An introduction to inorganic chemistry 1+2 Flashcards

1
Q

what are the most abundant elements employed in mammalian biochemistry?

A

C,N,O,H,S,P but augmented by a range of other elements many of which are metals , I, Se, Cl, Na, K, Ca, Mg, Co, Cu, Ni, Zn,Fe, Mo, V

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2
Q

What are many of the metals associated with

A

a protein - 1/3 of proteins are metalloproteis

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3
Q

what does each period correspond to?

A

the completion of the s and p subshells

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4
Q

what happens to atomic radii down a group and across a period (left to right)

A

increases down a group and from left to right across a period

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5
Q

what happens to ionisation energy across the 1st period?

A

across the 1st period ionisation energy increases left to right

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6
Q

what is electron affinity

A

is is a measure of how strongly an atom or molecule can attract an extra
electron

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7
Q

what is electronegativity?

A

the ability of an atom within a compound to attract electrons towards itself

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8
Q

what is polarisability?

A

the essentially underpins the idea of Hard and soft Lewis acids and bases’ it is the ease with which an atom or ion can be distorted by an electric field.

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9
Q

what are the hardest atoms and ions?

A

the hardest atoms and ions are those with low ionisation energy and low electron affinity

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10
Q

what are the softest atoms and ions

A

those with low ionisation energy and low electron affinity

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11
Q

soft acids and bases are

A

more polarisable and form bonds with more covalent character

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12
Q

what are the biological roles performed by metals

A

structural
catalytic
redox
other

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13
Q

hard acids and bases are

A

less polarisable and form bonds with more ionic character

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14
Q

what are the factors that influence the role of the metal

A

valency, ionic radius, polarisability
hydration energy (ease with which water molecules can be removed from the metal ion).
radius of the hydrated ion.

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15
Q

Lewis acids and bases

A

theory introduced by the American chemist G.N Lewis

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16
Q

what does the theory state

A

that hard acids prefer hard bases while soft acids prefer soft bases

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17
Q

what did this theory allow?

A

metal ligand interactions to be described- ligand is the Lewis base and metal the Lewis acid

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17
Q

define a Lewis acid

A

substance accepts an electron pair

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17
Q

define Lewis base

A

substance that donates an electron pair

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18
Q

properties of hard acids

A

high charge density
small ionic radius
not easily polarisable
Na+, K+, Mg2+, Ca2+, Fe3+, Co3+

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19
Q

Properties of hard bases

A

not easily polarised
high electronegativity
vacant, high energy orbitals
hard to oxidise
H2O,-OH, CO2-, CO22- , NO-3, PO3- 4, ROH, RO-, R2O, NH3, RNH2, CL-

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19
Q

Acid intermediate

A

Fe2+, Co2+,Ni2+, Cu2+, Zn2+

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20
Q

base intermediate

A

NO-2, Br-, Imidazole

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20
Q

soft acid

A

low charge density
large ionic radius
more polarisable Cu+

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21
soft base
high polarisability low electronegativity low energy vacant orbitals easily oxidised RSH, RS-, CN-, CO
22
shape of a molecule can be defined by ?
bonds electron pairs within it so it is possible to predict the geometry of coordination compounds.
23
linear
2 numbers of pairs alkyne (sp)
24
Equilateral triangle
alkene sp2 3 numbers of pairs
25
tetrahedron
alkane sp3 3 numbers of pairs
26
trigonal bi-pyramidal square pyramid (less stable)
AsF5 sp3d 5 numbers of pairs
27
octahedron
6 numbers of pairs SF6 sp3d
28
what do different metals prefer?
different coordination numbers ( different numbers of ligands bonded to the metal)- hence, different geometries
29
what are the most common coordination geometries found in biological systems?
4 and 6 and 5
30
are many metals fixed to only one geometry
are not fixed to only one coordination geometry
31
what are the common geometries
tetrahedral square planar octahedral
32
what can ligands be
monodentate or polydentate
33
define polydentate
more than one point of attachment to the metal
34
define monodentate
only one point of attachment to the metal
35
what types of ligands feature in biology
both types of ligand feature in biology, but the polydentate ligands are critical features of a range of important biological molecules
36
examples of ligands
copper glycine ciprofloxacin EDTA
37
what are macrocyclic ligands
in biological sense, these are a special case of polydentate ligands a macrocyclic molecule is a cyclic molecule with at least 9 atoms containing at least 3 donor atoms Lewis base typically N, O, S or P
38
are macrocyclic complexes generally thermodynamically and kinetically more stable than non-cyclic ligands
yes they are
39
why are they more stable
essentially its the chelate effect simply stated, complexes with polydentate ligands will be more stable than complexes with similar mono dentate ligands, favourable entropic factor accompanying the release of nonchelating ligands from the metal ion. it is generally the case that stability increases with the number of donor atoms in the ring
40
biological examples
the porphyrin unit a simplified haem unit
40
what's the clinical significance of chelation?
metal ions are widely distributed throughout the body a range of drugs can behave as chelating ligands, chelation changes both the physical and chemical characteristics of both components ie the metal and the ligand
41
what is the clinical significance of chelation
the tetracyclines broad spectrum antibiotics - value has decreased over recent years due to resistence treatment of choice for certain infections -chlamydia rickettsia brucella Lyme disease also respiratory and genital mycoplasma infections tigecycline reserved for treatment of complicated skin and soft tissue infections and complicated abdominal infections caused by multiple antibacterial resistant organisms
41
what is the tetracyclines mode of action?
bacteriostatic agents tagets 305 subunit selective -very little binding to mammalian ribosomes block binding of aminoacyl tRNA in the A-site involving Mg2+ ions
42
examples of tetracyclines
doxycycline , monocycline oxytetracycline, tetracycline demeclocycline
42
are most metal chelates insoluble?
yes most of the metal chelates are insoluble
43
what is absorption of tetracyclines affected by?
extent of chelation with metal ions
44
tetracyclines form what?
form chelates with a range of metal ions Ca2+, Mg2+, Al3+, Fe2+, Zn2+
45
with M3+ what is produced?
they form 3:1 drug-metal chelates
46
with M2+ what is produced ?
2:1 drug metal chelates
47
iron (II)
ferrous sulfate , ferrous fumarate and ferrous gluconate
48
calcium (II)
calcium carbonate
49
What do aluminium and or magnesium hydroxide based antacids do?
reduce the absorption of the tetracyclines
50
who cannot have tetracyclines
not recommended for children under the age of 12 due to discolouration of the teeth (ranges from greyish to yellow) the effect is dose dependent and permanent tetracyclines are also not recommended for pregnant or breast feeding women - this is connected to the effect on skeletal growth
51
what isa key aspect of metal ions ?
in their ability to stabilise conjugate bases
52
what does this do to the pka of the parent acid
it is frequently lowered
53
what is calmodulin?
proteins involved in the meditation of the Ca2+ signal in large number of pathways sometimes found as part of enzyme complexes phosphorylase kinase
54
describe calmodulin?
small acidic protein dumbbell shaped protein that binds 4x Ca2+ ions the major donor groups from the protein that bind to the Ca2+ ions are carbonyl and carboxylate groups binding is complex involving a specific set of Lewis bases so as not to stabilise cross-links within the protein.
55
key properties of Ca2+ ions
binding- it is selective but differs from Mg2+ ion in a number of key ways can interact with neutral oxygen donors carbonyls and ethers it can bind to a number of centres at once - irregular coordination geometry ligands- Ca2+ ions readily exchange water with other ligands - with a complex, the ligands on the ion are fluctional
55
Ca2+ and its biological roles
metabolism- numerous enzymes inside cells cell division- S-100 proteins, immune system cell death (apoptosis)- internal proteases binding to membranes- C-2 domains of enzymes Phosphorylation -activation of kinases involved in fertilisation of the egg hormone transmitter release- homeostasis blood clotting- involved in both the intrinsic and extrinsic pathways
56
Mg2+ ions and DNA/RNA
although the role of Mg2+ ions in a number of RNA/DNA units is significant , it is perhaps its role in tRNA and ribosomes that are amongst the most important
57
tRNAs contain regions known as?
half crucifixs Mg2+ ions are key to holding this shape
58
what do ribozymes require Mg2+ ions to do ?
catalyse their splicing reactions
59
what is RNA
RNA ribonucleic acid multiple functions chemically, RNA is relatively simple RNA forms a range of stable structures RNA can perform catalytic functions (ribozymes)
60
tRNA requirement
at least one strong site and many weaker sites fold stabilisation half crucifix structures
60
what Is DNA?
DNA- deoxyribonucleic acid serves as the information store chemically DNA is a relatively simple molecule DNA can detect its own replication The DNA double helix is remarkably stable
61
rRNA
Stabilisation of fold and association with 30S 50S and 70S subunits
62
mRNA
attachment to ribosomes
63
ribozymes
Mg2+ acts to bind the RNA enzyme to the RNA enzyme to the RNA substrate
64
DNA
Crucifix structures
65
DNA/ RNA
polymerase
66
magnesium is required as
requires of various polynucleotides
67
kinases
the reversible phosphorylation of protein , resulting in a conformational change in that protein provides a useful control mechanism that allows for the activity of an enzyme to be modulated
68
what's under this control mechanism
many proteins are under this controlled mechanism
69
what do protein kinases do?
add the phosphate group
69
phosphorylation takes place in which 3 amino acids
serine threonine or tyrosine the phosphate is supplied as the Mg-ATP complex
70
phosphateses
remove the phosphate group
71
where is the ATP bound
The ATP is bound into the protein via the adenine leaving the phosphate chain exposed , or weakly bound
72
what does an anion centre on the protein do?
An anion centre on the protein then helps to move the triphosphate into position so it can transfer the terminal phosphate group group to the requisite amino acid
73
is phosphorylation restricted to a single site?
no it is not restricted to a single site on the protein and the protein may be phosphorylated by more than one kinase this allows convergence of cell signalling pathways