🔬🧲I've recently encountered a very illustrative example of the solvent effect on the appearance of ¹H NMR spectra. ☝️If your spectrum looks poor in one solvent, try another; sometimes, the difference is remarkable.
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NMR of Coca-Cola 😁. Depending on where you are in the world, the company uses either high fructose corn syrup or cane sugar. In ¹H and ¹³C NMR, you can easily find glucose, fructose, and sucrose.
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It is often happens that proton spectra show either overlap of signals or higher-order effects because of small chem. shift differences. In this cases a simple changing of solvent or addition of aromatic solvent can dramatically simplify the spectrum 👇🏻
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🍌 ¹H NMR Spectroscopy of Banana! Ever wondered what’s inside a banana at the molecular level? We have acquired the 1H NMR spectrum of a water banana extract in DMSO-d6.
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ℹ️🧲 Here are 9 essential facts about ¹³C NMR spectroscopy you have to be aware of before starting the experiment. 📝Source: Essential Practical NMR for Organic Chemistry by S.A.Richards and J.C.Hollerton second edition, Wiley, 2023 and my experience).
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🪄If you need to resolve some signals in your 1H NMR spectrum, it is often enough to add some other solvent ☝🏻. As a rule - Benzene-D6 is used because of it specific electronic properties 👌.
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Each week I’ll post multiplets I found interesting. Today’s selection - doublet of doublets of triplets of doublets 🤯. Check out ³J H-F 19,7 Hz, which is much stronger than other J H-H.
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Trifluoroacetic acid (TFA) can help to acquire Carbon spectra of heterocyclic compounds with exchangeable protons. TFA protonates nitrogen atoms of Het-Ar and suppress proton exchange, which makes Carbon signals narrower.
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☝️🧲 This information can be quite useful when the question is, for example, «tetrazole or azide?» or when you're asking, «Is there an azide group in my substrate?»
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🧲🔥❗️Plane of symmetry makes cis isomer optically inactive (meso form, achiral). Trans isomer has C2 axis of symmetry which doesn’t cancel its optical activity.
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The answer to the previous challenge. The right one was ¹H and/or ¹³C.
🔑🧲 Key thing about ¹H NMR is that for both molecules corresponding signals appear as singlets(!) because of the symmetry, but their ¹³C satellites are different.
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Since the pyr. ring has three double bonds, 6 p-electrons exist, which are sufficient for aromatic ring formation without involving the lone pair electrons of the N atom ✅. Since the lone pair electrons remain free, quat. salts retain the aromaticity❗️.
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If rotamery is a real problem for you, e.g. for structure elucidation - try just to change the solvent 😉. From my experience - it is better to use DMSO-d6 instead of CDCl3 in most cases for this purposes☝️.
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The answer to the prev. post. The reason for the "awful" 🤯 spectrum in the case of dry DMSO is the presence of strong intra- and intermolecular hydrogen bonding , which leads to the formation of a large number of different species in the solution.
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(1/2)
🧲 Magnetize your samples! When acquiring large amounts of 1H's in routine mode, it's important to consider that some protons may have long T₁ relaxation times, which can impact their integrals. ☝️
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🎄⁉️🧲 The last NMR challenge this year 😎. Write your thoughts in the comments section. Also suggest what solvent for the compounds would be the best choice. HINT: both molecules have one CH signal in ¹H spectrum (singlet) 😉.
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Multiplet of the week. Doublet of heptets (or doublet of septets if you prefer). NOTE: the multiplet was analysed in auto mode using MNova software.
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ℹ️ Here is one of the tricks I often use in my NMR structure elucidation practice.
❗️Inter- or intramolecular proton exchange can be a real problem for a heterocyclic aromatic compound that has plenty of exchangeable acidic protons (OH, NH, CONH, etc. (1/2)
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☝️The most obvious solution is not always the right one! Why is the NOESY (1D and 2D) experiment not suitable in this particular case❓Share your thoughts in the comments👇 or stay tuned for the next post😉.
nOe - nuclear Overhauser effect.
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🧲 ᗑ The most interesting multiplet I’ve seen recently. This one particular Proton at 2.41 ppm has 5 different couplings: ³J to Fluorine, geminal ²J, 2*³J and ⁴J to the protons of the cyclobutane ring.
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🔬🧲 Electronic structure affects not only the ¹H signals of pyridine but also those of ¹⁹F, and in a more dramatic way. Here are the ¹⁹F spectra of various fluoropyridines ☝️.
NOTE: here R-aliph. The same for each.
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☝️🧲 The solution to the prev. challenge. In the trans isomer, the fluorine atoms occupy the same chemical environment. In the cis isomer, one of the fluorines is closer to both OH groups, while the other is closer to both methyne protons. So, the right answer was ¹⁹F NMR 😉.
¹H-¹³C HSQC NMR experiment. The key technique for structure elucidation purposes.
Basic NMR experiments series. Part 4/6. Stay tuned for HMBC and NOESY. If you’re not comfortable with this format - find the posts on IG or TG.
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❗️🧲 The solution to the previous challenge is ¹H NMR experiment. Triazole ring in the top molecule is symmetrical (both protons are chem. eq.); CHs of triazole in the bottom molecule chem. ineq. (different position relative to Arylated Nitrogen).
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Ref. deconv. is a technique that able to remove distortions that affect all peaks in a spectrum in the same way e.g. bad shimming. The key idea is finding the distortion function of a ref. signal (singlet) followed by the whole .fid's correction using this function.
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¹H NMR of Milk 🧲🥛: This is the Proton NMR spectrum of milk without any specific sample preparation. 🔍 However, with modern NMR techniques and methodologies, it is now possible to analyze dozens of metabolites in this product.
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There is a tradition on this page to spoil your weekend with NMR brainteasers 🤣. This was a question from subscribers ❤️. Write your thoughts in the comments section or use the poll below 👇
Weekday NMR challenge ❗️🧲. Here is the HSQC spectrum (1-bond ¹H-¹³C correlation) of the compound. What’s the structure of the compound? Explain your reasoning or use the poll👇.
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Before problem solving- choose the right solvent 😉. Looking at HNMR of the same substrate in different solvents is calming 😌, isn’t it? 👀
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The craziest molecule I’ve seen recently:
@EnamineLtd
@MykhailiukChem
‘s group chemists push the boundaries of organic synthesis literally every day. Such molecules are known to have strong “W”-like ⁴J(H-H). In this case it is ~9 Hz.
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