# Nitroxyl Production and Application for Biomedical Research

Roman M Balabin, Konstantin Chingin, Huanwen Chen

► To cite this version:

Roman M Balabin, Konstantin Chingin, Huanwen Chen. Nitroxyl Production and Application for Biomedical Research. École thématique. The Chemistry and Biology of Azanone, JXSRMYY, Nan-chang, China. 2024, pp.44. hal-05083660

HAL Id: hal-05083660

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Submitted on 25 May 2025

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# Nitroxyl Production and Application for Biomedical Research

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Roman Balabin, Konstantin Chingin and
Huanwen Chen

School of Pharmacy –
Jiangxi TCM University, Nanchang
Faculty of Chemical and Environmental Engineering –
Gubkin University, Moscow
Eastern Mediterranean Department –
Bond Street Holdings, Charlestown, Nevis

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# Outline

* Part A. Bios / CVs

* Part B. Agriculture

* Part C. Haber process

* Part D. Nitrogen Fixation by Ambient Plasma

* Part E. Project Timeline

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Part A. Bios / CVs
Huanwen Chen: CV

• Formal: **Huanwen Chen** (陈煥文)

• Education and work:

• Jilin University (Changchun, China)

• Purdue University (USA)

• ETH Zurich (Switzerland)

• East China University of Technology (Nanchang)

• Jiangxi University of Chinese Medicine (Nanchang)
Huanwen Chen: results

• Google Scholar & AMiner (2024):

○ 370+ SCI papers, 20+ cover papers

○ 100+ patents, 40+ projects completed

• Awards:

• National Outstanding Young Scientists Fund

• Yangtze River Scholar

• Ten Thousand Talents National Programme

• Liang Shuquan Award

• First prizes of Natural Science (Jiangxi Province, x3)

• First prize of Technical Invention Award (Jiangxi Province)

• Third prize of the Department of Homeland Security (USA)

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# Konstantin Chingin: CV

* Formal: **Konstantin S. Chingin** (Константин Чингин)

* Education and work:

* Moscow Institute of Physics and Technology (Russia)

* **ETH Zurich** (Switzerland)

* **Stanford University** (USA)

* Karolinska Institutet (Stockholm, Sweden)

* East China University of Technology (Nanchang)

* Jiangxi University of Chinese Medicine (Nanchang)

* Thermo Scientific (Bremen, Germany)

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ETH zürich

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Stanford
University

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Karolinska
Institutet

Thermo
SCIENTIFIC
# Konstantin Chingin: results

## Scopus (2024):

* 97 papers, 1842 citations, *h*-index = 28, 3 NSFC grants

## Awards:

* Chinese Government Friendship Award (2018)

* Excellent report award, ICFBT conference (2017)

* Sino-Russian co-operation award, Ministry of Healthcare, Russia (2016)

* Lushan Friendship Award, Jiangxi Province (2015)

## Renju (連珠 / 五子棋):

* World Championship – 2^nd^ place (2007), 3^rd^ place (2005)

* Team World Championship – 1^st^ place (2004, 2006)

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# Roman Balabin: CV

* Formal: **Roman M. Balabin** (Роман Балабин)

## Education and work:

* IT Lyceum #1533 (UNESCO ASPnet, Moscow)

* Faculty of Chemical Engineering, **Gubkin University**

* Bruker Optics (Bremen, Germany)

* Max Planck Institute for Polymer Research (Germany)

* University of Göttingen (Germany)

* University of Heidelberg (Germany)

* University of Basel (Switzerland)

* ITMO University (Saint Petersburg, Russia)

* **ETH Zurich** (Switzerland)

* **BrainWare Analytics** (BWAN, Switzerland)

* Bond Street Holdings (BSH, Nevis)

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GUBKIN
UNIVERSITY

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BRUKER

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UNIVERSITÄT
GÖTTINGEN

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Universität
Basel

ETH zürich

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# Roman Balabin: results

* Google Scholar (2024):

○ 63 papers, 6153 citations, *h*-index = 40

* Awards:

• euroSAMPL (2024)

• HyDRA Challenge (2023)

• “Film science!” (2020)

• “Discover Russia” (2019)

• Bridges across Cultures (2019)

• Poster Award, GRC BioMolecules (2011)

• Poster Prize, Asilomar Conference on MS (2010)

• Top Referee, *Analytica Chimica Acta* (2008)

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Part B. Agriculture
# Agriculture: pre-history

* **Hunting and gathering:**

* Our “norm”: >90% of human history

* Diverse and (mostly) healthy diet

* High mobility of population

* Extremely low population density

* **Neolithic Revolution:**

* **First Agricultural Revolution**

* Began independently in different parts of the globe: >11 separate centers of origin

* Surely in Holocene after the **Last Glacial Period** (ca. 11'700 BP)

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# Agriculture: struggle for food

* **Permanent settlements:**

* Civilization as we know it

* Division of labor = increase in productivity

* Specialization (new professions) and trade

* **Slow but steady progress:**

* Irrigation and drainage

* Monocropping vs. Crop rotation

* **Fertilizers:** nitrogen, phosphorus and potassium

* **Norfolk four-course system in the UK:**

* Included **clover** (三叶草属) as **nitrogen fixator**

* Popular by ca. 1700

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# Agriculture: struggle for food

* **Permanent settlements:**

* Civilization as we know it

* Division of labor = increase in productivity

* Specialization (new professions) and trade

* **Slow but steady progress:**

* Irrigation and drainage

* Monocropping vs. Crop rotation

* **Fertilizers:** nitrogen, phosphorus and potassium

* **Traditional farming systems in the tropics:**

* Almost invariably include **legumes** (荚果) for centuries

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# Intensive Farming

* Industrial agriculture:

* Intensive farming arose in the **Industrial Revolution**

* Higher use of inputs: capital, labor and (agro)chemicals

* Higher crop yields per unit area

* Need an **external source** of nitrogen:

* **Guano** from Chincha Islands near Peruvian coast

* Completely **unsustainable**

* Chincha Islands War in 1864–1866

* **Saltpeter** (sodium nitrate) as an alternative:

* “Saltpeter War” in 1879–1883

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# Intensive Farming

## Industrial agriculture:

* Intensive farming arose in the **Industrial Revolution**

* Higher use of inputs: capital, labor and (agro)chemicals

* Higher crop yields per unit area

## Need an **external source** of nitrogen:

* **Guano** from Chincha Islands near Peruvian coast

* Completely **unsustainable**

* Chincha Islands War in 1864–1866

## Saltpeter (sodium nitrate) as an alternative:

* “Saltpeter War” in 1879–1883

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# The End of Civilization by 1930s

## William Crookes (1832–1919):

* President of the British Association for the Advancement of Science

* Lecture to the Association:
  "the **fixation of nitrogen is vital** to the progress of civilized humanity" (1898)

* Book "The Wheat Problem" (1905)

* Major achievement:
  Recognition of the fertilizer deficit

* Major thesis:
  All nitrogen reserves (guano, saltpeter, etc.) will be absolutely **depleted in one generation** – by 1930s

* Significant attention and influence:
  press coverage and interest from professionals

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William Crookes 19

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# The End of Civilization by 1930s

* Jermain Creighton in a cycle “How the Nitrogen Problem Has Been Solved” (1919):

* “Starvation will be averted through the laboratory”

* Six ways to solve the problem:

* Direct oxidation – the **Norwegian arc process**

* Absorption of dinitrogen by metal carbides (cyanamide)

* Reaction of dinitrogen and dihydrogen – **Haber process**

* Reaction of dinitrogen with metals

* Reaction of dinitrogen with carbon

* Oxidation of N₂ during the combustion of coal or gas

HOW THE NITROGEN PROBLEM HAS BEEN
SOLVED.* †

BY

HENRY JERMAIN MAUDE CREIGHTON,
Department of Chemistry, Swarthmore College.
Member of the Institute.

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Part C. Haber Process
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# Haber Process

* Today **Haber-Bosch process** (HB) from 1909 is the main industrial procedure for nitrogen fixation:

$$N_2 + 3H_2 \rightleftharpoons 2NH_3$$

* Parameters:

* Catalyst: $Fe/Fe_3O_4$ + additives

* Pressure: ~200 bar

* Temperature: ~500 °C
# From Lab to Plant

* Two Nobel Prizes:

* **Fritz Haber** (1918) and **Carl Bosch** (1931)

* Bosch: a rare Nobel Prize for chemical engineering

* Practical implementation of HB:

* **Oppau plant** in 1913 by BASF (Ludwigshafen, GE)

* Osmium (Os) as a catalyst

* Uranium (Ur) was also tested

* Iron oxide ($Fe_3O_4$) was found to be effective by **Alwin Mittasch** after ca. 10'000 attempts

* Alternative processes:

* Casale, Claude, Mont-Cenis, etc. are not popular

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# From Lab to Plant

* Two Nobel Prizes:

* **Fritz Haber** (1918) and **Carl Bosch** (1931)

* Bosch: a rare Nobel Prize for chemical engineering

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* Practical implementation of HB:

* **Oppau plant** in 1913 by BASF (Ludwigshafen, GE)

* Osmium (Os) as a catalyst

* Uranium (Ur) was also tested

* Iron oxide ($Fe_3O_4$) was found to be effective by **Alwin Mittasch** after ca. 10'000 attempts

* Alternative processes:

* Casale, Claude, Mont-Cenis, etc. are not popular

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The Greatest Fix

* The greatest fix in the history of *Homo sapiens*:

* Allowed to overcome the risk of **global famine**

* We would have required **four times** more land to produce the same amount of food

* Half of the **nitrogen in human tissues** originates from the Haber-Bosch process

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# Ecological Problems

* Recent problems:

* Energy ineffective

* Requires non-renewable resources:

* methane / natural gas is needed for hydrogen

* 5% of the world's natural gas production

* 2% of the total energy supply

* Anthropogenic disruption to the nitrogen cycle

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Recent Alternatives

* Extensive research of alternative strategies:

* Homogeneous catalysts

• Electro catalytic methods

* Photocatalytic approaches

• Biological

* Plasma-based

* None has been able to rival HB:

• Cost efficiency

• Scalability

* Selectivity

* Simplicity

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Part D. Nitrogen Fixation by Ambient Plasma
# WDRAC: Water dimer radical-cation, $(H_2O)_2^{+·}$

* WDRACs, $(H_2O)_2^{+·}$, could co-exist in two different conformations:

* ion-radical structure, $H_3O^+···OH^-$, with rather standard hydrogen bond

* two-center-three-electron non-classical **hemibonded** configuration or $(H_2O···OH_2)^{+·}$.

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* WDRACs react with organic substances in three different ways:

* as electron acceptors

* as **proton donors**

* as reagents for the $OH^-$ moiety exchange

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# Ambient catalyst-free nitrogen fixation

* Ambient disproportionation reaction of N₂ with water dimer radical-cations (WDRACs) is possible

* It has a general form of:

$$N_2 + (H_2O)_2^{+\bullet} \rightleftharpoons NH_2OH^{+\bullet} + HNO$$

* It does not produce ammonia

* Two much more valuable chemicals are produced:

* Hydroxylamine, NH₂OH

* Nitroxyl, HNO

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## Efficient catalyst-free N₂ fixation by water radical cations under ambient conditions

Received: 10 August 2023

Accepted: 5 February 2024

Published online: 20 February 2024

Xiaoping Zhang¹, Rui Su²,³, Jingling Li¹, Liping Huang², Wenwen Yang¹, Konstantin Chingin², Roman Balabin ②, Jingjing Wang², Xinglei Zhang¹, Weifeng Zhu², Keke Huang³, Shouhua Feng³ & Huanwen Chen ①,²

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# The Mechanism: Triplet State Excitation

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* Unusual reaction mechanism that includes electronic excitation of dinitrogen, N₂*:

$$N_2^* + (H_2O)_2^{\bullet\cdot} \Rightarrow \text{HONH-HNOH}^{\bullet\bullet*}$$

$$\text{HONH-HNOH}^{\bullet\bullet*} \Rightarrow \text{NH}_2\text{OH}^{\bullet\bullet} + \text{HNO}$$
# The Mechanism: Double Proton Transfer

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* As well as formation of a rare chemical structure, HONH-HNOH⁺⁺:

$$N_2^* + (H_2O)_2^{\bullet\bullet} \Rightarrow \text{HONH-HNOH}^{\bullet\bullet*}$$

$$\text{HONH-HNOH}^{\bullet\bullet*} \Rightarrow \text{NH}_2\text{OH}^{\bullet\bullet} + \text{HNO}$$
Scaled-up setup and vibrational spectroscopy

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<figure><img src="image_57.png" /><figcaption>b</figcaption></figure>

<figure><img src="image_58.png" /><figcaption>c</figcaption></figure>

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<figure><img src="image_60.png" /><figcaption>e</figcaption></figure>

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# Hydroxylamine: $NH_2OH$

* Significance for chemical industry:

* **Two most popular active chemical groups** (–OH and –$NH_2$) bound together in one small molecule

* World capacity: >800 000 tons annually

* Projected growth rate of 3-6% per year

* Produced and used as an aqueous solution

* Used for synthesis of:

* Polycaprolactam / Nylon-6

* **Methomyl** or Lannate (carbamate insecticide)

* Anticancer and sulfa drugs:

* including Hydroxycarbamide and Sulfamethoxazole

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# Hydroxylamine: $NH_2OH$

* Significance for chemical industry:

We propose to **shift the paradigm** of plasma-based nitrogen fixation from a cumbersome multi-step $NH_3/NO_y$ production to a **direct single-step** hydroxylamine synthesis.

<figure><img src="image_65.png" /></figure>

* Used for synthesis of:

* Polycaprolactam / Nylon-6

* **Methomyl** or Lannate (carbamate insecticide)

* Anticancer and sulfa drugs:

* including Hydroxycarbamide and Sulfamethoxazole

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# Nitroxyl or Azanone: HNO

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* **Significance for medicine:**

* Interacts with the cysteine residues of contractile proteins in myocardial cells

* Can improve myocardial contractility

* Plays a role in **treating heart failure**

* **Respiratory therapy:**

* Reacts slowly in the gas phase at low concentrations

* Nitric oxide (NO) is now used for treatments of:

* COVID-19

* Other lung infections

* The market of heart failure drugs is **steadily increasing** worldwide

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# Nitroxyl or Azanone: HNO

* Preparation of HNO is **complex and expensive**

* Detailed research of chemical pathways

* Current methods:

* From NO: precursor is unstable and toxic

* From Angeli's salt ($Na_2N_2O_3$): precursor is extremely expensive

* Today **market prices**:

* The price of pure HNO is up to RMB 800'000 per 1 g

* Our method:

* 1 kWh of electricity can produce about 50 mg of HNO

* Approximately RMB 40'000 per 1 g

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# Nitroxyl or Azanone: generation

* Preparation of HNO is **complex and expensive**

* Detailed research of chemical pathways

* Current methods:

* From NO: precursor is unstable and toxic

* From Angeli's salt ($Na_2N_2O_3$): precursor is extremely expensive

* Today **market prices**:

* The price of pure HNO is up to RMB 800'000 per 1 g

* Our method:

* 1 kWh of electricity can produce about 50 mg of HNO

* Approximately RMB 40'000 per 1 g

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# Press Reaction: Interest and Support

## Behind the Paper

### Vitalizing nitrogen: N₂ fixation by water radical cations

Published in Chemistry

Feb 21, 2024

Konstantin Chingin, Roman M. Balabin & Huanwen Chen

3 contributors

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Новости

Общество

Образование

Культура

Здравоохранение

Мода

Туризм

Мир домашних животных

### Жигулёвец стал соавтором нового метода связывания азота

22 февраля 2024 09:40

<figure><img src="image_75.png" /></figure>

Открыт новый плазменный метод связывания атмосферного азота водой. Среди авторов – два россиянина, один из которых родился в Жигулёвске.

ПРОБЛЕМЫ И МЕТОДЫ НАУКИ

Как вода связала азот

<figure><img src="image_76.png" /></figure>

<figure><img src="image_77.png" /></figure>

Эе | ЛІ | Ее | Мм | Ее | НІ | ТІ | Ы,

## НОВОСТИ НАУКИ

### Биодоступный азот можно получить связыванием в водной плазме

18.03.2024 • РОМАН БАЛАБИН • ХИМИЯ • 68 КОММЕНТАРИЕВ

<figure><img src="image_78.png" /></figure>

N+1

15:42 | 27.02.24 | * 5:1

Химия

<figure><img src="image_79.png" /></figure>

Ссылка

Молекулярный азот прореагировал с водяной плазмой

При этом образовались гидроксиламин и нитроксил

Михаил Бойм
Part E. Project Timeline
# The Project

## Experimental part:

* Spectroscopic analysis

* Investigation of formic acid synthesis in CO/water plasma

* Investigation of CO₂/water & N₂O/water plasma configurations

<figure><img src="image_80.png" /></figure>

## Theoretical part:

* Calculation of N₂ fixation at CCSD(T) level

* Plasma parameters by numerical methods @ GPGPU

## Industrial part:

* Contact with hydroxylamine/nitroxyl producers

* Obtaining the grant of a patent

* Industrial project detailing

<figure><img src="image_81.png" /></figure>
# Our Qualifications

* Expertise in chemical research and engineering

* Knowledge of R&D practices

* Basic business skills:

* **Brainware Analytics GmbH** (Switzerland)

* Office at Technopark Zurich

* EU VAT: CHE-202.748.777

* Commercial register CH-170.4.011.342-9

* Industry:

* computer hardware, provision of IT services

* Registered persons:

* "Balabin, Roman, Russian citizen, in Schlieren, managing director, with sole signature and shareholder" (SHAB)

<figure><img src="image_82.png" /></figure>

<figure><img src="image_83.png" /></figure>
# Project Timeline: 2025-2027

<table><thead><tr><th rowspan="2">Time</th><th colspan="3">Field</th></tr><tr><th>Experimental</th><th>Theoretical</th><th>Industrial</th></tr></thead><tbody><tr><td rowspan="4">2025</td><td>Q1</td><td rowspan="2">Building of a new plasma setup with optical profiling</td><td rowspan="2">Calculation of nitrogen fixation by water dimer radical-cation at CCSD(T) level</td><td>General market analysis</td></tr><tr><td>Q2</td><td>Gathering of leads and ideas</td></tr><tr><td>Q3</td><td rowspan="2">The new setup optimization</td><td rowspan="2">Going beyond CC-methods: application of Weizmann-1 scheme, iFCI, and MBE-FCI on (H<sub>2</sub>O)<sub>2</sub><sup>•</sup></td><td>SWOT matrix analysis</td></tr><tr><td>Q4</td><td>Contact with hydroxylamine/nitroxyl producers, wholesalers, and consumers in South Central China</td></tr><tr><td rowspan="4">2026</td><td>Q1</td><td>Investigation of methanol-plasma parameters & CH<sub>3</sub>OH dimer production</td><td>Plasma parameters estimation by numerical methods</td><td>Contact with hydroxylamine/nitroxyl producers, wholesalers, and consumers in East China</td></tr><tr><td>Q2</td><td>Investigation of MTBE-plasma parameters & MTBE dimer production</td><td rowspan="2">Calculation of formic acid synthesis in plasma at CCSD(T) level</td><td>Creation of a launch strategy</td></tr><tr><td>Q3</td><td>Investigation of formic acid synthesis in CO/water plasma</td><td>Initiating the process of obtaining the grant of a patent</td></tr><tr><td>Q4</td><td>Investigation of CO<sub>2</sub>/water & N<sub>2</sub>O/water plasma configurations</td><td>Calculation of the long-lived intermediates in CO<sub>2</sub>/water plasma at CCSD(T) level</td><td>Getting declarations of intent (LOIs) from the potential shareholders</td></tr><tr><td rowspan="4">2027</td><td>Q1</td><td rowspan="3">Building of a new plasma reactor based on the previous findings</td><td rowspan="2">Estimation of lifetimes of dihydroxyhydrazine and its analogs by TD-DFT, CIS, and CC2 methods</td><td>Acquiring third-party funds</td></tr><tr><td>Q2</td><td>Industrial project detailing: Process engineering for nitrogen fixation by water plasma</td></tr><tr><td>Q3</td><td rowspan="2">The reactor test & optimization</td><td rowspan="2">Benchmarking of recent DFT methods: SCAN, B05, and B13+ functionals</td></tr><tr><td>Q4</td><td></td></tr></tbody></table>
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References (1)

1. Zhang, X.; Su, R.; Li, J.; Huang, L.; Yang, W.; Chingin, K.; Balabin, R.; Wang, J.; Zhang, X.; Zhu, W.; et al. Efficient Catalyst-Free N₂ Fixation by Water Radical Cations under Ambient Conditions. Nature Communications, 2024, 15, 1535. https://doi.org/10.1038/s41467-024-45832-9

2. Zhang, X.; Hu, P.; Duan, M.; Chingin, K.; Balabin, R.; Zhang, X.; Chen, H. Ambient Catalyst-Free Oxidation Reactions of Aromatic Amines Using Water Radical Cations. Chemical Science, 2024, 15, 16125-16132. https://doi.org/10.1039/d4sc04519j

3. Barylyuk, K. V.; Chingin, K.; Balabin, R. M.; Zenobi, R. Fragmentation of Benzylpyridinium "Thermometer" Ions and Its Effect on the Accuracy of Internal Energy Calibration. Journal of the American Society for Mass Spectrometry, 2010, 21, 172-177. https://doi.org/10.1016/j.jasms.2009.09.023

4. Zhu, L.; Hu, Z.; Gamez, G.; Law, W. S.; Chen, H.; Yang, S.; Chingin, K.; Balabin, R. M.; Wang, R.; Zhang, T.; et al. Simultaneous Sampling of Volatile and Non-Volatile Analytes in Beer for Fast Fingerprinting by Extractive Electrospray Ionization Mass Spectrometry. Analytical and Bioanalytical Chemistry, 2010, 398, 405-413. https://doi.org/10.1007/s00216-010-3945-8

5. Chingin, K.; Frankevich, V.; Balabin, R. M.; Barylyuk, K.; Chen, H.; Wang, R.; Zenobi, R. Direct Access to Isolated Biomolecules under Ambient Conditions. Angewandte Chemie International Edition, 2010, 49, 2358-2361. https://doi.org/10.1002/anie.200906213

6. Chingin, K.; Balabin, R. M.; Frankevich, V.; Barylyuk, K.; Nieckarz, R.; Sagulenko, P.; Zenobi, R. Absorption of the Green Fluorescent Protein Chromophore Anion in the Gas Phase Studied by a Combination of FTICR Mass Spectrometry with Laser-Induced Photodissociation Spectroscopy. International Journal of Mass Spectrometry, 2011, 306, 241-245. https://doi.org/10.1016/j.ijms.2011.01.014

7. Chingin, K.; Balabin, R. M.; Frankevich, V.; Chen, H.; Barylyuk, K.; Nieckarz, R.; Fedorov, A.; Zenobi, R. Optical Properties of Protonated Rhodamine 19 Isomers in Solution and in the Gas Phase. Physical Chemistry Chemical Physics, 2010, 12, 14121. https://doi.org/10.1039/c0cp00482k

8. Chingin, K.; Balabin, R. M.; Barylyuk, K.; Chen, H.; Frankevich, V.; Zenobi, R. Rhodamines in the Gas Phase: Cations, Neutrals, Anions, and Adducts with Metal Cations. Physical Chemistry Chemical Physics, 2010, 12, 11710. https://doi.org/10.1039/c000807a

9. Balabin, R. M.; Smirnov, S. V. Interpolation and Extrapolation Problems of Multivariate Regression in Analytical Chemistry: Benchmarking the Robustness on near-Infrared (NIR) Spectroscopy Data. The Analyst, 2012, 137, 1604. https://doi.org/10.1039/c2an15972d

10. Balabin, R. M. Communications: Is Quantum Chemical Treatment of Biopolymers Accurate? Intramolecular Basis Set Superposition Error (BSSE). The Journal of Chemical Physics, 2010, 132, 231101. https://doi.org/10.1063/1.3442466

11. Balabin, R. M. Intermolecular Dispersion Interactions of Normal Alkanes with Rare Gas Atoms: Van Der Waals Complexes of n-Pentane with Helium, Neon, and Argon. Chemical Physics, 2008, 352, 267-275. https://doi.org/10.1016/j.chemphys.2008.06.015

12. Balabin, R. M. Experimental Thermodynamics of Free Glycine Conformations: The First Raman Experiment after Twenty Years of Calculations. Physical Chemistry Chemical Physics, 2012, 14, 99-103. https://doi.org/10.1039/c1cp20805e

13. Syunyaev, R. Z.; Balabin, R. M. Frequency Dependence of Oil Conductivity at High Pressure. Journal of Dispersion Science and Technology, 2007, 28, 419-424. https://doi.org/10.1080/01932690601107773
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14. Lu, H.; Zhang, H.; Chingin, K.; Xiong, J.; Fang, X.; Chen, H. Ambient Mass Spectrometry for Food Science and Industry. TrAC Trends in Analytical Chemistry, 2018, 107, 99–115. https://doi.org/10.1016/j.trac.2018.07.017.

15. Zhang, X.; Ren, X.; Chingin, K. Applications of Direct Analysis in Real Time Mass Spectrometry in Food Analysis: A Review. Rapid Communications in Mass Spectrometry, 2021, 35, e9013. https://doi.org/10.1002/rcm.9013.

16. Wei, Y.; Chen, L.; Zhou, W.; Chingin, K.; Ouyang, Y.; Zhu, T.; Wen, H.; Ding, J.; Xu, J.; Chen, H. Tissue Spray Ionization Mass Spectrometry for Rapid Recognition of Human Lung Squamous Cell Carcinoma. Scientific Reports, 2015, 5, 10077. https://doi.org/10.1038/srep10077.

17. Balabin, R. M. Conformational Equilibrium in Alanine: Focal-Point Analysis and Ab Initio Limit. Computational and Theoretical Chemistry, 2011, 965, 15–21. https://doi.org/10.1016/j.comptc.2011.01.008.

18. Syunyaev, R. Z.; Balabin, R. M. Polarization of Fluorescence of Asphaltene Containing Systems. Journal of Dispersion Science and Technology, 2008, 29, 1505–1514. https://doi.org/10.1080/01932690802316868.

19. Balabin, R. M. Enthalpy Difference between Conformations of Normal Alkanes: Effects of Basis Set and Chain Length on Intramolecular Basis Set Superposition Error. Molecular Physics, 2011, 109, 943–953. https://doi.org/10.1080/00268976.2011.558858.

20. Balabin, R. M. Boryl Substitution of Acetaldehyde Makes It an Enol: Inconsistency between Gn/CBS and Ab Initio/DFT Data. The Journal of Physical Chemistry A, 2010, 114, 3698–3702. https://doi.org/10.1021/jp911802v.

21. Schmid, T.; Sebesta, A.; Stadler, J.; Opilik, L.; Balabin, R. M.; Zenobi, R. Tip-Enhanced Raman Spectroscopy and Related Techniques in Studies of Biological Materials. SPIE Proceedings, 2010, 7586, 758603. https://doi.org/10.1117/12.845471.

22. Balabin, R. M.; Safieva, R. Z.; Lomakina, E. I. Universal Technique for Optimization of Neural Network Training Parameters: Gasoline near Infrared Data Example. Neural Computing and Applications, 2008, 18, 557–565. https://doi.org/10.1007/s00521-008-0213-3.

23. Balabin, R. V.; Volkomirskaya, L. B.; Gulevich, O. A.; et al. Georadar Sensing from Terrestrial Surface and Shafts: Approaches to Evaluation of Rock Fracturing. Physics of Wave Phenomena, 2015, 23, 143–153. https://doi.org/10.3103/s1541308x15020107.

24. Likhatsky, V. V.; Balabin, R. M.; Syunyaev, R. Z. Calculation of Dipole Moment of Fractal Asphaltene Cluster. Journal of Dispersion Science and Technology, 2011, 32, 1502–1508. https://doi.org/10.1080/01932691.2010.516129.

25. Balabin, R. M. Dispersed Structure of Ethanol-Gasoline Fuel According to Dynamic Light Scattering Method. Journal of Dispersion Science and Technology, 2008, 29, 457–463. https://doi.org/10.1080/01932690701718925.

26. Barylyuk, K.; Fritsche, L.; Balabin, R. M.; Nieckarz, R.; Zenobi, R. Gas-Phase Basicity of Several Common MALDI Matrices Measured by a Simple Experimental Approach. RSC Advances, 2012, 2, 1962. https://doi.org/10.1039/c1ra01117k.

27. Balabin, R. M. The Keto-Enol Equilibrium in Substituted Acetaldehydes: Focal-Point Analysis and Ab Initio Limit. Molecular Physics, 2011, 109, 2341–2351. https://doi.org/10.1080/00268976.2011.587457.
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