mcat

Aldol rxns in metabolism

Acetyl CoA + oxaloacetate to (s)-citryl coa, glyceraldehyde-3-phosphate + dihydroxyacetone phosphate to fructose 1,6-bisphosphate

Class II aldolase

Metal cation (usually Zn2+) bound in active site to stabilize negative charge of intermediate, e.g. F 1,6-BP aldolase

Equilibrium favors formation of which acid

Weaker

Lower pKa means

Higher acidity

Bases for complete formation of enolate anion

Hydride (for aldehydes), LDA (for ketones)

pKeq =

pKa left acid - pKa right acid

Higher pKa means

Less acidity

pKa for ketones compared to aldehydes

Higher

Thermodynamically stable enolate

More substituted

Hydride attacks

More thermodynamically stable alpha carbon

LDA, low temp attacks

Least sterically hindered alpha carbon (kinetically stable)

Heat in an aldol reaction

Creates irreversible a-b double bond

Ket + alc + acid (+ heat) =

Acetal + water

Ald/ket + water =

Hydrate

Ald + alcohol + acid/base =

Hemiacetal

Ald/ket + diol + acid (e.g. TsOH) (+ heat) =

Cyclic acetal

Ald/ket + primary amine + acid =

Imine + water

Ketone + dithiol + Raney Ni =

Loss of carbonyl

Ald/ket + secondary amine + acid =

Enamine + water

Ald/ket + primary amine-hydroxide + acid =

Oxime + water

Ald/ket + primary diamine or alkylamine + acid =

Hydrazone

Ald/ket + cyanide + acid =

Cyanohydrin

ald + organometallic + water (separate step) =

Secondary Alcohol

Ket + organometallic + water (separate step) =

Tertiary alcohol

Ald or ester if LiAlH4 + NaBH4 or LiAlH4 + alc or water (separate step if Li) =

Primary alcohol

Ket + NaBH4 or LiAlH4 + alc or water (separate step if Li) =

Secondary alcohol

Oxidation of ald =

Carboxylic acid

Tollen’s reagent selective for

Ald, creates carboxylic acid

Alcohol + strong base or alkali metal =

Alcoxide (ion) + H2

Ethanol + adh1b =

Acetaldehyde/ethanal

Acetaldehyde + aldh2 =

Acetic acid/ethanoic acid

Jones reagent

Sodium dichromate, sulfuric acid, water; for oxidation rxns/carboxylic acid formation with primary alc + sulfuric acid and water (also CrO3, acid, + acetone)

Primary Alc + PCC =

Aldehyde

Secondary alc + jones/pcc =

Ketone

Oxidation of alcohols needs

Alpha hydrogen

TBDMSCl + imidazole

Protecting group for alcohols, remove using TBAF

ROH + TsCl and pyr or MsCl and triethylamine =

ROTs or ROMs for better leaving group

SN2 attack stereochemistry

Causes inversion

Huckel’s rule for aromaticity

4n + 2 pi e-

Carboxylic acid conversion to amide need

DCC

Order of reactivity of various carboxylic acid derivatives to nu: substitution

Acid halide > acid anhydride > thioester > ester > amide

Borane (BH3) selectively reduces

Carboxylic acid, removes carbonyl

Carboxylic acid + LiAlH4 =

Rid of carbonyl group

Carboxylic acid + alc + acid =

Ester

Carboxylic acid + base + acid halide =

Acid anhydride

Induction

Electron withdrawing, increase reactivity

Acid anhydrides have induction or resonance

Induction bc competing resonance structures

Resonance

Electron donating, lower reactivity

Amides have induction or resonance

Resonance bc N is not as electronegative

Carboxylic acid decarboxylation happens when

If another carbonyl is two carbons away from the carboxylic acid carbonyl

First order integrated rate law

ln[A]t = -kt + ln[A]0

Half life of first order reaction is independent of

[A]

Half life of first order reaction

.693/k

Second order integrated rate law

1/[A]t = kt + 1/[A]0

Half life for second order reaction

1/k[A]0

Zero order integrated rate law

[A]t = -kt + [A]0

Half life of zero order reaction

[A]0/2k

Arrhenius equation

k = Ae^(-Ea/RT)

Graph of Arrhenius

lnk = -Ea/R * 1/T + lnA

Rate constant at two diff temps

ln (k2/k1) = -Ea/R * (1/T2 - 1/T1)

Adding an inert gas to equilibrium has what effect

None

Changing the volume in an equilibrium with equal mols of gas on both sides has what effect

None

How does temperature affect Kc for exothermic rxn

Inverse

How does temperature affect Kc for endothermic rxn

Direct

When reaction quotient (Qc) < Kc

rxn goes to right

Reduction occurs at

Cathode

Standard cell potential

1.10 V

Keq is concentration

Independent

Adiabatic vs isothermal curve

Adiabatic is more steep

Central sleep apnea

5+ apneas per hour, cheyne-stokes breathing

Obstructive sleep apnea

15+ apneas per hour

Retest reliability

consistency when a measure is taken multiple times

Inter-rater reliability

consistency when two different people measure the same thing

Content validity

the extent to which an assessment measures the entire construct fully/comprehensively

Predictive validity

the extent to which an assessment is able to predict something it should be able to predict

Gestalt principle of similarity

items that are similar are grouped together

Gestalt principle of pragnanz

reality is reduced to its simplest form

Gestalt principle of proximity

objects that are close together are grouped together

Gestalt principle of continuity

lines are seen as following the smoothest path

Gestalt principle of closure

objects that are grouped together are seen as a whole

binocular cues

convergence, retinal disparity (2.5 in)

monocular cues

relative position, interposition, relative height, motion parallax

Meissner’s corpuscle

glabrous skin, constantly changing stim, light touch, papillary dermis, fast adapting i, small receptive field, grip control

Pacinian/Lamellar corpuscle

deep touch, constantly changing stim, hypodermis, fast adapting ii, vibration

Merkel disk

light touch, hairy/glabrous skin, cont, stratum basale to papillary dermis, slow adapting i, small receptive field, fine details

Ruffini’s ending

deep touch using stretch collagen, cont, reticular dermis, slow adapting ii, large receptive field

hair follicle

light touch, reticular dermis, constantly changing stim

lower motor neuron signs

atrophy, fasciculations/twitches, hypotonia, hyporeflexia

motor unit

lower motor neuron + its skeletal muscle cells

upper motor neuron signs

hyperreflexia, clonus, hypertonia, extensor plantar reflex

weeks 1-8

embryogenesis

week 24

50% survival outside womb

full term

week 39 (37-42)

cluster a personality disorder

odd or eccentric behavior

cluster b personality disorder

intense emotional and relationship problems

cluster c personality disorder

anxious, avoidant, or obsessive

cluster a personality disorder types

paranoid, shizoid, schizotypal

cluster b personality disorder types

antisocial, histrionic, borderline, narcissistic

cluster c personality disorder types

avoidant, dependent, obsessive-compulsive personality disorder

freud’s theory of development

psychosexual, 5 stages in childhood, avoid fixation in a stage