BIOL 2421 Microbiology         Lecture Notes: Microbial Metabolism   Dr. Weis

Metabolism:

            Def: sum of all biochemical reactions in living organisms

            Requirements: Energy, enzymes

            Two types of metabolic reactions:

            a) catabolism: breakdown of complex chemical compounds, releasing energy

                                    e.g. hydrolytic, exergonic

            b) anabolism: synthesis of chemical compounds, requiring energy

                                    e.g. dehydration synthesis, endergonic

Metabolism reaction rates depend on the number of molecules (substrate) available and the activation energy. 
The rate limiting step is the slowest step in the chemical process.

Reaction rates can be affected by temperature (heat, cold), pH, pressure/concentration, distance.


Energy: the ability to do work or to move matter.

              Forms: Kinetic and Potential

              Energy use: Chemical, Electrical, Mechanical, Electromagnetic (radiation)

              Chemical Energy Types: ATP, GTP, UTP

              Synthesized from phosphate and a nitrogen base (Adenine, Guanine, Uracil)

                                                ADP + Pi + E  çè ATP

            Recall that when energy is released to do the work of the cell, part of that energy is lost to the environment as heat.


Enzymes: Normally protein based catalysts that lower the activation energy of the reaction. 
The activation energy is the amount of energy needed to disrupt the stable electron configurations of a molecule so that the electrons can be rearranged.

Enzymes:

                        a) Act on specific substances (substrate) to create a product

                        b) Catalyze one reaction

                        c) Contains an active functional site

                        d) Three dimensional shape (primary, secondary, tertiary, quaterinary)

                        e) Exist in both active and inactive forms

                        f) Are not changed or used up in the chemical process/reaction

                        g) Named for chemical class of reactions catalyzed, -ase ending

                        h) Two parts: apoenzyme (protein) + cofactor / coenzyme = holoenzyme

            Examples of coenzymes (organic cofactors)

                        CoEnzyme A

                        Vitamin

                                    Vitamin B based: NAD+, NADP+, FAD

            Examples of cofactors (nonorganic molecules)

                        Metal Ions of Copper, Iron, Zinc, Magnesium, Calcium, Manganese

 Categories of Enzymes

            a) Hydrolases

                        add water to catabolize molecule

            b) Isomerases

                        rearrange atoms within molecule

            c) Ligases/Polymerases

                        join molecules together

            d) Lyases

                        split molecules apart

            e) Oxidoreductase

                        redox reactions

            f) Transferases

                        move functional group between molecules

Factors affecting enzymes:

                        Temperature, pH, acids, bases, heavy metals, alcohol, UV light:

                                    Changes beyond optimum can cause denaturing

                                    The breakdown of  the 3D structure.
                                    Might be reversible as long as the enzyme was not coagulated

  Factors affecting enzymes:

                        substrate concentration, if constituents high enough, can saturate enzyme’s  active site causing no further increase in reaction rate.

                        inhibitors: competitive and noncompetitive ; reversible and irreversible

                                   * Competative inhibitors fill active site and block enzyme, no Rxn

                                                i. Reversible: can be competitively removed

                                                ii. Irreversible: bind permanently

                                    * Noncompetative inhibitors bind to another site called the allosteric site and changes the shape of the active site making it nonfunctional.

                        Allosteric inhibitors that bind can play a role in feedback inhibition for the end product.

                                                i. Inhibitory: stops enzyme activity

                                                ii. Excitatory: activates the inactive enzyme


Recent findings indicate another different enzyme structure:
From ribosome, called ribozymes
Functions like a normal protein based enzyme, but only works on RNA to remove sections and splice sections of RNA. 
This "new" enzyme is now considered the primary core of a ribosome.


Summary:

            Enzyme specificity

            Induced Fit

            Enzyme substrate complex

            Concentration of enzyme determines metabolic rate. 

            Enzyme synthesis is regulated by DNA and based on negative feedback controls.


Energy Production

Redox reactions

            Oxidation is the loss/removal of electrons from an atom or molecule

            Reduction is the gain of an electron

      Redox processes are controlled series of coupled reactions to prevent large amounts of heat from being released all at once.

Dehydrogenation

            Use of hydrogen in oxidative reactions.  The removal of the electron belonging to hydrogen and leaving a proton or H+ atom that may be released to the surrounding medium.

The energy released during Redox reactions in trapped in the chemical bonds that form ATP in a process called phosphorylation.  ADP + E + Pi forms Adenosine-Pi ~Pi~Pi (ATP)

Electrons do not normally exist free in cytoplasm.  If released from an atom, electrons will be carried on Vitamin derivatives

            NAD+ --> NADH

            NADP+ --> NADPH

            FAD--> FADH2


Phosphorylation Types

A> Substrate level: High energy phosphate is directly transferred to ADP, seen in glycolysis steps.

B> Oxidative Phosphorylation:  electrons are transferred to carriers down an electron transport chain (located in the cytoplasm of prokaryotes and the mitochondrial matrix of Eukaryotes) to the final electron acceptor, which could be O2 or some other molecule.

The release of energy from one electron carrier to the next to help make ATP is called chemiosmosis.

C> Photophosphorylation: converts light energy to chemical energy (ATP) in photosynthetic cells.  This chemical energy is then used to synthesize organic molecules.


Glucose Metabolism

            6 carbon carbohydrate oxidized as primary source of cellular energy (E).

            Catabolism creates “waste” products

            Microorganisms can use cellular respiration or fermentation to produce E.


STEP ONE: Glycolysis

            Splitting or breakdown of glucose into 2 molecules of Pyruvate [Pyruvic acid]

            If other carbohydrates are used, must be broken down into intermediary

            Occurs in Cytoplasm

            Anaerobic

            Pathways : Embden-Meyerhoff, Pentose-Phosphate, Entner-Doudoroff


            Classic Pathway (Embden-Meyerhoff)

                        End products:

                        2 Pyruvic Acid

                        2 net ATP [4 ATP made – 2 ATP used]

                                    ATP produced by substrate level phosphorylation

                                    Mg++ required as cofactor

                        2NADH

                        2H2O

            Pentose - Phosphate Pathway

                        Breakdown of 5 and 6 carbon sugars

                        End Products:

                                    1 ATP

                                    1 NADPH

                                    CO2

                                    7, 6, 5, 4 Carbon sugar intermediates that can go on to

                                                                        form AA

                                                                        form nucleotides

                                                                        enter glycolysis

                                                                        perform photosynthesis

            Entner-Duodoroff Pathway

                        Breakdown of glucose

                        Use different enzymes than glycolysis

                        End Products

                                    1 net ATP [2ATP produced – 1 ATP used]

                                    1 NADPH

                                    1 NADH

                                    2 Pyruvic acids

                                    2 H2O

                        seen in some G(-) bacteria such as Pseudomonas

                        Seen in some G(+) bacteria such as Enterococcus faecalis


STEP TWO: Presence or absence of Oxygen

                        With oxygen: Aerobic respiration

                        Without oxygen:


Aerobic Respiration

            Final electron acceptor is Oxygen (O2)

            Krebs Cycle + Oxidative Phosphorylation

            Redox reactions that oxidize pyruvic acid derivatives and reduce coenzymes such as NAD+ and FAD

Pyruvic acid--> CO2 [decarboxylation] + Acetate --> Acetate +CoA + NADH--> Acetyl CoA

            Oxaloacetic acid + Acetyl CoA à Citric Acid (6-Carbon)


Krebs Cycle {TCA, Citric Acid} Summary:

6 Carbon [C] Citric acid goes to 5 Carbon alpha-ketoglutaric acid + NADH + CO2

5 C molecule goes to a 4 C + NADH + CO2 + ATP via substrate level phosphorylation

4 C molecule undergoes several changes; H comes off to be picked up by FAD and NAD+

Generate Oxaloacetic acid that combines with Acetyl CoA to form Citric Acid


Electron Transport Chain [ETC]

            In the plasma membranes of prokaryotes

            Contains three carrier molecules for redox reactions

                        a) Flavoprotiens based on Vitamin B

                        b) Cytochromes based on Iron pigments

                        c) Coenzyme Q

            Function:

                        Transfer of high E electrons from NADH to chain flavoproteins.

                        The H+ is pumped away from the chain and put on the other side of the plasma membrane in the Periplasm of bacteria.

                         The electrons are then transported

                                    Either to Iron – Sulfur proteins if NADH started

                                    Or to CoQ if FADH2 transported the electrons

                        Then continues down the cytochromes [B, C, A]

                        The last cytochrome, A3

                        Then passes the electrons to oxygen which becomes negatively charged  

                                     O2- attracted to the H+ that has come through the ATP synthetase wheel pump due to concentration gradients.  

                        An ADP molecule is then joined to a phosphate to form ATP when a H+ moves across.

                        The electrons on the O2 combine with the H+ to form water.

                        Regenerates FAD+ and NAD+ for reuse in Krebs Cycle

Carrier molecules in ETC are diverse

            a) Differ between bacterial genuses

            b) Altered based on environmental changes

            c) Cytochrome A+ A3 = Cytochrome oxidase in some bacteria

                        Cytochrome oxidase +  bacteria : Pseudomonas, Neisseria

                        Cytochrome oxidasebacteria : E. coli, Salmonella, Proteus

            The mechanism of making ATP via oxidative phosphorylation using the electron chain is called chemiosmosis.

            38 total for Prokaryotes, 36 total of Eukaryotes (some energy is lost when electrons are shuttled through the mitochondria. No such loss occurs in Prokaryotes)

Prokaryote Summary:  Glucose + 6 O2 ===> 6 CO2  + 6 H2O  + 38 ATP + Heat


Final Electron Acceptors

     Aerobic Respiration

            Oxygen

                        O2 - + 2H+ --> H20 + ATP

     Anaerobic Respiration:

            Final electron acceptor is something other than Oxygen

            Example:  Nitrate Ion (NO3 -)    as electron acceptor can generate one of the following:

                                                            NO2-   nitrite ion

                                                            N2O    nitrous oxide

                                                            N2       nitrogen gas

                            Sulfate Ion (SO4=)   to form H2S (hydrogen sulfide gas)

                            Carbonate Ion (CO3=)   to form CH4 (methane gas)

     Fermentation

            Anaerobic

            Partial oxidation

            Does not use Krebs Cycle or Oxidative phosphorylation

            Use organic intermediary molecules as final electron acceptor to create end products

            Small amounts of ATP are generated by substrate level phosphorylation.

Primary function is to regenerate NADH to NAD+ for glycolysis. There are small amounts of ATP available, since most energy stored in product

Pyruvic acid is converted into another organic product depending on the organism.

            a) Lactic Acid

            b) Acetic Acid

            c) Acetone

            d) Butyric acid

            e) CO2

            f) H2

            g) Alcohols: Isopropyl, Ethanol

            h) Contaminants that can cause tissue damage and death [necrosis]

Identification of end products is useful in identifying organisms as well as for use in industry or commercial products.

Two major types of fermentation are:

            Lactic Acid Fermentation (Pyruvic acid to Lactic Acid) seen in bacteria

            Alcohol Fermentation (Pyruvic acid to Acetaldehyde to Ethanol) seen in yeasts



Protein Metabolism

            Catabolism via proteases and peptidases so that the Amino acids can cross the membrane. 
To use in an energy pathway, they must be converted to other substances that can enter the glycolysis or Krebs Cycle.

            These processes are

                        a) Deamination : removal of the NH3 group (then converted to NH4+)

                                                   remaining molecule can enter an energy pathway

                        b) Decarboxylation: removal of the –COOH (carboxyl) group

                        d) Dehydrogenation: removal of the Hydrogen



Lipid Metabolism

            Catabolism of the fats involve the splitting of the glycerol and fatty acids by lipases.

            Glycerol can enter the glyolytic pathway

            Fatty acids are converted to Acetyl CoA via Beta oxidation


Biochemical Testing for Bacterial Identifcation

Biochemical tests are designed to use metabolic processes to help:

Recall that nutritional classifications of bacteria categorize them as chemotheterotrophs


Metabolic Pathways for Energy Use

Energy is produced by aerobic respiration, anaerobic respiration, and fermentation.

45% of the energy generated is given off as heat.

Microbes use the remaining ATP energy for life processes: metabolism, growth, responsiveness and reproduction. 
     Specific examples include

            a) active membrane transport

            b) motility

            c) generation of new cellular components via biosynthesis


Biosynthesis

A) Polysaccharide

            Synthesize simple sugars from

                        Carbon intermediaries in the Krebs cycle

                        Amino Acids

                        Lipids (glycerol)

            Stored as glycogen (Glucose-6 + ATP -> ADGP)

            Cell wall components such as peptidoglycan (Fructose-6 + UTP -> UDPG)

B) Lipid

            Glycerol + FA

            Makes components of cell membrane

            Makes components of cell wall and waxes [mycolic acid] in acid fast bacteria

            Pigment production

            Energy Storage

C) AA and Protein

            Some microbes require a few essential amino acids, some can synthesize all

            Glucose (or metabolism intermediaries) + inorganic salts with enzymes

            Krebs cycle precursors such as pyruvic acid + amine -> Amino Acid

                        Processes using NH3

                                    Amination

                                    Transamination with Vitamin B6 as a coenzyme

            AA form basis for proteins used as

                        Enzymes

                        Structural components

                        Toxins

      Ribosomal ribozymes involved in protein synthesis

D) Purine and Pyrimadine

            Nitrogen-bases.  Purines are Adenine and Guanine.  Pyrimadines are T,C,U

            5 carbon sugar (pentoses) from alternate carbohydrate metabolism

            AA [glutamine, aspartic acid] from Krebs cycle intermediaries, with carbon form N base ring

            Nucleotides form DNA, RNA, ATP, NAD+, NADP

            Phosphate group from ATP


Integration of Metabolism
            Share common intermediaries: Breakdown of one is used in synthesis of another

            Function in both catabolism and anabolism => amphibolic pathways

     Cells regulate metabolism

                        * create or destroy transport membrane proteins

                        * enzyme synthesis and control

                       * use of environmental nutrients or synthesize from metabolites


Protein Synthesis

DNA--> Transcription of mRNA
RNA--> Translation using mRNA, tRNA, and rRNA to create a Protein

DNA ==> RNA==>Protein

Nucleotides: DNA and RNA compared

            DNA

                        Code (genetic)

                        Double strand

                        Helix unwinds

                        Template for RNA, RNA polymerase

                        Base pairing  A<==>T,  G <==>C

            RNA

                        mRNA, tRNA, rRNA

                        single strand

                        Base pairing  A<==>U, G<==>C

                        mRNA codons

                        tRNA anticodons

                        rRNA 2 subunits, P site (start), A site (ready next)

                        Bacteria do NOT have introns (non coding segments)


Many genes (~60 - 80 %) are constitutive and not regulated so that their products are made at a fixed rate. These genes are always "on" and will code for proteins (i.e. enzymes) that the cell needs for major life processes, such as those enzymes required for glycolysis. Other enzymes are regulated so that they are made only when needed. These control methods are known as induction and repression and controlthe the formation and amounts of enzymes present but do not control the activities.

Repression

inhibits gene expression by blocking RNA polymerase to initiate transcription

result: decreases the synthesis of enzymes

mediated by repressors (regulatory proeteins)


Induction

turns on transcription of a gene to synthesize protein (i.e. an enzyme)

mediated by inducers

response: enzyme induction


Control of Protein Synthesis

            Bacterial Genes

                        * Structural Genes – genetic codes for the proteins to be used by the cell

                        * Operator Genes -- controls transcription (the "go or stop" signals) for the expression of the structural genes

                        * Promoter region – binding site for RNA polymerase on the DNA to start transcription

                                    Entire unit above is called an operon (Operon = Operator site, Promoter site, and Structural Genes)

                                    Two types of operons:

                                                Inducible Operon

Starts with an active repressor binding with the operator, so the operon is "off"

 When an Allosteric Inducer (such as a nutrient) blocks the repressor protein and inhibits binding to the operator, the operon is now turned "on" to allow transcription.
This process is called "inducible".

                                                Repressible Operon:

                                                             If a repressor protein is inactive, then the operon is turned "on" and the structural genes are transcribed

When a co-repressor is available, it can then bind to the repessor protein which then binds to the operator region.

Once the repressor protein is active/activated, then the operon is turned "off" and the structural genes are not transcribed.
This process is called "repressible".

                       

Regulatory genes control mRNA synthesis which in turn codes for the various proteins that affect the operon.

                        Repressor Genes – located at a distant site on the DNA and is also can be considered part of the operon system

                                    Regulator genes that control and block the operator genes via repressor protein that can

                                    Blocking the operator genes prevents RNA polymerase activity.

                        An inducer binds to repressor proteins to inactivate it and allow the RNA polymerase to bind to the promoter region to begin mRNA synthesis from a specific operon (on DNA) to start transcription.