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                                    Earliest
                                    fungal wall chemistry 
                                     
                                    
                                     
                                    1.     
                                    Braconnot - 1811
                                    
                                     
                                     
                                    
                                     
                                    Found
                                    there was always an alkali-resistant
                                    nitrogen-containing residue left after
                                    hot-alkali (1-6N KOH) treatment of
                                    mushrooms. 
                                    However,less N than in protein. 
                                    Named residue fungin.
                                    
                                     
                                     
                                    
                                     
                                    2.     
                                    Odier - 1825
                                    
                                     
                                     
                                    
                                     
                                    Discovered
                                    novel N compound associated with insect
                                    exoskeleton. 
                                    Named it chitin.
                                    
                                     
                                     
                                    
                                     
                                    Same
                                    compound, but chitin* name stuck. 
                                     
                                    
                                     
                                    poly
                                    ß-1->4-N-acetylglucosamine 
                                     
                                    
                                     
                                    *Chitin
                                    = tanic 
                                    156 
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                                    Average
                                    chemical composition of fungal vegetative
                                    walls 
                                     
                                    
                                     
                                    1.     
                                    Polysaccharides ~ 75-85%
                                    
                                     
                                                        
                                    microfibrillar (main structural)
                                    
                                     
                                                        
                                    nonmicrofibrillar (amorphous
                                    polysaccharides –
                                    
                                     
                                     less
                                    structural to nonstructural).
                                    
                                     
                                     
                                    
                                     
                                    2.     
                                    Protein ~ 10-15% (both structural*
                                    and enzymatic)
                                    
                                     
                                     
                                    
                                     
                                    3.     
                                    Lipid ~ 5-10% (structural)
                                    
                                     
                                                        
                                    Also   
                                    1) 
                                    pigments (usually small amounts,
                                    sometimes high)
                                    
                                     
                                                                    
                                    2) 
                                    phosphate
                                    
                                     
                                                                    
                                    3) 
                                    other inorganic ions
                                    
                                     
                                                                    
                                    4) 
                                    polymerized organic acids (polyuronides).
                                    
                                     
                                    *hydrophobins
                                    
                                     
                                    157
                                    
                                     
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                                    Other
                                    wall polysaccharides 
                                     
                                    
                                     
                                    1.     
                                    Mannans - as mannoproteins*
                                    
                                     
                                     
                                    
                                     
                                    2.     
                                    S-glucans (soluble** a
                                    &/or
                                    ß glucans)
                                    
                                     
                                     
                                    
                                     
                                    3.     
                                    R-glucans (microfibrillar and
                                    nonmicrofibrillar ß glucans)
                                    
                                     
                                     
                                    
                                     
                                    4.     
                                    Numerous types of
                                    heteropolysaccharides
                                    
                                     
                                     
                                    
                                     
                                    5.     
                                    Various polyuronides (polymers of
                                    glucuronic &/or galacturonic acids)
                                    
                                     
                                     
                                    
                                     
                                    6.     
                                    Variety of aminopolysaccharides other
                                    than chitin or chitosan.
                                    
                                     
                                     
                                    
                                     
                                    *       
                                    Many studies in S.
                                    cerevisiae
                                    
                                     
                                    **     
                                    In strong alkali
                                    
                                     
                                    160
                                    
                                     
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                                    Why
                                    study fungal chitin? 
                                      
                                    1.     
                                    Chitin is chemically unique and not
                                    found in human cells. 
                                    2.     
                                    Chitin serves a vital role as a main
                                    structural component of fungal walls. 
                                    3.     
                                    Chitin synthase substrate analogs
                                    inhibit fungal growth and sometimes lead to
                                    fungal deal 
                                    4.     
                                    Fungal cell walls serve as main
                                    protective barriers between pathogen and
                                    host, so wall components including chitin
                                    should represent virulence factors 
                                    165
                                    
                                     
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                                    "Review" 
                                    Polysaccharides
                                    of fungi and fungal-like protoctista 
                                     
                                    
                                     
                                    Microfibrillar
                                    polysaccharides
                                    
                                     
                                            
                                    b(1->3)
                                    - (1->6) glucans (most of R glucan)
                                    
                                     
                                            
                                    b(1->4)
                                    glucan = cellulose
                                    
                                     
                                            
                                    b
                                    (1->4) N-acetylglucosamine = chitin
                                    
                                     
                                     
                                    
                                     
                                    Very
                                    weakly microfibrillar polysaccharide
                                    
                                     
                                     
                                    
                                     
                                            
                                    b(1->4)
                                    glucosamine = chitosan
                                    
                                     
                                                        
                                    other wall polysaccharides
                                    
                                     
                                     
                                    
                                     
                                            
                                    also Mannans - as mannoproteins
                                    
                                     
                                     
                                    
                                     
                                            
                                    S-glucans (mostly a,
                                    but some b
                                     glucans)
                                    
                                     
                                     
                                    
                                     
                                    Heteropolysaccharides
                                    [ mostly soluble in H2O (HOT) and
                                    alkali (COLD), but some resistant (only
                                    soluble in hot alkali)] 
                                     
                                    
                                     
                                    Various
                                    polyuronides (polymers of glucuronic and
                                    galacturonic acids) 
                                     
                                    
                                     
                                    Various
                                    aminopolysaccharides other than chitin or
                                    chitosan – e.g., galactosamine
                                    polysaccharide
                                    
                                     
                                     
                                    
                                     
                                    162/163
                                    
                                     
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                                    Mannoproteins 
                                     
                                    
                                     
                                    Why
                                    studied?
                                    
                                     
                                     
                                    
                                     
                                    1.     
                                    Main antigenic determinants of
                                    S. cerevisiae and most other fungi
                                    (particularly medically important fungi)
                                    
                                     
                                     
                                    
                                     
                                    2.     
                                    Can be altered by mutagenesis so
                                    structure-function relationships can be
                                    studied. 
                                    e.g., How affect mating? 
                                    How affect secretion?*
                                    
                                     
                                     
                                    
                                     
                                    3.     
                                    Microbial model for protein
                                    glycosylation via dolichol-p lipid
                                    intermediate
                                    
                                     
                                     
                                    
                                     
                                    *       
                                    many secreted fungal enzymes are
                                    glycosylated.
                                    
                                     
                                     
                                    
                                     
                                    see
                                    OR 5 for details
                                    
                                     
                                    175
                                    
                                     
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                                    Fungal
                                    cell wall monosaccharides 
                                     
                                    
                                     
                                    Most
                                    fungi
                                    
                                     
                                            
                                    1.        
                                    D-glucose
                                    
                                     
                                            
                                    2.        
                                    N-acetylglucosamine
                                    
                                     
                                            
                                    3.        
                                    D-mannose
                                    
                                     
                                     
                                    
                                     
                                    Monosaccharides
                                    with taxon association
                                    
                                     
                                     
                                    
                                     
                                            
                                    4.        
                                    D-galactose (Ascomycota)
                                    
                                     
                                            
                                    5.        
                                    D-galactosamine ( 
                                    " 
                                    )
                                    
                                     
                                            
                                    6.        
                                    L-fucose (Mucorales &
                                    Basidiomycota)
                                    
                                     
                                            
                                    7.        
                                    D-glucosamine (Mucorales)
                                    
                                     
                                            
                                    8.        
                                    D-xylose (Basidiomycota)
                                    
                                     
                                            
                                    9.        
                                    Uronic acids (Mucorales)
                                    
                                     
                                        
                                    10.          
                                    D-rhamnose (Ascomycota)*
                                    
                                     
                                     
                                    
                                     
                                    *somewhat
                                    rare      
                                    
                                     
                                    179
                                    
                                     
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                                    Monosaccharide
                                    correlations* for chitin/b-glucan
                                    group 
                                     
                                    
                                     
                                            
                                    Euascomycotina**
                                    
                                     
                                            
                                    Homobasidiomycotina**
                                    
                                     
                                            
                                    Chytridiomycota
                                    
                                     
                                     
                                     
                                    
                                      
                                        | 
                                            
                                          
                                           
                                         | 
                                        
                                           gal
                                          
                                           
                                         | 
                                        
                                           gal-NH2
                                          
                                           
                                         | 
                                        
                                           fu
                                          
                                           
                                         | 
                                        
                                           Xy
                                          
                                           
                                         | 
                                       
                                      
                                        | 
                                           Euascomycotina
                                          
                                           
                                         | 
                                        
                                           +
                                          
                                           
                                         | 
                                        
                                           +
                                          
                                           
                                         | 
                                        
                                           -
                                          
                                           
                                         | 
                                        
                                           -
                                          
                                           
                                         | 
                                       
                                      
                                        | 
                                           Homobasidiomycotina
                                          
                                           
                                         | 
                                        
                                           -
                                          
                                           
                                         | 
                                        
                                           -
                                          
                                           
                                         | 
                                        
                                           +
                                          
                                           
                                         | 
                                        
                                           +
                                          
                                           
                                         | 
                                       
                                      
                                        | 
                                           Chytridiomycota
                                          
                                           
                                         | 
                                        
                                           -
                                          
                                           
                                         | 
                                        
                                           -
                                          
                                           
                                         | 
                                        
                                           -
                                          
                                           
                                         | 
                                        
                                           -
                                          
                                           
                                         | 
                                       
                                     
                                     
                                    
                                     
                                     
                                    
                                     
                                    *
                                    Not known if will stand test of time
                                    
                                     
                                    **
                                    & Fungi Imperfecti counterparts
                                    
                                     
                                    183
                                    
                                     
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