0 0 0 0
31 63 1 0 0 0 0
34 71 1 0 0 0 0
35 66 1 0 0 0 0
37 67 1 0 0 0 0
38 68 1 0 0 0 0
M END</inlineContents>
</jmolApplet>
</jmol>
|- align="center"
| '''2D Structure'''
| '''3D Structure'''
|}

Molecular Weight: 518.5634<br />
Molecular Formula: C<sub>30</sub>H<sub>30</sub>O<sub>8</sub><br />
Melting Point: 177 - 182 C

== How Gossypol Works ==
<table border="0" cellpadding=10>
<tr>

<td>
{| border="1" style="fix: right; clear: left; margin: 1 1 1em 1em; border-collapse: collapse;"
! [[Image:CLBphoto5.jpg|thumb|150px|center|Gossypol Expression in Cotton]]
|-
! ''[http://www.anbg.gov.au anbg.gov.au]''
|}
</td>

<td>
<div align=justify>
'''Gossypol suppresses P24Ag in semen.'''<br />

Appropriate quantities of Gossypol acetate (gp) suppress P24Ag in semen of HIV(+) men. Gp has shown its role as an inhibitor on the replication of HIV. It has been found that 15 out of 18 test subjects have shown P24Ag (-) in their semen and it remained consistent while taking gp. However this test was discontinued when AIDs symptoms was found in 10 of the 18 patients and 5 developed infections including PCP, pulmonary tuberculosis, cryptosporidium and CMV enteritis, esophageal candida.
</div>
</td>

</tr>
</table>

== Uses and Dosage ==

The amount of Gossypol to intake depends on the strength of the medicine and the reason for intake. Follow the instructions on the medicine bottle if not advised by a caregiver or doctor.

Heat or moisture might lead to breakdown of the medicine and it might not function as normal. Keep the medicine locked and beyond the reach of children.
Do not take Gossypol without a doctor's advice if you are taking:
* Digoxin
* Water Pills
* Iron
* Isoproterenol
* Medicine for pain or swelling
* Potassium
* Alcohol / Breastfeeding

Possible Side Effects:
* Breathing problems or chest pains
* Hives, rash and swollen skin
* Muscle Weakness
* Hair Loss, nausea, or bowel problems.

== Synthetic Studies ==

Various studies have undertaken the task of the total synthesis of Gossypol. In 1937 Adams and Geissman proposed the following scheme which synthesises Gossypol via its derivative Desapogossypolone tetramethyl ether.