Ch. 12: Bioenergetics and Regulation of Metabolism Flashcards
why are biological systems often considered open systems?
because they can exchange both energy and matter with the environment
in the body, how is energy exchanged? how is matter exchanged?
energy is exchanged in the form of mechanical work when something is moved over a distance, OR as heat energy
matter is exchanged through food consumption and elimination, as well as respiration
at what level are most biochemical studies performed?
cellular or subcellular, NOT the entire organism
why are the cellular or subcellular studies considered closed systems?
there is no exchange of matter with the environment
defn: internal energy
the sum of all of the different interactions between and within atoms in a system (vibration, rotation, linear motion, and stored chemical energies all contribute)
how does the fact that the system is closed affect the change in internal energy?
it can come only in the form of work (changes in pressure and volume) or heat
why is heat the only quantity of interest in determining internal energy?
because pressure and volume (which together are work) are constant in most living systems
defn: bioenergetics
the term used to describe energy states in bilogical systems
what information do changes in free energy (G) provide? (2)
- info about chemical reactions
- can predict whether a chem reaction is favorable and will occur
in biological systems, what is the crucial role that ATP plays?
crucial role in transferring energy from energy-releasing catabolic processes to energy-requiring anabolic processes
what determines whether a chemical reaction proceeds?
by the degree to which enthalpy and entropy change during a chemical reaction
defn: enthalpy
measures the overall change in heat of a system during a reaction
what is true about change in enthalpy (H) and thermodynamic heat exchange (Q) at constant pressure and volume?
they are equal
defn: changes in entropy (S)
measure the degree of disorder or energy dispersion in a system
unit: entropy
J/K
eqn + func: Gibbs free energy equation
predicts the direction in which a chemical reaction proceeds spontaneously
char: spontaneous vs. nonspontaneous reactions vs. equilibrium
SPONTANEOUS = proceed forward, exhibit a net loss of free energy, have negative deltaG
NONSPONTANEOUS = would be spontaneous in reverse, have net gain of energy, positive deltaG
APPROACHING EQUILIBRIUM = free energy approaches zero, no net change in concentration of reactants or products
defn: change in free energy vs. change in standard free energy
CHANGE IN FREE ENERGY = predicts changes occurring at any concentration of products and reactants and at any temperature
STANDARD FREE ENERGY = the energy change that occurs at standard concentrations of 1 M, pressure of 1 atm, temperature of 25 deg C
how can change in free energy and change in standard free energy be related? (eqn)
where R is the universal gas constant
T is temperature
Q is the reaction quotient
biochemical analysis works well under all standard conditions except one, what is that one?
pH
values: modified standard state
ΔG°′ indicates that it is standardized to the neutral buffers used in biochem
what is the general trend of the relationship between deltaG and the ratio of products to reactants?
products > reactants tend to have more negative deltaG
reactants > products tend to have more positive deltaG
the human body can make use of different energy sources with roughly the same efficiency, so are all nutrient molecules created equally?
no (i.e fats are more energy-rich than carbohydrates, proteins, or ketones)
value of energy: complete combustion of fat vs. carbohydrates, proteins, or ketones
fat: 9 kcal/g of energy
others: 4 kcal/g
why are fats preferred for long-term energy storage?
fats are so much more energy-dense than other biomolecules
analogy: fats vs. carbs for storage
fats = 16 GB flash drive
carbs = 8 GB flash drive
they occupy the same amount of physical space, but fat holds twice as much data
what is the readily available form of energy fot the cell?
ATP! (adenosine triphosphate)
what is ATP formed from?
substrate-level phosphorylation and oxidative phosphorylation
why do we want ATP to be a mid-level carrier and not a higher-level one?
think about your wallet – if you never had the ability to get change back after a purchase what type of bill would you want in abundance? one dollar bills!
similarly, ATP cannot get back the “leftover” free energy after a reaction, so it’s best to use a carrier with a smaller free energy
main source of production for ATP + 2 secondary sources
main: mitochondrial ATP synthase
secondary: 1. during glycolysis 2. indirectly from GTP in the citric acid cycle
structure + generated from + consumed by: ATP
- consists of an adenosine molecule attached to 3 phosphate groups
- generated from ADP and Pi with energy input from an exergonic reaction or electrochemical gradient
- consumed either through hydrolysis or the transfer of a phosphate group to another molecule
what results if one phosphate is removed from ATP? if 2 phosphates are removed from ATP?
1 phosphate –> adenosine diphosphate (ADP) is produced
2 phosphates –> adenosine monophosphate (AMP) produced
in a single day, what % of a person’s body weight does an average sized person use in ATP? how many grams of ATP are available at any given time?
what accounts for this discrepancy?
90%
50g
continuous recycling of ATP, ADP, and Pi more than 1000 times per day accounts for this discrepancy
func (2): ATP
to fuel energetically unfavorable reactions or to activate or inactive other molecules
it is the major energy currency in the body and is a mid-level energy carrier
what makes ATP such a good energy carrier? + how
its high-energy phosphate bonds
the negative charges on the phosphate groups experience repulsive forces with one another and the ADP and Pi molecules that form after hydrolysis are stabilized by resonance
is ATP more stable before or after hydrolysis? what thermodynamic value does this acccount for?
after, although its not UNSTABLE before hand
accounts for the negative value of deltaG
values: deltaGknot for
standard conditions
at pH 7 and with excess magnesium
ADP
AMP
standard conditions: - 55 kJ/mol
at pH 7 and excess magnesium: - 30.5 kJ/mol
ADP similar to above
AMP: -9.2 kJ/mol
in what reaction layout is ATP hydrolysis most likely to be in countered?
in the context of coupled reactions
how is ATP used in many coupled reactions?
as an energy source
defn: ATP cleavage
the transfer of a high-energy phosphate group from ATP to another molecule which generally activates or inactivates the target molecule
how is the overall free energy of the reaction determined with the phosphoryl group transfers that happen with ATP cleavage?
by taking the sum of the free energies of the individual reactions
how can we conceptualize the free energy of hydrolysis?
the transfer of the phosphate group to water
how can one determine the free energy of the phosphoryl group transfer to another biological molecule?
use Hess’s law and calculate the difference in free energy between the reactants and products
true or false: many key enzymes in ATP synthesis and other biochemical pathways have oxidoreductase activity
true
sign of delta G and E for spontaneous redox reactions
negative deltaG
positive E (electromotive force)
what are 6 molecules that act as soluble, high-energy electron carriers in the cytoplasm?
- NADH
- NADPH
- FADH2
- ubiquinone
- cytochromes
- gluatathione
what happens to electrons as they are passed down the electron transport chain?
they give up their free energy to form the proton-motive force across the inner mitochondrial membrane
are their electron carriers other than the soluble ones we have just discussed?
yes there are also membrane-bound electron carriers embedded within the inner mitochondrial membrane
what is an example of an inner mitochondrial membrane bound electron carrier
flavin mononucleotide (FMN), which is bonded to complex I of the ETC and can also act as a soluble electron carrier
proteins with prosthetic groups containing iron-sulfur clusters are particularly well suited for what
the transport of electrons
defn: riboflavin
a modified vitamin B2 contained in flavoproteins
defn: flavoproteins
nucleic acid derivatives
generally either flavin adenine dinucleotide (FAD) or flavin mononucleotide (FMN)
what are flavoproteins most notable for?
their presence in the mitochondria and chloroplasts as electron carriers
2 other funcs: flavoproteins
- involved in the modification of other B vitamins to active forms
- function as coenzymes for enzymes in the oxidation of fatty acids, the decarboxylation of pyruvate, and the reduction of glutathione
what is one of the key differences between general chemistry and biochemistry?
whether or not equilibrium is seen as a desirable state
biochemists: no
what do biochemists seek instead of equilibrium?
homeostasis
defn: equilibrium vs. homeostasis
equilibrium = a fixed state, thus preventing us from storing any energy for later use or creating an excitable environment
homeostasis = a physiological tendency toward a relatively stable stat that is maintained and adjusted, often with the expenditure of energy
what is the impact of the fact that most compounds in the body are actually maintained at a homeostatic level that is different from equilibrium?
we can store potential energy
reactions can proceed such that equilibrium is put off for a long time
what do the pathways that are operational in fuel metabolism depend on?
the nutritional status of the organism
what 2 things are very pronounced when going from the well-fed state to an overnight fast?
- shifts between storage and mobilization of a particular fuel
- shifts among the types of fuel being used
2 aka + defn: + char postprandial state
aka: absorptive state, well-fed state
occurs shortly after eating and generally lasts 3-5 hours after eating a meal
marked by greater anabolism and fuel storage than catabolism
defn: anabolism vs. catabolism
anabolism = synthesis of biomolecules
catabolism = breakdown of biomolecules for energy
what happens during the postprandial state?
nutrients flood fro the gut and make their way via the hepatic portal vein to the liver, where they can be stored or distributed to other tissues of the body
what happens just after eating? (4)
- blood glucose levels rise and stimulate the release of insulin
- insulin promotes glycogen synthesis in liver and muscle
- after the glycogen stores are filled, the liver converts excess glucose to fatty acids and triacylglycerols
- insulin promotes triacylglycerol synthesis in the adipose tissue and protein synthesis in muscle, as well as glucose entry into both tissues