Suppor(tin)g iron for catalytic ammonia formation

Dinitrogen fixation, i.e. converting abundant yet inert nitrogen gas into useable forms, has tantalised chemists for decades. One goal is the transformation of dinitrogen (N2) to ammonia using transition-metal catalysts under acidic and reducing conditions. Just a handful of complexes have been reported so far that can catalyse ammonia formation, and only a few of these are iron based, despite the prevalence of iron in the enzymes that can perform this process biologically. Researchers in the US have now discovered a new iron-based bimetallic system that can catalytically transform N2 to ammonia, providing additional studies that help understand this mechanism (Figure 1).

Iron complexes that catalyse ammonia formation from dinitrogen

Figure 1: Existing iron systems that can transform N2 to ammonia, and the tin-iron system in this study (bottom right)

The bimetallic system reported by the researchers is a tin-supported iron complex, analogous to other bimetallics previously studied in the group. Dinitrogen complexes were targeted since N2 coordination to a metal centre activates it towards further reactivity. The researchers prepared two tin-iron dinitrogen complexes, by either one or two electron reductions of a metal-bromide precursor (LSnFeBr) under a nitrogen atmosphere, to form the neutral LSnFe(N2) (1) or the anionic [LSnFe(N2)] (2), respectively. These complexes were characterised using a range of spectroscopic, electronic and structural techniques, which confirmed both coordination of N2 as well as a direct tin-iron interaction (Figure 2).

Characterisation of tin-iron dinitrogen complexes

Figure 2. A) X-ray crystal structures of tin-iron dinitrogen complexes 1 and 2. B) Characterisation of the N2 functionalisation product 3 with the crystal structure (left) and NMR spectra (right).

The further-reduced anionic species, 2, showed a greater extent of dinitrogen activation compared to the neutral species (1). This was determined by a lower infrared N-N stretching frequency and a longer N-N bond in the solid-state structure of 2, both of which indicate a weaker and more activated N-N bond. The researchers therefore selected 2 for further functionalisation reactivity, and found that the reaction with Me3SiCl (an electrophile) resulted in successful N2 functionalisation, forming the diazenido complex LSnFeN2SiMe3 (3). The diazenido complex was also characterised using a range of techniques (Figure 2b), with the solid-state structure clearly showing the silyl electrophile adding to the N2 ligand. Isolated diazenido complexes, like 3, are extremely rare in the literature, and the researchers attribute this apparent stability of 3 to the presence of the supporting tin centre within the bimetallic system. The importance of the tin-support in this system was further demonstrated by computational analyses of complexes 13, whereby the charge of the distal (and reactive) nitrogen correlated with the charge on the tin centre.

Scheme and table showing catalytic ammonia formation using tin iron complexes and other iron systems

Figure 3: Catalytic ammonia formation from N2 using the tin-iron complexes, with comparison to previously reported iron systems.

The researchers tested all three tin-iron complexes for catalytic ammonia formation, using [Ph2NH2]OTf as an acid and CoCp2* as a reducing agent (Figure 3). Both the neutral dinitrogen complex (1) and the diazenido complex (3) proved successful, with generating up to 5.9 turnovers of ammonia. Additionally, the comparable activity of 3 lends further support to the likely presence of a diazenido intermediate in the mechanism. A comparison with existing iron systems shows that the presence of an iron-support greatly enhances the catalysis compared to unsupported iron (see entry 8, Figure 3), indicating the significance of this metal-support and paving the way towards future catalyst design.

 

To find out more, please read:

Bimetallic iron–tin catalyst for N2 to NH3 and a silyldiazenido model intermediate

Michael J. Dorantes, James T. Moore, Eckhard Bill, Bernd Mienert and Connie C. Lu

Chem. Commun., 2020, 56, 11030-11033

 

Samantha Apps acknowledges Michael Dorantes, for proofreading this post, as well as Prof. Connie Lu and the Lu Lab as her colleagues over the last year.

 

About the blogger:

Dr. Samantha Apps just finished her post as a Postdoctoral Research Associate in the Lu Lab at the University of Minnesota, USA, and obtained her PhD in 2019 from Imperial College London, UK. She has spent the last few years, both in her PhD and postdoc, researching synthetic nitrogen fixation and transition metal complexes that can activate and functionalise dinitrogen. Outside of the lab, you’ll likely find her baking at home, where her years of synthetic lab training has sparked a passion in kitchen chemistry too.

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ChemComm Milestones – Zewei Quan

In 2017, Zewei Quan published his first independent research article ‘Mild synthesis of monodisperse tin nanocrystals and tin chalcogenide hollow nanostructures‘. We wanted to find out why Zewei chose to publish this work with ChemComm and how his research has progressed in 2020. Read more in the interview below.

What are the main areas of research in your lab and how has your research progressed since publishing your first article?
My research is mainly based on the design and synthesis of novel inorganic materials to understand their structures and promote their applications. Two classes of inorganic compounds, i.e., metal and metal halide in the form of nanocrystal or single crystal, are being actively explored in my group. We are keen to understand the underlying structure-property relationship of these intriguing materials at both atomic and mesoscale levels.

Since my first article in ChemComm, after I became a faculty, we have made a series of progresses in two main aspects. First, high pressure is adopted to investigate the structural responses at atomic level and the corresponding property variations under compression. As for metal halides with soft lattices, intriguing pressure-induced optical behaviors have been demonstrated, including band-gap narrowing in three-dimensional (3D) double perovskite of Cs2AgBiBr6, remarkable emission enhancement in one-dimensional (1D) cuprous halide complex of CsCu2I3, and emission color modulations in zero-dimensional (0D) hybrid metal halide, (bmpy)9[ZnBr4]2[Pb3Br11]. As for noble metal nanomaterials (Au and Pd), a series of pressure-induced phase transformations have been observed, to uncover their intrinsic phase stability and atomic movement path between different phases. Second, in addition to atomic structure, we are also interested in producing novel meosclae superstructures based on anisotropic nanoparticles and exploring their collective optical properties. Notably, well-defined nanodumbbells have been self-assembled into an orientationally ordered 2D degenerate crystal with a 6-fold symmetry, in which these NDs possess no translational order but three allowed orientations with a rotational symmetry of 120 degrees.

What do you hope your lab can achieve in the coming year?
In the coming year, we look forward to exploring the structure-dependent optical properties of 0D metal halides. The self-trapped exciton (STE) emission of these hybrid metal halides has several intriguing features, however, is still rarely investigated in past decades. We plan to utilize the high pressure method to understand the key factors in determining their STE emission characteristics including energy, intensity and quantum yield, and then design and prepare the target systems with appropriate structural parameters and desired optical properties.

Describe your journey to becoming an independent researcher.
After I received my B.Sc. degree from Wuhan University in 2004, I went to Changchun Institute of Applied Chemistry, Chinese Academy of Science to start my graduate study under the supervision of Prof. Jun Lin, and obtained my Ph.D. degree in 2009. My interest was mainly focused on the synthesis and characterization of high-quality luminescent nanocrystals. After that, I begun to work at SUNY Binghamton with Prof. Jiye (James) Fang, and then worked at Los Alamos National Laboratory with Dr. Hongwu Xu and Dr. James Boncella as an Oppenheimer Fellow. During this postdoctoral period, I enjoyed investigating the self-assembly behaviors of colloidal nanoparticles and the high-pressure structural variations of several typical nanocrystals. I have been a Professor of Chemistry at Southern University of Science and Technology (SUSTech) in Shenzhen, China since 2015.

What is the best piece of advice you have ever been given?
The best piece of advice for my career is “Be a super-postdoc to start your independent research”. When I had my own research group, in addition to teaching courses and writing proposals, I devoted most of my effort to constructing the lab, designing and performing the experiments, analyzing the data and writing the papers, like a super postdoc. This advice is very helpful to train the junior members with capabilities to perform their own research projects.

Why did you choose to publish your first article in ChemComm?
I chose to publish my first independent work in ChemComm, to present a mild synthesis method of monodisperse nanocrystals. ChemComm is a classical journal with a decent reputation, and the scope covers most fields in chemistry. I believe my work published in ChemComm would have a broad readership. Right now, I have two other papers published in ChemComm, and hopefully will have more soon.

Biography: Zewei Quan is currently a Professor in the Department of Chemistry at Southern University of Science and Technology (SUSTech). He obtained his Ph.D. in inorganic chemistry from Changchun Institute of Applied Chemistry, Chinese Academy of Sciences (with Prof. Jun Lin) in 2009. After that, he worked as a postdoctoral fellow and later a research scientist at the State University of New York at Binghamton with Prof. Jiye Fang (2009-2012). He then joined Los Alamos National Laboratory as an Oppenheimer Fellow (2012-2015). His current research interests include solution-phase synthesis, self-assembly, and high-pressure study of inorganic functional materials.
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ChemComm Milestones – Soumyajit Das

We’ve been enjoying getting to know the first-time authors who have decided to publish in ChemComm and we hope that you have too. This week, we spoke to Soumyajit Das who recently published his #ChemComm1st article: Revisiting indeno[2,1-c]fluorene synthesis while exploring the fully conjugated s-indaceno[2,1-c:6,5-c′]difluorene

Read about Soumyajit below

What are the main areas of research in your lab and what motivated you to take this direction?
We are working on π-conjugated molecules and materials, and wish to contribute to the field of polycyclic aromatic, antiaromatic and proaromatic hydrocarbons. We are currently engaged in extending the scope of fully conjugated indenofluorene (IF) isomers into the higher-order indacenodifluorene (IDF) isomers which are rare in literature. The motivation came from my earlier training in the field of conducting polymers and polyradicaloid hydrocarbons, in addition to the recent developments in the field of physical and synthetic organic chemistry associated with the organic semiconductors

Can you set this article in a wider context?
Our article is about a mild synthetic approach to synthesize the formally antiaromatic indeno[2,1-c]fluorene, an electron-accepting fragment of fullerene-C60 that showed promise in bulk-heterojunction devices, and extension of the same synthetic approach to construct the s-indaceno[2,1-c:6,5-c’]difluorene as the second constitutional isomer of the potentially tetraradicaloid s-indacenodifluorene (s-IDF) family. The IDF isomers may be viewed as two indenofluorene units conjoined through one shared benzene (outer) ring, and they represent the non-alternant isoelectronic motifs for synthetically challenging octacene considering the bonding picture of the outer conjugated circuit as [34]annulene. [2,1-c:6,5-c’]s-IDF showed smaller HOMO-LUMO and singlet-triplet (theoretical) energy gap compared to its first structural isomer s-indaceno[1,2-b:5,6-b’]difluorene. Consequently, a broad electronic absorption spectrum reaching the NIR region and NMR line broadening at elevated temperatures were also observed. Notably, only two IDF isomers (including ours) were now reported in the literature. Given the efficiency of our synthetic route and the interesting chemistry associated with the existing isomers, we are excited to develop the related unexplored non-benzenoid π-conjugated systems.

What do you hope your lab can achieve in the coming year?
I am still at an early stage of building my independent research career, and the current pandemic has already affected the research activity in the group. Publishing our first paper has already been a good achievement for us since we are just one-year-old group at IIT Ropar. I am hoping that the normal research activity in the laboratory resumes soon so we can explore many possibilities in the coming year including the extension of our present research findings. Since our research has the potential to be multidisciplinary, I am also exploring new research directions by finding collaborations with applied physicists and device engineers.

Describe your journey to becoming independent researcher.
After finishing my M.Sc. in chemistry in 2007 from IIT Guwahati (India), I joined Dr. Sanjio S Zade’s group at IISER Kolkata (India) to work on the zirconocene-mediated synthesis of novel heterocycles including their polymerizations. There I was attracted to the fascinating field of π-conjugated materials, and to further explore the field, I joined Prof. Jishan Wu’s group in the NUS Singapore in 2012 to work on the open-shell polycyclic hydrocarbons. To my delight, the findings of my postdoctoral research were published in some of the renowned high-impact journals, and naturally, I started applying for the academic positions in India from 2016 onward with a very optimistic mindset. I realized then how competitive it was to get an academic position. It took me almost 2.5 years to get the assistant professor position in IIT Ropar after finishing my postdoc, after a couple of rejections and failures. Meanwhile, I gained the industrial experience by working as a scientist in the medicinal chemistry units of Sai Life Sciences (2016-2018) and Aurigene (2018-2019). Perhaps the lack of job satisfaction in the industries and the keen desire to become an independent researcher kept me motivated to search for assistant professorship positions in Indian institutes/universities till my age eligibility was allowed, and I kept on applying for that. After joining IIT Ropar on March 2019, I quickly applied for the available funding opportunities and I am pleased to say that currently my research is funded by the Science and Engineering Research Board of India (SRG, 2019-2021) and the institute seed grant (ISIRD, 2019-2022). I look forward to building a vibrant and successful research group while continuing my journey.

What is the best piece of advice you have ever been given?
It’s tough to answer. Professionally, the good one was ‘work hard, but stay alert to unexpected things’, which I pass to my students too. Personally, when the failures hurt, my wife used to say ‘you failed because you have a better opportunity waiting, so don’t quit’.

Why did you choose to publish in ChemComm?
I chose ChemComm because it is renowned, having a high impact, and broad readership across all the chemical science subdisciplines. My first publication was ChemComm in 2010, and I am very glad to be a part of this journal again by contributing my research group’s first publication as the corresponding author.

Soumyajit’s Biography:

  • Assistant Professor: 03/2019 – Present, Indian Institute of Technology Ropar, India.
  • Senior Scientist: 03/2018 – 02/2019, Aurigene Discovery Technologies, Bangalore, India.
  • Research Scientist: 09/2016 – 02/2018, Sai Life Sciences, Pune, India.
  • Research Fellow: 03/2012 – 08/2016, National University of Singapore. Supervisor: Prof. Jishan Wu
  • Ph.D. in Chemistry: 11/2007 – 02/2012, Indian Institute of Science Education & Research Kolkata. Supervisor: Prof. Sanjio S. Zade

Follow Soumyajit on Twitter: @chmsdas

#ChemCommMilestones

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ChemComm Milestones – Yizhen Liu

Yizhen Liu published his first independent article with ChemComm in 2016. We wanted to find out more about Yizhen’s experience as a first-time author and what it was like to publish with our journal. Check out his #ChemComm1st article here: A DNA kinetics competition strategy of hybridization chain reaction for molecular information processing circuit construction.

Read more from Yizhen below:

What are the main areas of research in your lab and how has your research progressed since publishing your first article?
My laboratory mainly focus on DNA molecular circuits and biosensors related to DNA single base mutation detection. Based on DNA chain replacement and toehold exchange reaction, we constructed a series of DNA molecular logic devices (4 ChemComm in total). The first work reported DNA three-digit keypad lock, and then we successively constructed 4 to 2 encoders, computational redundant modules and three-bit molecular registers. In the work of the 4 to 2 encoder, for the first time we combined the logic judgment function of DNA circuit with the detection of single base mutation, so that the sensor based on hybridization analysis can not only recognize the presence of single base mutation, but also realize the information feedback of the mutation site region.

What do you hope your lab can achieve in the coming year?
In the coming year, we hope to make breakthroughs in specific enrichment and intelligent sensing of low abundance SINGLE base mutations in DNA.

Describe your journey to becoming independent researcher.
I obtained my Bachelor’s degree in Chemistry (2008) and Doctoral degree in Analytical Chemistry (2014) from Wuhan University. My doctoral thesis was on nucleic acid colorimetric sensing based on DNA gold nanoparticles and surface-enhanced Raman analysis method. During this process, I developed a strong interest in DNA circuits. Using molecules to build computing hardware can well combine my major with my hobby in computer science. Therefore, after I got recruited by Shenzhen University as an independent researcher, I focused more on the fields related to DNA nanotechnology, and by attending professional academic conferences and learning from excellent reports of domestic and foreign researchers, my understanding of this frontier field has sufficiently deepened. My first review invitation as an independent researcher also came from ChemComm. Being a reviewer has greatly helped me to stick to the current academic frontier and offered me inspiration in my research.

What is the best piece of advice you have ever been given?
As my father always teaches me that “details determine success or failure”, I am strict with myself in every thing I do in my work and life, paying attention to every detail and always thinking twice, which has indeed brought me many successes, big and small.

Why did you choose to publish your first article in ChemComm?
In fact, my first academic paper was published in ChemComm. ChemComm is very friendly to young researchers and encourages all kinds of novel ideas to be published, which impressed me a lot. In 2016, together with my sophomore students, I was very glad to publish my first paper (and the third one in my academic career) in ChemComm as an independent researcher. We modified the hybridization chain reaction to construct a molecule-level DNA three-digit keypad lock, and were honored to be selected as the outside front cover paper. This bond between ChemComm and my academic career has been continuously strengthened and I sincerely wish ChemComm a prosperous future!

Biography: Yizhen Liu is an Associate Professor of College of Chemistry and Enviromental Engineering at Shenzhen University. Liu obtained his BAchelor’s degree in Chemistry (2008) and Doctoral degree in Analytical Chemistry (2014) from Wuhan University. His thesis work with Prof. Jiming Hu focused on colorimetric and surface-enhanced Raman biosensors based on DNA gold nanoparticles. After receiving his PhD in 2014, he joined the College of Chemistry and Environmental Engineering at Shenzhen University to start his independent research. His current research interests include DNA logic circuits, DNA sensing methods and efficient solar seawater desalination technologies. Outside the lab, you might find him occasionally wandering the PUBG world, training in team leadership. Find him: yzliu@szu.edu.cn

 

 

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Capturing toxic gases with a recyclable porous material

Toxic gas removal is essential for preserving the safety of the public and the environment. Examples include gases such as ammonia (NH3) or carbon monoxide (CO) that can be lethal in just parts-per-million concentrations. Typically, removal of these gases is achieved using porous materials with high surface areas such as zeolites, and more recently covalent- or metal-organic frameworks (COFs or MOFs), which soak up the gases by adsorption to sites within the pores of the structure. Ideally such structures would also be recyclable, whereby the gas can be captured and then safely released without damage to the molecular framework of the material. A collaborative effort by researchers across the world has now demonstrated a recyclable strategy for ammonia adsorption by a MOF, using frustrated Lewis pair chemistry to achieve at least 5 cycles of gas capture and release.

SION105-Eu MOF structure

Figure 1. Left: the structure of SION105-Eu, showing its porous nature; right: the chemical structure of the anionic tctb linker ligand (tctb3-)

The researchers selected SION105-Eu as a highly stable MOF, which uses the triply anionic tctb linker that contains a sterically hindered Lewis acidic boron centre (Figure 1). Normally, ammonia (a Lewis base) will interact with a Lewis acidic boron centre to form a Lewis acid-base adduct. However, the steric demands around the Lewis-acidic boron in the tctb linker ligand prevent the formation of a true adduct with ammonia, instead forming a “frustrated Lewis pair” where the ammonia-boron interaction is considered reversible. This notion therefore allows for ammonia capture by adsorption in the MOF through interaction with the boron centre of the ligand, followed by subsequent ammonia release, since a permanent ammonia-boron interaction is prevented by the steric demands of the linker. Additionally, prevention of permanent adsorption of ammonia within the pores of the MOF prevents any possible collapse of the structure/decomposition, which further enhances the recyclability of the material.

The researchers measured the adsorption of ammonia by SION105-Eu by suspending the MOF in an aqueous solution of NH3 at ambient pressures (i.e. with a loose cap on the vial) or high pressures (with a closed vial cap). They observed up to 10 wt% adsorption in the ambient pressure system, and up to 36 wt% adsorption in the closed system (Figure 2, top). The researchers noted retention of the MOF crystallinity upon ammonia adsorption by powder X-ray diffraction measurements (PXRD), where the same pattern was observed before and after (Figure 2, bottom). The PXRD patterns in Figure 2 (bottom) also confirmed the weak, “frustrated Lewis pair” type interactions between the MOF and NH3, by the appearance of only two new peaks as shown in the squared regions of Figure 2 (bottom).

NH3 adsorption by SION105-Eu MOF

Figure 2. Top: Gravimetrically determined ammonia adsorption over time; bottom: powder XRD patterns before (blue) and after (red) ammonia adsorption

 

The recyclability of the MOF was tested by first allowing ammonia adsorption by suspension of the MOF in an ammonia solution for 6 hours, followed by ammonia release through heating the saturated MOF at 75 °C for 30 minutes. The researchers demonstrated this process could be achieved 5 times without change to the ammonia adsorption capacity or structure of the MOF. Overall, this study shows a new frustrated Lewis pair strategy for gas capture and release to render a MOF material recyclable, which has the potential to be applied beyond ammonia removal to other toxic gases.

 

To find out more, please read:

A recyclable metal–organic framework for ammonia vapour adsorption

Tu N. Nguyen, Ian M. Harreschou, Jung-Hoon Lee, Kyriakos C. Stylianou and Douglas W. Stephan

Chem. Commun., 2020, 56, 9600-9603

 

About the blogger:

Dr. Samantha Apps is a Postdoctoral Research Associate in the Lu Lab at the University of Minnesota, USA, and obtained her PhD in 2019 from Imperial College London, UK. She has spent the last few years, both in her PhD and postdoc, researching synthetic nitrogen fixation and transition metal complexes that can activate and functionalise dinitrogen. Outside of the lab, you’ll likely find her baking at home, where her years of synthetic lab training has sparked a passion in kitchen chemistry too.

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SU 120: Celebrating 120 Years of Soochow University

Situated in the historical and picturesque city of Suzhou, a metropolis well reputed in the world for its classic gardens, Soochow University (SU) was founded in 1900 and represents one of the first modern universities in China. Soochow University is a top comprehensive university in Jiangsu Province, listed as a key university of “Project 211” and a member of “the Double First-Class” Initiative.

The College of Chemistry, Chemical Engineering and Materials Science grew out of the Chemistry Department of Soochow University, which was founded in 1914 and was one of the earliest chemistry departments in China. The chemistry research at SU focuses on precision synthesis, micro/nano materials for environmental science, energy and materials, health chemistry and diagnosis, precision catalysis and application as well as green chemistry and chemical engineering. As a result of the scientific and technological innovation strategy “Think Big and Start Small”, Soochow University has harvested fruitful results in chemistry innovation. As indicated by data from Nature Index and Lens in 2017, the field of chemistry at Soochow University headed the list of mainland universities among the global innovative scientific research institutions and universities. Noticeably, both the disciplines of Chemistry and Materials Science at the College are listed in the top 1‰ around the world according to the latest Essential Science Indicators (ESI).

“Following the rapid developments in new technology and equipment, today we are living in a golden age of chemistry.” says Prof. Jianlin Yao, Dean of the College of Chemistry, Chemical Engineering and Materials Science, Soochow University. “Soochow University chemists will continue to work on original innovation, breakthrough techniques and technology transfer in practical application, and all of us are committed to the sustainable development goals of humanity.”

To celebrate the 120th anniversary, we are sharing a special virtual issue of research articles from Soochow University chemists. Authors across the university have contributed more than 60 articles on topics ranging from synthetic chemistry to biological chemistry and other cross chemistry disciplines. We hereby invite you to read through these selected articles to witness the achievements made by Soochow University in the past few years (2015-2020).

Find the collection online here!

Jianlin Yao

Soochow University

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ChemComm Milestones – Amie Norton

If you haven’t heard already, we are speaking to first-time independent researchers who have chosen to publish their first article with ChemComm. This week, we spoke to Amie E. Norton who recently published her #ChemComm1st article: Phase transformation induced mechanochromism in a platinum salt: a tale of two polymorphs

Find out more from Amie below:

What are the main areas of research in your lab and what motivated you to take this direction?
I work as a Research Chemist at the USDA-ARS. As a Research Chemist at the USDA, I work in the grain quality laboratory. One focus of my research is to synthesize new materials (such as nanomaterials) out of the grain. The motivation to take the research in this direction was that I realized I could use my expertise in a new field, thus merging my Ph.D and the new job I was hired to do. The other focus of my research is to design rapid testing of grain products to measure biochemical components to ensure grain quality. I work under Dr. Michael Tilley to accomplish our research program goals under National Plan 306. Rapid testing of materials to measure biochemical components to ensure grain quality falls under this plan.

Can you set this article in a wider context?
I worked in vapochromic sensors, anion sensors and mechanochromic materials. Our end goal was to design rapid testing methods for anions in drinking water and to have a fundamental understanding on these vapochromic materials. These materials were Pt(II) square planar materials that would change colours when the environment around them changed. They would change colours when introduced to a certain anion or vapor. The complexes were stacking Pt(II) complexes, when the complexes were yellow, they would stack in a dimer or monomer orientation, such as a Pt…Pt…Pt orientation of short…long distances. When the Pt complexes were red, they stacked in a linear chain the Pt…Pt…Pt orientation was short…short distances. The surprising thing is that the Pt(II) complex was often selective in anion sensing to just one anion. The selectivity was built into the complex. I was interested in nitrate as a sensing anion so I decided to play around with adding nitric acid to see if adding a proton helps with the anion exchange with the complex going from yellow to red (understanding the role of pH in the anion exchange). I stumbled on this mechanochromic behaviour and then I grew crystals out of nitric acid (pH 1) and acetone. We went to mount the crystals and they started to change when we touched them with a mounting loop. I knew that structural determination of both of the crystalline forms of mechanochromic material were rare as long range order is often lost in the material after the mechanochromic event. I decided to study this behaviour. It turned out to be one of the most interesting projects, but the discovery of the material was serendipitous.

Describe your journey to becoming independent researcher.
I received a Bachelor’s of Science degree in Chemistry from the University of Missouri (Mizzou). During my time at Mizzou, I studied abroad twice, once in London and once in a two week business class in Prague and Vienna. I also minored in Religious Studies and Sociology; I find that we need to be well-rounded in science. I completed a Ph.D at the University of Cincinnati in 2017 where I worked on vapochromic and anion sensors. My Ph.D taught me how to conduct research, and I mentored 30 undergraduates in the lab setting during this time. I feel it’s important to share knowledge and mentor the next group of future scientists.

Afterwards, I worked at NIOSH (National Institute of Occupational Safety and Health) and learned Real-time Sensing Methods. I helped build a robot out of a Roomba vacuum to survey a room for chemical hazards. Next, I worked as a post-doctoral researcher at Bowling Green State University from 2018-2019 working on photo-active materials. I now work for the USDA-ARS as a Research Chemist (2019-present). Currently, I am working on developing new materials out of grain. My current position has allowed me to learn many aspects of grain research. While I came in with little knowledge of the entire process, I am now able to contribute knowledge from my other areas of study and apply them to my current job. The process of getting grain from the field to our tables is actually a very involved process which I’m proud to be a part of. One thing in my career I have always done is welcome a challenge and take the opportunity to learn new skills as they might be needed in my future work.

What is the best piece of advice you have been given?
There are two pieces of advice that I’ve been given that I always try to follow. My parent’s advice growing up was to have “humble confidence”. The definition of “humble confidence” is to be confident without being arrogant, and to be modest while still projecting competence. The other piece of advice I received was from my Ph.D advisor. He taught me that in research when you see something unusual, most people want to run away from it. Make that unusual more dramatic by designing an experiment to figure out what caused it. Some of the most interesting discoveries are found by the unusual. Do not run away from it, instead become more inquisitive about it.

Why did you choose to publish in ChemComm?
ChemComm has a good reputation. The communication fit well with ChemComm. I felt like the information should be a rapid communication.

#ChemCommMilestones


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ChemComm Milestones – Hemant Joshi

Hemant Joshi recently published his first independent research article with ChemComm. We wanted to celebrate this exciting milestone by finding out more about Hemant and his research. Check out his #ChemComm1st article: Selenium coordinated palladium(II) trans-dichloride molecular rotor as catalyst for site selective annulation of 2‐arylimidazo[1,2‐a]pyridines

What are the main areas of research in your lab and what motivated you to take this direction?
We are a young research group who started in July 2019. Our research group mainly works on two different research areas: molecular rotors chemistry and homogenous catalysis by pincer complexes. We are trying to develop new and better catalysts for site-selective catalysis. The main motivation behind choosing these fields is my early training as a chemist in homogeneous catalysis and the interesting yet challenging chemistry associated with these fields.

Can you set this article in a wider context?
Our article describes first synthesis of a new class of intramolecular secondary interactions (SeCH…Cl) controlled molecular rotors having Cl−Pd−Cl rotor attached to Se−Pd−Se axle. These molecular rotors showed low rotational barriers which is essential for these molecular machines. The rotor was used as a catalyst for annulation of 2‐arylimidazo[1,2‐a]pyridines. The molecular rotor catalyst was designed in such a way that phenyl ring of ligand is involved in CH−π interactions with 2‐arylimidazo[1,2‐a]pyridines, which interestingly leads to revers regioselective annulated product which is otherwise challenging to obtain.

What do you hope your lab can achieve in the coming year?
Currently, the main focus is to build my independent research profile at CuRaj and to extend the possible network of collaborations to explore more challenging problems in the future. Our group’s main focus is to develop unidirectional molecular rotors with low rotational barriers.

Describe your journey to becoming independent researcher.
Since my early academic days, I was more inclined towards experimental chemistry which was the main driving force for me to choose a chemistry major during my masters. As a PhD research scholar, I joined Dr. Ajai K. Singh’s lab at the Indian Institute of Technology Delhi, India. My doctoral work was mainly focused on synthesis of new air stable metal complexes and metal chalcogenide nanoparticles for catalytic organic synthesis. To further strengthen my training as a chemist and to gain interdisciplinary research experiences, I started my post-doctoral research in Prof. John A. Gladysz’s laboratory at the Texas A&M University, College Station, USA. In Dr. Gladysz’s lab I was introduced to the beautiful word of molecular gyroscopes. Training with both of my previous advisors helped me to learn about how research labs function, and how to carry out projects and run the lab. The training from these labs built the foundation of my independent research which I would like to take up at CuRaj.

What is the best piece of advice you have ever been given?
The two best pieces of advice which helped me are from my parents and my research advisor. The first: to be a better human being and help others which helped in my personal life. The second which was useful in my professional career: run behind solving problems and not high impact factors.

Why did you choose to publish in ChemComm?
ChemComm is renowned journal known to publish interdisciplinary research with urgency. Our research group is glad to start with ChemComm.

Dr. Hemant Joshi is an Assistant Professor of Chemistry at Central University of Rajasthan (CuRaj), India. Hemant obtained his undergraduate (BSc) degree in chemistry from University of Rajasthan, India (2008) and master’s degree from Malaviya National Institute of Technology Jaipur, India (2010). After completing his master’s degree, Hemant joined the PhD program at the Indian Institute of Technology Delhi, India in 2010. His thesis work with Prof. Ajai K. Singh was focused on synthesis of new air stable metal complexes and metal chalcogenide nanoparticles for catalytic organic synthesis. In early 2016, Hemant joined the laboratory of Prof. John A. Gladysz at the Texas A&M University, College Station, USA. In his post-doctoral research work, he was engaged in building new molecular gyroscopes with large cage sizes and understanding their rotational behaviors. Hemant moved back to India in August 2018, and joined BITS Pilani, Pilani Campus, as DST Inspire faculty. In July 2019, Hemant started his independent research career at Central University of Rajasthan. Find him on Twitter: @hkjiitd

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ChemComm Milestones – Marco Di Antonio

Marco Di Antonio recently published his first independent research article with ChemComm. We wanted to celebrate this exciting milestone by finding out more about Marco and his research. Check out his #ChemComm1st article: A short peptide that preferentially binds c-MYC G-quadruplex DNA

What are the main areas of research in your lab and what motivated you to take this direction?

My group is interested in developing chemical and biological tools to underpin key chemical and structural changes that DNA undergoes during ageing and diseases development. I have always been fascinated by the relevance of DNA in biology, and to apply fundamental chemistry knowledge to unravel the mysteries behind DNA biology. Indeed, I have been working within this research framework pretty much during my entire career. What attracted me the most to this research topic is the idea that human genomic DNA, which is around 2 meters long, is compacted in a volume of few m2 in a cell. The 3-dimensional architecture that DNA adopts when compacting within a cell nucleus, as well as the chemical modifications that it undergoes to achieve compaction, are key to biological processes such as cell-differentiation, ageing and cancer development. Therefore, we are very interested in understanding what is the role of chemistry and chemical modifications in DNA compaction.

Although we have distinct research projects currently ongoing in my group, they are all aimed at developing chemical biology tools to unravel the fundamental mechanisms that regulate DNA structural dynamics in the context of ageing and diseases, such as cancer. We are particularly interested in non-helical structures that DNA can adopt, and we combine chemistry and biology to investigate how the formation of such non-canonical DNA structures affect human biology.

Can you set this article in a wider context?

It has been almost 70 years since the DNA double-helical structure was described for the first time. Since then, several other DNA structures have been reported. Amongst those, G-quadruplexes have emerged as a stable alternative to the double-helix due to their thermodynamic and kinetic stability. Increasing evidence supports G-quadruplex formation in the context of living cells; therefore, developing chemical tools to target these structures against the canonical DNA double helix is essential.

Several molecules that target selectively G-quadruplexes already exists, but there is a chemical need to develop new probes that can target one individual G-quadruplex over the ~700,000 that can form in the human genome. This will allow us to investigate the biology regulated by the targeted G-quadruplex structure and disentangle it from the other G-quadruplexes present in the genome. In this manuscript, we describe a short-peptide that displays preferential selectivity for the G-quadruplex structure present in the promoter region of the oncogene MYC and negligible biding towards other G-quadruplex structures. This has a double impact in the context of G-quadruplex biology: i) it provides a starting point to the design novel peptide-based probes to target specifically other G-quadruplexes besides MYC ii) it will allow biological investigation of the role(s) played by the stabilisation of MYC G-quadruplex, which is relevant in the context of cancer treatment.

What do you hope your lab can achieve in the coming year?
Publishing our first research paper has already been an incredible achievement, considering this has happened a bit more than just a year after starting my group and in the middle of a pandemic! For this, I am particularly thankful to Andrew Jamieson and his PhD student Danielle Morgan who have collaborated with us on this project and have been extremely supportive. For the coming year, it would be great to close a couple of projects that we have currently ongoing but it is a bit too early to predict this! My group started only with a PhD student (Denise Liano) and a PDRA (Aisling Minard), to whom I am very grateful for their relentless work, and we have already come a long way so keeping this trajectory for the next year would be great. We will be expanding in October with two new PhD students joining the team, so I really look forward the vibrant scientific environment that we are establishing within the group, which is helping my creativity significantly!

Describe your journey to becoming independent researcher.

The journey to become an independent academic is not an easy one, I would lie if I said the opposite. But this does not mean that is impossible, and I would encourage anyone reading this to try without even thinking about giving up a single time, if they really want to become independent researchers.

Personally, I have studied for my MSci in Chemistry in Pavia University (2007) and continued for a PhD in Padua University (2011). During my PhD, I almost exclusively worked in a synthetic chemistry laboratory, where I developed some novel G-quadruplex binding small-molecules. After getting my PhD, I was lucky enough to get a postdoctoral offer from Cambridge University to work in the group of Prof. Sir. Shankar Balasubramanian. I have been working in Shankar’s group as a Research Associate for 4 years and then as a Senior Research Associate for 3 more years. My time in Cambridge has been scientifically transformative, I have been moving from synthetic chemistry to biochemistry, cell-biology and genomics. The amount of new skills developed and the extremely intellectually challenging environment that characterises Shankar’s group have been key to develop independent thinking and to start my academic career. It has allowed me to develop a comprehensive view of nucleic acids chemistry and biology that now is at the foundation of my research group.

In December 2017, BBSRC awarded me a David Phillips Fellowship which I have used to start my group at Imperial College Chemistry. Although my research is still very much focused on the chemical biology of nucleic acids, I felt that moving to Imperial has been key to establish my research group in a new environment that is helping me to flourish as an independent scientist.

During my last 3 years of postdoc I started to apply for independent positions, and I am not afraid to share that I failed most of those applications both for fellowships and lectureships. So, my two key pieces of advice to anyone who wants to become independent researcher are: i) give yourself plenty time to make the transition, it will take at least 1 year from applying for a fellowship to get it, even if you get the first one you apply for! So, don’t wait until the end of your contract before giving it a shot; ii) Expect to fail! This is totally normal, and you shouldn’t take it personally, but rather learn from mistakes and improve your applications!

What is the best piece of advice you have ever been given?
The best piece of advice I have been given is from my former post-doc supervisor Prof Sir Shankar Balasubramanian, who always told me: “less is more”. It sounds like a very simple sentence, but as scientists we always tend to overcomplicate things and add extra experiments or extra information in our papers. Being able to disentangle key experiments from non-essential ones, as well as writing up a research paper with the least possible amount of words and jargon, is an essential skill that every scientist needs to keep working on. This is by far the best piece of advice I ever received, and I apply it every time that I design experiments with my group members, or when I write a paper!

Why did you choose to publish in ChemComm?
This is partially connected to my answer for the question above. I love publishing scientific research in the form of a communication, as it forces you to distil out essential and important information from what can be described in more details in supplementary information. Beside the format, ChemComm allows me to quickly and effectively disseminate important proof-of-concept experiments that can be transformative for the chemical community. For us, the findings of a short peptide that shows potential for selective recognition of an individual G-quadruplex were novel and essential to be disseminated quickly. Therefore, I had no hesitation to select ChemComm as a platform to present our first paper. Furthermore, I published with Chem Comm during my post-doc and I was impressed by the quick turnaround of the editors and the smooth submission portal, so it was a very easy decision for us!

Marco obtained his MSci degree in Organic Chemistry from University of Pavia in 2007 and moved to Padua University for his Ph.D in Molecular Sciences under the supervision of Prof. Manlio Palumbo and Prof. Mauro Freccero. Marco obtained his PhD in 2011 and moved to the UK to join Cambridge University. At Cambridge, he worked in the group of Prof. Sir. Shankar Balasubramanian, where he started a scientific transition from synthetic organic chemistry to molecular and cell biology. This scientific approach across boundaries is embedded in his research group that works at the interface between chemistry and biology. In December 2017 Marco was awarded a BBSRC David Phillips Fellowship, which enabled him to move to Imperial College Chemistry to start his research group.

 

 

 

 

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Bill Morandi: Winner of the ChemComm Emerging Investigator Lectureship 2020!

On behalf of the ChemComm Editorial Board, we are pleased to announce the winner of the 2020 ChemComm Emerging Investigator Lectureship – Professor Bill Morandi (ETH Zurich)! Our warmest congratulations to Bill!

Bill Morandi studied at the ETH Zurich from 2003–2012, earning a B.Sc. in Biology, an M.Sc. in Chemical Biology and a PhD in Organic Chemistry working with Prof. Erick M. Carreira. After a postdoc with Prof. Robert H. Grubbs at CalTech, he led an independent Max Planck Research Group from 2014–2018 at the Max-Planck-Institut für Kohlenforschung in Germany. Since July 2018, he is a tenured Associate Professor at the Laboratorium für Organische Chemie (ETH Zurich), where he holds a chair in synthetic organic chemistry.

His research program targets the development of new concepts in catalysis, with a particular emphasis on employing inexpensive and sustainable catalysts to transform broadly available feedstocks, such as polyols and hydrocarbons, into valuable building blocks for applications in medicine and materials science. His research program has been recognized by several honours, including the Novartis Early Career Award in Organic Chemistry, the Bayer Early Excellence in Science Award, the Carl Duisberg Memorial Prize from the German Chemical Society, the Ružička Prize from the ETH Zurich and the Academy Prize for Chemistry from the Göttingen Academy of Sciences and Humanities. You can also learn more about Bill’s group and research on Twitter @morandilab.

“I dedicate this award to current and past group members who have all made invaluable contributions to the group’s success in the past 6 years. It is certainly a special honour to receive this award as I greatly value the scientific excellence of the journal Chemical Communications

Learn more about Bill’s research by reading his Communication in ChemComm:

Atom-economical cobalt-catalysed regioselective coupling of epoxides and aziridines with alkenes
Gabriele Prina Cerai & Bill Morandi
Chem. Commun., 2016, 52, 9769-9772

This article will be free to read from 10th August – 7th September 2020.

As part of the Lectureship award, Bill will be presenting a number of lectures over the coming year. Details of the lectures will be announced in due course but keep an eye on Twitter @ChemCommun for details!

Keep up-to-date with our latest journal news on Twitter @ChemCommun or via our blog! Learn more about ChemComm online!

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