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Chowdhury, Azhad U.

Publications and source records attributed to Chowdhury, Azhad U..

12 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Probing DNA structural heterogeneity by identifying conformational subensembles of a bicovalently bound cyanine dye

DNA is a re-configurable, biological information-storage unit, and much remains to be learned about its heterogeneous structural dynamics. For example, while it is known that molecular dyes templated onto DNA exhibit increased photostability, the mechanism by which the structural dynamics of DNA affect the dye photophysics remains unknown. Here, we use femtosecond, two-dimensional electronic spectroscopy measurements of a cyanine dye, Cy5, to probe local conformations in samples of single-stranded DNA (ssDNA–Cy5), double-stranded DNA (dsDNA–Cy5), and Holliday junction DNA (HJ–DNA–Cy5). A line shape analysis of the 2D spectra reveals a strong excitation–emission correlation present in only the dsDNA–Cy5 complex, which is a signature of inhomogeneous broadening. Molecular dynamics simulations support the conclusion that this inhomogeneous broadening arises from a nearly degenerate conformer found only in the dsDNA–Cy5 complex. These insights will support future studies on DNA’s structural heterogeneity.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2022

Oblique Packing and Tunable Excitonic Coupling in DNA‐Templated Squaraine Rotaxane Dimer Aggregates

Abstract When molecules are aggregated such that their excited states form delocalized excitons, their spatial arrangement, or packing, can be coarsely controlled by templating and finely controlled by chemical substitution; however, challenges remain in controlling their packing on intermediate length scales. Here, we use an approach based on mechanically interlocked molecules to promote an elusive oblique packing arrangement in a series of three squaraine rotaxane dimers. We template the squaraine rotaxane dimers using DNA and observe two excitonically split bands of near‐equal intensity in their absorption spectra – a distinct signature of oblique packing, validated by theoretical modeling of the experimental results. Additional fine control of packing is demonstrated by fluorinating the macrocycle of the rotaxane, which promotes denser packing and stronger excitonic interactions.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Improving Rare-Earth Mineral Separation with Insights from Molecular Recognition: Functionalized Hydroxamic Acid Adsorption onto Bastnäsite and Calcite

Enhancing the separation of rare-earth elements (REEs) from gangue materials in mined ores requires an understanding of the fundamental interactions driving the adsorption of collector ligands onto mineral interfaces. In this work, we examine five functionalized hydroxamic acid ligands as potential collectors for the REE-containing bastnäsite mineral in froth flotation using density functional theory calculations and a suite of surface-sensitive analytical spectroscopies. These include vibrational sum frequency generation, attenuated total reflectance Fourier transform infrared, Raman, and X-ray photoelectron spectroscopies. Differences in the chemical makeup of these ligands on well-defined bastnäsite and calcite surfaces allow for a systematic relationship connecting the structure to adsorption activity to be framed in the context of interfacial molecular recognition. Here we show how the intramolecular hydrogen bonding of adsorbed ligands requires the inclusion of explicit water solvent molecules to correctly map energetic and structural trends measured by experiments. We anticipate that the results and insights from this work will motivate and inform the design of improved flotation collectors for REE ores.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Interfacial acidity on the strontium titanate surface: a scaling paradigm and the role of the hydrogen bond

A fundamental understanding of acidity at an interface, as mediated by structure and molecule–surface interactions, is essential to elucidate the mechanisms of a range of chemical transformations. While the strength of an acid in homogeneous gas and solution phases is conceptually well understood, acid–base chemistry at heterogeneous interfaces is notoriously more complicated. Using density functional theory and nonlinear vibrational spectroscopy, we present a method to determine the interfacial Brønsted–Lowry acidity of aliphatic alcohols adsorbed on the (100) surface of the model perovskite, strontium titanate. Here, while shorter and less branched alkanols are known to be less acidic in the gas phase and more acidic in solution, here we show that shorter alcohols are less acidic whereas less substituted alkanols are more acidic at the gas–oxide interface. Hydrogen bonding plays a critical role in defining acidity, whereas structure–acidity relationships are dominated by van der Waals interactions between the alcohol and the surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Additive manufacturing of strong silica sand structures enabled by polyethyleneimine binder

Abstract Binder Jet Additive Manufacturing (BJAM) is a versatile AM technique that can form parts from a variety of powdered materials including metals, ceramics, and polymers. BJAM utilizes inkjet printing to selectively bind these powder particles together to form complex geometries. Adoption of BJAM has been limited due to its inability to form strong green parts using conventional binders. We report the discovery of a versatile polyethyleneimine (PEI) binder for silica sand that doubled the flexural strength of parts to 6.28 MPa compared with that of the conventional binder, making it stronger than unreinforced concrete (~4.5 MPa) in flexural loading. Furthermore, we demonstrate that PEI in the printed parts can be reacted with ethyl cyanoacrylate through a secondary infiltration, resulting in an increase in flexural strength to 52.7 MPa. The strong printed parts coupled with the ability for sacrificial washout presents potential to revolutionize AM in various applications including construction and tooling.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Ion Pairing Mediates Molecular Organization Across Liquid/Liquid Interfaces

Liquid/liquid interfaces play a central role in scientific fields ranging from nanomaterial synthesis and soft matter electronics to nuclear waste remediation and chemical separations. This diversity of functions arises from an interface’s ability to respond to changing conditions in its neighboring bulk phases. Understanding what drives this interfacial flexibility can provide novel avenues for designing new functional interfaces. However, limiting this progress is an inadequate understanding of the subtle intermolecular and interphase interactions taking place at the molecular level. Here, we use surface-specific vibrational sum frequency generation spectroscopy combined with atomistic molecular dynamics simulations to investigate the self-assembly and structure of model ionic oligomers consisting of an oligodimethylsiloxane (ODMS) tail covalently attached to a positively charged methyl imidazolium (MIM + ) head group at buried oil/aqueous interfaces. We show how the presence of seemingly innocuous salts can impart dramatic changes to the ODMS tail conformations in the oil phase via specific ion effects and ion-pairing interactions taking place in the aqueous phase. These specific ion interactions are shown to drive enhanced amphiphile adsorption, induce morphological changes, and disrupt emergent hydrogen-bonding structures at the interface. Tuning these interactions allows for independent control over the oligomer structure in the oil phase versus interfacial population changes and represents key mechanistic insight that is needed to control chemical reactions at liquid/liquid interfaces.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Probing the electrolyte/electrode interface with vibrational sum frequency generation spectroscopy: A review

Over the past decades, Lithium-ion batteries have seen extensive improvements, and as a result are now the primary choice in many applications for their power, energy, and durability. In recent years, battery cost has reduced by orders of magnitude through adoption of new materials and processes. Despite these advances, interfaces in these battery systems are yet to be fully understood. This is seen as a major limitation to further increase cycle life, calendar life, abuse tolerance, and performances. A major obstacle is a lack of comprehensive understanding of the complex dynamic chemical processes occurring at the electrolyte/electrode interface. In this context, vibrational sum frequency generation (vSFG) spectroscopy possesses the unique capability of probing a molecularly thin interfacial layer to obtain molecular-level information through nonlinear optical interaction. Probing the molecular level processes at the interfaces using such a versatile technique would be a game changer in the advancement of current battery research knowledge. This review article summarizes recent vSFG studies on the electrolyte/electrode interface of various electrode materials and nonaqueous electrolytes for LIBs and discusses future research perspectives. Finally, overall, this focused review highlights the advantages and versatility of vSFG that can be used to further advance present-day battery research.

25 ENERGY STORAGE↗
DOE OSTI2020

Mapping the Interfacial Chemistry and Structure of Partially Fluorinated Bottlebrush Polymers and Their Linear Analogues

Polymer interfaces are key to a range of applications including membranes for chemical separations, hydrophobic coatings, and passivating layers for antifouling. While important, challenges remain in probing the interfacial monolayer where the molecular ordering and orientation can change depending on the chemical makeup or processing conditions. In this work, we leverage surface specific vibrational sum frequency generation (SFG) and the associated dependence on molecular symmetry to elucidate the ordering and orientations of key functional groups for poly(2,2,2-trifluoroethyl methacrylate) bottlebrush polymers and their linear polymer analogues. These measurements were framed by atomistic molecular dynamic simulations to provide a complementary physical picture of the gas–polymer interface. Simulations and SFG measurements show that methacrylate backbones are buried beneath a layer of trifluoroethyl containing side groups that result in structurally similar interfaces regardless of the polymer molecular weight or architecture. The average orientational angles of the trifluoroethyl containing side groups differ depending on polymer linear and bottlebrush architectures, suggesting that the surface groups can reorient via available rotational degrees of freedom. Results show that the surfaces of the bottlebrush and linear polymer samples do not strongly depend on molecular weight or architecture. As such, one cannot rely on increasing the molecular weight or altering the architecture to tune surface properties. This insight into the polymer interfacial structure is expected to advance the design of new material interfaces with tailored chemical/functional properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Hydrogen-Bond-Driven Chemical Separations: Elucidating the Interfacial Steps of Self-Assembly in Solvent Extraction

Chemical separations, particularly liquid extractions, are pervasive in academic and industrial laboratories, yet a mechanistic understanding of the events governing their function are obscured by interfacial phenomena that are notoriously difficult to measure. In this work, we investigate the fundamental steps of ligand self-assembly as driven by changes in the interfacial H-bonding network using vibrational sum frequency generation. Our results show how the bulk pH modulates the interfacial structure of extractants at the buried oil/aqueous interface via the formation of unique H-bonding networks that order and bridge ligands to produce self-assembled aggregates. These extended H-bonded structures are key to the subsequent extraction of Co2+ from the aqueous phase in promoting micelle formation and subsequent ejection of the said micelle into the oil phase. The combination of static and time-resolved measurements reveals the events underlying complexities of liquid extractions at high [Co2+]:[ligand] ratios by showing an evolution of interfacially assembled structures that are readily tuned on a chemical basis by altering the compositions of the aqueous phase. The results of this work point to new principles to design-applied separations through the manipulation of surface charge, electrostatic screening, and the associated H-bonding networks that arise at the interface to facilitate organization and subsequent extraction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Vibrational sum frequency generation using shaped near infrared light

A vibrational sum frequency generation spectroscopy system with pulse shaping is provided. The pulse shaping provides tunable NIR-Shaped light pulses based on user input parameters which may be specified to customize the system for different experimental and testing conditions or needs.

42 ENGINEERING↗
DOE OSTI2020

Molecular Recognition at Mineral Interfaces: Implications for the Beneficiation of Rare Earth Ores

Ce-bastnäsite is the single largest mineral source for light rare-earth elements. In view of the growing industrial importance of rare-earth minerals, it is critical to develop more efficient methods for separating the valuable rare-earth-containing minerals from the surrounding gangue. In this work, we employ a combination of periodic density functional theory (DFT) and molecular mechanics (MM) calculations together with the de novo molecular design program HostDesigner to identify bis-phosphinate ligands that preferentially bind to the (100) Ce-bastnäsite surface rather than the (104) calcite surface. DFT calculations for a simple phosphinate ligand were employed to qualitatively understand key behaviors involved in ligand–metal, ligand–solvent, and solvent–metal interactions. These insights were then used to guide the search for flexible, rigid, and semirigid hydrocarbon linkers to identify candidate bis-phosphinate ligands with the potential to bind preferentially to Ce-bastnäsite. Among the five most promising bis-phosphinate ligands suggested by theoretical studies, three ligands were synthesized and their adsorption characteristics to bastnäsite (100) interfaces were characterized using vibrational sum-frequency (vSFG) spectroscopy, attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, and isothermal titration calorimetry (ITC). The efficacy of the selective interfacial molecular binding was demonstrated by identifying a bis-phosphinate ligand capable of providing an overall higher surface coverage of alkyl groups relative to a monophosphinate ligand. The results highlight the interplay between adsorption binding strength and maximum surface coverage in determining ligand efficiency to render the mineral surface hydrophobic. DFT calculations further indicate that all tested ligands have higher affinity for Ce-bastnäsite than for calcite. Finally, this is consistent with the ITC data showing stronger adsorption enthalpy to bastnäsite than to calcite, making these ligands promising candidates for selective flotation of Ce-bastnäsite.

58 GEOSCIENCES↗