WO2005047832A1 - Method of spectroscopy - Google Patents
Method of spectroscopy Download PDFInfo
- Publication number
- WO2005047832A1 WO2005047832A1 PCT/GB2004/004693 GB2004004693W WO2005047832A1 WO 2005047832 A1 WO2005047832 A1 WO 2005047832A1 GB 2004004693 W GB2004004693 W GB 2004004693W WO 2005047832 A1 WO2005047832 A1 WO 2005047832A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- sample
- excitation source
- spectroscopy
- vibrational mode
- excitation
- Prior art date
Links
- 238000004611 spectroscopical analysis Methods 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims description 25
- 230000005284 excitation Effects 0.000 claims abstract description 42
- 238000001514 detection method Methods 0.000 claims abstract description 11
- 230000003595 spectral effect Effects 0.000 claims abstract description 7
- 238000001228 spectrum Methods 0.000 claims description 15
- 230000008859 change Effects 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 7
- 230000001419 dependent effect Effects 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 36
- 230000003993 interaction Effects 0.000 description 10
- 238000005084 2D-nuclear magnetic resonance Methods 0.000 description 9
- 238000013459 approach Methods 0.000 description 5
- 230000001934 delay Effects 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000004470 2D-IR spectroscopy Methods 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- BYXHQQCXAJARLQ-ZLUOBGJFSA-N Ala-Ala-Ala Chemical compound C[C@H](N)C(=O)N[C@@H](C)C(=O)N[C@@H](C)C(O)=O BYXHQQCXAJARLQ-ZLUOBGJFSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 108010017893 alanyl-alanyl-alanine Proteins 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000004141 dimensional analysis Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004001 molecular interaction Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000012306 spectroscopic technique Methods 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000002460 vibrational spectroscopy Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
- G01J3/02—Details
- G01J3/10—Arrangements of light sources specially adapted for spectrometry or colorimetry
- G01J3/108—Arrangements of light sources specially adapted for spectrometry or colorimetry for measurement in the infrared range
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
- G01J3/28—Investigating the spectrum
- G01J3/44—Raman spectrometry; Scattering spectrometry ; Fluorescence spectrometry
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N2021/653—Coherent methods [CARS]
- G01N2021/655—Stimulated Raman
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/636—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited using an arrangement of pump beam and probe beam; using the measurement of optical non-linear properties
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
Definitions
- the invention relates to a method of spectroscopy, in particular multidimensional spectroscopy.
- information obtained from the second excitation pulse differs from the information obtained from the first excitation pulse providing an extra dimension.
- a Fourier transformation is applied to the time spectrum from each excitation pulse to obtain a respective frequency spectrum.
- the frequency spectra are plotted on orthogonal axes to form a surface. Peaks on the surface provide additional information concerning interactions within the sample.
- 2D-NMR plots can be used to determine molecular structure and provide unique, characteristic features ("fingerprints") for identifying components in a solution.
- fingerprints unique, characteristic features
- 2D-NMR suffers from a lack of sensitivity, with detection limits typically on the order 10 15 -10 18 molecules.
- 2D-NMR provides only limited resolution in the time domain.
- techniques analogous to those used in 2D-NMR spectroscopy have been adopted in 2D vibration or infrared (IR) spectroscopy, where vibrational modes of an atom or molecule are excited.
- Fig. 1 shows an apparatus for performing a method of spectroscopy according to the present invention.
- the invention relates to a method of spectroscopy relying on excitation of a vibrational mode of atoms or molecules in a system for example by excitation by an infrared excitation source. Interactions between vibrations in the system allow two or more dimensional information to be obtained with suitable excitation regimes.
- the present invention relies on heterodyne detection allowing the output signal to vary linearly with the concentration of the sample. As a result much lower concentrations can be analysed than with, for example homodyne detection where there is a quadratic dependence on concentration and hence a vanishingly small signal for low concentrations.
- the invention relies on a heterodyning field either from an external source or relying on a field generated by local oscillators within the sample such that linear terms dominate quadratic terms in the output signal.
- Fig. 1 the apparatus is shown generally as including a sample 10, excitation sources comprising lasers emitting radiation typically in the infrared band and a detector 14.
- Tunable lasers 12 and 18 emit excitation beams of respective wavelengths/wavenumbers 3164cm “1 and 2253cm "1 which excite one or more vibrational modes of the molecular structure of the sample and allow multi-dimensional data by tuning the frequencies or providing variable time delays.
- a third, fixed frequency beam at 795nm is generated by a third laser 16 to provide an output or read out in the form of an effectively scattered input beam, frequency shifted (and strictly generated as a fourth beam) by interaction with the structure of sample 10.
- the detected signal is typically in the visible or near infrared part of the electromagnetic spectrum eg at 740nm, comprising photons of energy not less than leV. .
- the sample is excited by successive beams spaced in the time domain.
- any appropriate multi-dimensional spectroscopic technique can be adopted, for example by varying the input in the frequency domain rather than the time domain.
- any number of dimensions can be obtained by additional pulses in the time domain or additional frequencies in the frequency domain.
- a transmission scheme is shown, a reflection scheme (where the sample reflects the detected beam) can be adopted where appropriate, for example in the case of surface deposited samples.
- parameters of the apparatus are varied so that heterodyne detection is achieved. This can be done either by providing an external heterodyne excitation source, for example comprising a further excitation laser or broadband laser source (not shown) or by tuning the excitation laser 12 or 20 appropriately.
- an external heterodyne excitation source for example comprising a further excitation laser or broadband laser source (not shown) or by tuning the excitation laser 12 or 20 appropriately.
- E H o is the homodyne signal from the sample; it can be thought of as the sum electric field which is emitted by the sample component of interest.
- E L0 is a "local oscillator" field, that is, a field of identical frequency present on the detector with a fixed phase difference ⁇ .
- E HO 2 > which varies quadratically is with the concentration of the chemical system under study.
- heterodyne detection a separate local oscillator is created and made to coincide in time and space on the detector. By so doing, and removing the (E L o) term byany appropriate technique which will be familiar to the skilled reader the cross term can be made to dominate the equation. With knowledge of the local oscillator strength, the output field is then linear in concentration.
- the present invention comprises a "coherence spectroscopy”.
- photons and molecular states comprise two halves that are separate but related. Interactions which change populations (for example, "an electron promoted to the first excited state") actually involve two interactions with the incident field, one acting on each half of the state in question. By contrast, single interactions with the incident field create what is known as a coherence, a purely quantum mechanical superposition of two molecular states.
- the system oscillates back and forth between the two states with a frequency related to the energy difference between them. This oscillation in turn emits a field at that characteristic frequency (for instance,
- the approach of the present invention provides a surprising level of sensitivity and, in the case of the signal field generated within the sample, relies on the fact that this is automatically a heterodyning field with the correct phase relationship.
- heterodyning detection is implemented, as mentioned this can be obtained either by varying parameters of the sample, or of an external field generator.
- a local oscillator field will be naturally present in the sample/solvent in the form of the non-resonant contribution inherently created.
- the E o and cross terms can be made to dominate equation (1) and we can effectively consider the signal as heterodyned.
- the signal is linear in concentration, and clearly far lower concentrations can be achieved before reaching the limit of detection.
- the relative size of the local oscillator contribution can be controlled, allowing a great deal of range in the concentrations that can be examined.
- Another way in which the relevant parameters of the sample can be controlled is by the addition of appropriate amounts of fluorescent absorptive molecules whose electronic absorption is resonant with a visible beam.
- the absorption results in a polarisation in the molecules which radiate and serve as the local oscillator field.
- This is a particularly useful method in that the concentration of local oscillator molecules can be precisely controlled. In that case an additional excitation source provides the required polarisation.
- the (E L0 ) 2 term can be removed by identifying and subtracting the characteristic local oscillation signal which can be obtained in a calibration step.
- conventional optical heterodyning can be adopted in which a local oscillator field is created external to the sample and directed to be incident on the detector with the sample field.
- Such local oscillator generation may be by, for instance, continuum generation in a suitable crystal liquid or solid with a portion of the visible beam.
- the specific parameters of the external signal are controlled so that the relevant terms dominate in equation (1) above, in contrast to conventional optical heterodyning systems where the linear contribution is swamped as discussed in more detail above.
- Removal of the (E L0 ) 2 term is then simply achieved using a lock-in detector whereby a mechanical wheel with slots in it ("a chopper”) is introduced into an excitation beam.
- the repetition rate with which the slots block the beam (reference frequency) is passed to a lock-in detector, which is basically a frequency filter - it measures the total net signal coming from the detector and extracts the component of the signal which occurs at the reference frequency. If the reference frequency is different from the repetition rate of the beam which causes the local oscillator signal, the component of the net signal due exclusively to the local oscillator is subtracted off. Then, the E L o term disappears, the E H o term is negligible, and the cross term is linear in concentration.
- the output signal is a cone of rays containing all of the spectral information in space;
- the detector 14 can in this case be a 2D array detector such as a charge coupled device (CCD) which captures the spectral information encoded into spatial dimensions.
- CCD charge coupled device
- additional dimensions are introduced either by time delays in the pulses or by frequency variations as discussed in more detail above to give yet further, fully detailed information concerning the spectrum generated by the sample.
- Heterodyning across the frequency band is achieved by "continuum generation” whereby a spread of local oscillator frequencies is generated in the sample for example by external excitation with white light to provide a heterodyning field to interact with the broadband excitation.
- the invention employs a geometry known as the "forward box" configuration (that is, the three beams from lasers 12, 16, 18 do not lie in the same plane) and broadband excitation beams (a large spread of input wavelengths is present in a single beam).
- a spread of output angles is created, and a unique output direction is created for a given combination of quasi-discrete wavelengths present in the two infrared beams.
- the spectral information is spread out into the spatial characteristics of the output beam, and the array detector effectively captures in one shot what would otherwise be built up by using narrower band excitation beams and tuning point-by-point.
- an ultraviolet or visible excitation probes excites an electronic resonance which in turn gives rise to fluorescence caused by transitions between electronic energy levels. This is in combination with direct infrared excitation of the type discussed above. In that case the additional "read out" signal from laser 16 is not required. Tuning of input infrared and ultraviolet beams and varying time delays yields multi-dimensional data again in a manner described in more detail above, but based on a population spectroscopy.
- the invention can be implemented in a range of applications and in particular any area in which multi-dimensional optical spectroscopy measuring, directly or indirectly, vibration/vibration coupling is appropriate, using two or more variable frequencies of light or time delays to investigate molecular identity and/or structure.
- the techniques are particularly effective at low molecular concentration.
- the invention improves the level of sensitivity for low-concentration detection such that gas phase and surface-deposited samples can be investigated to allow identification of components and their concentrations in complex mixtures such as proteins present in a solution, with a suitable choice of frequency range.
- any appropriate specific component and techniques can be adopted to implement the invention.
- at least one tuneable laser source in the infrared and at least one other tuneable laser source in the ultraviolet, visible or infrared can be adopted and any appropriate laser can be used or indeed any other appropriate excitation source.
- a further fixed- frequency beam may also be incorporated in the case of two infrared excitation beams as discussed with reference to Fig. 1 and again any appropriate source can be adopted.
- the sample and solvent can be of any appropriate type whereby its composition is controlled to tune the system as described in more detail above, and in any appropriate phase including gas phase and liquid/solution phase.
- Any appropriate detector may be adopted, for example a CCD or other detector as is known from 2D IR spectroscopy techniques.
- excitation wavelengths is generally described above as being infrared but can be any appropriate wavelength required to excite a vibrational mode of the structure to be analysed. Although the discussion above relates principally to two-dimensional analysis, any number of dimensions can be introduced by appropriate variation of the parameters of the input excitation, for example frequency, time delay/number of pulses or any other appropriate parameter.
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- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP04798417A EP1685370A1 (en) | 2003-11-07 | 2004-11-05 | Method of spectroscopy |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB0326088.2 | 2003-11-07 | ||
GBGB0326088.2A GB0326088D0 (en) | 2003-11-07 | 2003-11-07 | Method of spectroscopy |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2005047832A1 true WO2005047832A1 (en) | 2005-05-26 |
Family
ID=29726188
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB2004/004693 WO2005047832A1 (en) | 2003-11-07 | 2004-11-05 | Method of spectroscopy |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP1685370A1 (en) |
CN (1) | CN1902471A (en) |
GB (1) | GB0326088D0 (en) |
WO (1) | WO2005047832A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10274310B2 (en) * | 2016-12-22 | 2019-04-30 | The Boeing Company | Surface sensing systems and methods for imaging a scanned surface of a sample via sum-frequency vibrational spectroscopy |
CN108896176B (en) * | 2018-05-14 | 2019-10-11 | 浙江大学 | A kind of Space Consistency bearing calibration of multi-optical spectrum imaging system |
-
2003
- 2003-11-07 GB GBGB0326088.2A patent/GB0326088D0/en not_active Ceased
-
2004
- 2004-11-05 WO PCT/GB2004/004693 patent/WO2005047832A1/en active Application Filing
- 2004-11-05 EP EP04798417A patent/EP1685370A1/en not_active Withdrawn
- 2004-11-05 CN CNA2004800400456A patent/CN1902471A/en active Pending
Non-Patent Citations (3)
Title |
---|
ASBURY J B; STEINEL T; FAYER M D: "Using ultrafast infrared multidimensional correlation spectroscopy to aid in vibrational spectral peak assignments", CHEMICAL PHYSICS LETTERS, vol. 381, 20 October 2003 (2003-10-20), pages 139 - 146, XP002314684 * |
M. CHO: "Ultrafast vibrational spectroscopy in condensed phases", PHYSCHEMCOMM, vol. 5, no. 7, 21 February 2002 (2002-02-21), pages 40 - 58, XP002314686 * |
RUBTSOV I V; WANG J; HOCHSTRASSER R M: "Dual frequency 2D-IR spectroscopy heterodyned photon echo of the peptide bond", PNAS, vol. 100, no. 10, 13 May 2003 (2003-05-13), pages 5601 - 5606, XP002314685 * |
Also Published As
Publication number | Publication date |
---|---|
EP1685370A1 (en) | 2006-08-02 |
GB0326088D0 (en) | 2003-12-10 |
CN1902471A (en) | 2007-01-24 |
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