What is Biochemistry? • A science that integrates life with chemistry • A science that attempts to determine how lifeless molecules combine to give the attributes of life • A science that operates by the principle that life’s molecules are selected for the functions they perform. • A science that delves into the world of the unseen for answers to life’s mysteries. What are the Challenges of Biochemistry? To understand the chemical complexity of a cell To determine how cells are able to extract and transform energy from their surroundings To learn how cells are capable of self-replication To determine how cells sense and respond to changes in their environment To understand the structural logic behind the selection of specific molecules for specific tasks How does Biochemistry Differ from Organic Chemistry? See Tutorial “Getting Started” • Organic chemistry is the chemistry of carbon compounds. Biochemistry is the study of carbon compounds that crawl -Mike Adam A Biochemist is a person who can’t tell the difference between a plant or an animal -E Harris What are the Objectives of Biochemistry 410 • To introduce students to the properties of molecules found in living cells. • To compare and contrast the properties of molecules in the different categories. • To demonstrate the structure-function principle of biochemistry. • To threaten, cajole, or otherwise persuade students that a knowledge of biochemistry is essential to understanding the properties of life. Chemical Perspective The Elements and Molecules of Life Peptide bond Glycosidic bond Ionic bond H-bond Hydrophobic bond Phosphodiester bond Disulfide bond Take Home: Weak and strong forces hold biomolecules together. Important Functional Groups in Biomolecules CH3- Methyl CH3CH2- Ethyl CH3CO Acetyl CH3(CH2)nC- Acyl O Phenyl R-SH Sulfhydryl R-S-S-R Disulfide Important Functional Groups (Continued) R-OH Hydroxyl (alcohol) R-NH3 Amino (amine) NH2 Guanidinium C NH- H2N O O-P-O O Phosphate Carboxyl CH2OH H CH3-C-COO Methyl Hydroxyl O OH + NH3 HO Amino HO OH Phenyl Hydroxyl H CH2-C-COO H HO-CH2-C-COO + NH3 + NH3 Acyl O CH3(CH2)nCH2-C-O-CH2 Sulfhydryl H HS- CH2-C-COO + NH3 Trimethylamine CH3(CH2)nCH2-C-O-CH2 O + O CH2 O-P-O CH2-CH2-N(CH3)3 Phospho O Biomolecules CH2COO HO-C-COO CH2COO O=C=O Citrate COO C=O Pyruvate CH3 COO HO-C H CH3 L-lactate CH2OH DHAP C=O CH2OPO3 COO C=O CH2 a-Keto CH2 glutarate COO COO CH2 CH2 COO Succinate Biomolecules (cont.) H OOC C C COO Fumarate H HS-CoA Acetyl-CoA Fatty Acyl-CoA BIOENERGY Electrical Mechanical Sound Light Osmotic Heat? Light to electrical Chemical to mechanical Sound to electrical CHEMICAL (Sight) (Muscle contraction) (Hearing) Basic Thermodynamics Q: How do we know when a given reaction or process will occur spontaneously or in a favored direction? A: Berthelot (1860) All spontaneous reactions occur with the liberation of heat. Therefore, spontaneous reactions are exothermic. A: Gibbs (1870). Heat is not the only index of spontaneity. Many spontaneous processes occur without liberating heat. The order or entropy must also be considered. Q: Is it possible for a reaction to actually absorb heat or remain isothermal and still be favored in one direction? A: Yes Q: Can you give an example? A: When ice melts or salt dissolves in water or when a gas confined to one chamber diffuses to occupy two chambers, these are spontaneous reactions that absorb heat. Q: So, knowing the favored direction must account for both energy release and order. A: Yes, energy as heat is called enthalpy. Enthalpy change or H measures energy released at constant pressure. In a favored reaction H is less than 0, i.e., H is negative. Entropy is a probability function. The probability that the system will exist in any form other than perfect order. In a favored reaction entropy change or S is positive. The combination gives rise to a state function called the free energy. A reaction will always be favored in the direction that free energy change is negative or less than 0. Q: Can you give me a equation that helps me see this A: Maximal (– G) Entropy G = H - TS occurs when H change Enthalpy Free energy is negative and change change S is positive Enthalpy: H Energy Change at constant pressure Energy locked in chemical bonds Bomb Calorimeter Glucose + 6O2 Initial State Final State 6CO2 + 6H2O H = heat evolved Take Home: Because energy differential is independent of path taken, energy from combustion in a bomb calorimeter is the same as in the body Oxidation of Palmitic Acid (C16H32O2) H2 O H2 O H2 O O2 CO2 H2O Initial State Reaction Final State H = q p = heat evolved at constant H pressure At constant pressure and volume, no work has been done against or by the surroundings. 1 atm H2 O 1 atm H2 O q Initial State 1 atm H2 O O2 At constant P, if the surroundings can do work on the system… more heat can be evolved w CO2 H2O q 1 atm q=E + w H2 O CO2 w = PV w = nRT Final State CH3(CH2)14COOH + 23O2 16CO2 + 16H2O ENTROPY S Relates to molecular order Energy unavailable during a chemical transition “A spontaneous reaction is one that favors movement from order to disorder…occurs with a positive change in entropy” “To go from disorder back to order requires input of energy” Take Home: Living system take chemicals from their disordered environment and assemble them into ordered arrays of structural molecules. Hence, living systems live on NEGATIVE entropy.