Attenuated total reflection (ATR) is a sampling technique used in conjunction with infrared spectroscopy which enables samples to be examined directly in the solid or liquid state without further preparation.[1]
Light undergoes multiple internal reflections in the crystal of high refractive index, shown in yellow. The sample is in contact with the crystal.An ATR accessory for IR spectroscopy.
ATR uses a property of total internal reflection resulting in an evanescent wave. A beam of infraredlight is passed through the ATR crystal in such a way that it reflects at least once off the internal surface in contact with the sample. This reflection forms the evanescent wave which extends into the sample. The penetration depth into the sample is typically between 0.5 and 2 micrometres, with the exact value determined by the wavelength of light, the angle of incidence and the indices of refraction for the ATR crystal and the medium being probed.[2] The number of reflections may be varied by varying the angle of incidence. The beam is then collected by a detector as it exits the crystal. Most modern infrared spectrometers can be converted to characterise samples via ATR by mounting the ATR accessory in the spectrometer's sample compartment. The accessibility, rapid sample turnaround and ease of use of ATR with Fourier transform infrared spectroscopy (FTIR) has led to substantial use by the scientific community.
This evanescent effect only works if the crystal is made of an optical material with a higher refractive index than the sample being studied. Otherwise light is lost to the sample. In the case of a liquid sample, pouring a shallow amount over the surface of the crystal is sufficient. In the case of a solid sample, samples are firmly clamped to ensure good contact is made and to remove trapped air that would reduce signal intensity. The signal to noise ratio obtained depends on the number of reflections but also on the total length of the optical light path which dampens the intensity. Therefore, a general claim that more reflections give better sensitivity cannot be made.[citation needed]
Typical materials for ATR crystals include germanium, KRS-5 and zinc selenide, while silicon is ideal for use in the Far-IR region of the electromagnetic spectrum. The excellent mechanical properties of diamond make it an ideal material for ATR, particularly when studying very hard solids, although the broad diamond phonon band between 2600 and 1900cm−1 significantly decreases signal to noise in this region. The shape of the crystal depends on the type of spectrometer and nature of the sample. With dispersive spectrometers, the crystal is a rectangular slab with chamfered edges, seen in cross-section in the illustrations. Other geometries use prisms, half-spheres, or thin sheets.[citation needed]
Applications
Infrared (IR) spectroscopy by ATR is applicable to the same chemical or biological systems as the transmission method. One advantage of ATR-IR over transmission-IR is the limited path length into the sample. This avoids the problem of strong attenuation of the IR signal in highly absorbing media such as aqueous solutions. For ultraviolet or visible light (UV/Vis) the evanescent light path is sufficiently short such that interaction with the sample is decreased with wavelength. For optically dense samples, this may allow for measurements with UV. Also, as no light path has to be established single shaft probes are used for process monitoring and are applicable in both the near and mid infrared spectrum.[citation needed]
Recently, ATR-IR has been applied to microfluidic flows of aqueous solutions by engineering microreactors with built-in apertures for the ATR crystal, allowing the flow within microchannels to pass across the crystal surface for characterisation,[3] or in dedicated flow cells.[4][5] Due to the ATR geometry and the resulting evanescent wave, it is possible with this technique to study transport phenomena and sorption kinetics through thin films.[6] The ability to passively characterise samples, with no sample preparation has also led to the use of ATR-FTIR in studying trace evidence in forensic science.
ATR-FTIR is also used as a tool in pharmacological research to investigate protein/pharmaceutical interactions in detail. Water-soluble proteins to be investigated require Polyhistidine-tags, allowing the macromolecule to be anchored to a lipid bilayer, which is attached to a Germanium crystal or other suitable optical media. Internal reflection with and without applied pharmaceutical or ligand will produce difference spectra to study conformational changes of the proteins upon binding.[7]
↑ Carter, Catherine F. (2010). "ReactIR Flow Cell: A New Analytical Tool for Continuous Flow Chemical Processing". Organic Process Research & Development. 14 (2): 393–404. doi:10.1021/op900305v.
↑ Minnich, Clemens B. (2010). "Determination of the Dispersion Characteristics of Miniaturized Coiled Reactors with Fiber-Optic Fourier Transform Mid-infrared Spectroscopy". Industrial & Engineering Chemistry Research. 49 (12): 5530–5535. doi:10.1021/ie901094q.
Infrared spectroscopy is the measurement of the interaction of infrared radiation with matter by absorption, emission, or reflection. It is used to study and identify chemical substances or functional groups in solid, liquid, or gaseous forms. It can be used to characterize new materials or identify and verify known and unknown samples. The method or technique of infrared spectroscopy is conducted with an instrument called an infrared spectrometer which produces an infrared spectrum. An IR spectrum can be visualized in a graph of infrared light absorbance on the vertical axis vs. frequency, wavenumber or wavelength on the horizontal axis. Typical units of wavenumber used in IR spectra are reciprocal centimeters, with the symbol cm−1. Units of IR wavelength are commonly given in micrometers, symbol μm, which are related to the wavenumber in a reciprocal way. A common laboratory instrument that uses this technique is a Fourier transform infrared (FTIR) spectrometer. Two-dimensional IR is also possible as discussed below.
Microscopy is the technical field of using microscopes to view objects and areas of objects that cannot be seen with the naked eye. There are three well-known branches of microscopy: optical, electron, and scanning probe microscopy, along with the emerging field of X-ray microscopy.
Fourier-transform spectroscopy is a measurement technique whereby spectra are collected based on measurements of the coherence of a radiative source, using time-domain or space-domain measurements of the radiation, electromagnetic or not. It can be applied to a variety of types of spectroscopy including optical spectroscopy, infrared spectroscopy, nuclear magnetic resonance (NMR) and magnetic resonance spectroscopic imaging (MRSI), mass spectrometry and electron spin resonance spectroscopy.
A semiconductor detector in ionizing radiation detection physics is a device that uses a semiconductor to measure the effect of incident charged particles or photons.
Forensic chemistry is the application of chemistry and its subfield, forensic toxicology, in a legal setting. A forensic chemist can assist in the identification of unknown materials found at a crime scene. Specialists in this field have a wide array of methods and instruments to help identify unknown substances. These include high-performance liquid chromatography, gas chromatography-mass spectrometry, atomic absorption spectroscopy, Fourier transform infrared spectroscopy, and thin layer chromatography. The range of different methods is important due to the destructive nature of some instruments and the number of possible unknown substances that can be found at a scene. Forensic chemists prefer using nondestructive methods first, to preserve evidence and to determine which destructive methods will produce the best results.
Vibrational circular dichroism (VCD) is a spectroscopic technique which detects differences in attenuation of left and right circularly polarized light passing through a sample. It is the extension of circular dichroism spectroscopy into the infrared and near infrared ranges.
Evolved gas analysis (EGA) is a method used to study the gas evolved from a heated sample that undergoes decomposition or desorption. It is either possible just to detect evolved gases using evolved gas detection (EGD) or to analyse explicitly which gases evolved using evolved gas analysis (EGA). Therefore different analytical methods can be employed such as mass spectrometry, Fourier transform spectroscopy, gas chromatography, or optical in-situ evolved gas analysis.
Photothermal microspectroscopy (PTMS), alternatively known as photothermal temperature fluctuation (PTTF), is derived from two parent instrumental techniques: infrared spectroscopy and atomic force microscopy (AFM). In one particular type of AFM, known as scanning thermal microscopy (SThM), the imaging probe is a sub-miniature temperature sensor, which may be a thermocouple or a resistance thermometer. This same type of detector is employed in a PTMS instrument, enabling it to provide AFM/SThM images: However, the chief additional use of PTMS is to yield infrared spectra from sample regions below a micrometer, as outlined below.
Fourier-transform infrared spectroscopy (FTIR) is a technique used to obtain an infrared spectrum of absorption or emission of a solid, liquid, or gas. An FTIR spectrometer simultaneously collects high-resolution spectral data over a wide spectral range. This confers a significant advantage over a dispersive spectrometer, which measures intensity over a narrow range of wavelengths at a time.
Angle-resolved low-coherence interferometry (a/LCI) is an emerging biomedical imaging technology which uses the properties of scattered light to measure the average size of cell structures, including cell nuclei. The technology shows promise as a clinical tool for in situ detection of dysplastic, or precancerous tissue.
The technique of vibrational analysis with scanning probe microscopy allows probing vibrational properties of materials at the submicrometer scale, and even of individual molecules. This is accomplished by integrating scanning probe microscopy (SPM) and vibrational spectroscopy. This combination allows for much higher spatial resolution than can be achieved with conventional Raman/FTIR instrumentation. The technique is also nondestructive, requires non-extensive sample preparation, and provides more contrast such as intensity contrast, polarization contrast and wavelength contrast, as well as providing specific chemical information and topography images simultaneously.
Incoherent broad band cavity enhanced absorption spectroscopy (IBBCEAS), sometimes called broadband cavity enhanced extinction spectroscopy (IBBCEES), measures the transmission of light intensity through a stable optical cavity consisting of high reflectance mirrors (typically R>99.9%). The technique is realized using incoherent sources of radiation e.g. Xenon arc lamps, LEDs or supercontinuum (SC) lasers, hence the name.
Stationary-wave integrated Fourier-transform spectrometry (SWIFTS), or standing-wave integrated Fourier-transform spectrometry, is an analytical technique used for measuring the distribution of light across an optical spectrum. SWIFTS technology is based on a near-field Lippmann architecture. An optical signal is injected into a waveguide and ended by a mirror. The input signal interferes with the reflected signal, creating a standing, or stationary, wave.
AFM-IR or infrared nanospectroscopy is one of a family of techniques that are derived from a combination of two parent instrumental techniques. AFM-IR combines the chemical analysis power of infrared spectroscopy and the high-spatial resolution of scanning probe microscopy (SPM). The term was first used to denote a method that combined a tuneable free electron laser with an atomic force microscope equipped with a sharp probe that measured the local absorption of infrared light by a sample with nanoscale spatial resolution.
The operation of a photon scanning tunneling microscope (PSTM) is analogous to the operation of an electron scanning tunneling microscope, with the primary distinction being that PSTM involves tunneling of photons instead of electrons from the sample surface to the probe tip. A beam of light is focused on a prism at an angle greater than the critical angle of the refractive medium in order to induce total internal reflection within the prism. Although the beam of light is not propagated through the surface of the refractive prism under total internal reflection, an evanescent field of light is still present at the surface.
Fourier transform infrared spectroscopy (FTIR) is a spectroscopic technique that has been used for analyzing the fundamental molecular structure of geological samples in recent decades. As in other infrared spectroscopy, the molecules in the sample are excited to a higher energy state due to the absorption of infrared (IR) radiation emitted from the IR source in the instrument, which results in vibrations of molecular bonds. The intrinsic physicochemical property of each particular molecule determines its corresponding IR absorbance peak, and therefore can provide characteristic fingerprints of functional groups.
Nano-FTIR is a scanning probe technique that utilizes as a combination of two techniques: Fourier transform infrared spectroscopy (FTIR) and scattering-type scanning near-field optical microscopy (s-SNOM). As s-SNOM, nano-FTIR is based on atomic-force microscopy (AFM), where a sharp tip is illuminated by an external light source and the tip-scattered light is detected as a function of tip position. A typical nano-FTIR setup thus consists of an atomic force microscope, a broadband infrared light source used for tip illumination, and a Michelson interferometer acting as Fourier-transform spectrometer. In nano-FTIR, the sample stage is placed in one of the interferometer arms, which allows for recording both amplitude and phase of the detected light. Scanning the tip allows for performing hyperspectral imaging with nanoscale spatial resolution determined by the tip apex size. The use of broadband infrared sources enables the acquisition of continuous spectra, which is a distinctive feature of nano-FTIR compared to s-SNOM. Nano-FTIR is capable of performing infrared (IR) spectroscopy of materials in ultrasmall quantities and with nanoscale spatial resolution. The detection of a single molecular complex and the sensitivity to a single monolayer has been shown. Recording infrared spectra as a function of position can be used for nanoscale mapping of the sample chemical composition, performing a local ultrafast IR spectroscopy and analyzing the nanoscale intermolecular coupling, among others. A spatial resolution of 10 nm to 20 nm is routinely achieved.
Microfluidic modulation spectroscopy (MMS) is an infrared spectroscopy technique that is used to characterize the secondary structure of proteins. Infrared (IR) spectroscopy is well known for this application.. However, the lack of automation, repeatability and dynamic range of detection in conventional platforms such as FTIR, have been major limitations which have been addressed with the development of microfluidic modulation spectroscopy.
This page is based on this Wikipedia article Text is available under the CC BY-SA 4.0 license; additional terms may apply. Images, videos and audio are available under their respective licenses.
