THE UNIVERSITY OF HONG KONG

DEPARTMENT OF CHEMISTRY

CHEM2304 & CHEM3342

Bioinorganic Chemistry
May 14, 2014 (Wednesday)

2:30 pm - 5:30 pm

Only approved calculators as announced by the Examinations Secretary can be used in this examination. It is
candidates' responsibility to ensure that their calculator operates satisfactorily, and candidates must record the
name and type of the calculator used on the front page of the examination script.

Answer ALL questions in Section A in BLUE answer book. (Total 50 marks)

Question 1 ( 5 marks)
Question 2 (18 marks)
Question 3 (11 marks)
Question 4 (16 marks)

Answer ALL questions in Section Bin RED answer book. (Total 50 marks)
Question 5 ( 15 marks)
Question 6 (15 marks)
Question 7 (5 marks)
Question 8 ( 15 marks)

Page 1 ofS

Section A
Answer ALL questions in this section in BLUE answer book. (Total 50 marks)
1.

Complete the following table.

Protein/Group
(a)
Chlorophyll
Catalase
(f)
(h)
Superoxide dismutase

Metal
Cobalt
(c)
Iron
(g)
Copper
(i)

Function
(b)
(d)
(e)
Catalyze Nz
0 2 carrier

-+

NH3

G)
(5 marks)

2.

Transferrin (holo form) and haemoglobin are two iron containing proteins found in the
circulation system in humans.
(a) Compare the two iron proteins in terms of their functions, iron oxidation state,
coordination environment, number of substrate binding site per protein, and
cooperativity in substrate binding.
(10 marks)
(b) Describe how transferrin is taken up by cells and how the substrate is released.
(4 marks)
(c) Natural iron sources exist as insoluble forms under aerobic conditions. How do
bacteria acquire iron from the environment? Include in your answer a description of
the class of iron compounds involved, its cellular uptake and iron release
mechanisms.
(4 marks)

3.

Potassium is an essential s-block element to human. In order to study K+ physiology in

cell, a coumarin-based fluorescent sensor (A) selective for potassium ion is synthesized.

(a) State two biological roles of potassium ions.

Page 2 of5

(2 marks)

(b) The concentration of K+ in the intracellular medium is higher than that in the
extracellular medium in the resting state of cells. This concentration difference is
created by a transport process mediated by Na+/K+-ATPase. How does this K+
transport process differ from the K+ transport through an ion channel?
(3 marks)
(c) Based on the structure of A, propose a structure that you would design for a selective
fluorescent probe to detect (i) Na+; and (ii) Hg2+ in cell respectively. Briefly explain
your design.
(4 marks)
(d) Suggest a physical method, other than imaging with chemical probes, that can
determine (i) the total potassium content and (ii) the distribution of potassium ion in
cells.
(2 marks)

4.

To study the reactive intermediates derived from 0 2 activating copper enzymes like
dopamine-~ monooxygenase and peptidylglycine-a-hydroxylating monooxygenase,
Karlin and co-workers reported the copper(I) carbonyl complex (B) as a model
compound. A solution of B is colourless. Upon bubbling 0 2 to the solution, a green
solution with new absorptions at Amax= 418 nm (E = 4300 M- 1cm-1), 615 nm (E = llOO
M- 1cm-1) and 767 nm (E = 840 111cm- 1) is obtained. It is found that a mononuclear
copper-0 2 complex (C) is formed. The resonance Raman spectrum of C shows an 0-0
stretch at ll21 cm- 1
NMe2

r?

_L~~co
Me2N~ MeY
N

02

(a) Is B diamagnetic or paramagnetic? Suggest how the magnetic property of a metal

1
complex can be deduced from 1H NMR. What will be the possible changes in the H
NMR signals of B if the Cu(I) centre is replaced by Co(II)?
(4 marks)
(b) If the 0 2 moiety in C is a superoxide, what will be the oxidation state of copper?
Explain how this assignment can be derived and supported by the available
spectroscopic data provided above.
(5 marks)

Page 3 ofS

(c) Predict the corresponding 0-0 stretching frequency if isotopically labelled

and

16 ' 18 02

are used instead of 16 ' 160 2.

(f = _2:_ [!i_ ; =
2n~

18 18
' 02

mi mz )
m1+m2

(3 marks)
(d) A similar Cu(II) complex D was reported in a related study. The X-band EPR
spectrum shows two peaks at g;1 = 2.253 and v- = 2.052 with A;;= 174 G and A..L =
31.5 G. Assign the two peaks (i) and (ii) with the corresponding g-value and explain
the origin of the 4-line hyperfine structure observed in peak (i) (63 Cu: 69%
65
abundance, I = 3/2; Cu: 31 % abundance, I = 3/2). Also sketch the corresponding
EPR spectrum if D undergoes a one-electron reduction.

r9
_(g'Z5.~"''
Me N
2

# "(;;,

2+

2500

2700

(i)

(ii)

1~

....

3100

....

3700

3000

(4 marks)

Section B
Answer ALL questions in this section in RED answer book. (Total 50 marks)
5.

(a) Azurin, a blue copper protein, is a good electron transfer agent when it is delivering
electrons to the enzyme copper nitrite reductase. It requires little change in geometry
when the metal ion is oxidized or reduced. What experimental evidences can be used
to confirm such a hypothesis?
(4 marks)
(b) Iron-sulfur proteins such as ferredoxin, are proteins characterized by the presence of
iron-sulfur clusters. What are the unusual features of the compositions and structures?
(6 marks)
(c) Briefly discuss the role of transition metals in photosynthesis.

6.

(5 marks)

(a) Smoking has been found to increase the uptake of gold drug (e.g. aurothiomalate)
metabolites into red blood cells. What are the chemical principles behind this
phenomenon (Hint: Cigarette smoke contains 30-160 g ofHCN per cigarette)?
(4 marks)
Page 4 of5

3
(b) How do you rationalize a Gd +-based MRI contrast agent? One of the contrast agents
has a relaxivity of 3.6 mM- 1s 1 When the concentration of the contrast agent in
blood is 400 M, the measured relaxation time (T 1) is 354 ms. Determine the
relaxation time when the concentration of the contrast agent in blood is 150 M.

(5 marks)
(c) Complexes of 99mTc (y; tl/2 6 h) are particularly suitable as diagnostic agents.
Suggest chemical principles why it is well chosen for this purpose, and estimate the
fraction of the active complex that would remain after a period of 18 hours.
(6 marks)
7.

The following Pt(II) complex is not an effective anticancer agent. Give a brief account
on why this complex is inactive.

0
Cl1,,,,

,,,NH3

Pt

"c1
(5 marks)

8.

(a) Write an account on the chemical principles of Zn2+ ion in hydrolytic enzymes such
as carbonic anhydrase. The metal coordinated ligands and coordination geometry
should be provided.
(5 marks)
(b) Zn2+ ion is spectroscopically silent. To examine Zn2+ binding to a particular protein
(or an enzyme), which metal ions can replace Zn2+ and what kinds of physical
techniques can be used accordingly?
(5 marks)
(c) Based on Hard and Soft Acid Base (HSAB) concept, what kinds of donors and
corresponding amino acid residues shall be involved in translocation of Zn2+ in a
zinc transporter?
(5 marks)

- END OF PAPER-

Page 5 ofS