Lecture 1/2: Water Flashcards

Water! (100 cards)

1
Q

Water has a ____ moment.

A

Dipole

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2
Q

Since water is so ____, it takes a lot of ____ to break bonds bw H2O molecules.

A

Since water is so polar, it takes a lot of energy to break bonds bw H2O molecules.

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3
Q

What is a disordered collection of clusters?

When is it not in clusters?

Bc of this it is known to have what type of structure?

A

- Liquid H2O

- When there are individual molecules of water @ BP

- Flickering

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4
Q

Liquid H2O’s collection of clusters explains:

  1. ?
  2. ?
  3. ? (?)
A
  1. Viscosity
  2. High BP (when compared to molecules of similar MW)
  3. Extraordinarily high heat capacity (thermal mass)
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5
Q

How many H-bonds are possible per H2O molecule?

Liquid water?

Ice?

A

4

Liquid water: 3.4 H-Bonds

Ice: 4 H-Bonds

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6
Q

Which is ice and water?

Why?

A

Left: Water

Right: Ice

- Due to less dense structure, allows it to float

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7
Q

Due to accessible melting point, H2O:

  • Occurs in a ____ ______ compatible with life
  • Facilitates ____ _______: (AKA- ice ……. = )
A
  • Occurs in a temperature range compatible with life
  • Facilitates biological turnover: (AKA- ice expands and rips apart cellulosic & woody plant = Carbon Cycle!)
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8
Q

Due to low boiling point: H2O

  • Permits ____ & ____ ____
  • _____ keeps atmosphere moist
A
  • Permits evaporation & heat loss
  • Vapor keeps atmosphere moist
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9
Q

Due to other aspects of polarity: H2O

  • Readily accomodates ____/_____ substances
  • Also affect the interactions of _____ groups (called?)
  • Strongly affects biochemical _______
A
  • Readily accomodates polar/ionic substances
  • Also affect the interactions of apolar groups (called? Hydrophobic Interactions)
  • Strongly affect biochemical thermodynamics
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10
Q

H2O deactivates _____ rxns.

  • ____ rxns work best in _____ ______ solvents. (EX:)
  • Water binds to _____ and ______ greatly deactivating them.
A

H2O deactivates nucleophilic rxns.

  • Nucleophilic rxns work best in polar organic solvents. (EX: Acetone, DMF, THF)
  • Water binds to nucelophiles and electrophiles greatly deactivating them.
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11
Q

Why are the deactivating effects of H2O towards nucleophilic rxns extemely beneficial, tho it seems disadvantageous?

A

Nonenzymatic rxns are extremely slow under physiological conditions (salty water, neutral pH, moderate temps)

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12
Q

H2O deactivates nucelophilic rxns and explains vital role that ____ play?

A

H2O deactivates nucelophilic rxns and explains vital role that enzymes play?

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13
Q

Due to H2O deactivating nueclophilic rxns, this explains the vital roles ezymes play which allows them to:

  1. ?
  2. ?
A
  1. bind substrates
  2. behave as virtual on/off switches
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14
Q

Enzymes bind substrates:

  • Increasing their ____ ____
  • Orienting them to maximize ______
  • Stabilizing rxn _____-_____
  • Making rxns go ______
A
  • Increasing their local concentration
  • Orienting them to maximize reactivity
  • Stabilizing rxn transition-states
  • Making rxns go much faster
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15
Q

Enzymes behave as virtual on/off switches:

  • No rxn in _____ of _____

–> rxn too slow = water _____

  • ______ potentially toxic ____-____
  • Allows for highly effective ______
A
  • No rxn in abscence of enzyme

–> rxn too slow = water suppresses

  • Reduces potentially toxic side-rxns
  • Allows for highly effective regulation
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16
Q

Ezymes ____ reactivity so that metabolism can proceed under _____ conditions.

EX: ?

A

Ezymes increase reactivity so that metabolism can proceed under physiological conditions.

EX: Glucose Phosphorylation

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17
Q

What is the breaking apart of molecules by H2O?

  1. ?
  2. ? (? attached)
A
  1. Ionic Hydrolysis: solid/gas and breaking into hydrated ions
  2. Covalent Hydrolysis: (phosphate attached) bring in water and hydrolved glucose and phosphate and breaking covalent bond
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18
Q

What refers to the continuous exchange of water w/in the hydrosphere?

AKA:

Bw? (6)

A

Water/Hydrologic Cycle

Bw: atmosphere, soil water, surface water, groundwater, plants, and animals

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19
Q

Water moves thru each region by what 4 transfer processes?

A
  1. Evaporation
  2. Transpiration
  3. Precipitation
  4. Runoff
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20
Q

What is the water transfer process from oceans and other water bodies into the atmosphere?

A

Evaporation

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21
Q

What is the water transfer process from land plants and animals into the atmosphere?

A

Transpiration

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22
Q

What is the water transfer process from water vapor condensing and falling to the earth/ocean?

A

Precipitation

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23
Q

What is the water transfer process from the land and reaching the sea?

A

Runoff

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24
Q

Life getting started was incredibly slow due to lack of _____.

A

catalysts

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25
Life most likely began in \_\_\_\_\_/\_\_\_\_ \_\_\_\_. Why?
Life most likely began in **desert/mt. slopes bc molecules such as peptides, oligosaccharides and metabolic intermediates (ie ATP) ONLY form upon loss of water.**
26
Steps of first life? 1. Drought concentrates \_\_\_\_\_, allowing them to _____ --\> loss of \_\_\_\_\_ 2. Solutes ____ by rain, relocating and ____ elsewhere
1. Drought concentrates **solutes,** allowing them to **combine** --\> loss of **H2O.** 2. Solutes **diluted** by rain, relocating and **reacting** elsewhere
27
After a few billion years, everything changed upon the appearance of small ____ of \_\_\_\_\_\_\_.
After a few billion years, everything changed upon the appearance of small **oligomers** of **ribonucelotides.**
28
RNA molecules were incredibly special bc they could: * fold into \_\_\_-\_\_\_ 3D \_\_\_\_\_. * act as \_\_\_\_. * ____ information. * eventually, _____ themselves.
* fold into **well-defined** 3D **structures.** * act as **catalysts.** * **store** information. * eventually, **replicate** themselves.
29
Simply put, Life is a \_\_\_\_-\_\_\_\_ system, able to ____ & ____ \_\_\_\_\_. (Rudimentary form of life became this)
Simply put, Life is a **self-adaptive** system, able to **evolve** & **gain** **options.**
30
Life "evolving and gaining options" refers to? Which eludes to \_\_\_\_\_, the search algorithm for change.
**Learning and adjusting** **Mutation**
31
This is an image of water undergoing rapid H+ \_\_\_\_\_/\_\_\_\_\_ @ equilibrium. AKA?
Water undergoes rapid H+ **dissociation/reassociation.** AKA: **autocrotolysis**
32
In reality there are no free H+'s; instead H+ ____ w/ neighboring _____ to form _____ ions. (= ?)
In reality there are no free H+'s; instead H+ **combines** w/ neighboring **H2O** to form **hydronium** ions. (= **H3O+**)
33
In liquid H2O, ____ \_\_\_\_ occurs; the fast transfering of one H+ to water, creating hydronium ion. \_\_\_\_ ____ creates a "\_\_\_ wire" to facilitate rapid H+ transfer in/out of active site.
In liquid H2O, **proton hopping** occurs; the fast transfering of one H+ to water, creating hydronium ion. **Carbonic Anhydrase** creates a "**proton** wire" to facilitate rapid H+ transfer in/out of active site.
34
In pH Acid/Base Rxns: pH = (rxn?) Kw = ?rxn = ?M --\> Measure of? [H+] = ? [A] = ? [HA] = ?
pH = **-log10[H3O+]** Kw = **[H3O+][OH-] = 10-14 M2** --\> Measure of **dissocation constant for water reacting w/ self** [H+] = **proton** [A] = **anion/ base** [HA] = **acid**
35
Neutrality of pH Acid/Base Rxns require x = ?
**[H3O+] = [OH-]** = x
36
What do pH meters measure? Where ___ is the activity coefficient and (H+) =
**pH meters measure proton activity (H+)** Where **A** is the activity coefficient and (H+) = **A[H+]**
37
Since pH meters are standardized by using *solutions of known concentration and activity*, pH of pure water is \_\_\_\_\_, but not _____ \_\_\_\_\_.
Since pH meters are standardized by using solutions of known concentration and activity, pH of pure water is **~7.00** but not **exactly 7.00.**
38
Ka = units? Henderson-Hasselbalch Equation?
Ka = **[H+][A-]/[HA]** ## Footnote **pH = pKa + log ([A-]/[HA])**
39
When: what are the concentration of anions to acids? pH = pKa pH = pKa + 1 pH = pKa - 1
**[A-] = [HA]** **[A-] = 10 x [HA]** **[A-] = 0.1 x [HA]**
40
On the basic/acid side of the pKa, what is the concentration of acid to anion?
_Basic Side:_ **[HA] \< [A-]** _Acidic Side:_ **[HA] \> [A-]**
41
Understanding biochemical processes and acid/base rxns are important when considering: * _____ have acid/base groups * Enzymes have acids and bases in _____ sites * DNA & RNA are \_\_\_\_\_\_\_\_
* **Metabolites** have acid/base groups * Enzymes have acids and bases in **active** sites * DNA & RNA are **polyelectrolytes**
42
What are weak acids & bases that help stabilize pH?
**Buffers**
43
Buffers obey __ \_\_\_\_\_\_ Principle, which states: "a ____ system compensates to a \_\_\_\_\_" meaning: ? Add H+ & they readjust--\> ? Add OH- & they readjust--\> ?
Buffers obey **Le Chatelier's** Principle, which states: "a **dynamic** system compensates to a **stress**" meaning: **adjusts equilibrium ratios in accordance to stabilize system** Add **H+** & they readjust--\> **A- + H+ = HA** Add **OH-** & they readjust--\> **HA + OH- = A- + H2O**
44
Buffers are most effective near their ___ values, bc that's where there is a sufficiently large pool of ___ the weak ___ and its conjugate \_\_\_.
Buffers are most effective near their **pKa** values, bc that's where there is a sufficiently large pool of ***both*** the weak **acid** and its conjugate **base**.
45
What is the largest biological buffer in the body that is the conjugate base of phosphoric acid?
**Orthophosphate**
46
What is the second largest biological buffer that is located in cells, helps oxidize foods and creates CO2?
**Bicarbonate**
47
What buffers are the biggest contributions of pH control, due to many metabolites are weak acids/bases?
**Biological Buffers**
48
What is the 3rd largest biological buffer that has high concentration in the heart?
**ATP**
49
What is the 4th largest biological buffer that is located in all cells, especially cytoplasm, and contains carboxyl and amino groups?
**Proteins**
50
What are the smallest biological buffers that are located in muscles and helps controls ATP in cells?
**Creatine Phosphate**
51
What is arguably the most important buffer system for acid/base homeostasis in humans that is found in all areas of the body? * Takes advantage of ____ production * Maintains a relatively constant __ pH by countering changes in \_\_\_, \_\_\_\_, \_\_\_\_, ____ \_\_\_\_\_, etc
**Bicarbonate Buffer System** * Takes advantage of **CO2** production Maintains a relatively constant **plasma** pH by countering changes in **acids,** **bases**, **anions,** **metal ions**, etc *
52
What is the equation for the Bicarbonate Buffer System? * ___ combines with ____ to form \_\_\_\_, which rapidly dissociates to form ___ ion and \_\_\_\_. * Rxn catalyzed by ____ \_\_\_\_\_\_\_
**CO2 + H2O = H2CO3 (minor species) = H+ + HCO3-** **CO2** combines with **water** to form **carbonic acid**, which rapidly dissociates to form **hydrogen** ion and **bicarbonate.** Rxn catalyzed by **carbonic** **anhydrase**
53
When the Bicarbonate Buffer sytem is partered with _____ \_\_\_\_\_\_ it becomes a powerful acid-base regulator.
When the Bicarbonate Buffer sytem is partered with **respiratory compensation** it becomes a powerful acid-base regulator.
54
What is the term that modifies circulating CO2 to create altered breathing rates? * What decreases CO2 levels by bringing in more O2 and expelling CO2? * What method increases CO2 levels by inhaling the previously expelled CO2?
* **Respiratory Compensation** * **Hypervenilating** * **Taking a paperbag and breathing in and out CO2**
55
Increasing the breathing rate and expelling excess CO2 results in? Occurs by pulling even more ____ toward production of \_\_\_ Excess acid is essentially "\_\_\_\_"
* **Respiratory Alkalosis** * Occurs by pulling even more **protons** toward production of **CO2** * Excess acid is essentially **"exhaled"**
56
Cells also buffer \_\_\_\_: In acid-base disturbances, shifts of H+ or HCO3- bw cells and ___ are mainly balanced by movements of Na+, K+, and Cl-
Cells also buffer **ECF:** In acid-base disturbances, shifts of H+ or HCO3- bw cells and **ECF** are mainly balanced by movements of Na+, K+, and Cl-
57
Protonation/Deprotonation of ___ molecules is rapid
Protonation/Deprotonation of **small** molecules is rapid
58
\_\_\_\_\_ means that the rxn rate is determined by how fast reactants collide \_\_\_ molecules collide quickly
**Diffusion-limited process** means that the rxn rate is determined by how fast reactants collide **Small** molecules collide quickly
59
Protonation/deprotonation of macromolecules: * Acid/base groups on _____ react immediately * Acid/base groups ____ \_\_\_\_\_ may never ionize * H-Bonds of buried helices and ß-sheets require the "\_\_\_\_ \_\_\_\_\_\_" - (\_\_\_ \_\_\_\_\_)
Acid/base groups on **surface** react immediately Acid/base groups **deep inside** may never ionize H-Bonds of buried helices and ß-sheets require the **conformational breathing**" - (**local unfolding**)
60
What is a digestive enzyme secreted into gastric juice in the stomach, which allows it to act optimally @ a pH ~1.5?
**Pepsin**
61
What is a digestive enzyme that acts in the small intestine and has a pH optimum that matches the *neutral pH* in the lumen of the small intestine?
**Trypsin**
62
What is a hydrolytic enzyme that operates well enough at neutral pH of intestine?
**Alkaline phosphatase**
63
Label the peaks of the graph with the appropriate enzyme.
64
What type of interactions are very important for biomolecules in aqeous solvent? 1. ? 2. ? 3. ? 4. ?
**Noncovalent "Weak" Interactions** 1. **H-Bonds** 2. **Ionic Interactions** 3. **Hydrophobic Interactions** 4. **Van der Waals Interactions**
65
"Weak" noncovalent interactions are individually \_\_\_\_, but the ________ is very significant.
"Weak" noncovalent interactions are individually **weak**, but the **aggregate** is very significant.
66
What allows proteins and nucleic acids to fold & unfold?
**"Weak" noncovalent interactions**
67
What type of "Weak" Noncovalent bond is this?
**H-Bond bw neutral groups**
68
What type of "Weak" Noncovalent bond is this?
**H-bond bw peptide bonds**
69
What type of "Weak" Noncovalent bond is this?
**Ionid Attraction Interaction**
70
What type of "Weak" Noncovalent bond is this?
**Ionic Repulsion Interaction**
71
What type of "Weak" Noncovalent bond is this?
**Hydrophobic Interactions**
72
What type of "Weak" Noncovalent bond occurs bw any 2 atoms in close proximity, is the longest and weakest and is due to "flickering dipoles"?
**van der Waals interactions**
73
With Gibbs Free energy (deltaG): energy needs to be ______ to *make* a bond and \_\_\_\_\_\_\_ to *break* a bond.
With Gibbs Free energy (deltaG): energy needs to be **released** to make a bond and **added** to break a bond.
74
In a _____ noncovalent interaction, intrinsically polar bonds interact.
**H-Bonds**
75
In a _____ noncovalent interaction, opposite charges attract and like repel.
**Electrostatic**
76
In a _____ noncovalent interaction, H-Bonding and electrostatic interactions combine.
**Salt Bridge**
77
In a _____ noncovalent interaction, displacement of water is driven by favorable entropy.
**Hydrophobic interactions**
78
In a _____ noncovalent interaction, stacking of aromatic rings occur due to greater e- delocalizations.
**Pi Stacking**
79
In a _____ noncovalent interaction, very weak forces occur bw oscillating dipoles.
**van der Waals interactions**
80
What is the order of Noncovalent interactions according to their _strengths_? 1. ? 2. ? 3. ? 4. ? 5. ? 6. ?
1. **Salt Bridge** 2. **H-Bonds** 3. **Electrostatic** 4. **Hydophobic** 5. **Pi Stacking** 6. **van der Waals**
81
What is fundamentally an "acid/base" interaction?
**H-Bonds**
82
H-Bonds require proton donors = electro+/-?
H-Bonds require proton donors = electro**+**
83
H-Bonds require proton acceptors = electro+/-?
H-Bonds require proton acceptors = electro**-**
84
When are H-Bonds the strongest?
When they are **linear.**
85
H-Bonds are found throughout nature bw: 1. ? 2. ? BUT, it depends on the ___ of the attached molecules and group
H-Bonds are found throughout nature bw: 1. **Peptide groups in polypeptides** 2. **Complementary bases of DNA** BUT, it depends on the **EN** of the attached molecules and group
86
H-Bonds are found throughout nature: * Exploit the properties of the universal \_\_\_\_\_\_ * Improve \_\_\_\_\_\_\_ * Essential for biospecific \_\_\_\_\_\_\_\_ * Easy to make & break bond to allow fast \_\_\_\_\_\_
H-Bonds are found throughout nature: * Exploit the properties of the universal **solvent** * Improve **solubility** * Essential for biospecific **recognition** * Easy to make & break bond to allow fast **kinetics**
87
Why are the stabilizing interactions in Hydrophobic Interactions NOT true bonds?
**There is no overlapping of atomic/molecular orbitals, which allows apolar groups to weakly interact.**
88
Wha is the Gibbs Equation?
89
In hydrophobic interactions, water binds tightly to apolar groups so that: Delta H \<\>\> for water-binding and water-release?
90
Hydrophobic interaction results in the release of water molecules which (in/de)creases randomness?
**Increases randomness (Delta S \>\> 0)**
91
As temperature strongly influences Delta G, when is it favorable vs unfavorable?
**At low T: \> 0, unfavorable** **High T: \< 0, favorable**
92
\_\_\_\_\_ groups facilitate protein folding: * protein folding ______ local entropy of protein * water release ____ entropy of overall system
**Hydrophobic** groups facilitate protein folding: * protein folding **decreases** local entropy of protein * water release **increases** entropy of overall system
93
\_\_\_\_\_\_ in hydrophobic interactions can swivel w/ ease, facilitating ______ \_\_\_\_\_\_. \_\_\_\_\_\_\_\_ maximizes packing within the protein, thereby maximizing release of bound \_\_\_\_\_\_.
**Side-chains** in hydrophobic interactions can swivel w/ ease, facilitating **protein folding.** **Variety in side-chains** maximizes packing within the protein, thereby maximizing release of bound **water**.
94
Strength of hydrophonic interaction is determined by:
Strength of hydrophonic interaction is determined by **the number of water molecules released per interaction.**
95
What is a measure of the number of water molecules needed to cover a particular hydrophobic side-chain?
**Water Accessible Area**
96
Hydrophobic interactions also play a dominant role in stabilizing _______ \_\_\_\_\_\_\_\_\_\_ \_\_\_\_\_\_\_\_. Hydrophobic groups on the surface interact with apolar lipid ________ of the inner ______ \_\_\_\_\_\_\_.
Hydrophobic interactions also play a dominant role in stabilizing **membrane bilayer structure**. Hydrophobic groups on the surface interact with apolar lipid **side-chains** of the inner **membrane bilayer**.
97
Amphipathic molecules possess BOTH: * _______ region (water-like, polar or charged) * _______ region (apolar) Long-chain fatty acids have very hydrophobic alkyl chains, each of which is surrounded by a layer of highly ordered ______ molecules.
Amphipathic molecules possess BOTH: * **hydrophilic** region (water-like, polar or charged) * **hydrophobic** region (apolar) Long-chain fatty acids have very hydrophobic alkyl chains, each of which is surrounded by a layer of highly ordered **water** molecules.
98
LABEL!
99
What occurs with amphipathic molecules in water?
100
In amphipathic molecules in water: What does clustering together in micelles do to the fatty acid molecules? Due to this, how many and where do water molecules form the shell of the ordered water? What stabilizes the micelle?
In amphipathic molecules in water: What does clustering together in micelles do to the fatty acid molecules? **Reduce the hydrophobic SA exposed to water** Due to this, how many and where do water molecules form the shell of the ordered water? **Fewer water molecules are req'd to form the shell of ordered water around a hydrophobic surface** What stabilizes the micelle? **The energy gained by freeing immobilized water molecules as entropy increases.**