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Research

2D NMR: Overview of Heteronuclear Correlation Techniques

Heteronuclear correlation spectroscopy is an analytical technique that investigates the coupling between different types of nuclei, often a proton and an X-nucleus, such as carbon-13 or nitrogen-15. This method is commonly used in nuclear magnetic resonance (NMR) spectroscopy to gain insights into complex chemical compounds&#39; structural and compositional aspects. A typical heteronuclear correlation spectrum displays X-nucleus chemical shifts on one axis and a proton spectrum on the other axis. Cross-peaks reveal the connection between specific protons and X-nuclei.
The main heteronuclear correlation experiments include HETCOR, HSQC, HMQC, and HMBC. HSQC, HMQC, and HMBC record the proton spectrum, whereas the X-nucleus spectrum is recorded by standard heteronuclear correlation spectroscopy or HETCOR. The HETCOR-HMQC-HSQC group of experiments cannot detect X-nuclei without an attached proton. HETCOR is used when ultrahigh peak resolution is required along the X-nucleus axis.
The heteronuclear single quantum correlation technique, or HSQC, investigates proton-to-X-nucleus single bond correlations. In an HSQC experiment, polarization is transferred from a proton nucleus to a neighboring X-nucleus and then back to the proton nucleus. The signal from the proton nuclei is then recorded. HSQC generates a spectrum like that of heteronuclear multiple-quantum correlation spectroscopy or HMQC but uses a different suppression method, providing better X-nucleus resolution along the axis.
Heteronuclear multiple-bond correlation, or HMBC, is a proton-detected experiment, like HMQC but with a longer initial delay time. This experiment is used to observe long-range proton to X-nucleus connectivity separated by 2-3 bonds, with some experiments going out to 4 or 5 bonds. In an HMBC experiment, direct one-bond correlations are suppressed as part of the sequence. The spectra of HMBC give rise to cross peaks that correlate which protons are coupled to what other specific X-nucleus is more than one bond away. The gradient HMBC (gHMBC) pulse sequence offers better suppression of interfering signals, making it particularly useful for analyzing complex molecules with overlapping signals.

Heteronuclear correlation spectroscopy is an analytical technique that investigates the coupling between different types of nuclei, often a proton and an ...

2D NMR: Heteronuclear Single-Quantum Correlation Spectroscopy (HSQC)

Heteronuclear single-quantum correlation spectroscopy (HSQC) is a 2D NMR technique that reveals one-bond correlations between hydrogen and a heteronucleus. The HSQC experiment is similar to the heteronuclear correlation experiment (HETCOR) but is more sensitive. In the HSQC spectrum, the proton chemical shift is plotted on the horizontal F2 axis, while the 13C chemical shift is plotted on the vertical F1 axis. The corresponding proton and 13C spectra are also shown. The HSQC contour plot does not have any diagonal peaks. All the cross-peaks indicate the protons directly attached to each carbon in a molecule. Similar to the COSY spectrum, imaginary lines are drawn in horizontal and vertical directions to identify the correlated peaks.
For example, the HSQC spectrum of 2-chlorobutane has a carbon signal at 11 ppm that can be assigned to the shielded methyl group and correlated to the proton multiplet at 1.01 ppm. The carbon signal at 24.8 ppm arises from the deshielded methyl group, which correlates to the proton multiplet at 1.52 ppm. Similarly, the methylene carbon signal at 33.3 ppm and methine carbon signal at 60.4 ppm correlate to the multiplets at 1.72 and 3.96 ppm, respectively.&#160; HSQC is a very useful technique for structurally elucidating complex molecules and is routinely used in protein NMR studies.

Heteronuclear single-quantum correlation spectroscopy (HSQC) is a 2D NMR technique that reveals one-bond correlations between hydrogen and a ...

Double Resonance Techniques: Overview

Double resonance techniques in Nuclear Magnetic Resonance (NMR) spectroscopy involve the simultaneous application of two different frequencies or radiofrequency pulses to manipulate and observe two distinct nuclear spins. One important application of double resonance is spin decoupling, which selectively suppresses coupling with one type of nucleus while observing the NMR signal from another nucleus, simplifying the spectrum and enhancing resolution.
Spin decoupling is usually achieved by irradiating the sample atoms with a suitable radio frequency (rf) pulse sequence, effectively eliminating all the coupling with one nuclide. This simplifies the observed spectrum, making it easier to analyze and understand the relationships between different nuclei.
Double resonance experiments can be classified as heteronuclear or homonuclear, depending on whether the two sets of nuclei are of different isotopes or the same isotope, respectively. They can also be selective or nonselective, depending on whether the irradiating frequency covers only a portion or all of the resonance frequencies.
In nonselective heteronuclear decoupling, samples are exposed to an appropriate radiofrequency range to remove all coupling with one nuclide. However, increased external field strengths necessitate more powerful irradiation across broader frequency ranges. In certain instruments, continuous irradiation creates enough heat to cause damage to thermally sensitive samples.
To overcome these problems, modern methods using a series of pulses and exact timing delays, like J-modulated spin echo pulse sequences, can be employed to eliminate or adjust coupling effects within the spectrum.
For example, the attached proton transfer (APT) experiment applies a J-modulated spin echo pulse sequence to focus on the phase of detected carbon signals. Carbon atoms attached to an even number of protons exhibit positive signals in the spectrum, while those bonded to an odd number of protons appear as negative signals.
It utilizes a combination of a 180&#176; proton pulse and broadband decoupling to simplify spectral interpretation and assign multiplicities. The 180&#176; pulse is applied to the protons during the APT experiment. Its role is to refocus the spin coupling evolution that naturally occurs due to interactions between protons and carbons.
Specifically, after the 90&#176; pulse creates transverse magnetization, the 180&#176; pulse ensures that the effects of coupling are frozen during the initial period where the decoupler is turned off. This means the chemical shifts evolve only during the time 1/J&#8203; (the coupling constant period) after the first 180&#176; pulse.
By carefully timing this pulse sequence, the experiment isolates carbon multiplicities by utilizing the J-coupling between carbons and their attached protons. After the coupling evolution period (1/J&#8203;), broadband decoupling is turned on. This removes the J-coupling signals, collapsing multiplets into single peaks for each carbon resonance.
The decoupling ensures that carbon signals are free of splitting, allowing for a clear differentiation of signals based on phase (positive or negative) rather than splitting patterns.
The APT technique selectively enhances carbon signals, providing valuable information about carbon-proton connectivity, the number of attached hydrogen atoms, and the overall molecular structure.

Double resonance techniques in Nuclear Magnetic Resonance (NMR) spectroscopy involve the simultaneous application of two different frequencies or ...

2D NMR: Homonuclear Correlation Spectroscopy (COSY)

Homonuclear correlation spectroscopy, or COSY, is a 2-dimensional NMR technique that provides information about coupled protons. Typically, the geminal and vicinal coupling are observed. For example, consider the COSY spectrum of ethyl acetate, where its 1D proton NMR spectrum is plotted along the vertical and horizontal axes with their corresponding chemical shift scale. Three spots on the diagonal corresponding to the three peaks in the 1D proton spectrum are called diagonal peaks. The COSY spectrum is symmetric about the diagonal, with signals above and below the diagonal called cross-peaks or off-diagonal peaks. An imaginary line is drawn from diagonal peaks parallel to the horizontal axis, leading to a cross peak. A vertical line is then drawn from the same cross peak towards the diagonal peak to correlate the peaks. The off-diagonal peaks correlating the multiplets at 1.25 and 4.2 ppm indicate that the methyl protons are coupled to the methylene protons. The signal at 2 ppm is not associated with cross-peaks because the protons are not involved in homonuclear coupling. A COSY spectrum is useful when overlapping multiplets complicate the corresponding 1D spectrum.

Homonuclear correlation spectroscopy, or COSY, is a 2-dimensional NMR technique that provides information about coupled protons. Typically, the geminal ...

Insensitive Nuclei Enhanced by Polarization Transfer (INEPT)

Insensitive Nuclei Enhanced by Polarization Transfer (INEPT) is an advanced Nuclear Magnetic Resonance (NMR) technique specifically designed to detect and enhance the signals of low-abundance nuclei, such as carbon-13 and nitrogen-15, in small molecules. The fundamental principle behind INEPT is the transfer of polarization from a more abundant and highly polarizable nucleus, typically hydrogen-1, to the low-abundance nucleus of interest. This process effectively boosts the NMR signal of the low-abundance nuclei, making them more easily detectable.
The INEPT technique involves a series of carefully timed radiofrequency (RF) pulses applied to the sample. These RF pulses excite the more abundant nuclei, causing them to align their spins in a specific manner. Through the process of spin coupling, the polarization of the more abundant nuclei is then transferred to the low-abundance nuclei. As a result, the NMR signal of these low-abundance nuclei is significantly enhanced, allowing for a more detailed analysis of the molecular structure.
Various pulse sequences have been developed to improve the observability of these low-abundance nuclei when coupled to a high-receptivity nucleus. The INEPT pulse sequence combines a spin echo and selective population inversion, which includes 90&#176; and 180&#176; pulses on the high-sensitivity (the I spins) and low-sensitivity nuclei (the S spins), respectively. Coupling-constant-based delays between pulses facilitate magnetization transfer through space or bond interactions. Additional RF pulses and delays invert the low-gamma magnetization, producing an observable NMR signal. The net result is an enhanced NMR signal from low-gamma nuclei that would otherwise be challenging to detect.
Various pulse sequences have been developed to improve the detection of low-abundance nuclei when coupled with high-receptivity nuclei such as protons. The INEPT sequence yields enhanced signals for insensitive nuclei, with half of the CH group producing negative peaks and the other half positive peaks. This pattern allows for discrimination between different types of carbon-hydrogen bonds within the molecule.
Decoupling methods can be employed to enhance sensitivity and resolution in distinguishing various carbon-hydrogen bonds, making INEPT an invaluable tool in the chemical and pharmaceutical industries.

Insensitive Nuclei Enhanced by Polarization Transfer (INEPT) is an advanced Nuclear Magnetic Resonance (NMR) technique specifically designed to detect and ...

2D NMR: Overview of Homonuclear Correlation Techniques

Homonuclear correlation spectroscopy (COSY) is a powerful technique used in Nuclear Magnetic Resonance (NMR) spectroscopy to study the correlations between nuclei of the same type within a molecule. It provides information about scalar couplings between adjacent nuclei, which helps determine connectivity and structural information. There are several COSY variants, each with its unique strengths and experimental parameters.
COSY90 is the standard two-dimensional (2D) COSY experiment that utilizes a second 90-degree pulse to achieve high sensitivity and resolution. It excels in analyzing small to medium-sized molecules and provides information on directly coupled protons. COSY45, similar to COSY90, uses 45-degree pulses instead of 90-degree pulses. This results in reduced sensitivity but improved resolution.
Long-range COSY (LR-COSY) extends the COSY experiment to detect scalar couplings between nuclei further apart in the molecule. It achieves this by combining multiple pulse sequences and magnetization transfers.
Relayed COSY is a variant of COSY that adds extra pulses to the standard pulse sequence to produce cross-peaks between cross-peaks, showing specific molecular connections hidden by overlapping signals.
TOCSY (Total Correlation Spectroscopy), also known as HOHAHA (Homonuclear Hartmann-Hahn Spectroscopy), reveals all through-bond connectivity between all coupled nuclei. TOCSY is especially useful for analyzing molecules with overlapping signals and complex coupling patterns.
NOESY (Nuclear Overhauser Effect Spectroscopy) measures the nuclear overhauser effect, which arises from dipole-dipole interactions between nuclei. It provides information about spatial proximity and can be used to determine the three-dimensional structure of a molecule.
ROESY (Rotating-frame Overhauser Enhancement Spectroscopy) is similar to NOESY but employs a different mechanism to obtain through-space correlations. It provides information about spatial proximity and is particularly useful for studying molecules with weak NOE signals.
In conclusion, choosing a COSY variant depends on the molecule or reaction under investigation and the desired information. The right COSY variant can be determined based on molecular size, coupling complexity, and the need for spatial or long-range connectivity data.

Homonuclear correlation spectroscopy (COSY) is a powerful technique used in Nuclear Magnetic Resonance (NMR) spectroscopy to study the correlations ...

Two-Dimensional (2D) NMR: Overview

The 1D NMR spectrum of large and complex molecules like natural products has complicated splitting patterns and overlapping signals, which can be easily interpreted using 2-dimensional (2D) NMR. Unlike 1D NMR, 2D NMR has two frequency axes that provide the coupling information between the nucleus A and nucleus B in a molecule. The process from which 2D spectra are obtained has four steps.
The first step is the preparation period, during which nucleus A is excited with a radiofrequency pulse. The second step is the evolution or wait period t1, which is incremented systematically, and no data is observed during this period. The next step is the mixing period, in which a second radiofrequency pulse is introduced, which transfers the magnetization to the spins of nucleus B. In the last step, the magnetization of nuclear spins from B is detected during the acquisition time t2 for each t1. Time domains t1 and t2 are Fourier transformed into frequency domains f1 and f2, and these correspond to two dimensions of 2D spectra, while the third dimension is the intensity. In 2D experiments, coupling between the same kind of nucleus is called homonuclear 2D experiments, whereas coupling between two types of nucleus is called heteronuclear 2D experiments. 2D spectra can be displayed as stacked or contour plots. When presented as stacked plots, 2D spectra are difficult to interpret. The contour plot is the horizontal cross-section of a stacked plot where the size of the circles shows the signal intensity. Its interpretation is straightforward and it is preferred for data analysis.

The 1D NMR spectrum of large and complex molecules like natural products has complicated splitting patterns and overlapping signals, which can be easily ...

Nuclear Overhauser Enhancement (NOE)

Irradiation of a spin-active nucleus causes an increase or decrease in the signal intensity of neighboring nuclei that are not necessarily chemically bonded or involved in J-coupling. &#160;This phenomenon, called the Nuclear Overhauser Enhancement (NOE), results from through-space interactions between the nuclear spins. The NOE effect decreases with increasing internuclear distance and is generally not observed beyond 4 angstroms. In NOE, dipole-dipole interactions between neighboring spin-active nuclei result in the transfer of nuclear spin polarization. These interactions can cause an increase or decrease in the signal intensity, which results in a positive or negative NOE, respectively.
NOE can be applied to improve the signal intensity of less sensitive nuclei such as carbon-13. Proton-decoupled carbon-13 spectra show a positive NOE effect, where the carbon signal intensities are substantially increased compared to those in proton-coupled spectra.
Targeted irradiation of specific nuclei can also reveal through-space proximity, which helps confirm stereochemistry and verify spectral peak assignments. The NOE effect is also applied in 2D NMR experiments, such as Nuclear Overhauser Effect Spectroscopy (NOESY), to determine the 3D structure of proteins.

Irradiation of a spin-active nucleus causes an increase or decrease in the signal intensity of neighboring nuclei that are not necessarily chemically ...

&sup1;H NMR of Labile Protons:  Deuterium (&sup2;H) Substitution

This lesson illustrates the role of deuterium substitution in simplifying the NMR spectrum of compounds comprising labile protons. One method employed is the use of deuterium. Amongst the three isotopes of hydrogen, deuterium (2H) has a nucleus composed of one proton and one neutron. When the D2O solvent is added to a pure dry ethanol solution, its labile proton is substituted with deuterium.
<img alt="Figure1" src="/files/ftp_upload/12280/12280-PT_Figure_1.svg" style="text-align: center; height: 700px;" />
Figure 1. The comparison of the proton NMR spectra of pure dry ethanol and the same in D2O solvent.
The signals from deuterium are not observed in a proton NMR spectrum, as deuterium&#8211;proton coupling is negligible, and no spin-spin splitting occurs between them. As shown in Figure 1, the NMR spectra of pure ethanol and ethanol in deuterium, the disappearance of the triplet in the latter, confirms that it corresponds to the labile &#8211;OH proton. Furthermore, the methylene protons that initially showed up as a multiplet transform to a quartet, proving that the multiplet is due to the coupling with the &#8211;OH proton and the methyl protons.

This lesson illustrates the role of deuterium substitution in simplifying the NMR spectrum of compounds comprising labile protons. One method employed is ...

&sup1;H NMR of Conformationally Flexible Molecules: Temporal Resolution

At room temperature, the chair conformer of cyclohexane undergoes rapid ring flipping between two equivalent chair conformers at a rate of approximately 105 times per second. These two chair conformers are in equilibrium. The rapid ring flipping results in the interconversion of the axial proton to an equatorial proton and an equatorial to the axial proton. Such interconversions are too rapid and cannot be detected on the NMR timescale. Hence, the NMR spectrometer cannot distinguish between the axial and equatorial protons, resulting in a single peak at &#948; 1.4.
Similarly, NMR averages all the conformations of any molecule with rapid conformational equilibria. For example, the CH3 protons in bromoethane have a single resonance and coupling constant for splitting by the CH2 protons due to the rapid internal rotation of the carbon-carbon bond. Lastly, besides conformational equilibria, the time-averaging effect of NMR spectroscopy is also observed in some chemical reactions.

At room temperature, the chair conformer of cyclohexane undergoes rapid ring flipping between two equivalent chair conformers at a rate of approximately ...

&sup1;H NMR of Labile Protons: Temporal Resolution

Protons bonded to heteroatoms such as nitrogen and oxygen exhibit a range of chemical shift values. This is due to the varying degree of hydrogen bonding between the proton and the heteroatom in other molecules. The extent of hydrogen bonding affects the electron density around the proton, thereby giving different chemical shift values for the protons in the proton NMR spectrum.
The &#8211;OH proton in alcohols typically appears in the range of &#948; 2 to 5 ppm but can vary depending on the specific alcohol and conditions. This &#8211;OH proton undergoes rapid proton exchange with other molecules and is referred to as a labile proton. So, the exact &#948; value of the &#8211;OH proton and the spin-spin coupling involving the &#8211;OH proton and the other protons in the alcohol depends on the rate of the &#8211;OH proton exchange. The proton exchange rate, in turn, depends on multiple factors, including the purity of the alcohol sample, temperature, and solvent.
<img alt="Figure1" src="/files/ftp_upload/12279/12279-PT_Figure_1.svg" style="text-align: center; height: 350px;" />
Figure 1. The triplet of a &#8211;OH proton in the proton NMR spectrum of neat ethanol.
For example, the &#8211;OH proton exchange in a pure dry ethanol sample is very slow on the NMR time scale, giving enough time for the spin-spin coupling. Consequently, as depicted in Figure 1, the proton NMR spectrum of pure dry ethanol shows a triplet for the &#8211;OH proton due to the spin-spin coupling with adjacent methylene protons. The methylene protons are seen as a multiplet due to the coupling with the &#8211;OH proton and the methyl protons.
The presence of trace amounts of an acid or base increases the proton exchange rate. The proton exchange becomes rapid, and the NMR spectrometer only records an average of all the possible environments for the &#8211;OH proton.
<img alt="Figure2" src="/files/ftp_upload/12279/12279-PT_Figure_2.svg" style="text-align: center; height: 325px;" />
Figure 2. The broad singlet of a &#8211;OH proton in the proton NMR spectrum of neat ethanol.
As a result, as recorded in Figure 2, the &#8211;OH proton exhibits a broad singlet. The protons from the adjacent methylene group present a quartet where the splitting is caused only by the adjoining methyl group.

Protons bonded to heteroatoms such as nitrogen and oxygen exhibit a range of chemical shift values. This is due to the varying degree of hydrogen bonding ...

&sup1;H NMR of Conformationally Flexible Molecules: Variable-Temperature NMR

The axial and equatorial protons in cyclohexane can be distinguished by performing a variable-temperature NMR experiment. In this process, except for one proton, the remaining eleven protons are replaced by deuterium. The deuterium substitution avoids the possible peak splitting caused by the spin-spin coupling between the adjacent protons. The remaining proton flips between the axial and equatorial positions.
<img alt="Figure1" src="/files/ftp_upload/13016/13016-PT_Figure_1.svg" style="text-align: center; height: 480px;" />
Figure 1. The temperature-dependent proton NMR spectra of cyclohexane.
Figure 1 depicts the proton NMR spectrum of the deuterium substituted sample, recorded at various temperatures. At room temperature, the rapid ring flipping of cyclohexane results in a single sharp peak. As the temperature is lowered to &#8722;60&#176;C, the rate of chair-chair interconversion reduces, resulting in the broadening of the peak.
Further lowering of the temperature broadens the peak, forming a saddle that splits into two peaks. On reaching a temperature lower than &#8722;89&#176;C, two sharp, well-resolved peaks corresponding to the equatorial and axial protons are formed. The peaks corresponding to the equatorial and axial protons occur at &#948; 1.62 and 1.14, respectively. At such low temperatures, the rate of chair-chair interconversion is reduced significantly, enabling the detection of the two distinct sets of protons on the NMR time scale.

The axial and equatorial protons in cyclohexane can be distinguished by performing a variable-temperature NMR experiment. In this process, except for one ...

Chemical Ionization (CI) Mass Spectrometry

The molecular ion peak of a molecule in the mass spectrum provides vital information for molecular identification. However, conventional electron impact ionization can lead to the rapid dissociation of some molecular ions before they reach the detector. A milder ionization method is required to increase the lifetime of such ionized analyte molecules. Chemical ionization (CI) is a gas-phase protonation reaction useful for mass-analyzing analyte molecules that are easily protonated to yield the corresponding conjugate acid. In this process, the sample is mixed with an excess reagent gas, which ensures the electron impact occurs primarily on the reagent gas. The charged species formed from the reagent protonates the analyte molecule, producing a relatively stable protonated analyte (conjugate acid) compared to the molecular ion. This results in an M+1 peak in the mass spectrum. The conjugate acid may then undergo fragmentation that generates additional signals.
For example, the CI of di-sec-butyl ether in methane gas illustrates this process. When the ether is mixed with excess methane gas as a reagent, electron impact occurs on methane rather than the ether. The resulting methane radical cation can react with another methane molecule to generate a methane radical and a methanium ion. The methanium ion is a source of gas-phase protons, which can protonate the ether to form its conjugate acid. The sequential reactions during the chemical ionization of di-sec-butyl ether are depicted in Figure 1.
<img alt="Figure1" src="/files/ftp_upload/12300/12300_PT_Figure_1.svg" style="text-align: center; height: 175px;" />
Figure 1: Chemical ionization of di-sec-butyl ether methane mixture.
This conjugate acid of the ether (m/z = 131) is relatively more stable than the molecular ion (m/z = 130) of ether formed via the conventional electron impact ionization. In the traditional route, the molecular ion undergoes fragmentation via &#945; cleavage, giving a signal at m/z = 101. Figure 2 illustrates the reactions that occur during electron impact ionization directly on di-sec-butyl ether.
<img alt="Figure2" src="/files/ftp_upload/12300/12300_PT_Figure_2.svg" style="text-align: center; height: 175px;" />
Figure 2: Electron impact ionization of di-sec-butyl ether and fragmentation of the molecular ion.
So, the mass spectra of di-sec-butyl ether ionized via CI feature an M+1 peak at m/z = 131. On the other hand, mass spectra of di-sec-butyl ether ionized via electron impact ionization do not show any peak at the m/z value of its molecular weight. Figures 3a and 3b show the mass spectra of di-sec-butyl ether ionized via the electron impact and chemical ionization methods, respectively.
<img alt="Figure3" src="/files/ftp_upload/12300/12300_PT_Figure_3.svg" style="text-align: center; height: 225px;" />
Figure 3:&#160;a) No m/z = 130 peak is visible in the mass spectrum obtained via electron impact ionization of di-sec-butyl ether. b) The m/z = 131 peak is clearly visible in the mass spectrum obtained via chemical ionization of di-sec-butyl ether.

The molecular ion peak of a molecule in the mass spectrum provides vital information for molecular identification. However, conventional electron impact ...

Electrospray Ionization (ESI) Mass Spectrometry

Higher molecular weight biomolecules are nonvolatile compounds that may decompose before ionizing or vaporizing during mass analysis with conventional electron impact ionization methods. Accordingly, electrospray ionization (ESI) is the favored method for vaporizing and ionizing biomolecules as it circumvents rapid fragmentation and enables the recording of mass signals for the entire biomolecule.
ESI utilizes electrical energy to transfer ions from the liquid phase of the sample into the gaseous phase. The analyte biomolecule is premixed with an ionic liquid&#8212;a nonmolecular compound serving as the ionization source. The solution is sprayed through a high-voltage capillary to generate a fine aerosol. The voltage difference applied between the capillary and the entrance of the analysis chamber causes the movement of charged droplets toward the analysis chamber. The ionic liquid from the aerosol evaporates during this movement, leaving behind a variably protonated or ionized analyte molecule. These charged species are detected in the mass spectrum at an m/z value equivalent to the sum of the analyte molecule&#39;s molecular mass and the ions&#39; molecular weight from the ionic liquid associated with the analyte molecule.
The position of mass signals varies depending on the type of cations present in the ionic liquid. For example, the presence of sodium ions in the ionic liquid leads to an (M+23) peak in the mass spectra, while the presence of a proton results in an (M+1) peak.

Higher molecular weight biomolecules are nonvolatile compounds that may decompose before ionizing or vaporizing during mass analysis with conventional ...

Mass Spectrometry: Aldehyde and Ketone Fragmentation

In mass spectrometry, the fragmentation of aliphatic aldehydes and ketones generally occurs through three key mechanisms: &#945;-cleavage, inductive cleavage, and the McLafferty rearrangement.
<ol>
	<li>&#945;-Cleavage 
	&#945;-Cleavage is a common fragmentation in carbonyl compounds where the bond adjacent to the carbonyl group is broken. This process produces an alkyl radical and an acylium cation, which is often detected in the mass spectrum due to its stability.</li>
	<li>Inductive Cleavage 
	In inductive cleavage, fragmentation yields an acyl radical and an alkyl cation. This occurs when electrons are drawn toward the carbonyl, weakening adjacent bonds and resulting in a distinctive fragmentation pattern. For example, in the mass spectrum of 5-methyl-2-hexanone, inductive cleavage produces an alkyl cation at a mass-to-charge (m/z) ratio of 71.</li>
	<li>McLafferty Rearrangement 
	The McLafferty rearrangement is a specific fragmentation pattern for carbonyl compounds with &#947;-hydrogen (hydrogen on the third carbon from the carbonyl group). The molecule undergoes a six-membered cyclic transition in this rearrangement, yielding a radical cation and a neutral alkene. For 5-methyl-2-hexanone, this rearrangement results in a peak at m/z 58.</li>
</ol>
Example: Fragmentation of 5-methyl-2-hexanone 
In the mass spectrum of 5-methyl-2-hexanone, the molecular ion undergoes these fragmentation patterns:
<ol style="list-style-type: circle;">
	<li>Inductive cleavage produces an alkyl cation at m/z 71.</li>
	<li>&#945;-Cleavage results in the base peak at m/z 43.</li>
	<li>McLafferty rearrangement creates a distinct peak at m/z 58.</li>
</ol>
An additional diagnostic feature in aldehydes is the M&#8722;1 peak, which arises due to the &#945;-cleavage of the aldehyde proton. In mass spectrometric analysis, this peak can help identify aldehydes, specifically among other carbonyl compounds.
Understanding these fragmentation pathways is crucial for interpreting mass spectra, particularly in identifying functional groups and distinguishing between similar compounds.

In mass spectrometry, the fragmentation of aliphatic aldehydes and ketones generally occurs through three key mechanisms: &#945;-cleavage, inductive ...

Matrix-Assisted Laser Desorption Ionization (MALDI)

Matrix-assisted laser desorption ionization (MALDI) is a powerful analytical technique used in mass spectrometry. It enables the identification and characterization of various biomolecules, including proteins, peptides, nucleic acids, and carbohydrates. MALDI spectrometry is widely employed in biological and medical research, as well as in fields like pharmacology and biochemistry.
The analyte of interest, a biomolecule or a mixture of biomolecules, is mixed with a suitable matrix material. The matrix is usually an organic compound, such as a small organic acid or a crystalline substance, that facilitates ionization. This analyte-matrix mixture is then deposited onto a target surface, inserted into the mass spectrometer, and dried. During drying, the matrix forms small crystals that incorporate the analyte molecules within their structure.
Once the sample is prepared, a pulsed laser is directed onto the target surface. The matrix molecules absorb the laser beam energy, causing them to heat up and vaporize rapidly. This process is known as laser desorption. As the matrix molecules vaporize, they carry the embedded analyte molecules. The vaporized analyte molecules become ionized through a process called proton transfer. The proton transfer occurs between the matrix and the analyte molecule. The matrix molecule donates a proton to the analyte molecule, resulting in the formation of protonated ions. The analyte ions are then accelerated by an electric field and further separated based on their mass-to-charge ratio in a time-of-flight mass analyzer.
The mass spectrum obtained from MALDI spectrometry provides valuable information about the mass and relative abundance of the analyzed biomolecules.

Matrix-assisted laser desorption ionization (MALDI) is a powerful analytical technique used in mass spectrometry. It enables the identification and ...

Mass Spectrometry: Alkyl Halide Fragmentation

Chlorine isotopes exist as 35Cl and 37Cl in a 3:1 ratio, while bromine isotopes exist as 79Br and 81Br in a 1:1 ratio. The mass spectrum of alkyl halides typically produces two distinct molecular ion peaks, the molecular ion peak, [M], and the molecular ion plus two, [M + 2] peak. The relative heights of these two peaks are proportional to the isotopic abundance ratios of the halide. For example, 2&#8208;chloropropane and 1&#8208;bromopropane display two peaks with relative peak heights in a 3:1 and 1:1 ratio, respectively.
Alkyl halides typically lose a non-bonding electron from the halogen to form molecular ions. The base peak results from the heterolytic cleavage of the carbon&#8211;halogen bond, where the bonding electrons go to the most electronegative atom, forming a cation and halogen atom. Interestingly, the &#9082;-cleavage is observed only in alkyl chlorides, not alkyl bromides. In alkyl chlorides, the&#160; C&#8211;Cl and C&#8211;C bonds exhibit similar strengths, while in alkyl bromides, the C&#8211;Br bond is weaker than the C&#8211;C bond. Consequently, the alkyl chlorides form a stable cation, where the positive charge is shared between the two atoms.
While less commonly discussed, fluoroalkanes and iodoalkanes exhibit unique fragmentation behavior. Fluoroalkanes, due to the strength of the C&#8211;F bond and the presence of only one isotope (19F), show limited fragmentation and lack isotopic peaks. Iodoalkanes, with their weak C&#8211;I bond and a single isotope (127I), predominantly fragment by losing iodine, resulting in simpler spectra with less isotopic splitting.

Chlorine isotopes exist as 35Cl and 37Cl in a 3:1 ratio, while bromine isotopes exist as 79Br and 81Br in a 1:1 ratio. The mass spectrum of alkyl halides ...

Mass Spectrometry: Carboxylic Acid, Ester, and Amide Fragmentation

The fragmentation patterns observed for compounds such as carboxylic acids, esters, and amides in the mass spectra include &#9082;-cleavage and McLafferty rearrangement. Fragmentation by &#9082;-cleavage preferentially occurs at the carbon-carbon bond at the &#9082;-position next to the carboxylic group to generate a neutral radical and a cation. Long chain compounds with hydrogen at their &#947;-carbon undergo McLafferty rearrangement to give a radical cation and a neutral alkene.
For example, the fragmentation of butyramide is demonstrated in Figure 1. The molecular ion peak of butyramide, which contains one nitrogen atom, shows an odd mass-to-charge ratio of 87. Fragmentation of butyramide molecular ion by &#9082;-cleavage produces a cation at a mass-to-charge ratio 44. In addition to &#9082;-cleavage, butyramide molecular ion also undergoes fragmentation via McLafferty rearrangement. The base peak at the mass-to-charge ratio 59 arises due to McLafferty rearrangement.
<img alt="Figure1" src="/files/ftp_upload/13051/13051_PT_Figure_1.svg" style="text-align: center; height: 250px;" />

The fragmentation patterns observed for compounds such as carboxylic acids, esters, and amides in the mass spectra include &#9082;-cleavage and McLafferty ...

Mass Spectrometry: Aromatic Compound Fragmentation

Upon ionization, aromatic compounds generate a molecular ion that is observed as a prominent peak in their mass spectra. For example, the molecular ion peak for benzene appears at a mass-to-charge ratio of 78, while toluene is observed at a mass-to-charge ratio of 92. The molecular ion benzene is highly stable and does not readily undergo further fragmentation due to the significant amount of energy required to disrupt the aromatic stability of the benzene ring. In contrast, the molecular ion of alkyl&#8208;substituted benzenes, such as toluene, can undergo fragmentation by losing a hydrogen atom, forming a benzylic carbocation. This carbocation can rearrange to form the resonance-stabilized tropylium cation, which appears in the mass spectra as a strong peak. In the case of toluene, this strong peak is observed at a mass-to-charge ratio of 91.

Upon ionization, aromatic compounds generate a molecular ion that is observed as a prominent peak in their mass spectra. For example, the molecular ion ...

Mass Spectrometry: Alcohol Fragmentation

Alcohols (R-OH) ionize to lose one non-bonded electron from the oxygen atom, forming molecular ions. Due to their tendency to fragment rapidly, the intensity of the molecular ion peak in the mass spectrum is weak or sometimes absent. The fragmentation patterns for alcohols occur in two ways, i.e. &#9082;-cleavage and dehydration. During &#9082;-cleavage, the bond at the &#9082;-position adjacent to the hydroxyl group cleaves to give a resonance-stabilized cation and a radical. However, intramolecular dehydration involves losing a water molecule from an alcohol, forming an alkene cation, which shows a peak at M&#8722;18. Consider the fragmentation of butanol as shown below. &#9082;-cleavage produces a base peak at a mass-to-charge ratio of 31. In the case of dehydration, the fragmentation forms an alkene radical cation at a mass-to-charge ratio of 56.
<img alt="Figure1" src="/files/ftp_upload/13046/13046-PT_Figure_1.svg" style="text-align: center; height: 175px;" />

Alcohols (R-OH) ionize to lose one non-bonded electron from the oxygen atom, forming molecular ions. Due to their tendency to fragment rapidly, the ...

Mass Spectrometry: Amine Fragmentation

Amines can be identified using mass spectroscopy based on their characteristic fragmentation patterns. The molecular ions of amines undergo fragmentation via &#9082;-cleavage. The &#9082;-cleavage of the carbon-carbon bonds in amines generates an alkyl radical and resonance-stabilized nitrogen-containing cation.
In amines, the number of nitrogen atoms affects the mass of the molecular ion, which is described by the nitrogen rule of mass spectrometry. This rule states that a compound containing a single or an odd number of nitrogen atoms produces a molecular ion with an odd molecular weight, while a compound with no or an even number of nitrogen atoms generates a molecular ion with an even molecular weight.
For example, the mass spectrum of 3-methyl-1-butanamine, which contains one nitrogen atom, displays a molecular ion having an odd mass-to-charge ratio of 87. Fragmentation of this molecular ion via &#9082;-cleavage produces a base peak, which features a mass signal at a mass-to-charge ratio of 30, corresponding with the loss of the 2-methyl propyl radical.
Similarly, the fragmentation of triethylamine via &#9082;-cleavage generates a cation at a mass-to-charge ratio of 86. The molecular ion peak shows an odd mass-to-charge ratio of 101, as shown below.
<img alt="Figure1" src="/files/ftp_upload/13048/13048_PT_Figure_1.svg" style="text-align: center; height: 105px;" />

Amines can be identified using mass spectroscopy based on their characteristic fragmentation patterns. The molecular ions of amines undergo fragmentation ...

Mass Spectrometry: Cycloalkene Fragmentation

The molecular ions of cycloalkenes undergo fragmentation via a retro-Diels&#8211;Alder reaction.

The reaction proceeds via the cleavage of two carbon-carbon bonds in the cycloalkene to yield ethene. The remaining part of the cycloalkene structure is a dienyl radical cation with a molecular weight of 28 u lower than the molecular ion. This fragmentation pathway is similar to the fragmentation of cycloalkanes releasing ethene, differing only in the resultant radical cation. An alkyl species forms from the cycloalkane, whereas a dienyl species originates from the cycloalkene.

Retro-Diels&#8211;Alder reactions of cycloalkenes are also similar to the McLafferty-rearrangement-type fragmentation observed in acyclic alkenes with hydrogen on the &#947; carbon. In both cases, cleavage occurs at two positions, yielding an ethene molecule and an alkenyl species. In acyclic alkenes, the cleavage occurs at one carbon-carbon bond and a carbon-hydrogen bond, along with rearranging hydrogen from one carbon to another. In cyclic alkenes, cleavage occurs at two carbon&#8211;carbon bonds without any atomic rearrangement. Figure 1 depicts the fragmentation of cyclohexene via a retro-Diels&#8211;Alder reaction.
<img alt="Figure1" src="/files/ftp_upload/13044/13044-PT_Figure_1.svg" style="text-align: center; height: 90px;" />
Figure 1: Fragmentation of cyclohexene via a retro-Diels&#8211;Alder reaction.
In addition to the retro-Diels&#8211;Alder reaction, branched cycloalkenes exhibit fragmentation via cleavage of the side chain to form a cycloalkene cation. For example, the fragmentation of 1-methyl-1-cyclohexene via a retro-Diels&#8211;Alder reaction and side-chain cleavage are shown in Figure 2.
<img alt="Figure2" src="/files/ftp_upload/13044/13044-PT_Figure_2.svg" style="text-align: center; height: 225px;" />
Figure 2: Fragmentation of 1-methyl-1-cyclohexene via (top) a retro-Diels&#8211;Alder reaction; (bottom) side-chain cleavage.
The corresponding signals of the isoprenyl radical cation and the cyclohexenyl cation are evident in the mass spectrum of 1-methyl-1-cyclohexene shown in Figure 3.
<img alt="Figure3" src="/files/ftp_upload/13044/13044-PT_Figure_3.svg" style="text-align: center; height: 250px;" />
Figure 3: Mass spectrum of 1-methyl-1-cyclohexene.

The molecular ions of cycloalkenes undergo fragmentation via a retro-Diels&#8211;Alder reaction.

The reaction proceeds via the cleavage of two ...

Mass Spectrometry: Alkyne Fragmentation

The fragmentation of alkynes preferentially occurs at the carbon&#8211;carbon bond between the &#945; and &#946; carbon of the alkyne bond to generate a 3-propynyl cation (or propargyl cation). In terminal alkynes, there is the only type of fragmentation that yields the 3-propynyl cation. The unsubstituted 3-propynyl cation exhibits a peak at a mass-to-charge ratio of 39. In internal alkynes, the 3-propynyl cation is substituted. For example, 2-pentyne fragments into methyl-substituted 3-propynyl cation, which subsequently features as a mass signal at the mass-to-charge ratio of 56. The 3-propynyl cation is resonance-stabilized, and the corresponding mass signal is intense in the mass spectrum of alkynes. Figure 1 shows the fragmentation of 1-pentyne into an ethyl radical and a resonance stabilized 3-propynyl cation.
<img alt="Figure1" src="/files/ftp_upload/13045/13045-PT_Figure_1.svg" style="text-align: center; height: 115px;" />
Figure 1: Fragmentation of 1-pentyne molecular ion to yield the 3-propynyl cation.
Another fragmentation pathway observed in terminal alkynes is the loss of hydrogen from the terminal sp carbon. This results in a mass signal with a mass-to-charge ratio of one unit less than the molecular ion. This M&#8211;1 peak is very intense and becomes the base peak in the mass spectra of many alkynes, so it can be used to identify alkynes.
<img alt="Figure2" src="/files/ftp_upload/13045/13045-PT_Figure_2.svg" style="text-align: center; height: 275px;" />
Figure 2: The mass spectrum of 1-pentyne.

The fragmentation of alkynes preferentially occurs at the carbon&#8211;carbon bond between the &#945; and &#946; carbon of the alkyne bond to generate a ...

Mass Spectrometry: Long-Chain Alkane Fragmentation

The molecular ions of linear alkanes prefer to fragment at the carbon-carbon bond away from the end of the chain since the cleavage of an inner bond creates a stable carbocation and a stable radical. Consequently, the mass signals of linear alkanes feature intense peaks in the middle of the mass-to-charge ratio plot with weaker peaks on either end. The fragmentation of each carbon-carbon bond with the release of a methyl group in each splitting leads to prominent peaks in the mass spectra separated by 14 u. Smaller mass signals near each prominent peak result arise from secondary fragmentation at the carbon-hydrogen bond.
For example, consider the fragmentation pattern of n-hexane shown in Figure 1 and the corresponding mass spectra in Figure 2.
<img alt="Figure1" src="/files/ftp_upload/12299/12299-PT_Figure_1.svg" style="text-align: center; height: 500px;" />
Figure 1: Fragmentation of n-hexane molecular ion.
<img alt="Figure2" src="/files/ftp_upload/12299/12299-PT_Figure_2.svg" style="text-align: center; height: 275px;" />
Figure 2: Mass spectrum of n-hexane.
The signals at a mass-to-charge ratio of 71, 57, 43, 29, and 15 indicate that the cleavage can occur at all carbon-carbon bonds in the molecule. However, the relative abundance of these peaks varies. The difference between molecular ion signal and signal at 71 indicates the separation of methyl groups (M.W. = 15 u) group from molecular ions. Further release of a CH2 group from that fragment (M.W. = 14 u) results in a signal at 57. The signals at 43, 29, and 15 are due to the subsequent releases of CH2 groups. The abundance of signals at 15 and 71 is minimal due to the least probability for the formation of unstable methyl carbocation or a methyl radical, respectively. The base peak at 43 indicates the most preferred fragmentation, which yields a pair of stable carbocation and radical.

The molecular ions of linear alkanes prefer to fragment at the carbon-carbon bond away from the end of the chain since the cleavage of an inner bond ...

Dichotic Listening

Source: Laboratory of Jonathan Flombaum&#8212;Johns Hopkins University

It is a well-known fact that the human ability to process incoming stimuli is limited. Nonetheless, the world is complicated, and there are always many things going on at once. Selective attention is the mechanism that allows humans and other animals to control which stimuli get processed and which become ignored. Think of a cocktail party: a person couldn&#8217;t possibly attend to all of the conversations taking place at once. However, everyone has the ability to selectively listen to one conversation, leading all the rest to become unattended to and nothing more than background noise. In order to study how people do this, researchers simulate a more controlled cocktail party environment by playing sounds to participants dichotically, i.e., by playing different sounds simultaneously to each ear. This is called a dichotic listening paradigm.
This experiment demonstrates standard procedures for investigating selective auditory attention with a paradigm called dichotic listening.

Dichotic Listening: Investigating Selective Auditory Attention

양분 청취법

Source: Laboratory of Jonathan Flombaum&#8212;Johns Hopkins University

It is a well-known fact that the human ability to process incoming stimuli is ...

Measuring Reaction Time and Donders' Method of Subtraction

Source: Laboratory of Jonathan Flombaum&#8212;Johns Hopkins University

The ambition of experimental psychology is to characterize the mental events that support the human ability to solve problems, perceive the world, and turn thoughts into words and sentences. But people cannot see or feel those mental events; they cannot be weighed, combined in test tubes, or grown in a dish. Wanting to study mental life, nonetheless, Franciscus Donders, a Dutch ophthalmologist in the early 1800s, came up with a property that he could measure&#8212;even back then: he measured the time it took for human subjects to perform simple tasks, reasoning that he could treat those measurements as proxies for the time it takes to complete the unobservable mental operations involved. In fact, Donders went one step further, developing a basic experimental paradigm known as the Method of Subtraction. It simply asks a researcher to design two tasks that are identical in nearly every way, excepting a mental operation hypothesized to be involved in one of the tasks and omitted in the other. The researcher then measures the time it takes to complete each task, and by subtracting the outcomes, he extracts an estimate of the time it takes to execute the one mental operation of interest. In this way, the method allows a researcher to isolate a mental operation. The time it takes to complete a task has become known as reaction time or latency. Even today, reaction time is by a wide margin the most prevalent dependent variable in experimental psychology. &#160;

This video will demonstrate the measurement of reaction time using Donders&#8217; Method of Subtraction.

Measuring Reaction Time and Donders&#039; Method of Subtraction

반응 시간 측정 및 돈더스의 뺄셈 방법 측정

Source: Laboratory of Jonathan Flombaum&#8212;Johns Hopkins University

The ambition of experimental psychology is to characterize the mental events that ...

Visual Search for Features and Conjunctions

Source: Laboratory of Jonathan Flombaum&#8212;Johns Hopkins University

How do people find objects in cluttered visual scenes? Think, for example, of looking for keys on a messy desk, finding the ripest-looking fruit at the grocery store, locating your car when you can&#8217;t quite remember where you parked it, or finding an old friend at an airport exit gate. Clearly, an understanding of visual perception is going to play a role in any answers, and more specifically, an understanding of visual attention will be crucial.
Visual attention refers to the ability to focus in on just part of an image, mustering one&#8217;s processing resources selectively to determine whether the thing being looked for&#8212;the target, in the standard experimental jargon&#8212;is present. To study search and attention, experimental psychologists have developed a widely used paradigm known (unsurprisingly) as visual search.
Psychologists have also motivated a great deal of research by the intuition that any good theory of search is going to have, to explain why some things are easy to find and others are hard to find. So in the context of the visual search paradigm, perceptual psychologists have often focused on contrasting easy searches with more difficult ones. The most influential contrast is between what researchers call a feature search and a conjunction search.

Investigating Visual Attention by Feature and Conjunction Search

특징 및 결합에 대한 시각적 검색

Source: Laboratory of Jonathan Flombaum&#8212;Johns Hopkins University

How do people find objects in cluttered visual scenes? Think, for example, of ...

Perspectives on Cognitive Psychology

Source: Laboratory of Jonathan Flombaum&#8212;Johns Hopkins University

As an Assistant Professor of Psychology and Cognitive Science at Johns Hopkins University, I teach Introduction to Cognitive Psychology. This large class primarily consists of freshman and sophomores majoring in related fields, like Psychology, Neuroscience, or Cognitive Science. One of the challenges I face in the classroom is teaching students to appreciate how data are obtained in the process of performing experiments. Students have difficulty in appreciating the chronology of experiments as they unfold in time.
This JoVE collection in Cognitive Psychology makes the experimental timeline absolutely clear and encourages students to understand the trajectory and not just jump to conclusions. The videos also present experiments as paradigms&#8212;to illustrate how researchers can implement tasks in different ways&#8212;depending on the questions at hand. Most of these questions translate to the real world and the limits of our cognition. For example, the video Measuring Verbal Working Memory Span demonstrates our limited memory capacity, which explains the difficulty in remembering long shopping lists.
These JoVE videos in Cognitive Psychology provide a perfect place for instructors to start if they are interested in demonstrating tasks in class. Better yet, the videos can be used to get students involved&#8212;to execute the procedures and to even be the participants. Thus, the collection perfectly introduces lab components to a Psychology class.

인지 심리학에 대한 관점

Source: Laboratory of Jonathan Flombaum&#8212;Johns Hopkins University

As an Assistant Professor of Psychology and Cognitive Science at Johns Hopkins ...

Binocular Rivalry

Source: Laboratory of Jonathan Flombaum&#8212;Johns Hopkins University

Why do people have two forward-facing eyes? By presenting the brain with two ever so slightly different images it becomes possible to comprehend visual problems that are far more difficult to process through a single eye. Chief among these is the problem of 3-D perception, seeing the world in three dimensions, despite retinal inputs in only two dimensions.
What happens if each eye receives two completely different images? That does not happen in nature, to be sure, but it can be contrived in the laboratory in a set-up called binocular rivalry.
Binocular rivalry is a common laboratory paradigm for investigating the ways that the brain integrates information from two eyes, and in recent years, the mechanisms responsible for producing conscious experience.

Binocular Rivalry: Studying Visual Perception and Neural Correlates of Consciousness

양안경합

Source: Laboratory of Jonathan Flombaum&#8212;Johns Hopkins University

Why do people have two forward-facing eyes? By presenting the brain with two ever ...

Multiple Object Tracking

Source: Laboratory of Jonathan Flombaum&#8212;Johns Hopkins University

In a staggeringly complex and engaging world, it is crucial to selectively process some stimuli at the expense of others. Experimental psychologists call this ability attention. Specifically, visual attention refers to the ability to selectively process aspects of a visual scene.
Many paradigms used to study visual attention involve brief, punctuated, and repeated trials. However, everyday situations often place sustained demands on attention, as opposed to requiring only brief focus. For example, compare driving through busy city streets, which demands sustained attention, with crossing a busy street, which demands just a few moments of caution. To investigate sustained visual attention, experimental psychologists typically rely on a paradigm called multiple object tracking.
This video demonstrates standard procedures for investigating sustained visual attention through multiple object tracking.

Multiple Object Tracking: Studying Sustained Visual Attention

다중 객체 추적

Source: Laboratory of Jonathan Flombaum&#8212;Johns Hopkins University

In a staggeringly complex and engaging world, it is crucial to selectively process ...

Approximate Number Sense Test

Source: Laboratory of Jonathan Flombaum&#8212;Johns Hopkins University

A common carnival game is to ask people to guess the number of jellybeans packed into a jar. The chances that anyone will get the exact number right are low. But what about the chances that someone will guess 17 or 147,000? Probably even less than the chances of guessing the correct answer; 17 and 147,000 just seem irrational. Why? After all, if the beans cannot be taken out and counted one-at-a-time, how can someone tell that an estimate is too high or too low?
It turns out that in addition to verbal counting (something clearly learned), people appear to possess hardwired mental and neural mechanisms for estimating numbers. To put it colloquially, it is what might be called an ability to guesstimate, or &#8220;ballpark.&#8221; Experimental psychologists call it the &#8220;Approximate Number Sense,&#8221; and recent research with an experimental paradigm of the same name has begun to uncover the underlying computations and neural mechanisms that support the ability to guesstimate.
This video demonstrates standard procedures for investigating nonverbal numerical estimation with the Approximate Number Sense Test.

대략적인 숫자 감지 테스트

Source: Laboratory of Jonathan Flombaum&#8212;Johns Hopkins University

A common carnival game is to ask people to guess the number of jellybeans packed ...

Mental Rotation

Source: Laboratory of Jonathan Flombaum&#8212;Johns Hopkins University

Visual mental imagery refers to the ability to conjure images in one&#8217;s mind&#8217;s eye. This allows people to process visual material above and beyond the constraints of a current point-of-view; for example, a person could imagine, using their mind&#8217;s eye, how something might look in a different color, or what it would look like if it were made from a different material or rotated and seen from a different perspective. Mental imagery seems to support important human behaviors in many contexts. For example, people report visualizing routes and maps when planning a route or giving directions. They report visualizing movements, such as swinging a bat, to prepare for an actual action. They also report the mental rotation of objects in order to consider how an object might fit into a receptacle or clear a barrier.
This video demonstrates how to use the mental rotation procedure in order to investigate visual mental imagery.

Mental Rotation: Investigating Visual Mental Imagery

정신 회전

Source: Laboratory of Jonathan Flombaum&#8212;Johns Hopkins University

Visual mental imagery refers to the ability to conjure images in one&#8217;s ...

Prospect Theory

Source: Laboratory of Jonathan Flombaum&#8212;Johns Hopkins University

What&#8217;s the value of a dollar? Currencies store value to facilitate trade. Implied in any economic transaction is the value of a unit of currency. But what is the subjective value of a dollar? For a long time, economists assumed the answer to this question to be, specifically, that a dollar has a value determined by the market and that the subjective value of a dollar is always that, more or less.

Beginning in the early 1970s, experimental psychologists Daniel Kahneman and Amos Tversky upended this assumption, showing that the subjective value of currency depends on a number of factors, most notably, whether losses or gains are being discussed, and the overall size of a transaction. To pump intuition, consider the fact that, to most people, it would seem reasonable to drive an extra half-mile in order to save $2 on a gallon of gas. But very few people would do the same to save $2 on the cost of a new car. So $2 is sometimes, but not always worth an extra half-mile drive. Value is context-dependent.

The theory devised by Kahneman and Tversky to describe how people psychologically value currency (and goods and services, generally) is called Prospect Theory. In 2002, Kahneman was awarded the Nobel Prize in Economics for Prospect Theory, along with related research using the methods and theories of experimental psychology to understand economic decision-making (Tversky passed away in 1996.).

Many of the primary implications of Prospect Theory were obtained through survey experiments. The surveys consisted of choices between gambles; for example, subjects might be asked whether they would prefer to receive $5 or risk receiving nothing with a 50% chance of winning $10.

This video will demonstrate procedures for designing the type of survey questions used in research on Prospect Theory.

Studying Prospect Theory Through Survey

전망 이론

Source: Laboratory of Jonathan Flombaum&#8212;Johns Hopkins University

What&#8217;s the value of a dollar? Currencies store value to facilitate trade. ...

Measuring Verbal Working Memory Span

Source: Laboratory of Jonathan Flombaum&#8212;Johns Hopkins University

Why is it relatively hard to remember everything on a shopping list if it includes more than just a handful of items? Why is it possible to remember a phone number that one just heard, but not two or three phone numbers at once? Why is it difficult to remember names when several new people are introduced at the same time?
The answer has to do with the fact that over short-durations people rely on a specialized memory system called working memory. Unlike long-term memory, working memory has a very limited capacity. It is there so that information can be kept in mind, studied, manipulated, and then transferred to other memory and cognitive systems. But in order to serve in this active role, it needs to be selective, admitting only limited amounts of information at a time.
Experimental psychologists tend to think that people possess independent working memory systems for different kinds of information, with a major division between verbal and visual information. Each of these systems has an independent capacity limit.
To measure a person&#8217;s verbal working memory capacity limit&#8212;often called, his or her memory span&#8212;experimental psychologists often use a verbal list paradigm.
This video will demonstrate the measurement of verbal working memory span using a verbal list paradigm.

구두 작업 기억 범위 측정

Source: Laboratory of Jonathan Flombaum&#8212;Johns Hopkins University

Why is it relatively hard to remember everything on a shopping list if it includes ...

The Precision of Visual Working Memory with Delayed Estimation

Source: Laboratory of Jonathan Flombaum&#8212;Johns Hopkins University

Human memory is limited. Throughout most of its history, experimental psychology has focused on investigating the discrete, quantitative limits of memory&#8212;how many individual pieces of information a person can remember. Recently, experimental psychologists have also become interested in more qualitative limits&#8212;how precisely is information stored?
The concept of memory precision can be both intuitive and elusive at once. It is intuitive, for example, to think a person can remember precisely how their mother sounds, making it possible to recognize one&#8217;s mother immediately over the phone or in a crowd. But how can one quantify the precision of such a memory? Exactly how similar is the memory to the voice itself?
To study the precision of memory and working memory, in particular, experimental psychologists have devised a paradigm known as delayed estimation. It has been used most often, thus far, to study the precision of visual memories, especially memory for color, and to understand how memory degrades the more one tries to remember at once. This video demonstrates standard procedures for investigating the precision of color working memory using delayed estimation, with a focus on how memory is affected as one tries to remember the colors of more objects simultaneously.

지연 추정을 통한 시각적 작업 기억의 정밀도

Source: Laboratory of Jonathan Flombaum&#8212;Johns Hopkins University

Human memory is limited. Throughout most of its history, experimental psychology ...

Verbal Priming

Source: Laboratory of Jonathan Flombaum&#8212;Johns Hopkins University

Human memory seems to work in two broad ways. Like modern computers, the human mind has explicit, or declarative, memory: ask a question, and a person gives the best answer they can. Input a query, and a computer program returns the contents of the relevant parts of its stored memory.
Humans also have a second kind of memory system, one not really typical of computers, one that experimental psychologists call implicit.
Implicit memory is a broad term that refers to the many ways past experiences influence present behavior. Pavlov&#8217;s famous dogs, for example, learned to associate the sound of a bell with mealtime. Eventually, they began salivating whenever they heard a bell, even if food was not delivered.
Humans also possess implicit memory. Implicit memories, for example, are the reason it can be difficult to fall asleep in a new place; people associate their bedroom environment and their nighttime routines with sleepiness.
Implicit memory is thought to guide human behavior in a wide array of circumstances. It is the kind of memory that guides manners and social behaviors, the kind of memory that puts relevant concepts and intuitions at a person&#8217;s fingertips. In many ways, implicit memory is what makes people prepared to process a new encounter in light of the past.
One way experimental psychologists investigate implicit memory is with a paradigm known as verbal priming. This video demonstrates a procedure for investigating the nature of implicit memory through verbal priming.

Verbal Priming: Investigating Implicit Memory

구두 프라이밍

Source: Laboratory of Jonathan Flombaum&#8212;Johns Hopkins University

Human memory seems to work in two broad ways. Like modern computers, the human ...

Incidental Encoding

Source: Laboratory of Jonathan Flombaum&#8212;Johns Hopkins University

Long-term memory is a critical feature of human cognition, and it has been a prominent focus of research in experimental psychology. Many paradigms designed to tap long-term memory rely on asking participants to learn or study content, then test memory about that content. This is a good approach if one wants to understand how memory supports educational achievement, for example, where explicit study is part of the process. But, in day-to-day life, people often form new memories&#8212;many of which last for a long time&#8212;incidentally. People do not remember what they read in a magazine, the moment a partner was met, or the plot of a favorite story because they try to. Somehow, a good deal of experience just gets encoded into memory as life goes by. To study this side of long-term memory, experimental psychologists use something called an incidental-encoding paradigm.
The paradigm is especially useful for investigating the kinds of experiences that tend to produce strong long-term memories. Researchers think about experiences in terms of the kind of engagement they demand&#8212;personal, purely intellectual, deep, or shallow, for example. The incidental-encoding paradigm can be used to contrast long-term memory formation during different kinds of engagement by varying the cover task used to expose an individual to stimuli. A cover task is a task that a participant is asked to complete without knowing that memory for the stimuli in the task is tested later.
This video demonstrates standard procedures for using the incidental-encoding paradigm and two different cover tasks to investigate long-term memory when explicit study of a stimulus is not demanded.

Incidental Encoding: Investigating Implicit Long-term Memory

부수적 코드화

Source: Laboratory of Jonathan Flombaum&#8212;Johns Hopkins University

Long-term memory is a critical feature of human cognition, and it has been a ...

Visual Statistical Learning

Source: Laboratory of Jonathan Flombaum&#8212;Johns Hopkins University

The visual environment contains massive amounts of information involving the relations between objects in space and time; certain objects are more likely to appear in the vicinity of other objects. Learning these regularities can support a wide array of visual processing, including object recognition. Unsurprisingly, then, humans appear to learn these regularities automatically, quickly, and without conscious awareness. The name for this type of implicit learning is visual statistical learning. In the laboratory, it is studied with an incidental-encoding paradigm: participants observe a stream of nonsense objects and complete a cover-task, a task unrelated to the underlying statistical structure in the stream. But statistical structure is present, and subsequent to a short exposure period&#8212;as short as 10 min in some experiments&#8212;a familiarity test reveals the extent of learning by the participants.
This video will demonstrate standard methods for inducing and testing visual statistical learning.

Incidental Encoding: Testing Visual Statistical Learning

시각적 통계 학습

Source: Laboratory of Jonathan Flombaum&#8212;Johns Hopkins University

The visual environment contains massive amounts of information involving the ...

Motor Learning in Mirror Drawing

Source: Laboratory of Jonathan Flombaum&#8212;Johns Hopkins University

Colloquially, the terms learning and memory encompass a broad range of behaviors and mental systems, everything from learning to tie a shoe to mastering calculus (and a lot in between). Experimental psychologists have divided up learning mechanisms into groups that seem to have different properties, and that seem to rely on different brain systems. A major division is between declarative and non-declarative memory, roughly, the sorts of things a person can express verbally&#8212;explicitly, like a birthdate, or what one ate for lunch&#8212;and things they cannot quite put into words&#8212;things they know implicitly, like how to get home despite not knowing the street names, or how to flip an omelet.

In the domain of non-declarative memory, a crucial kind of learning involves motor learning, sometimes also called procedural memory. Learning to drive a car is a good example. At first it is usually arduous and seems to involve explicit attempts to remember what to do next. Eventually it becomes second nature, though, something that a person just kind of knows how to do&#8212;and does better and better with time&#8212;but that can be hard to explain to someone else.
Mirror drawing is a common laboratory paradigm for investigating the acquisition of learned motor skills, the kind involved in driving, for example. This video demonstrates standard procedures for mirror drawing.

Mirror Drawing: Investigating the Acquisition of Motor Skills

거울 보고 그림그리기의 운동 학습

Source: Laboratory of Jonathan Flombaum&#8212;Johns Hopkins University

Colloquially, the terms learning and memory encompass a broad range of behaviors ...

Education Cognitive Psychology

Science Education (심리학)

Science Education (심리학)

Science Education (심리학)

Science Education (심리학)

Science Education (심리학)

Science Education (심리학)

Science Education (심리학)

Science Education (심리학)

Science Education (심리학)

Science Education (심리학)

Science Education (심리학)

Science Education (심리학)

Science Education (심리학)

Science Education (심리학)

Science Education (심리학)