nature_catalysis
Cobalt phthalocyanine (CoPc) recently garnered considerable interest as an electrocatalyst
when it was shown that molecular dispersion on carbon nanotubes (CNT) unlocks CoPc’s
intrinsic ability to reduce CO2 to methanol. Doctoral student Christina Zeng of the Panetier Group and experimental
collaborators have published a mechanistic study in Nature Catalysis demonstrating
that selectivity for methanol requires the specific solvation environment provided
by heterogenizing CoPc with a molecular level of dispersion. This places the active
site within the Stern layer and prevents aggregation into the diffuse layer. Computational
results show that the Stern layer cations provide thermodynamic and kinetic stabilization
necessary for methanol production, furthering our understanding of CoPc, heterogenized
molecular catalysts, and the role the micro-environment can play in catalysis in general.
ChemSusChem
The Panetier group, with doctoral student Sandeep Dash, in collaboration with the
Jiang group at the University of Cincinnati, recently published a highly impactful
work in ChemSusChem on the "Ambient Electroreductive Carboxylation of Unactivated
Alkyl Chlorides and Polyvinyl Chloride Upgrading." In this paper, the research team
employs electroanalytical methods, control experiments, and computational studies
to investigate the electrochemical C–Cl bond activation of alkyl chlorides and the
subsequent carboxylation step in the presence of carbon dioxide. DFT calculations
show that CO2 binding occurs at the resting state to yield a metallocarboxylate intermediate and
that the C-Cl bond activation step is the rate-determining transition state, with
an activation energy of 19.3 kcal/mol. Readers interested in the carboxylation of
unactivated alkyl chlorides can find additional information about the article at https://doi.org/10.1002/cssc.202400517
Catalysis
The Panetier group, with doctoral student Sandeep Dash, in collaboration with the
Jiang group at the University of Cincinnati, recently published a study on the "Effect
of Beta-Fluorinated Porphyrin in Changing Selectivity for Electrochemical O2 Reduction" in Materials Today Catalysis as a part of the special issue "Molecular
Electrocatalysis for Small Molecule Activation Reactions." In this paper, the research
team employs electrochemical, spectroscopic, and DFT experiments to explore the two-
and four-electron pathways for the oxygen reduction reaction (ORR) using cobalt porphyrin
electrocatalysts. Based on DFT calculations, the authors show that the formation of
a phlorin intermediate could occur before O2 reduction and that a stronger H2O2 binding in the cobalt-based beta-fluorinated porphyrin species is responsible for
the observed experimental selectivity for H2O (a four-proton and four-electron process). Readers interested in ORR can find additional
information about the article at https://doi.org/10.1016/j.mtcata.2024.100053.
Yang paper 2024
A doctoral student from the Grewer laboratory, who just graduated, Dr. Yang Dong,
and former graduate student Dr. Jiali Wang (now postdoc at Yale University) published
a paper in the Journal of Biological Chemistry with the title "Transient kinetics
reveal the mechanism of competitive inhibition of the neutral amino acid transporter
ASCT2". This paper details the mechanism of interaction of a competitive inhibitor,
LcBPE, with the ASCT2 transporter binding site. Most importantly, binding of the
inhibitor is electrogenic, despite being a neutral, zwitterionic molecule, suggesting
asymmetric charge distribution of the bound inhibitor in the membrane dielectric.
These findings have implications for future development of inhibitors for this cancer-relevant
glutamine transporter. Publication link: Journal of Biological Chemistry
Graphical abstract
Dr. Xiaoxin Zhao from the Solmaz research group has published her work that provides
mechanistic insights into the transport of secretory vesicles, which is important
for the secretion of proteins including neurotransmitters and hormones in the prestigious
journal Life Science Alliance. She has established a structural model for the interaction
of the proteins Rab6 and BicD2. Rab6 is a key modulator of protein secretion and
widely regarded as marker for secretory vesicles. It recruits the dynein adapter protein
BicD2 to secretory vesicles, which in turn recruits the motors dynein and kinesin-1
for transport. The BicD2 binding site is located in two regions of Rab6, which undergo
structural changes upon transition from the inactive to the active state, explaining
why the active state has a higher affinity to BicD2 . Mutations of Rab6 that abolish
binding to BicD2 severely diminished the motility of secretory vesicles in cells,
highlighting the importance of this interaction for overall motility. These results
provide insights into the transport of secretory vesicles, which is important for
signaling, neurotransmission and brain development. Results will help devise therapies
for diseases caused by BicD2 mutations, which selectively affect the affinity to Rab6
and other cargoes.
Citation Zhao X, Quintremil S, Rodriguez Castro ED, Cui H, Moraga D, Wang T, Vallee RB, Solmaz
SR (2024). Molecular mechanism for recognition of the cargo adapter Rab6(GTP) by the
dynein adapter BicD2. Life Sci Alliance 7. doi: 10.26508/lsa.202302430.
Fifty years
Fifty years of lithium-ion batteries and what is next? M. Stanley Whittingham and
Jie Xiao
The first rechargeable lithium batteries were built 50 years ago, at the same time
as the Materials Research Society was formed. Great strides have been made since then
taking a dream to domination of portable energy storage. During the past two decades,
the demand for the storage of electrical energy has mushroomed both for portable applications
such as the iPhone and electric vehicles and for more than 1-GWh grid applications.
As storage and power demands have increased, the batteries have evolved with their
chemistries being pushed to the limits. This has resulted in the energy densities
almost doubling and the cost dropping by more than an order of magnitude. However,
the present electrochemical systems are still too costly to penetrate major new markets,
still higher performance is required, and environmentally acceptable and sustainable
materials are required.
J.Am.Chem.Soc.
The Fang Group at Binghamton University has just published an article “Randomly Layered
Superstructure of In2O3 Truncated Nano-Octahedra and Its High-Pressure Behavior” in Journal of the American
Chemical Society. This paper describes the synthesis, self-assembly, and structural
analysis of In2O3 nano-octahedra featuring vertex truncation. Through secondary electron imaging and
small-angle X-ray scattering (SAXS), it was determined that the superlattice comprises
randomly distributed layers with a hexagonally close-packed 2D structure. Notably,
SAXS revealed an irreversible translation of octahedra within the superlattice under
pressure, marking a significant advancement in understanding the behaviors of 2D superlattices
under external force. Read more here J. Am. Chem. Soc., 2024, 146, xxxx – xxxx. Publication link
Applied Electronic Materials
Zhen Lei, a doctoral student in Professor Dimitrov’s group, has recently published
his first paper at Binghamton, shedding light on the puzzling issue of sporadic void
formation at the interface between Ni and Sn-based (SAC 305) solder joints. Until
recently, this problem impacting electronic assemblies operating at high temperatures
was considered unavoidable. However, collaborative research with Professor Peter Borgesen
has unveiled a link to impurities introduced during the Ni electrodeposition process.
Zhen's research is focused on identifying the specific species in electrodeposited
Ni films responsible for nucleating and growing micrometer-sized voids at the interface
between Ni3Sn4 intermetallic compounds and SAC 305 solder. Through a comprehensive study involving
various factors like Ni deposition parameters, deoxygenation, and electrolyte modifications,
Zhen pinpointed that inclusions, likely in the form of Ni(OH)2 or NiOOH, decompose during the reflow process, triggering the formation of interfacial
voids. This breakthrough in understanding the root-cause of the problem and its mechanism
opens avenues for developing targeted strategies to eliminate voiding issues.
acschemneuro
A former doctoral student from the Grewer laboratory, Dr. Laura Zielewicz (now at
Pfizer) has published her work on a novel prodrug inhibitor approach to block glutamate
release through reverse transport in ACS Chemical Neuroscience. She developed several
aspartate derivatives, which were shown to be effective in preventing potassium-induced
glutamate efflux, when binding to the intracellular substrate recognition site of
the transporters under pathophysiological conditions encountered during a stroke.
At the same time, glutamate uptake was not impaired, when ion concentrations were
in the normal, physiological range. This method could have wide-ranging applications
for studying glutamate-induced neuronal cell death.
Dalton Transactions
Professor Besson, graduate student Christopher Hossack and collaborator Prof. Cahill
from the George Washington University give an overview of their recent work about
f-element chemistry in a Frontier article published in Dalton Transactions. They show
how the use of the new class of ligand developed by the Besson group allows the synthesis
of a range of lanthanoid complexes with unique structural, optical and magnetic properties.
The authors also comment on the future opportunities (and challenges!) opened by those
results, including applications in the retreatment of nuclear fuel and the creation
of novel multifunctional materials combining attractive optical and magnetic properties.
Dimitrov group has published an Account “Copper-Based Nanomaterials for Fine-Pitch
Interconnects in Microelectronics”. In this Account, the authors present a novel approach
employing self-supported nanoporous copper (np-Cu) films for low-temperature joint
formation in electronic packaging. The key innovation lies in the incorporation of
tin (Sn) into the np-Cu structure, which enables joint formation at significantly
reduced sintering temperatures. The main goal is to create intermetallic compound
(IMC)-based connections between two Cu substrates. This incorporation of Sn is achieved
through an all-electrochemical bottom-up process, involving the conformal deposition
of a thin Sn layer onto finely structured np-Cu, initially formed through the dealloying
of copper-zinc (Cu-Zn) alloys.
This Account not only delves into state-of-the-art technologies that employ nanostructured
films as materials for interconnections but also highlights optimization studies for
the Sn-coating processes. The coating process is executed through a carefully calibrated
galvanic pulse plating technique, designed to preserve the structural porosity. This
meticulous fine-tuning guarantees an optimal Cu/Sn atomic ratio, facilitating the
formation of the desired precursor bonding intermetallic compound (IMC), Cu6Sn5. Furthermore,
this study explores the potential applicability of the synthesized Cu-Sn IMC nanomaterial
for enabling low-temperature joint formation. This is done via sintering, conducted
at temperatures ranging from 300°C down to 200°C under 20 MPa pressure in a forming
gas atmosphere. In conclusion, a cross-sectional examination of the formed joints
reveals robust densified bonds with minimal porosity, primarily composed of the ultimately
targeted Cu3Sn IMC.
Yang Dong from the Grewer laboratory published her discovery of a conserved allosteric
inhibition mechanism in glutamate/neutral amino acid transporters from the solute
carrier 1 (SLC1) family in eLife. Her work not only demonstrated the existence and
location of the allosteric binding site at the subunit interface of neutral amino
acid transporters ASCT1 and 2, but also identified a novel allosteric inhibitor, with
a structure unrelated to previous glutamate transporter inhibitors. This research,
which was performed in collaboration with the Schlessinger laboratory at Mount Sinai
School of Medicine, extends previous work of the Grewer/Schlessinger groups on competitive
inhibitors, for the first time characterizing an allosteric inhibitor for ASCTs.
photo PlosResearch Paper from the Vallee and Solmaz Groups provides mechanistic insights into
how mutations of the protein BicD2 cause devastating brain and muscle development
diseases in infants
Mutations in the human protein BicD2 have been found to cause a subset of cases of
spinal muscular atrophy, which is the most common genetic cause of death in infants,
and other devastating brain and muscle developmental defects in infants. BicD2 facilitates
several transport pathways in the cell that are important for brain and muscle development,
however it is not clear how the human disease mutations result in the associated diseases. A new collaborative paper from the research groups of Dr. Sozanne Solmaz, Associate
Professor in our Chemistry Department, and Richard Vallee from the Department of Pathology,
Columbia University Irving Medical Center, New York sheds insights into underlying
disease causes of these human BicD2 mutations. They examined the effects of known BicD2 mutations using in vitro biochemical and
in vivo electroporation-mediated brain developmental assays. They found a clear relationship
between the ability of BicD2 to bind to two distinct target proteins in controlling
two distinct associated brain development processes that are active in brain progenitor
cells or postmitotic neurons, respectively. Several of the disease mutations change
the affinity towards these two target proteins in a distinct manner, resulting in
preferential binding to one of the two target proteins and preferential activation
of the associated brain developmental pathway. Errors in these brain developmental
processes likely contribute to the specific human brain malformations associated with
these BicD2 mutations.
Citation Yi, J, Zhao X, Noell CR, Helmer P, Solmaz SR*, Vallee RB*. Role of Nesprin-2 and RanBP2
in BICD2-associated brain developmental disorders. PLoS Genet. 2023,19:e1010642.
Rozners group has published a paper “Triplex-Forming Peptide Nucleic Acid Controls
Dynamic Conformations of RNA Bulges” in Journal of the American Chemical Society.
This study demonstrates the ability to control the dynamic equilibria of RNA’s structure,
which is important for studying structure–function relationships in RNA biology and
may have potential in novel therapeutic approaches targeting disease-related RNAs.
Ryan, C. A.; Rahman, M. M.; Kumar, V.; Rozners, E. Triplex-Forming Peptide Nucleic
Acid Controls Dynamic Conformations of RNA Bulges. J. Am. Chem. Soc. 2023, 145, 10497–10504.
ACS Energy Letters
The Fang lab at Binghamton University, in collaboration with researchers from Cornell
University, has recently published a study in ACS Energy Letters. This paper highlights
a unique class of spinel nanocatalysts composed of shape-controlled CoMn2O4 nanocrystals. Compared to other Co- and Mn-based spinels, notably, the CoMn2O4 nano-octahedra exhibited unmatched electrocatalytic activity for oxygen reduction
in alkaline media to date. Read more hereACS Energy Lett. 2023, 8, 8, 3631–3638
Solmaz lab
Solmaz lab
The Solmaz lab (Binghamton University) has published a collaborative paper with the
Wang lab (Rensselaer Polytechnic Institute) and the Trybus lab (University of Vermont)
in the prestigious journal eLIFE. In the paper, a cargo-recognition alpha-helix was
identified in the protein Nup358, which is required for activation of a transport
pathway that is essential for brain development. Read more here.
Angewandte Chemie
The Hirschi Lab
The Hirschi lab (Binghamton University) and the Arnold lab (Cal Tech) were recently
featured by Ben List in SynFacts for their biocatalytic study involving 'Enzymatic
Nitrene Insertion into C-H Bonds for the Synthesis of Enantioenriched Amides.'
The Fang group successfully synthesized two types of Pd-Bi nanocrystals with different
crystal structures, known as monoclinic phase and fcc phase. They further identified
that the monoclinic phase exhibits superior catalytic activity for alkaline oxygen
reduction reaction, one of the significant reactions in the fuel cell system. This
discovery has been published in J. Am. Chem. Soc.
Ming Zhou, Jiangna Guo, Bo Zhao, Can Li, Lihua Zhang and Jiye Fang, J. Am. Chem. Soc.
2021, 143, 38, 15891–15897.
Working together with collaborators, Fang group recently published a research article,
“Synthesis of Core@Shell Cu-Ni@Pt-Cu Nano-Octahedra and Their Improved MOR Activity”
in Angewandte Chemie, one of the prime chemistry journals in the world (2019 Impact
Factor: 12.959). This work demonstrated a colloidal seed‐mediated approach to prepare
octahedral CuNi@Pt‐Cu core@shell nanocrystals using CuNi octahedral cores as the template.
By precisely controlling the synthesis conditions, uniform Pt‐based thin-shells can
be achieved. The resultant carbon‐supported CuNi@Pt‐Cu core@shell nano‐octahedra showed
superior activity in electrochemical methanol oxidation reaction (MOR), indicating
that both the lattice strain and shape effects play a key role in this catalyst improvement.
Eriks Rozners and Venubabu Kotikam have published an Account “Amide-Modified RNA:
Using Protein Backbone to Modulate Function of Short Interfering RNAs”. Remarkably,
this major chemical modification has unexpectedly little effect on structure and stability
of the RNA duplex and, at certain positions of short interfering RNAs, eliminates
some of the undesired off-target activity while improving their on-target activity.
The article was chosen by Editors as the Cover Image of the September 2020 issue of
Accounts of Chemical Research.
Dimitrov and Fang groups together with a Cornell research team recently published
their development of fraction-controlled Pt-Cu-based porous film electrocatalysts
used for alkaline oxygen reduction reaction (ORR) in ACS Catal. The catalysts prepared
using an electrochemical deposition-stripping synthetic approach show superb electrocatalytic
ORR activity in 0.1M KOH with control of the introduced Au composition. After a composition
optimization, the de-alloyed Pt37Cu56Au7 ternary catalyst exhibits a 7.2-fold higher
mass activity than that of the standard Pt/C and the longest durability among all
tested samples including the Pt/C. “Enhanced ORR Kinetics on Au-Doped Pt-Cu Porous Films in Alkaline Media”, Yunxiang
Xie, Yao Yang, David A. Muller, Hector D. Abruna, Nikolay Dimitrov, and Jiye Fang,
ACS Catal., 10 (xx) 9967 - 9976, (2020).
journal issue image
Bane and Tumey groups
The Bane group (Chemistry) and Tumey group (Pharmaceutical Sciences) recently reported
on an expanded repertoire of substrates that can be recognized by the microbial transglutaminase
(mTG) enzyme. Applications of mTG utilizing the noncanonical substrates are demonstrated
in providing isopeptide diversity and enabling side-chain hydrazide derivatization
on peptides and proteins. Together, the work shines light on hitherto undiscovered
capabilities of mTG and further broadens the versatility of this enzyme in biotechnology.
This publication is the second full-length paper generated from the partnership between
the Bane and Tumey groups.
T. I. Chio, B. R. Demestichas, B. M. Brems, S. L. Bane, L. N. Tumey, Expanding the
Versatility of Microbial Transglutaminase Using α-Effect Nucleophiles as Noncanonical
Substrates. Angew. Chem. Int. Ed. 2020, 59, 13814-13820. doi: 10.1002/anie.202001830
The Dimitrov group reported on the development and application of all-electrochemically
synthesized nanoporous (np) Au-Cu-Pt alloy thin film as catalysts for formic acid
oxidation (FAO) reaction. The work emphasizes a pursuit of most efficient catalytic
routes for the production of clean energy like by smart materials design at atomic
level, involving controlled alloy electrodeposition followed by oxidative copper removal.
The unique advantage of the best performing np Au-Cu-(2.6%)Pt catalyst is associated
with its exclusive selectivity in support of the preferred direct FAO mechanism along
with unseen long-lasting no-passivation behavior in the course of wide-potential-range
cycling tests.
Ultralow Pt-loading Nanoporous Au-Cu-Pt Thin Film as Highly Active and Durable Catalyst
for Formic Acid Oxidation, Yunxiang Xie and Nikolay Dimitrov, Applied Catalysis B:
Environmental, 2019, October 31 (https://doi.org/10.1016/j.apcatb.2019.118366) [Epub ahead of print].
A collaborative work from the Qiang group and the Vugmeyster group at CU Denver has
been published on PNAS. This work solved the very first molecular structure of a post-translational
modified beta-amyloid fibril. This site-specific modification, with the phosphorylation
at residue S8 on Abeta sequence, induces the formation of a more-ordered N-terminal
fibril structure with more thermodynamic stable core. In addition, this modification
leads to rapid cross-seeded fibrillation to the wild-type Abeta, which may accelerate
the pathological amyloid deposition.
The Panetier group, in collaboration with the Jurss group at the University of Mississippi,
reported a joint experimental and computational study on the use of three novel cobalt
catalysts for electrochemical CO2 reduction in aqueous solutions. This study shows
that as the rigidity of the macrocycle is increased, selectivity and activity for
CO2 reduction over the competing hydrogen evolution reaction is enhanced. As such
the most rigid catalyst performs CO2 reduction in water with an overpotential of 420
mV and a Faradaic yield of 93%.
X. Su, K.M. McCardle, L. Chen, J.A. Panetier and J.W. Jurss, Robust and Selective
Cobalt Catalysts Bearing Redox-Active Bipyridyl-N-heterocyclic Carbene Frameworks
for Electrochemical CO2 Reduction in Aqueous Solutions, ACS Catal. 2019, 9, 7398−7408Chem
Biol. 2019 May 6. doi: 10.1021/acschembio.9b00194 [Epub ahead of print].
Laura Zielewicz from the Grewer laboratory published her research on the mechanism
of inhibition of glutamate transporters in ACS Chemical Biology. This work shows that
binding of negatively-charged inhibitors occurs within the transmembrane electric
field, resulting in voltage dependence of inhibitor binding and dissociation. This
finding is important for our understanding of how glutamate interacts with the transporter
at the excitatory synapse in the mammalian brain.
Transient Kinetics Reveal Mechanism and Voltage Dependence of Inhibitor and Substrate
Binding to Glutamate Transporters. Zielewicz L, Wang J, Ndaru E, Grewer CT ACS Chem
Biol. 2019 May 6. doi: 10.1021/acschembio.9b00194 [Epub ahead of print].
The Panetier group, in collaboration with researchers from Texas A&M University and
DePaul University, reported a joint experimental and computational study on the use
of imidazolium-functionalized manganese tricarbonyl bipyridine complexes for CO2reduction.
This study, which was published in JACS, suggests that imidazolium groups in the secondary
coordination sphere promote the formation of a local hydration shell that facilitates
the protonation of CO2 reduction intermediates.
S. Sung, X. Li, L.M. Wolf, J.R. Meeder, N.S. Bhuvanesh, K.A. Grice, J.A. Panetier,
and M. Nippe, Synergistic Effects of Imidazolium-Functionalization on fac-Mn(CO)3 Bipyridine
Catalyst Platforms for Electrocatalytic Carbon Dioxide Reduction, J. Am. Chem. Soc. 2019, 141,
6569-6582.
In collaboration with colleagues from University of Rochester and Elizabethtown College,
Rozners group has published a paper “Synthetic, Structural, and RNA Binding Studies
on 2-Aminopyridine-Modified Triplex-Forming Peptide Nucleic Acids” in Chemistry: A
European Journal. The study was designated as Very Important Paper by the reviewers
and featured as a Cover Picture of the March 21 issue of Chemistry: A European Journal.
Kotikam, V., Kennedy, S. D., MacKay, J. A., and Rozners, E. Synthetic, Structural,
and RNA Binding Studies on 2-Aminopyridine-Modified Triplex-Forming Peptide Nucleic
Acids. Chem. Eur. J. 2019, 25,4367- 4372.
Elias Ndaru published work on the synthesis and characterization of novel inhibitors
of alanine cysteine serine transporter ASCT2, in collaboration with the laboratory
of Dr. Avner Schlessinger from Mount Sinai School of Medicine. Amino acid derivatives
with sulfonic acid ester and sulfonamide linkages were identified as ASCT2 inhibitors
with the most potent compound displaying an affinity in the low microM range.
A collaborative work from the Qiang and An groups has recently been published on PNAS.
This work describes the studies of thermodynamic intermediate states of interactions
between pH-Low insertion (pHLIP) peptides and membrane bilayers, using advanced solid-state
NMR spectroscopy. A multi-stage pH-modulated membrane insertion model for pHLIP peptides
was proposed. Graduate and undergraduate students S. Otieno, S. Hanz, B. Chakravorty
from the Qiang group, and graduate students A. Zhang and L. Klees from the An group
contributed to this work.
S.A. Otieno, S.Z. Hanz, B. Chakravorty, A. Zhang, L.M. Klees, M. An, and W. Qiang,
pH-dependent thermodynamic intermediates of pHLIP membrane insertion determined by
solid-state NMR spectroscopy. Proc. Natl. Acad. Sci. U.S.A., 2018, 115(48), 12194-12199.
The Fang group, in collaboration with researchers from Cornell and NTU, recently reported
their observation of phase transitions of formamidinium lead iodide (FAPbI3) under
pressure. The article was just accepted by J. Am. Chem. Soc. FAPbI3 is a hybrid compound,
consisting of a perovskite alpha-phase and hexagonal (non-perovskite) delta-phase.
Study on the pressure-induced structural evolution of this organic-inorganic compound
is a hot topic. For the first time, the authors determined that the pressure could
accelerate the alpha- to delta-FAPbI3 transformation.
Shaojie Jiang, Yiliang Luan, Joon I. Jang, Tom Baikie, Xin Huang, Ruipeng Li, Felix
O. Saouma, Zhongwu Wang, Timothy J. White and Jiye Fang, Phase Transitions of Formamidinium
Lead Iodide Perovskite under Pressure, J. Am. Chem. Soc., 2018, 140(42), 13952-13957.
The honor thesis research of an undergraduate student Vladislav Roytman is the subject
of a recent publication in Chem. Eur. J. from the Vetticatt group at Binghamton University.
This paper details the use of 13C kinetic isotope effects and DFT calculations as
a novel probe to distinguish between of enol and enamine mechanisms in aminocatalysis.
Roytman, V. A.; Karugu, R. W.; Hong, Y.; Hirschi, J. S.; Vetticatt, M. J. 13C Kinetic
Isotope Effects as a Quantitative Probe To Distinguish between Enol and Enamine Mechanisms
in Aminocatalysis Chem. Eur. J. 2018, 24(32), 8098-8102.
