behavior

JoVE行動学は、人間や動物の行動を理解するための観察および実験手法を公開しています。このセクションには、内外の刺激に対する遺伝的原因と生理学的反応を分析する方法と、関係する脳領域を調べる方法が含まれています。

行動学

biochemistry

JoVE生化学は、生体分子（タンパク質、核酸、炭水化物、脂質、代謝物など）の構造と機能、および生物学的プロセス中に起こるそれらの相互作用と変換についての理解を深める方法を出版しています。

生化学

bioengineering

JoVE生物工学は、物理学と生命科学を融合して基本的な生物学的プロセスと機能を理解する方法と技術を出版しています。このセクションでは、病気の測定、診断、治療を改善するための物理科学的ツールとアプローチについても特集します。

生物工学

biology

JoVE生物学は、細胞生物学、分子生物学、生命体生物学の分野で使用される方法を出版しています。これは、標準的な技法の新しいアプリケーションから、生物の基本的な生物学的機能を理解することを目的とした新規のアプローチにまで及びます。

生物学

cancer research

JoVEがん研究は、がん生物学の研究で使用される技術を出版しています。このセクションでは、発がん、薬剤耐性のメカニズム、診断、転移、革新的な治療法に取り組む研究方法論を取り上げます。

がん研究

chemistry

JoVE化学は、分析化学、有機化学、高分子化学、物理化学、無機化学など、幅広い分野の方法を出版しています。このセクションには、高度なまたはユニークなアプリケーション向けの材料および低分子の設計・調整も含まれています。

化学

developmental biology

JoVE発生生物学では、分子、細胞、組織、器官、および生物全体のレベルにおける、試験管内および/または生体内での生物発生を研究するのに使用される方法と技術を出版しています。

発生生物学

engineering

JoVE工学では、工学と応用物理学で利用される方法と技術を出版しています。方法には、機械、電気、化学のエンジニア、物理学者、材料科学者からの寄稿が含まれます。

工学

environment

JoVE環境学は、地球のプロセスと生態系を研究し、環境問題に対処するための研究方法と技術を出版しています。このセクションでは、農業および食品科学だけでなく、幅広い学際的な環境研究分野からの実験室およびフィールドベースの方法を取り上げます。

環境学

genetics

JoVE遺伝学は、ゲノミクス、遺伝子発現、遺伝子工学、後生遺伝学など、遺伝学のすべての分野（すべての生物）に取り組む方法を出版しています。このセクションでは、塩基配列決定技術とその応用の進歩についても特に取り上げます。

遺伝学

immunology and infection

JoVE免疫学と感染では、病原体に対する生物学的反応、感染に対する免疫反応、基本的な微生物学、および感染性微生物に対する新しい治療法を評価するための方法と技術を出版しています。

免疫・感染学

medicine

JoVE医学では、生物医学研究方法と臨床応用を出版しています。このセクションでは、疾患の動物モデル、医療処置、手術、患者のケーススタディ、および臨床試験の方法論について説明します。

医学

neuroscience

JoVE神経科学では、脳と神経系の構造、機能、生理学、および病態生理学を研究するための方法を出版しています。このセクションには、神経疾患および神経障害の潜在的な治療基盤と外科技術も含まれています。

神経科学

jove journal

JoVE Journal

科学ビデオジャーナル。査読された論文。学際的。

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Research

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 ...

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: 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 ...

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 ...

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 ...

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 ...

&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 ...

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: 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 ...

&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 ...

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 ...

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 ...

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 ...

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 ...

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: 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 ...

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: 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: 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 ...

Analyzing Situations in Helping Behavior

Source: Julian Wills &#38; Jay Van Bavel&#8212;New York University
Social psychologists and personality psychologists both attempt to predict human behavior, but they focus on very different factors. Whereas personality psychologists focus on how personality traits, character, and individual differences affect behavior, social psychologists focus primarily on the power of social situations in shaping behavior.
We often underestimate the role that social situations can play in determining behavior. We often believe that people who smile are pleasant and happy, people who act rudely are mean, and people who stumble in the street are clumsy. Social psychologists have repeatedly demonstrated that these beliefs may be unfounded, and instead emphasize the importance of the social context in which behavior takes place.
Why are some people more apt to help people in need than others? Most of us would surmise it is a function of their personalities&#8212;some people are more inclined to help than others. However, psychological research shows that the social situation is often more likely to influence a person&#8217;s inclination to be helpful than their personality (which includes religiosity and ethics).
The classic experiment of Darley and Batson tested the Biblical parable of the Good Samaritan in which a priest and a Levite&#8212;two pious, upstanding citizens&#8212;passed by an injured man in need, whereas a non-religious Samaritan stopped to help.1 &#160;
This video highlights some of the experimental techniques used by Darley and Batson in the difficult task of separating personality and situational factors when analyzing human behavior.

援助行動における状況の分析

Source: Julian Wills &#38; Jay Van Bavel&#8212;New York University
Social psychologists and personality psychologists both attempt to predict human ...

Using fMRI to Dissect Moral Judgment

Source: William Brady &#38; Jay Van Bavel&#8212;New York University
In examining the roles of reason and emotion in moral judgments, psychologists and philosophers alike point to the trolley dilemma and the footbridge dilemma. With the trolley dilemma, most people say that it is appropriate to pull a switch to stop a train from hitting five people by diverting it to kill one person. However, with the footbridge dilemma, most people say it is inappropriate to push a large man off of a bridge in order to hit a train (killing him) and stop it from running into five people. Reason would dictate that in both of the foregoing dilemmas, one life should be sacrificed to save five lives. But to many people, pushing the large man just &#8220;feels wrong&#8221; because it triggers more negative emotions than pulling a switch. In this case, emotion seems to trump reason. &#160;
In recent years, psychology and neuroscience have entered the debate over the roles of reason and emotion in moral judgment. Researchers can scan brain activity as individuals make making moral judgments. Research shows that different brain areas associated are active during contemplation of the footbridge dilemma versus the trolley dilemma.
Inspired by Greene, Sommerville, Nystrom, Darley and Cohen, this video demonstrates how to design moral dilemma tasks and integrate them into experiments using using functional magnetic resonance imaging (fMRI) technology.1

道徳的な判断の解剖に fMRI を用いてください。

Source: William Brady &#38; Jay Van Bavel&#8212;New York University
In examining the roles of reason and emotion in moral judgments, psychologists and ...

Perspectives on Social Psychology

Social Psychology is a complex field&#8212;one that investigates how social contexts affect people&#8217;s actions, thoughts, and attitudes. It brings the scientific method into our everyday lives by addressing questions relevant to interactions amongst individuals near and far or even over the internet. For example, the video about ostracism details an approach to induce feelings of exclusion without direct face-to-face contact. 
These videos are meant to show the wide reactionary nature of human beings, which also makes the experimental process more complicated. By providing students and scientists a transparent look at the intricate research methods behind classic experiments, this collection strengthens their understanding into just how researchers manipulate contexts to elicit behaviors&#8212;some that we are not even aware of harboring. For instance, the video "Implicit Association Test" explores how to measure unconscious attitudes for sensitive topics, like racial prejudice.
This collection in Social Psychology provides the perfect introduction to this subject and insight into future directions, such as integration with neuroscience and big data collected via social media outlets.

社会心理学の視点

Social Psychology is a complex field&#8212;one that investigates how social contexts affect people&#8217;s actions, thoughts, and attitudes. It brings the ...

Evaluating the Accuracy of Snap Judgments

Source: Diego Reinero &#38; Jay Van Bavel&#8212;New York University
Social psychologists have long been interested in the way people form impressions of others. Much of this work has focused on the errors people make in judging others, such as the exaggerated influence of central traits (such as &#34;warm&#34; and &#34;cold&#34;), the insufficient weight given to the context in which others&#39; behavior takes place, and the tendency for people to make judgments that conform to their initial expectations about another. However, this focus on errors masks the fact that people are quite good at making fairly accurate judgments about other people&#39;s characteristics, an ability that was no doubt important over the course of human evolution.
Indeed, the human ability to make quick sense of social situations and people ranks among our most valuable skills. What is particularly impressive about our ability to make sense of others is not just how little information we need to make inferences, but how well calibrated we can be with so little information. This video shows some experimental techniques used by psychology researchers, including Ambady and Rosenthal in their seminal work,1 and explores the process of making inferences in the context of students&#39; evaluations of their teachers.

スナップ判断の精度の評価

Source: Diego Reinero &#38; Jay Van Bavel&#8212;New York University
Social psychologists have long been interested in the way people form impressions of ...

A Minority of One: Conformity to Group Norms

Source: William Brady &#38; Jay Van Bavel&#8212;New York University
It is obvious that we are influenced by those around us, but in the early to mid 1900's, psychologists began to study how potent social influence can be on our thoughts and behaviors. Motivated in part by attempts to explain the behaviors of Nazi soldiers in World War II, one topic of considerable interest at the time in psychology was conformity, the phenomenon in which people match their attitudes, behaviors, or beliefs to group norms. 
While behaviorist psychology explained conformity in terms of simple reinforcement learning (e.g., it is rewarding to follow the group), Gestalt psychologists argued that conformity is the result of perception being determined just as much by our social world as the physical world. Starting in 1951, Solomon Asch conducted a series of experiments to test the Gestalt idea that group norms can influence our perception of the world, even when the group norm is incorrect in a judgment of something that can be measured objectively. The experiments involved participants making a judgment about which of three comparison lines matched the length of a standard line. The experiments consisted of a group of people who were confederates with the exception of the one participant, and on certain judgments the confederates purposely claimed that the wrong comparison line matched the standard. This allowed the experimenter to measure whether the participant would conform to the objectively incorrect majority judgment. Solomon's experiments not only demonstrated the power of group norms on behavior, but it also laid the groundwork for decades of social psychological research studying social influence.
Inspired by Asch, this video demonstrates how to design a task to test the power of conformity on judgments.1

Assessing the Power of Conformity on Judgment Making

少数派のひとり: グループの規範への適合性

Source: William Brady &#38; Jay Van Bavel&#8212;New York University
It is obvious that we are influenced by those around us, but in the early to mid ...

Misattribution of Arousal and Cognitive Dissonance

Source: Peter Mende-Siedlecki &#38; Jay Van Bavel&#8212;New York University
A host of research in psychology suggests that feelings of psychological arousal may be relatively ambiguous, and under certain circumstances, can lead us to make inaccurate conclusions about our own mental states. Much of this work flows from seminal research conducted by Stanley Schacter and and Jerome Singer. If someone experiences arousal and does not have an obvious, appropriate explanation, they may attempt to explain their arousal in terms of other aspects of the situation or social context.

For example, in one classic study, participants were told they were receiving a drug called &#8220;Suproxin,&#8221; in an attempt to test their vision.1 In reality, they received shots of epinephrine, which typically increases feelings of psychological arousal. While some participants were told that the drug would have side effects similar to epinephrine, others were not informed of the side effects, others were misinformed, and others received a placebo with no arousing side effects. Participants then interacted with a confederate, who was either behaving in a euphoric or an angry manner. The authors observed that participants who had no explanation for their feelings of arousal (e.g., the uninformed condition) were most susceptible to the confederates. In other words, these participants took on the confederates&#8217; emotion (either euphoria or anger) most strongly.&#160;

A subsequent study generalized this effect to the domain of interpersonal attraction in a natural setting.2 Researchers had male participants meet an attractive female experimenter by walking across either a high, narrow suspension bridge (high arousal), or a lower, more stable bridge (low arousal). After the participants completed a questionnaire in which they were asked to describe an ambiguous picture, the experimenter provided them with her phone number, which they were instructed to call if they had any further questions. Notably, the men who walked across the arousing suspension bridge provided descriptions with more sexual content, and they were more likely to call the experimenter after the study. The authors concluded that these men misattributed their psychological arousal arising from the bridge-crossing to the interaction with the female experimenter, and subsequently interpreted their arousal as a sign of attraction towards her.

Zanna and Cooper (1974)3 applied these principles to the study of cognitive dissonance. They predicted that people who experience cognitive dissonance, but are able to attribute their psychological arousal towards some other, external influence, would be less likely to change their attitudes about a topic, compared to people who lack a source of external explanation. This work follows in the tradition of earlier research on cognitive dissonance by Leon Festinger in 1962, suggesting that dissonance itself is a psychologically arousing phenomenon, which can be experienced as discomfort or tension.4

覚醒、認知的不協和の誤

Source: Peter Mende-Siedlecki &#38; Jay Van Bavel&#8212;New York University
A host of research in psychology suggests that feelings of psychological ...

Marginal Dishonesty: The Adding-to-10 Task

Source: Julian Wills &#38; Jay Van Bavel&#8212;New York University
Classical economic theory asserts that people are rational and self-interested. In addition to seeking wealth and status, people are motivated by other goals. As a result, financial motives can sometimes be dwarfed by other internal needs, such as maintaining a positive self-concept or affiliating with other group members. 
Ethical dilemmas, such as the temptation to cheat on taxes, can result when these motives are in conflict. On the one hand, people may be tempted to save money by underreporting their taxable income. On the other hand, no one wants to perceive themselves as a dishonest, free-rider. As a result, people are reluctant to fully exploit unethical opportunities because doing so can severely undermine their self-image as morally upstanding individuals. Instead, people cheat to a much smaller degree than they are capable of: just enough to gain additional resources, but not so much as to compromise their self-image. 
This tendency for marginal dishonesty, or the "fudge factor," is an important principle in social psychology and can be tested through a variety of techniques. Mazar, Amir, and Ariely originally described six separate experiments involving (dis)honesty and a theory of self-concept maintenance.1 The "Adding-to-10 Task" is one of the experimental techniques discussed and is prevalent in research that involves testing honesty. This video demonstrates how to produce and interpret the Adding-to-10 Task.

辺縁不正: 10 に追加タスク

Source: Julian Wills &#38; Jay Van Bavel&#8212;New York University
Classical economic theory asserts that people are rational and self-interested. In ...

Ostracism: Effects of Being Ignored Over the Internet

Source: Peter Mende-Siedlecki &#38; Jay Van Bavel&#8212;New York University
Social ostracism is defined as being ignored and excluded in the presence of others. This experience is a pervasive and powerful social phenomenon, observed in both animals and humans, throughout all stages of human development, and across all manner of dyadic relationships, cultures, and social groups and institutions. Some have argued that ostracism serves a social regulatory function, which can enhance group cohesion and fitness by removing unwanted elements.1 As such, the feeling of ostracism can serve as a warning to alter one&#8217;s behavior, in order to rejoin with the group.2
Research in social psychology has focused extensively on the affective and behavioral consequences of social ostracism. For example, individuals who have been ostracized report feeling depressed, lonely, anxious, frustrated, and helpless,3 and while they may now evaluate the source of their ostracism more negatively, they will also often try to ingratiate themselves to them.2 Furthermore, it has been speculated that the fear of ostracism is ultimately driven by a strong need to belong and to feel included, and serves as a social pressure leading to conformity, compliance, and impression management.4
In a model developed by Williams (1997), ostracism uniquely targets four core needs&#8212; belonging, self-esteem, control, and meaningful existence&#8212;triggering negative mood, anxiety, physiological arousal, and hurt feelings.5 In return, to defend against such psychological discomfort, ostracized individuals may attempt to cope by reinforcing these core needs. For example, they may attempt to visibly conform to group norms to reestablish their place amongst the collective.

Effect of Social Ostracism on Sense of Belonging and Conformity

インターネットで無視されて村八分: 効果

Source: Peter Mende-Siedlecki &#38; Jay Van Bavel&#8212;New York University
Social ostracism is defined as being ignored and excluded in the presence of ...

Inducing Emotions

Source: William Brady &#38; Jay Van Bavel&#8212;New York University
Psychologists have long known that people behave differently in good moods versus bad moods, and this general principle extends to consumer behavior. Economists, as well, have come to appreciate that an individual&#8217;s financial decisions are not solely the result of extensive cost-benefit calculations; other factors like emotion are at play. Further, incidental emotions affect the behavior of buyers and sellers even though they are unrelated to the transaction at hand. While earlier research focused on the impact of global feelings (positive-negative), more recent research examines more specific emotions (e.g., anger and fear). In consumer settings, research shows that anger triggers greater risk-seeking behavior among buyers and sellers and that fear triggers the opposite, i.e., conservative behavior. &#160;
The following experiment tests how two specific negative emotions&#8212;disgust and sadness&#8212;influence people&#8217;s financial valuation of objects.1 The experiment examines the relationships between induced emotional states (disgust and sadness) and the endowment effect. Inherent in this experiment is a common technique for inducing specific emotions in a laboratory setting. Once the emotions are created, they can then be implemented in a number of experimental conditions.

Induced Incidental Emotional and the Endowment Effect

感情を誘発します。

Source: William Brady &#38; Jay Van Bavel&#8212;New York University
Psychologists have long known that people behave differently in good moods versus bad ...

Persuasion: Motivational Factors Influencing Attitude Change

Source: William Brady &#38; Jay Van Bavel&#8212;New York University
Decades of social psychological research sought to understand a fundamental question that pervades our social life including politics, marketing and public health; namely, how are people persuaded to change their attitudes towards an idea, person, or object? Traditional work found that there are key factors that influence whether persuasion is successful or not including the source of the persuasive message (&#34;source&#34;), and the argument content of the message (&#34;content&#34;). For example, expert sources and messages with sound arguments are typically more persuasive. However, as more studies were conducted, conflicting findings began to arise in the field: some studies found that expert sources and good arguments were not always required for successful persuasion.In the 1980&#39;s, psychologists Richard Petty, John Cacioppo and their colleagues proposed a model to account for the mixed findings in studies on persuasion.1,2 They proposed the Elaboration Likelihood Model of persuasion, which stated that persuasion occurs via two routes: a central route or a peripheral route. When persuasive messages are processed via the central route, people engage in careful thinking about the messages, and therefore, the content (i.e., the quality of the argument) matters for successful persuasion. However, when messages are processed via the peripheral route, the source (e.g., an expert source) is more important for successful persuasion.
If people are motivated to pay attention to the message topic, they tend to process the message via the central route, and thus message content is more important. On the other hand, when people are not motivated to pay attention to a message topic, the message is more likely to be processed via the peripheral route and thus the source of the message is more important. Inspired by Petty, Cacioppo, and Goldman, this video demonstrates how to design a task to test different routes to successful persuasion using messages.1

説得: 動機づけ要因態度の変化

Source: William Brady &#38; Jay Van Bavel&#8212;New York University
Decades of social psychological research sought to understand a fundamental question ...

Creating the Minimal Group Paradigm

Source: Julian Wills &#38; Jay Van Bavel&#8212;New York University
The study of intergroup relations, such as prejudice, conflict, and discrimination, has always been a central topic in social psychology. Does discrimination stem from competition with other groups, a history of conflict, or derogatory stereotypes? Despite an abundance of real-world examples, the ingredients that lead to intergroup discrimination are often unclear. 
To help solve this problem, a group of psychologists created "minimal groups" to strip away confounds like monetary self-interest and a history of conflict that are normally involved in intergroup discrimination. In minimal groups, participants are randomly assigned to completely novel groups. Thus, any consequences emerging from this minimal group induction must stem from identifying with a social group and separating the social world into "us" and "them." Research using minimal groups has shown that, despite the arbitrary nature of group membership, participants willingly discriminate by favoring members of their in-group over members of the out-group.
The minimal group paradigm is widely used in social psychology to study the most basic elements of intergroup relations. This method was first introduced in a 1971 paper called Social Categorization and Intergroup Behaviour by Henri Tajfel and colleagues.1 Across three experiments, the authors documented the in-group favoritism that emerges from a rather minimal group induction. This video will demonstrate how to produce the minimal group induction in a manner similar to the first experiment, where groups were ostensibly created based on dot estimation tendencies.

最小限のグループ パラダイムを作成します。

Source: Julian Wills &#38; Jay Van Bavel&#8212;New York University
The study of intergroup relations, such as prejudice, conflict, and discrimination, has ...

The Implicit Association Test

Source: Julian Wills &#38; Jay Van Bavel&#8212;New York University
One of the core constructs in social psychology is the notion of an attitude toward an object or person. Traditionally, psychologists measured attitudes by simply asking people to self-report their beliefs, opinions, or feelings. This approach has limitations, however, when measuring socially sensitive attitudes, like racial prejudice, because people are often motivated to self-report unprejudiced, egalitarian beliefs (despite harboring negative associations). In order to bypass this social-desirability bias, psychologists have developed a number of tasks that attempt to measure implicit attitudes that are less amenable to deliberate control (and potential distortion).
The Implicit Association Test, or IAT, is one of the most influential measures of these unconscious attitudes. The IAT was first introduced in a 1998 paper by Anthony Greenwald and colleagues.1 This video will demonstrate how to conduct the IAT used in the final experiment, where European American participants (who report explicit egalitarian attitudes) exhibit implicit preferences for their own race.

The Implicit Association Test: Measuring Unconscious Attitudes

潜在連合テスト

Source: Julian Wills &#38; Jay Van Bavel&#8212;New York University
One of the core constructs in social psychology is the notion of an attitude toward an ...

Nonconscious Mimicry Occurs when Affiliation Goals are Present

Source: Diego Reinero &#38; Jay Van Bavel&#8212;New York University
People are social chameleons and regularly engage in nonconscious behavioral mimicry. This occurs when an individual unwittingly imitates the behaviors of another person, such as crossing one's legs moments after a person sitting adjacent does so, or adjusting one's body posture to match a conversation partner. Rapport between two people increases behavioral mimicry, just as mimicry also increases rapport. Psychologists have posited that this mimicry is attributed to a perception-behavior link;1 seeing a person engage in a behavior activates that behavioral representation, which then makes the perceiver more likely to engage in that behavior him- or herself.
The following experiment expands on these previous findings by testing whether people, without intention or awareness, use mimicry to their advantage. Because goals activate behavioral strategies and plans of action that help people pursue those goals,2 Lakin and Chartrand hypothesized that individuals would mimic another person more when they have a goal to affiliate than when they do not.3

Effects of Affiliation Goals on Nonconscious Mimicry

提携の目的は、現在ときに意識的模倣発生します

Source: Diego Reinero &#38; Jay Van Bavel&#8212;New York University
People are social chameleons and regularly engage in nonconscious behavioral mimicry. ...

Effects of Thinking Abstractly or Concretely on Self-control

Source: Diego Reinero &#38; Jay Van Bavel&#8212;New York University
Whether it's refraining from having a second serving of ice cream, studying instead of attending a fun party, or deciding to put money away in a savings account, sacrificing short-term outcomes in favor of long-term outcomes (i.e., delaying gratification) is a central tenant of self-control. When people apply self control, they engage numerous psychological processes to help them achieve their goal. These self-regulatory processes have been studied by psychologists for decades.
A decision to resist tempting short-term rewards can depend on an individual's mindset and focus. Psychologists have found evidence that how someone construes an event can influence how they make judgments and decisions, a theory called Construal Level Theory (CLT). In particular, CLT asserts that the same object or event can be represented at multiple levels of abstractness or psychological distance, most commonly either a high-(abstract/distant) or low-(concrete/near) level of construal.1 Thinking about a situation with high-level construal entails emphasizing the global, superordinate, central features of an object or event (i.e,, zooming out and looking at the big picture), whereas thinking about a situation with low-level construal entails focusing on its unique and specific features. For example, thinking about children playing catch with high-level construal, one might describe this activity as "children having fun", whereas with a low-level construal, one might focus instead on specific features such as the color of the ball or age of the children.
The following experiment tests whether approaching a decision or situation with high-level construal will lead to greater self-control than low-level construal. This experiment utilizes a common method of priming a participant's level of construal through asking a series of "why" (high-level manipulation) or "how" (low-level manipulation) questions.2

Effect of Construal High/Abstract vs Low/Concrete-Level on Decision and Self-Control

自己制御における抽象的か具体的を思考の効果

Source: Diego Reinero &#38; Jay Van Bavel&#8212;New York University
Whether it's refraining from having a second serving of ice cream, studying instead of ...

Thinking Too Much Impairs Decision-Making

Source: Peter Mende-Siedlecki &#38; Jay Van Bavel&#8212;New York University
When we are considering a tough choice between two or more attractive options, we often end up actively weighing the pros and cons of each alternative. By reflecting on their advantages and disadvantages, we attempt to fit a complex, subjective decision into an orderly set of criteria. However, research in psychology suggests that this sort of introspective approach might not always yield the most optimal outcomes.1
In other words, sometimes thinking hard about a problem or a choice may not produce desired results. Similar results have been demonstrated in the domains of emotion (participants who ruminated about a bad mood showed less mood improvement than participants who were merely distracted from their mood;2 and memory (verbalizing the details of a criminal&#8217;s face led to poorer recognition in a photo array of possible suspects.3 Furthermore, Wilson and colleagues observed that reflecting on the reasons behind one&#8217;s attitudes (i.e., considering &#8220;why&#8221; one feels a certain way) can disrupt the consistency between attitudes and behavior, and can even change attitudes.4
Why might this be the case? Wilson and colleagues speculate that often we don&#8217;t typically have a very good understanding of why we actually feel the way we do.5 Upon introspection of our feelings, we may hone in on irrelevant but salient details that may offer plausible explanations, but may also have little direct influence on our actual attitudes. Wilson and Schooler devised an experiment designed to test this possibility in the domain of subjective preferences. Specifically, they compared participants&#8217; evaluations of a series of jams with experts&#8217; evaluations, and tested whether asking participants to analyze the reasons for their choices would have a negative impact on their evaluations.

Introspection Illusion: Reason-Analysis Impairs Decision-Making

あまりにも多くを考えて意思決定を損なう

Source: Peter Mende-Siedlecki &#38; Jay Van Bavel&#8212;New York University
When we are considering a tough choice between two or more attractive options, ...

Education Social Psychology

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