The authors gratefully acknowledge the financial support of &#34;Excilight&#34; project &#34;Donor-Acceptor Light Emitting Exciplexes as Materials for Easy-to-tailor Ultra-efficient OLED Lightning&#34; (H2020-MSCA-ITN-2015/674990) financed by Marie Sk&#322;odowska-Curie Actions within the framework programme for research and innovations &#34;Horizon-2020&#34;.

The authors have nothing to disclose.

Electrochemical and spectroelectrochemical techniques have no limitations; one can analyze both solid state and liquid solutions in a broad range of temperature and other conditions with these techniques. The important thing in all of these cases is that compounds/materials are analyzed under the applied potential, replicating real world conditions for working organic electronics devices. The only difference is that in electrochemistry, the formation of charge carriers, is observed.
The methods presented here show the usefulness of the analysis of charged carriers generated in organic compounds that correlate with their applicability in organic electronics. Moreover, the electrochemical and spectroelectrochemical techniques are cheaper and less demanding than that of typical methods used in charge carrier analysis, but there are some critical steps and modifications to the protocol that are needed depending on the obtained results.
During electrochemical characterization, always start with a particular concentration. If a set of the compounds is compared, then all materials need to have the same molar concentration. The best is to start with 1 mM concentration and 50 mV/s scan rate as indicated in the protocol in this study, but it is good to know the concentration of the sample on the observed electrochemical behavior. Always try to measure at least three scans. The first two scans are usually different because the starting conditions (equilibrium) are different. The second and the third scans should be the same. If the second and third scans are the same, then there are probably no side reactions observed in this system (Figure 2a). In an oxidation process, a new peak at a lower potential appears showing that the conductive material was deposited on the WE18,19,24,25,29,30,31,32. If the height of the lower peak increases in successive scans, then probably the conjugated polymer was deposited18,19,24,25,29,30,31,32. If all the currents decrease in successive scans, then the nonconductive product of degradation was deposited on the electrode. If a very small peak is observed before the main oxidation or reduction peak (especially for polymers), then this is probably charge-trapping process19,23,31,34. If a very sharp dedoping peak of oxidation or reduction is observed, then this is probably caused by the decomposition of crystalline structures on an electrode formed through the electrocrystallization process during oxidation35.
Always check the behavior of the test compound before, during, and after redox peaks. It means that at least three CV scans should be registered: with upper (in the case oxidation) or lower vertex potential lower or higher, respectively, then the potential of peak maximum, with upper or lower vertex potential set to exactly on the peak maximum and with vertex potentials higher (oxidation) and lower (reduction) than potential of the peak maximum. The observed process may vary and sometimes two processes may be observed under one peak theoretically. Always compare the collected cyclic voltammograms of the electrolyte (step 2.6), the ferrocene (step 2.9), the compound (step 2.13), and the ferrocene with compound (step 2.19); there are several issues to be taken into account.
Always compare the CV signals of the electrolyte and the test compound, if any signals from the electrolyte is visible on the cyclic voltammogram of the measured compound, then the electrolyte must be changed because its electrochemical window is too low, or the electrolyte is contaminated. If the signal (redox couple) of ferrocene (step 2.9) and ferrocene with compound (step 2.19) are at the same position, then everything is performed properly. If the peaks are shifted between each other, then check the RE and repeat the measurement. If the signal (oxidation, reduction, or redox couple potential) of the test compound with added ferrocene (step 2.19) is at a higher potential than that of the pure compound (step 2.13), then consider the values (oxidation, reduction, or redox couple potential) from the cyclic voltammogram of the pure compound. The shift is caused by the higher amount of ferrocene in the solution. When two oxidation processes are observed, the first process (oxidation or reduction) which is always on the WE may affect the active surface; this may cause an increase in the oxidation potential of the second process (Figure 9).

Worldwide, researchers are continually searching for new organic materials that can be used in organic electronics with desirable performance or stability, which drops due to extended use. In the case of organic devices, it is important to understand the behavior of the charge carrier to fully know the rules driving the device behavior. Analysis of the effect of the molecular structure on the generation of the charge carrier and the dynamics and maintenance of the balance of injected charge carriers, both positive (holes) and negative (electrons), is crucial to improve the efficiency and stability of the organic devices. This ensures the effective recombination of these individual charges and consequently significantly improves the photoluminescence efficiency of the organic light emitting diodes (OLEDs)1,2. For organic photovoltaics (OPVs)3,4 as well as organic field effect transistors (OFETs)5,6, it is necessary to have materials with high charge carrier mobility. In addition to the analysis of charge carriers, several important parameters of organic electroactive materials help in predicting where the material could be used: ionization potential (IP), electron affinity (EA) energy levels, and band-gap between them7,8,9,10.
In this work, we present a method for the efficient measurement of cyclic voltammetry (CV) that can be used in the analysis of all types of electroactive materials. This technique provides information about redox properties, the doping/dedoping mechanism, the stability, the conversion and storage of energy, etc. It also allows for the estimation of electron affinity and ionization energy of the test compounds in a much cheaper and faster way compared to other high vacuum methods. The aforementioned parameters correlate with the energy levels of highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO).
The method presented in this article can be used to analyze all types of conjugated compounds such as those with delocalized &#960;-electrons in their structures. Conjugated compounds may be small molecules with large polymeric chains. Small molecules can also be monomers; during the initial reaction (photochemical, electrochemical, or chemical) monomers can form polymers. In OLED application, the energy level values are necessary to enable the use of the correct host for the emitter in a thermally activated delayed fluorescence (TADF) guest-host system or to decide with which compounds the exciplex donor-acceptor layer could be formed and what additional layers (electron transporting layer (ETL), hole transporting layer (HTL), electron blocking layer (EBL), and hole blocking layer (HBL)) will be necessary to synthesize stable efficiently charged balanced OLED devices11,12,13,14,15,16,17. Additional electrochemical measurements allow the investigation of possible side reactions during the process of degradation of the active layer and the formation of low mobile charge carriers (bipolarons)18,19,20,21,22.
Coupling electrochemical and spectroelectrochemical methods allows for easy, accurate, and reliable determination of the degree of oxidation or reduction of conjugated compounds and their degradation potential, which is crucial for stability23,24,25,26,27,28. Ultraviolet-visible and near-infrared (UV-Vis-NIR) spectroscopy coupled with electrochemistry can characterize the fundamental chromatic properties of all new conjugated compounds, such as the changing of the absorption band during doping18,19,20,21,22,23,24,25,26,27,28,29,30.
In a study related to the doping mechanism, it is important to define the type of charge carriers. In this process, two classes of charged quasiparticles take part, one with uncompensated spin (polarons) and the second being diamagnetic (bipolarons); electron paramagnetic resonance (EPR) spectroscopy provides invaluable assistance, which directly allows one to observe and track changes in populations of paramagnetic polarons29,30,31,32. In small molecules, it is difficult to form bipolarons, but these molecules can be quite conjugated and have bipolaron-inducing properties; it is important to check if and at which potential polarons and bipolarons are formed in the structure. Bipolarons are at least one order lower in mobility than that of polarons; therefore, if bipolarons are formed in working devices, then it could lead to an unbalanced ratio of the charge carriers, which would result in high current and overheating of the OLED device or may well be the centers of degradation33.
The method of measurement proposed in this study is cheap and faster and allows for the determination of the most valuable operative parameters for a large number of electroactive materials without the need for special devices that are based on newly synthesized materials to check its performance. By applying electrochemistry and spectroelectrochemistry, it is possible to select one material that is really promising from hundreds of new materials. In addition, it is possible to obtain detailed information regarding the processes of doping and their effects on the chemical structure of the test conjugated systems using electrochemical and spectroelectrochemical methods, which allows constructing more efficient organic electronics devices.

<table>
	<tbody>
		<tr>
			<td>Potentiostat</td>
			<td>Metrohm</td>
			<td>Autolab PGSTAT100</td>
			<td></td>
		</tr>
		<tr>
			<td>EPR</td>
			<td>JEOL</td>
			<td>JES-FA200</td>
			<td></td>
		</tr>
		<tr>
			<td>UV-Vis detector</td>
			<td>Oceanoptics</td>
			<td>QE6500</td>
			<td></td>
		</tr>
		<tr>
			<td>NIR detector</td>
			<td>Oceanoptics</td>
			<td>NIRQuest</td>
			<td></td>
		</tr>
		<tr>
			<td>Dichloromethane (DCM)</td>
			<td>Sigma-Aldrich</td>
			<td>106048</td>
			<td></td>
		</tr>
		<tr>
			<td>Tetrabutylammonium tetrafluoroborate (Bu4NBF4)</td>
			<td>Sigma-Aldrich</td>
			<td>86896</td>
			<td></td>
		</tr>
		<tr>
			<td>2-propanol, 99.9%</td>
			<td>Sigma-Aldrich</td>
			<td>675431</td>
			<td></td>
		</tr>
		<tr>
			<td>Acetone, 99.9%</td>
			<td>Sigma-Aldrich</td>
			<td>439126</td>
			<td></td>
		</tr>
		<tr>
			<td>Ultrasonic Bath</td>
			<td>Elma</td>
			<td>S30H</td>
			<td></td>
		</tr>
		<tr>
			<td>Tetrahydrofuran &#62;99.9%</td>
			<td>Sigma-Aldrich</td>
			<td>401757</td>
			<td></td>
		</tr>
		<tr>
			<td>ferrocene &#62;98%</td>
			<td>Sigma-Aldrich</td>
			<td>F408</td>
			<td></td>
		</tr>
		<tr>
			<td>decamethylferrocene &#62;97%</td>
			<td>Sigma-Aldrich</td>
			<td>378542</td>
			<td></td>
		</tr>
	</tbody>
</table>

using cyclic voltammetry, uv-vis-nir, and epr spectroelectrochemistry to analyze organic compounds

Cyclic voltammetry (CV) is a technique used in the analysis of organic compounds. When this technique is combined with electron paramagnetic resonance (EPR) or ultraviolet-visible and near-infrared (UV-Vis-NIR) spectroscopies, we obtain useful information such as electron affinity, ionization potential, band-gap energies, the type of charge carriers, and degradation information that can be used to synthesize stable organic electronic devices. In this study, we present electrochemical and spectroelectrochemical methods to analyze the processes occurring in active layers of an organic device as well as the generated charge carriers.

The most common application of CV analysis is the estimation of IP and EA. Even though there are a couple ways to obtain CV data, it is strongly recommended to calculate them based on the onset of redox peaks (Figure 3). This approach allows unifying the calculation procedure. Not all of the tested materials undergo reversible oxidation/reduction processes (Figure 3); in such situations, it is not possible to calculate based on average potentials (average from potentials correspond to a maximum of cathodic-reduction and anodic-oxidation peaks). However, it is almost always possible to run the tangent to a peak as shown in Figure 3. With the intersection with the background line and use of Equations 1 and 2, the IP and EA values are estimated as 5.35 eV and &#8722;2.90 eV, respectively. There are also several different scales used to evaluate IP and EA based on CV measurements. The most commonly used scales for organic materials are &#8722;4.8 and &#8722;5.1 eV as equivalent to 0.00 V versus Normal Hydrogen Electrode (NHE). However, all of the scales are only an approximation; remember this when comparing different results. The crucial thing is to state what parameters were considered for calculations. In this case, the value &#8722;5.1 eV has been chosen as it should correspond to the formal potential of the ferrocene redox couple; in the Fermi scale, it is 0.40 V versus Saturated Calomel Electrode (SCE) in acetonitrile, which is in agreement with the previous measurement.
There are many articles published regarding the analysis of CV. Herein, we show when the process is not going to be as it is expected. The analysis is based on thiophene derivative: NtVTh (structure shown in Figure 4), which undergoes degradation upon oxidation (Figure 5).
NtVTh has two oxidation potentials: the first at 0.70 V and the second at 0.84 V (Figure 5). During the first cycle, the reduction peak is not observed, indicating an irreversible process. Electrochemical characteristics of NtVTh show that polymerization does not occur and after the first oxidation potential, some electro-inactive layer of reaction products deposits at the electrode surface, thus hindering the polymerization process. What is visible is the reaction with the radical cation on the vinyl bond, where the molecule is losing its conjugation and form dimers on the electrode.
While it is difficult to extract information about charge carriers from the CV, it is possible to distinguish between polarons and bipolarons when supported by a UV-Vis-NIR spectrometer. The neutral poly(OiPrThEE) was characterized by two wide absorption &#960;|&#960;* transitions bands with peaks maxima at &#955;max1 = 363 nm and &#955;max2 = 488 nm, related to the aromatic form of the undoped polythiophene derivative. During the oxidative doping, new polaronic and bipolaronic bands are generated. The UV-Vis spectrum obtained during the poly(OiPrThEE) oxidation revealed the diminishing the neutral polymer absorption band (300-550 nm) (Figure 6) together with the formation of a new absorption band (550-950 nm) of the radical cations of bithiophene and p-phenylenevinylene with maxima at 692 nm. The isosbestic point of the oxidation process was located at 604 nm. The bipolaronic band appeared between the 950 nm and 1700 nm with a maximum located at 1438 nm.
EPR spectroscopy is the technique that detects materials with an unpaired electron, this includes organic radicals39. There are several parameters that could be extracted from EPR spectra, but one of the most interesting is to estimate where the radicals are localized. Electrons, similar to protons, possess spin. By placing an electron in an external magnetic field, this spin can be split two ways: parallel and antiparallel to the magnetic field, giving two energy levels. This phenomenon is known as the Zeeman effect40,41. In case of organic radicals, the unpaired electron interacts not only with the external magnetic field but also with magnetic nuclei (nuclei which have a nonzero spin; I&#8800;0). A number of degenerate energy levels are equal to 2I + 1, where I is the spin quantum number of the nucleus with which the unpaired electron interacts42. The interaction of the unpaired electron with a larger number of magnetic nuclei leads to further splitting of the energy levels and to hyperfine structure of EPR spectra registration43 (Figure 7).
For molecules where the unpaired electron interacts with an even larger number of nuclei, the individual spectral line could overlap, which results in registration of a single, broad signal44,45,46 (Figure 8). This is typical for conjugated polymers, where the generated radical ion during a redox process is delocalized47,48.
The combination of EPR spectroscopy with electrochemical methods allows the characterization of charge carriers (radical ion) generated during the redox process as well as the determination of the mechanism of these processes49,50. If well-resolved (peaks are separated; not in the form of one broad peak) spectra are registered, as in the case of electrochemical reduction of s-tetrazine derivative (Figure 7), then the analysis of the hyperfine structure of spectra leads to conclusions about the localization of unpaired electron. One way to analyze this kind of spectra is to conduct simulation with special software and to fit simulated spectra with the experimental one51. This is especially helpful when the hyperfine structure is complex due to the interaction of the unpaired electron with large numbers of protons. In case of the s-tetrazine derivative shown in Figure 7, simulation of EPR spectra (red line) indicates the interaction of the unpaired electron with four nitrogen atoms of s-tetrazine.
<img alt="Figure 1" class="xfigimg" src="/files/ftp_upload/56656/56656fig1.jpg" /> 
Figure 1: Electrochemical and spectroelectrochemical cells used for measurements. The figure presents the scheme setup of electrochemical/spectroelectrochemical cells using cyclic voltammetry, ultraviolet-visible and near-infrared (UV-Vis-NIR), and electron paramagnetic resonance (EPR) spectroelectrochemical measurements. <a href="https://www-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/56656/56656fig1large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 2" class="xfigimg" src="/files/ftp_upload/56656/56656fig2.jpg" /> 
Figure 2: Cyclic voltammetry (CV) of properly measured compound COPO1 (a) and the CV with an unstable reference potential dibenzothiophene-S,S-dioxide with ferrocene (b)52. The figure shows two cyclic voltammograms. (a) presents correctly registered CV and (b) shows a voltammogram registered using a reference electrode with no stable potential. <a href="https://www-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/56656/56656fig2large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 3" class="xfigimg" src="/files/ftp_upload/56656/56656fig3.jpg" /> 
Figure 3: Cyclic voltammetry (CV) of compound COPO1 in a wide range of potentials. Estimation of the onset potentials for EA and IP calculations of the COPO1 compounds52. EA=&#8722;2.90 eV and IP = 5.35 eV. <a href="https://www-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/56656/56656fig3large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 4" class="xfigimg" src="/files/ftp_upload/56656/56656fig4.jpg" /> 
Figure 4. EPR six spectral line of manganese standard. The paramagnetic signal of manganese used for calibration of the signal shift. <a href="https://www-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/56656/56656fig4large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 5" class="xfigimg" src="/files/ftp_upload/56656/56656fig5.jpg" /> 
Figure 5: Cyclic Voltammetry (CV) of compound NtVTh. Cyclic voltammograms of 15 mM NtVTh in 0.1 M Bu4NBF4/CH3CN and relative to ferrocene standard presenting the degradation process involved on working electrode. Scan rate 0.05 V/s: (a) was taken in the range &#8722;1.4 V to 0.8 V, and (b) in the range &#8722;1.4 V to 0.9 V. <a href="https://www-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/56656/56656fig5large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 6" class="xfigimg" src="/files/ftp_upload/56656/56656fig6.jpg" /> 
Figure 6: Ultraviolet-visible and near-infrared (UV-Vis-NIR) spectroelectrochemistry of poly(OiPrThEE) derivative. UV-Vis-NIR spectra presenting the evolution of absorption band through the generation of charge carriers on polymer structure. <a href="https://www-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/56656/56656fig6large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 7" class="xfigimg" src="/files/ftp_upload/56656/56656fig7.jpg" /> 
Figure 7: EPR spectroelectrochemical analysis of tetrazine derivative. (a) Structure of s-tetrazine derivative; (b) EPR spectra registered during electrochemical reduction of s-tetrazine derivative (black line-experimental and red line simulated spectrum). <a href="https://www-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/56656/56656fig7large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 8" class="xfigimg" src="/files/ftp_upload/56656/56656fig8.jpg" /> 
Figure 8: EPR spectroelectrochemical polaron signal of the conjugated polymer. Electron paramagnetic resonance (EPR) spectra registered during the first step of oxidation of conjugated polymer (EPR spectra of polaron species). <a href="https://www-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/56656/56656fig8large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 9" class="xfigimg" src="/files/ftp_upload/56656/56656fig9.jpg" /> 
Figure 9: Cyclic voltammetry (CV) of ferrocene and decamethylferrocene. Comparison of two electrochemical standards as pure and as mixture showing the shift of the potential. <a href="https://www-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/56656/56656fig9large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>

Watch this Scientific Journal Video about Using Cyclic Voltammetry, UV-Vis-NIR, and EPR Spectroelectrochemistry to Analyze Organic Compounds at JoVE.com

Using Cyclic Voltammetry, UV-Vis-NIR, and EPR Spectroelectrochemistry to Analyze Organic Compounds

In this article, we describe electrochemical, electron paramagnetic resonance, and ultraviolet-visible and near-infrared spectroelectrochemical methods to analyze organic compounds for application in organic electronics.

Cyclic voltammetry (CV) is a technique used in the analysis of organic compounds. When this technique is combined with electron paramagnetic resonance ...

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26.2K 次观看.  Silesian University of Technology. 这些方法可以帮助确定电活性有机分子的分子结构对带电载体的代和动力学、分项电位、电子亲和力和键图值的影响。这些方法是一种廉价而快速的方法，用于确定许多电活性材料最有价值的参数，而无需构建特殊器件。该方法可用于分析所有类型的电子活性化合物，如非本地双电子化合物，包括小分子和大聚合物链。要开始 CV 程序，请用 1.5 毫升电解质溶液填充干净?...

视频: Using Cyclic Voltammetry, UV-Vis-NIR, and EPR Spectroelectrochemistry to Analyze Organic Compounds

Analysis of Volatile and Oxidation Sensitive Compounds Using a Cold Inlet System and Electron Impact Mass Spectrometry

This video presents a protocol for the mass spectrometrical analysis of volatile and oxidation sensitive compounds using electron impact ionization. The analysis of volatile and oxidation sensitive compounds by mass spectrometry is not easily achieved, as all state-of-the-art mass spectrometric methods require at least one sample preparation step, e.g., dissolution and dilution of the analyte (electrospray ionization), co-crystallization of the analyte with a matrix compound (matrix-assisted laser desorption/ionization), or transfer of the prepared samples into the ionization source of the mass spectrometer, to be conducted under atmospheric conditions. Here, the use of a sample inlet system is described which enables the analysis of volatile metal organyls, silanes, and phosphanes using a sector field mass spectrometer equipped with an electron impact ionization source. All sample preparation steps and the sample introduction into the ion source of the mass spectrometer take place either under air-free conditions or under vacuum, enabling the analysis of compounds highly susceptible to oxidation. The presented technique is especially of interest for inorganic chemists, working with metal organyls, silanes, or phosphanes, which have to be handled using inert conditions, such as the Schlenk technique. The principle of operation is presented in this video.

This video presents a protocol for the mass spectrometrical analysis of volatile and oxidation sensitive compounds using electron impact ionization. The presented technique is especially of interest for inorganic chemists, working with metal organyls, silanes, or phosphanes which have to be handled using inert conditions, such as the Schlenk technique.

挥发和氧化敏感的化合物使用冷进气系统和电子轰击质谱分析

This video presents a protocol for the mass spectrometrical analysis of volatile and oxidation sensitive compounds using electron impact ionization. The ...

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Development of a Backbone Cyclic Peptide Library as Potential Antiparasitic Therapeutics Using Microwave Irradiation

Protein-protein interactions (PPIs) are intimately involved in almost all biological processes and are linked to many human diseases. Therefore, there is a major effort to target PPIs in basic research and in the pharmaceutical industry. Protein-protein interfaces are usually large, flat, and often lack pockets, complicating the discovery of small molecules that target such sites. Alternative targeting approaches using antibodies have limitations due to poor oral bioavailability, low cell-permeability, and production inefficiency.
Using peptides to target PPI interfaces has several advantages. Peptides have higher conformational flexibility, increased selectivity, and are generally inexpensive. However, peptides have their own limitations including poor stability and inefficiency crossing cell membranes. To overcome such limitations, peptide cyclization can be performed. Cyclization has been demonstrated to improve peptide selectivity, metabolic stability, and bioavailability. However, predicting the bioactive conformation of a cyclic peptide is not trivial. To overcome this challenge, one attractive approach it to screen a focused library to screen in which all backbone cyclic peptides have the same primary sequence, but differ in parameters that influence their conformation, such as ring size and position.
We describe a detailed protocol for synthesizing a library of backbone cyclic peptides targeting specific parasite PPIs. Using a rational design approach, we developed peptides derived from the scaffold protein Leishmania receptor for activated C-kinase (LACK). We hypothesized that sequences in LACK that are conserved in parasites, but not in the mammalian host homolog, may represent interaction sites for proteins that are critical for the parasites&#39; viability. The cyclic peptides were synthesized using microwave irradiation to reduce reaction times and increase efficiency. Developing a library of backbone cyclic peptides with different ring sizes facilitates a systematic screen for the most biological active conformation. This method provides a general, fast, and facile way to synthesize cyclic peptides.

A simple and general method for the synthesis of cyclic peptides using microwave irradiation is outlined. This procedure enables the synthesis of backbone cyclic peptides with a collection of different conformations while retaining the side chains and the pharmacophoric moieties., and therefore, allows to screen for the bioactive conformation.

一个主干环肽库作为潜在的抗寄生虫治疗微波辐射的发展

Protein-protein interactions (PPIs) are intimately involved in almost all biological processes and are linked to many human diseases. Therefore, there is ...

Synthesis of Cyclic Polymers and Characterization of Their Diffusive Motion in the Melt State at the Single Molecule Level

We demonstrate a method for the synthesis of cyclic polymers and a protocol for characterizing their diffusive motion in a melt state at the single molecule level. An electrostatic self-assembly and covalent fixation (ESA-CF) process is used for the synthesis of the cyclic poly(tetrahydrofuran) (poly(THF)). The diffusive motion of individual cyclic polymer chains in a melt state is visualized using single molecule fluorescence imaging by incorporating a fluorophore unit in the cyclic chains. The diffusive motion of the chains is quantitatively characterized by means of a combination of mean-squared displacement (MSD) analysis and a cumulative distribution function (CDF) analysis. The cyclic polymer exhibits multiple-mode diffusion which is distinct from its linear counterpart. The results demonstrate that the diffusional heterogeneity of polymers that is often hidden behind ensemble averaging can be revealed by the efficient synthesis of the cyclic polymers using the ESA-CF process and the quantitative analysis of the diffusive motion at the single molecule level using the MSD and CDF analyses.

A protocol for the synthesis and characterization of diffusive motion of cyclic polymers at the single molecule level is presented.

环状聚合物的合成及其在熔融状态扩散运动的表征在单分子水平

We demonstrate a method for the synthesis of cyclic polymers and a protocol for characterizing their diffusive motion in a melt state at the single ...

Using Capillary Electrophoresis to Quantify Organic Acids from Plant Tissue: A Test Case Examining Coffea arabica Seeds

Carboxylic acids are organic acids containing one or more terminal carboxyl (COOH) functional groups. Short chain carboxylic acids (SCCAs; carboxylic acids containing three to six carbons), such as malate and citrate, are critical to the proper functioning of many biological systems, where they function in cellular respiration and can serve as indicators of cell health. In foods, organic acid content can have significant impact on taste, with increased SCCA levels resulting in a sour or &#34;acid&#34; taste. Because of this, methods for the rapid analysis of organic acid levels are of particular interest to the food and beverage industries. Unfortunately, however, most methods used for SCCA quantification are dependent on time-consuming protocols requiring the derivatization of samples with hazardous reagents, followed by costly chromatographic and/or mass spectrometric analyses. This method details an alternate method for the detection and quantification of organic acids from plant material and food samples using free zonal capillary electrophoresis (CZE), sometimes simply referred to as capillary electrophoresis (CE). CZE provides a cost-effective method for measuring SCCAs with a low limit of detection (0.005 mg/ml). This article details the extraction and quantification of SCCAs from plant samples. While the method provided focuses on measurement of SCCAs from coffee beans, the method provided can be applied to multiple plant-based food materials.

Using Capillary Electrophoresis to Quantify Organic Acids from Plant Tissue: A Test Case Examining Coffea arabica Seeds

This article presents a method for the detection and quantification of organic acids from plant material using free zonal capillary electrophoresis. An example of the potential application of this method, determining the effects of a secondary fermentation on organic acid levels in coffee seeds, is provided.

利用毛细管电泳从植物组织量化有机酸:一个测试用例检查<em&gt;小粒种咖啡</em&gt;种子

Carboxylic acids are organic acids containing one or more terminal carboxyl (COOH) functional groups. Short chain carboxylic acids (SCCAs; carboxylic ...

Fizzy Extraction of Volatile Organic Compounds Combined with Atmospheric Pressure Chemical Ionization Quadrupole Mass Spectrometry

Chemical analysis of volatile and semivolatile compounds dissolved in liquid samples can be challenging. The dissolved components need to be brought to the gas phase, and efficiently transferred to a detection system. Fizzy extraction takes advantage of the effervescence phenomenon. First, a carrier gas (here, carbon dioxide) is dissolved in the sample by applying overpressure and stirring the sample. Second, the sample chamber is decompressed abruptly. Decompression leads to the formation of numerous carrier gas bubbles in the sample liquid. These bubbles assist the release of the dissolved analyte species from the liquid to the gas phase. The released analytes are immediately transferred to the atmospheric pressure chemical ionization interface of a triple quadrupole mass spectrometer. The ionizable analyte species give rise to mass spectrometric signals in the time domain. Because the release of the analyte species occurs over short periods of time (a few seconds), the temporal signals have high amplitudes and high signal-to-noise ratios. The amplitudes and areas of the temporal peaks can then be correlated with concentrations of the analytes in the liquid samples subjected to fizzy extraction, which enables quantitative analysis. The advantages of fizzy extraction include: simplicity, speed, and limited use of chemicals (solvents).

Fizzy extraction is a new laboratory technique for analysis of volatile and semivolatile compounds. A carrier gas is dissolved in the liquid sample by applying overpressure and stirring the sample. The sample chamber is then decompressed. The analyte species are liberated to the gas phase due to effervescence.

挥发性有机化合物与大气压化学电离四极杆质谱联用

Chemical analysis of volatile and semivolatile compounds dissolved in liquid samples can be challenging. The dissolved components need to be brought to ...

Grafting Multiwalled Carbon Nanotubes with Polystyrene to Enable Self-Assembly and Anisotropic Patchiness

We demonstrate a straightforward protocol to graft pristine multiwalled carbon nanotubes (MWCNTs) with polystyrene (PS) chains at the sidewalls through a free-radical polymerization strategy to enable the modulation of the nanotube surface properties and produce supramolecular self-assembly of the nanostructures. First, a selective hydroxylation of the pristine nanotubes through a biphasic catalytically mediated oxidation reaction creates superficially distributed reactive sites at the sidewalls. The latter reactive sites are subsequently modified with methacrylic moieties using a silylated methacrylic precursor to create polymerizable sites. Those polymerizable groups can address further polymerization of styrene to produce a hybrid nanomaterial containing PS chains grafted to the nanotube sidewalls. The polymer-graft content, amount of silylated methacrylic moieties introduced and hydroxylation modification of the nanotubes are identified and quantified by Thermogravimetric Analysis (TGA). The presence of reactive functional groups hydroxyl and silylated methacrylate are confirmed by Fourier Transform Infrared Spectroscopy (FT-IR). Polystyrene-grafted carbon nanotube solutions in tetrahydrofuran (THF) provide wall-to-wall collinearly self-assembled nanotubes when cast samples are analyzed by transmission electron microscopy (TEM). Those self-assemblies are not obtained when suitable blanks are similarly cast from analogous solutions containing non-grafted counterparts. Therefore, this method enables the modification of the nanotube anisotropic patchiness at the sidewalls which results into spontaneous auto-organization at the nanoscale.

A procedure for the synthesis of polystyrene-grafted multiwalled carbon nanotubes using successive chemical modification steps to selectively introduce the polymer chains to the sidewalls and their self-assembly via anisotropic patchiness is presented.

用聚苯乙烯接枝多壁纳米碳纳米管使自组装和各向异性斑块

We demonstrate a straightforward protocol to graft pristine multiwalled carbon nanotubes (MWCNTs) with polystyrene (PS) chains at the sidewalls through a ...

Time-resolved Photophysical Characterization of Triplet-harvesting Organic Compounds at an Oxygen-free Environment Using an iCCD Camera

Here, we present a sensible method of the acquisition and analysis of time-resolved photoluminescence using an ultrafast iCCD camera. This system enables the acquisition of photoluminescence spectra covering the time regime from nanoseconds up to 0.1 s. This enables us to follow the changes in the intensity (decay) and emission of the spectra over time. Using this method, it is possible to study diverse photophysical phenomena, such as the emission of phosphorescence, and the contributions of prompt and delayed fluorescence in molecules showing thermally activated delayed fluorescence (TADF). Remarkably, all spectra and decays are obtained in a single experiment. This can be done for solids (thin film, powder, crystal) and liquid samples, where the only limitations are the spectral sensitivity of the camera and the excitation wavelength (532 nm, 355 nm, 337 nm, and 266 nm). This technique is, thus, very important when investigating the excited state dynamics in organic emitters for their application in organic light-emitting diodes and other areas where triplet harvesting is of paramount importance. Since triplet states are strongly quenched by oxygen, emitters with efficient TADF luminescence, or those showing room temperature phosphorescence (RTP), must be correctly prepared in order to remove any dissolved oxygen from solutions and films. Otherwise, no long-lived emission will be observed. The method of degassing solid samples as presented in this work is basic and simple, but the degassing of liquid samples creates additional difficulties and is particularly interesting. A method of minimizing solvent loss and changing the sample concentration, while still enabling to remove oxygen in a very efficient and a repeatable manner, is presented in this work.

Here, we present a method of the spectroscopic characterization of organic molecules by means of time-resolved photoluminescence spectroscopy on the nanosecond-to-millisecond timescale in oxygen-free conditions. Methods to efficiently remove oxygen from the samples and, thus, limit luminescence quenching are also described.

利用 iccd 摄像机对无氧环境下的三重收集有机化合物进行光物理表征

Here, we present a sensible method of the acquisition and analysis of time-resolved photoluminescence using an ultrafast iCCD camera. This system enables ...

Raman and IR Spectroelectrochemical Methods as Tools to Analyze Conjugated Organic Compounds

In the presented work, two spectroelectrochemical techniques are discussed as tools for the analysis of the structural changes occurring in the molecule on the vibrational level of energy. Raman and IR spectroelectrochemistry can be used for advanced characterization of the structural changes in the organic electroactive compounds. Here, the step-by-step analysis by means of Raman and IR spectroelectrochemistry is shown. Raman and IR spectroelectrochemical techniques provide complementary information about structural changes occurring during an electrochemical process, i.e. allows for the investigation of redox processes and their products. The examples of IR and Raman spectroelectrochemical analysis are presented, in which the products of the redox reactions, both in solution and solid state, are identified.

A protocol of step-by-step Raman and IR spectroelectrochemical analysis is presented.

拉曼光谱和红外光谱电化学法作为分析共轭有机化合物的工具

In the presented work, two spectroelectrochemical techniques are discussed as tools for the analysis of the structural changes occurring in the molecule ...

Controlled Photoredox Ring-Opening Polymerization of O-Carboxyanhydrides Mediated by Ni/Zn Complexes

Here, we describe an effective protocol that combines photoredox Ni/Ir catalysis with the use of a Zn-alkoxide for efficient ring-opening polymerization, allowing for the synthesis of isotactic poly(&#945;-hydroxy acids) with expected molecular weights (&#62;140 kDa) and narrow molecular weight distributions (Mw/Mn &#60; 1.1). This ring-opening polymerization is mediated by Ni and Zn complexes in the presence of an alcohol initiator and a photoredox Ir catalyst, irradiated by a blue LED (400 - 500 nm). The polymerization is performed at a low temperature (-15 &#176;C) to avoid undesired side reactions. The complete monomer consumption can be achieved within 4 - 8 hours, providing a polymer close to the expected molecular weight with narrow molecular weight distribution. The resulted number-average molecular weight shows a linear correlation with the degree of polymerization up to 1000. The homodecoupling 1H NMR study confirms that the obtained polymer is isotactic without epimerization. This polymerization reported herein offers a strategy for achieving rapid, controlled O-carboxyanhydrides polymerization to prepare stereoregular poly(&#945;-hydroxy acids) and its copolymers bearing various functional side-chain groups.

Controlled Photoredox Ring-Opening Polymerization of O-Carboxyanhydrides Mediated by Ni/Zn Complexes

A protocol for the controlled photoredox ring-opening polymerization of O-carboxyanhydrides mediated by Ni/Zn complexes is presented.

镍/锌配合物介导的O-Carboxyanhydrides 的控制 Photoredox 环开聚合

Here, we describe an effective protocol that combines photoredox Ni/Ir catalysis with the use of a Zn-alkoxide for efficient ring-opening polymerization, ...

Development of Heterogeneous Enantioselective Catalysts using Chiral Metal-Organic Frameworks (MOFs)

Substrate size discrimination by the pore size and homogeneity of the chiral environment at the reaction sites are important issues in the validation of the reaction site in metal-organic framework (MOF)&#8211;based catalysts in an enantioselective catalytic reaction system. Therefore, a method of validating the reaction site of MOF-based catalysts is necessary to investigate this issue. Substrate size discrimination by pore size was accomplished by comparing the substrate size versus the reaction rate in two different types of carbonyl-ene reactions with two kinds of MOFs. The MOF catalysts were used to compare the performance of the two reaction types (Zn-mediated stoichiometric and Ti-catalyzed carbonyl-ene reactions) in two different media. Using the proposed method, it was observed that the entire MOF crystal participated in the reaction, and the interior of the crystal pore played an important role in exerting chiral control when the reaction was stoichiometric. Homogeneity of the chiral environment of MOF catalysts was established by the size control method for a particle used in the Zn-mediated stoichiometric reaction system. The protocol proposed for the catalytic reaction revealed that the reaction mainly occurred on the catalyst surface regardless of the substrate size, which reveals the actual reaction sites in MOF-based heterogeneous catalysts. This method for reaction site validation of MOF catalysts suggests various considerations for developing heterogeneous enantioselective MOF catalysts.

Development of Heterogeneous Enantioselective Catalysts using Chiral Metal-Organic Frameworks MOFs

Here, we present a protocol for active site validation of metal-organic framework catalysts by comparing stoichiometric and catalytic carbonyl-ene reactions to find out whether a reaction takes place on the inner or outer surface of metal-organic frameworks.

使用气性金属-有机框架 （MoF） 开发异构异构选择性催化剂

Substrate size discrimination by the pore size and homogeneity of the chiral environment at the reaction sites are important issues in the validation of ...