Transcript Walker_Applications_Broadband

New Applications of Broadband
Rotational Spectroscopy
1.
Wednesday 18th April 2012
ERC Starting Grant Presentation
Nicholas R. Walker
(Left) The CP-FTMW spectrometer re-located to Newcastle University
(Right) Some components of the instrument.
Wednesday 18th April 2012, ERC Proposal Presentation, Nicholas R. Walker
Career Background
2.
1996-2003 Worked at 5 different institutions in Europe and
North America. 48 peer-reviewed articles and achieved an hindex of 21.
2003-2011 Royal Society University Research Fellowship, University
of Bristol.
2012
Susanna Stephens, Nicholas Walker
and the CP-FTMW spectrometer in
Newcastle.
Wednesday 18th April 2012, ERC Proposal Presentation, Nicholas R. Walker
The Broadband Advantage
1946 - First high resolution microwave spectroscopic measurements.
1981 – cavity FT-MW
spectroscopy (Balle and Flygare).
12166.0
2006 – Construction of the chirped-pulse
Fourier transform microwave
spectrometer (Pate1).
12166.4
Frequency / MHz
1. G.G. Brown et al., Rev. Sci. Instr. 79, 053103 (2008)
8000
12000
16000
Frequency / MHz
3
Wednesday 18th April 2012, ERC Proposal Presentation, Nicholas R. Walker
The Broadband Advantage
13850
13860
13870
Frequency / MHz
8000 10000 12000 14000 16000 18000
Frequency / MHz
Balle Flygare FTMW
1MHz
Measurement bandwidth
Time required for data acquisition
14 hours
* G.G. Brown et al., J. Mol. Spec., 238 200 (2006)
CP-FTMW*
11GHz
48 minutes
4.
Wednesday 18th April 2012, ERC Proposal Presentation, Nicholas R. Walker
5.
Objectives
Address problems outside of traditional
boundaries of microwave spectroscopy.
Pd, C2H4, C2H2
Metal ion solvation
Role of metals in
biochemistry
Chemical analysis
Methodology
Microwave spectroscopy
Infrared spectroscopy
Theory
Wednesday 18th April 2012, ERC Proposal Presentation, Nicholas R. Walker
Theme 2 – Microscopic Ion Solvation
6.
Ni+(CO2)5
Ni+(CO2)4
Ni+(CO2)3
N.R. Walker, R.R. Wright and A.J.
Stace, J. Am. Chem. Soc. 121, 48374844 (1999)
N.R. Walker, R.S. Walters, G.A.
Grieves and M.A. Duncan, J.
Chem. Phys. 121, 10498-10507
(2004)
Wednesday 18th April 2012, ERC Proposal Presentation, Nicholas R. Walker
Theme 2 – Microscopic Ion Solvation
7.
H2OAgCl: N.R. Walker and coworkers, Angew. Chem. Int. Ed. 49, 181183 (2010)
H2OAgF: N.R. Walker and co-workers,
J. Mol. Spectrosc. 267, 163-168 (2011)
A. Mizoguchi, Y. Ohshima and Y. Endo, J.
Chem. Phys. 135, 064307 (2011)
Strategic Collaborations
World
Key Collaborators
BH Pate (Virginia)
DJ Tozer (Durham)
W Jaeger (Alberta)
M Schnell (Hamburg)
MA Duncan (Georgia)
BJ Howard, SR MacKenzie (Oxford)
Tew, Legon, Western (Bristol)
Europe
Other Competitors
Alonso (Valladolid)
Endo (Tokyo)
8.
Wednesday 18th April 2012, ERC Proposal Presentation, Nicholas R. Walker
Concluding Remarks
• PI has an outstanding track record of success achieved through
work at 5 different institutions in the U.K. and North America.
• State-of-the-art, globally unique instrument proven through many
published works since mid-2010.
• Wide range of problems of contemporary importance.
• Expansive programme can only be pursued because of the
speed and power of CP-FTMW spectroscopy.
• Newcastle University have committed funding for a postgraduate
studentship to the proposed work.
I will welcome questions. Thank you for your attention.
9.
Wednesday 18th April 2012, ERC Proposal Presentation, Nicholas R. Walker
Theme 1 objective: Determine precisely all bond lengths and angles in
isolated species of Mn(C2H4), Mn(C2H2), Mn-CCH and Mn-CH2 where M=Ni,
Pd, Pt.
Theme 2 objective: Determine the geometries of (H2O)nAgCl and
(H2O)nAgF where n=1-6 to characterise the emerging solvent environment
and identify whether the structures of these complexes follow divergent trends
(with increasing n) even at these small sizes of unit. Subsequent experiments
will use the same methodology to explore the microscopic solvation of CuCl,
CuF, AuCl and AuF
Theme 3 objective: Determine precisely bond lengths and angles in
complexes formed between the ionic copper atom of a copper chloride
molecule and one or more glycine or imidazole molecules. Equivalent
interactions involving alanine, histidine and cysteine will be characterised in
subsequent experiments. IR and MW spectra of the complexes will be
analysed to determine vibrational band shifts and characterise the structures.
Theme 4 objective: Spectrometer will be coupled with gas chromatography
to demonstrate new measurement dimension for the technique. The instrument
will be used to distinguish the chemicals present in wine and fruit juice.
Project Plan
Postgrad. 1
Year 1
Year 2
Postgrad. 2
Measure and
analyse MW spectra
of MC2H4 and
MC2H2 where M is
nickel, palladium or
platinum.
Write automation
programmes
Measure and
analyse MW
spectra of
(H2O)nAgCl,
(H2O)nAgF
(where n=2,3)
Measure and
analyse MW and IR
spectra of MCCH,
MCH2 where M=Ni,
Pd, Pt.
DFT calculations
Measure MW
and IR spectra
of
(H2O)nAgCl,
(H2O)nAgF
(where n=4,5,6).
Postgrad. 3
Install laser to
obtain IR spectra
of metal ionsolvent
complexes. Obtain
IR spectra of
(H2O)nAgCl,
(H2O)nAgF
(where n=2,3)
Construct slit
nozzle.
DFT
calculations
Postdoctoral
researcher
Modify instrument to
generate complexes
containing amino
acids. Measure and
analyse MW and IR
spectra of
(gly)CuCl and
(imid)CuCl.
Obtain MW and IR
spectra of (gly)n
CuCl,
(imid)nCuCl
where n=2,3.
DFT calculations
Postdoctoral
researcher
Postgrad. 1
Postgrad. 2
Postgrad. 3
Year 3
Measure and
analyse MW spectra
of M2C2H4,
M2C2H2,
M3C2H4,
M3C2H2, M2CCH,
M2CH2, M3CCH,
M3CH2,
Measure MW
and IR spectra
of
(H2O)nCuCl,
(H2O)nCuF
(where n=4,5,6)
Measure and
analyse MW and IR
spectra of
(ala)CuCl,
(cys)CuCl and
(hist)CuCl.
DFT calculations
Measure and
analyse MW and
IR spectra of
(hist)nCuCl
(n=2,3,4)
(ala)nCuCl
(n=3,4) and
(cys)nCuCl.
(n=3,4)
Year 4
Thesis write-up
Thesis write-up
Measure and
analyse MW and IR
spectra of
(ala)nCuCl and
(cys)nCuCl.
(n=1,2)
Measure MW and
IR spectra of
(H2O)nAuCl,
(H2O)nAuF
(where n=1-6)
Thesis write-up
Construct GC-CPFTMW
spectrometer and
trial performance
for analysis of
wine and juice.
Year 5
Budget
Cost Category
Personnel:
PI
Senior Staff
Post docs
Students
Other
Total Personnel:
Direct Costs:
Indirect Costs
(overheads):
Subcontracting
Costs:
Total Costs of
project:
Requested
Grant:
Other Direct Costs:
Equipment
Consumables
Travel
Publications, etc
Other
Total Other Direct
Costs:
Total Direct Costs:
Max 20% of Direct
Costs
22
Year
Total
(Y1-5)2
52
Year
36,745
77,232
80,026
82,918
85,910
362,831
47,341
17,324
50,515
35,860
53,904
37,116
57,511
28,756
61,366
9,883
270,637
128,939
101,410
163,607
171,046
169,185
157,159
762,407
136,611
48,020
6,237
140,835
28,011
6,454
28,991
6,680
30,006
6,914
31,062
7,157
277,446
166,090
33,442
190,868
175,300
35,671
36,920
38,219
476,978
292,278
338,907
206,717
206,105
195,378
1,239,385
58,456
67,781
41,343
41,221
39,076
247,877
3,520
3,680
10,600
3,400
Year
42
Year 1
(No overheads)
Year
32
(by year and total)
350,734
410,088
248,060
250,846
238,134
1,497,862
(by year and total)
350,734
410,088
248,060
250,846
238,134
1,497,862
For the above cost table, please indicate the % of working time the PI dedicates to the
project over the period of the grant:
90%
Recent Results
1.914(1) Å
2.062(6) Å
2.1531(3) Å
40.9(13)
78.052(6)
H2OCuCl rapidly inverts on the
timescale of molecular rotation.
2.2724(8) Å
2.0633(3) Å
2.1719(9) Å
1.354(40) Å
H2SCuCl is
rigidly pyramidal
C2H4AgCl. The C=C double bond
in ethene lengthens by 0.0124 Å on
attaching to AgCl (Similar for CuCl)
(Owing to * electron donation
from C2H4 to the metal)
These studies are further described in publications;
Angew. Chem. Int. Ed., 49, 181-183 (2010)
J. Chem. Phys., 134, 134305 (2011)
J. Chem. Phys. 135, 014307 (2011)
J. Chem. Phys. 135, 024315 (2011)
Wednesday 18th April 2012, ERC Proposal Presentation, Nicholas R. Walker
S.L. Stephens, D.P. Tew, V.A.
Mikhailov, N.R. Walker and A.C.
Legon, , J. Chem. Phys. 135,
024315 (2011)
C2H4 AgCl
The r(C=C) bond distance is 0.013
Å longer than that found in free
C2H4.
PtC2H4
r(C=C) = 1.3518(4) Å1
r(Ag-*) = 2.1719(9) Å
r(Ag-Cl) = 2.2724(8) Å
PtC2H2
PtCCH
Wednesday 18th April 2012, ERC Proposal Presentation, Nicholas R. Walker
Theme 3 – Copper Binding Sites in Enzymes
What can we learn about biochemistry from gas phase spectroscopy?
Molecular recognition
Alonso and co-workers: Use a combination of
microwave spectroscopy and high accuracy theory to
spectroscopically distinguish between different
conformers of amino acids and carbohydrates.
e.g., alanine (left)
S. Blanco et al., J. Am. Chem. Soc., 126, 11675 (2004)
Conformation
Zwier and co-workers: Drive changes in
conformation using infrared light and
measure the efficiency of the
isomerisation.
B.C. Dian et al., Science, 296, 2369 (2002)
N-acetyl-tryptophan methyl amide
Wednesday 18th April 2012, ERC Proposal Presentation, Nicholas R. Walker
Copper
centre
Type I
(T1Cu)
Type II
(T2Cu)
Type III
(T3Cu)
A (CuA)
B (CuB)
Coordination environment
Example
2  histidine (N atoms), 1  cysteine (S atom), in trigonal
planar + 1 other axial ligand
Square planar coordination by N or N/O ligands
Plastocyanin
Pair of Cu centres, 3  histidine
Hemocyanin
Pair of Cu atoms coordinate with 2  histidine, 1 
methionine, backbone CO, 2  bridging cysteine ligands,
3  histidine in trigonal pyramidal
Cytochrome coxidase
Cytochrome coxidase
Enzymes
Glycine
Cysteine
Histidine
Alanine
Imidazole
Wednesday 18th April 2012, ERC Proposal Presentation, Nicholas R. Walker
Theme 4 - Rotational Spectroscopy
Beyond the Complexity Limit
• Task of assigning spectra becomes increasingly difficult when a sample
contains many different chemicals.
• Technology behind broadband rotational spectroscopy advancing quickly.
• Broadband rotational spectroscopy distinguishes between molecules on the
basis of their structure rather than their mass/charge ratio.
Double resonance
Automated spectral
assignment
Separating power
Flexibility
Speed
Sensitivity
Slit nozzle
GC-CP-FTMW
New Challenges and Opportunities
Analysis
Biology
-D-fructofuranose
Molecular Dynamics

Syn.
Anti.
Conformational isomerisation of
cyclopropane carboxaldehyde1
1) B.C. Dian, G.G. Brown, K.O. Douglass and B.H. Pate, Science, 320, 924 (2008)
Laser ablation source
Laser ablation source informed by the
designs currently used by Duncan and
co-workers, Gerry and co-workers,
Ziurys and co-workers.
OCAgI
109
AgI
107
AgI
CF3I
AgI
8000
10000
12000 14000 16000
Frequency/MHz
18000
OCAgI
OC109AgI
109
AgI
107
OC107AgI
AgI
Exp.
Sim.
OCICF3
13200
13400
13600
13800
14000
Frequency / MHz
14200
14400