Search NASA⌕ Search

SEARCH · Search NASA

Results for “THIOLS”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 451 records · Page 25
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Tunable Catalytic Performance of Palladium Nanoparticles for H 2 O 2 Direct Synthesis via Surface-Bound Ligands

There is a critical need for sustainable routes to produce hydrogen peroxide, H 2 O 2 . A promising approach involves direct synthesis from molecular hydrogen and oxygen at (sub)ambient temperatures using unmodified supported Pd catalysts, which are limited by low selectivities. Controlling the environment of Pd active sites via surface ligands is shown to enhance selectivity. Trends among a myriad of surface ligands (i.e., phosphines, thiols, weakly bound molecules) suggest that those containing H-bonding groups lead to the highest H 2 O 2 production, potentially by affecting reaction energetics via H-bonding with key intermediates. These insights lay the groundwork for ligand design to achieve the optimal catalyst performance for H 2 O 2 synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

How a Formate Dehydrogenase Responds to Oxygen: Unexpected O 2 Insensitivity of an Enzyme Harboring Tungstopterin, Selenocysteine, and [4Fe–4S] Clusters

The reversible two-electron interconversion of formate and CO 2 is catalyzed by both nonmetallo- and metallo-formate dehydrogenases (FDHs). The latter group comprises molybdenum- or tungsten-containing enzymes with the metal coordinated by two equivalents of a pyranopterin cofactor, a cysteinyl or selenocysteinyl (Sec) ligand supplied by the polypeptide, and a catalytically essential terminal sulfido ligand. In addition, these biocatalysts incorporate one or more [4Fe–4S] clusters for facilitating long-distance electron transfer. However, an interesting dichotomy arises when attempting to understand how the metallo-FDHs react with O 2 . Whereas existing scholarship portrays these enzymes as being unable to perform in air due to extreme O 2 lability of their metal centers, studies dating as far back as the 1930s emphasize that some of these systems exhibit formate oxidase (FOX) activity, coupling formate oxidation to O 2 reduction. Therefore, to reconcile these conflicting views, we explored context-dependent functional linkages between metallo-FDHs and their cognate electron acceptors within the same organism vis-à-vis catalysis under atmospheric O 2 . Here, we report the discovery and characterization of an O 2 -insensitive FDH2 from the sulfate-reducing bacterium Desulfovibrio vulgaris Hildenborough (DvH) that ligates tungsten, Sec, and four [4Fe–4S] clusters. By advancing a robust expression platform for its recombinant production, we eliminate both the requirement of nitrate or azide during purification and reductive activation with thiols and/or formate prior to catalysis. Because the distinctive spectral signatures of formate-reduced DvH-FDH2 remain invariant under anaerobic and aerobic conditions, we benchmarked the enzyme activity in air, identifying CO 2 as the catalytic product. Full reaction progress curve analysis discloses a high catalytic efficiency when probed with a high-potential artificial electron acceptor. Furthermore, we show that DvH-FDH2 enables near-stoichiometric hydrogen peroxide production without superoxide release to achieve O 2 insensitivity. Notably, simultaneous electron transfer to cytochrome c and O 2 reveals that metal-based electron bifurcation is operational in this system. Taken together, our work proves the co-occurrence of redox bifurcated FDH and FOX activities within a metalloenzyme scaffold. These findings set the stage for uncovering previously unknown O 2 -insensitive flavin-based electron bifurcation mechanisms, as well as for developing authentic formate/air biofuel cells, engineering O 2 -stable FDHs and biohybrid metallocatalysts, and discerning formate bioenergetics of gut microbiota.

13C NMR↗
DOE OSTI2022

Tyrosinase-Mediated Synthesis of Nanobody–Cell Conjugates

A convenient enzymatic strategy is reported for the modification of cell surfaces. Using a tyrosinase enzyme isolated from Agaricus bisporus, unique tyrosine residues introduced at the C-termini of nanobodies can be site-selectively oxidized to reactive o-quinones. These reactive intermediates undergo rapid modification with nucleophilic thiol, amine, and imidazole residues present on cell surfaces, producing novel nanobody–cell conjugates that display targeted antigen binding. We extend this approach toward the synthesis of nanobody–NK cell conjugates for targeted immunotherapy applications. The resulting NK cell conjugates exhibit targeted cell binding and elicit targeted cell death.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Competition between Dissolved Organic Matter and Freshwater Plankton Control Methylmercury Isotope Fractionation during Uptake and Photochemical Demethylation

Isotope fractionation related to photochemical reactions and planktonic uptake at the base of the food web is a major uncertainty in the biological application of mercury (Hg) stable isotopes. In freshwater systems, it is unclear how competitive interactions among methylmercury (MeHg), dissolved organic matter (DOM), and phytoplankton govern the magnitude of mass-dependent and mass-independent fractionation. This study investigated how DOM alters rates of planktonic MeHg uptake and photodegradation and corresponding Hg isotope fractionation in the presence of freshwater phytoplankton species, Raphidocelis subcapitata. Outdoor sunlight exposure experiments utilizing R. subcapitata were performed in the presence of different DOM samples using environmentally relevant ratios of MeHg-DOM thiol groups. The extent of Δ199Hg in phytoplankton incubations (2.99‰ St. Louis River HPOA, 1.88‰ Lake Erie HPOA) was lower compared to paired abiotic control experiments (4.29 and 2.86‰, respectively) after ~30 h of irradiation, resulting from cell shading or other limiting factors reducing the extent of photodemethylation. Although the Δ 199 Hg/Δ 201 Hg ratio was uniform across experiments (~1.4), Δ 199 Hg/δ 202 Hg slopes varied dramatically (from -0.96 to 15.4) across incubations with R. subcapitata and DOM. In addition, no evidence of Hg isotope fractionation was observed within R. subcapitata cells. This study provides a refined examination of Hg isotope fractionation markers for key processes occurring in the lower food web prior to bioaccumulation, critical for accurately accounting for the photochemical processing of Hg isotopes across a wide spectrum of freshwater systems.

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

Ion-Conducting Dynamic Solid Polymer Electrolyte Adhesives

Cross-linked polymer electrolytes containing structurally dynamic disulfide bonds have been synthesized to investigate their combined ion transport and adhesive properties. Dynamic network polymers of varying cross-link densities are synthesized via thiol oxidation of a bisthiol monomer, 2,2'-(ethylenedioxy)diethanethiol, and tetrathiol cross-linker, pentaerythritol tetrakis(3-mercaptopropionate). At optimal loading of lithium bis(trifluoromethane-sulfonyl-imide) (LiTFSI) salt, the ionic conductivities (σ) at 90 °C are about 1 × 10–4 and 1 × 10–5 S/cm at the lowest and highest cross-linking, respectively. Notably, in comparison to the equivalent nondynamic network, the dynamic network shows a positive deviation in σ above 90 °C, which suggests the enhancement of ion transport occurs from the difference in structural relaxation on account of the dissociation of disulfide bonds. Lap shear adhesion and conductivity tests on ITO-coated glass substrates reveal the dynamic network exhibits a higher adhesive shear strength of 0.2 MPa (vs 0.03 MPa for the nondynamic network) and higher σ after the application of external stimulus (UV light or heat). The adhesive strength and σ are stable over multiple debonding/rebonding cycles and, thus, demonstrating the utility of these structurally dynamic networks as solid polymer electrolyte adhesives.

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

Nonequilibrium Thermodynamics of Colloidal Gold Nanocrystals Monitored by Ultrafast Electron Diffraction and Optical Scattering Microscopy

Metal nanocrystals exhibit important optoelectronic and photocatalytic functionalities in response to light. These dynamic energy conversion processes have been commonly studied by transient optical probes to date, but an understanding of the atomistic response following photoexcitation has remained elusive. In this paper, we use femtosecond resolution electron diffraction to investigate transient lattice responses in optically excited colloidal gold nanocrystals, revealing the effects of nanocrystal size and surface ligands on the electron–phonon coupling and thermal relaxation dynamics. First, we uncover a strong size effect on the electron–phonon coupling, which arises from reduced dielectric screening at the nanocrystal surfaces and prevails independent of the optical excitation mechanism (i.e., inter- and intraband). Second, we find that surface ligands act as a tuning parameter for hot carrier cooling. Particularly, gold nanocrystals with thiol-based ligands show significantly slower carrier cooling as compared to amine-based ligands under intraband optical excitation due to electronic coupling at the nanocrystal/ligand interfaces. Finally, we spatiotemporally resolve thermal transport and heat dissipation in photoexcited nanocrystal films by combining electron diffraction with stroboscopic elastic scattering microscopy. Taken together, we resolve the distinct thermal relaxation time scales ranging from 1 ps to 100 ns associated with the multiple interfaces through which heat flows at the nanoscale. Our findings provide insights into optimization of gold nanocrystals and their thin films for photocatalysis and thermoelectric applications.

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

Insights into Nucleation and Growth of Colloidal Quaternary Nanocrystals by Multimodal X-ray Analysis

Copper chalcogenide nanocrystals find applications in photovoltaic inks, bio labels, and thermoelectric materials. We reveal insights in the nucleation and growth during synthesis of anisotropic Cu 2 ZnSnS 4 nanocrystals by simultaneously performing in situ X-ray absorption spectroscopy (XAS) and small-angle X-ray scattering (SAXS). Real-time XAFS reveals that upon thiol injection into the reaction flask, a key copper thiolate intermediate species is formed within fractions of seconds, which decomposes further within a narrow temperature and time window to form copper sulfide nanocrystals. These nanocrystals convert into Cu 2 ZnSnS 4 nanorods by sequentially incorporating Sn and Zn. Real-time SAXS and ex situ TEM of aliquots corroborate these findings. Our work demonstrates how combined in situ X-ray absorption and small-angle X-ray scattering enables the understanding of mechanistic pathways in colloidal nanocrystal formation.

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

Statistical Multiobjective Optimization of Thiospinel CoNi 2 S 4 Nanocrystal Synthesis via Design of Experiments

Thiospinels, such as CoNi 2 S 4 , are showing promise for numerous applications, including as catalysts for the hydrogen evolution reaction, hydrodesulfurization, and oxygen evolution and reduction reactions; however, CoNi 2 S 4 has not been synthesized as small, colloidal nanocrystals with high surface-area-to-volume ratios. Traditional optimization methods to control nanocrystal attributes such as size typically rely upon one variable at a time (OVAT) methods that are not only time and labor intensive but also lack the ability to identify higher-order interactions between experimental variables that affect target outcomes. Herein, we demonstrate that a statistical design of experiments (DoE) approach can optimize the synthesis of CoNi 2 S 4 nanocrystals, allowing for control over the responses of nanocrystal size, size distribution, and isolated yield. After implementing a 2 5–2 fractional factorial design, the statistical screening of five different experimental variables identified temperature, Co:Ni precursor ratio, Co:thiol ratio, and their higher-order interactions as the most critical factors in influencing the aforementioned responses. Second-order design with a Doehlert matrix yielded polynomial functions used to predict the reaction parameters needed to individually optimize all three responses. A multiobjective optimization, allowing for the simultaneous optimization of size, size distribution, and isolated yield, predicted the synthetic conditions needed to achieve a minimum nanocrystal size of 6.1 nm, a minimum polydispersity (σ/$\bar{d}$) of 10%, and a maximum isolated yield of 99%, with a desirability of 96%. The resulting model was experimentally verified by performing reactions under the specified conditions. Furthermore, our work illustrates the advantage of multivariate experimental design as a powerful tool for accelerating control and optimization in nanocrystal syntheses.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Toward Spatial Control of Reaction Selectivity on Photocatalysts Using Area-Selective Atomic Layer Deposition on the Model Dual Site Electrocatalyst Platform

Photocatalytic water splitting is a promising route to low-cost, green H 2 . However, this approach is currently limited in its solar-to-hydrogen conversion efficiency. One major source of efficiency loss is attributed to the high rates of undesired side and back reactions, which are exacerbated by the proximity of neighboring oxidation and reduction sites. Nanoscopic oxide coatings have previously been used to selectively block undesired reactants from reaching active sites; however, a coating encapsulating the entire photocatalyst particle limits activity as it cannot facilitate both half-reactions. In this work, area selective atomic layer deposition (AS-ALD) was used to selectively deposit semipermeable TiO 2 films onto model metallic cocatalysts for enhancing reaction selectivity while maintaining a high overall activity. Pt and Au were used as exemplary reduction and oxidation cocatalyst sites, respectively, where Au was deactivated toward ALD growth through self-assembled thiol monolayers while TiO 2 was coated onto Pt sites. Electroanalytical measurements of monometallic thin film electrodes showed that the TiO 2 -encapsulated Pt effectively suppressed undesired H 2 oxidation and Fe(II)/Fe(III) redox reactions while still permitting the desired hydrogen evolution reaction (HER). A planar model photocatalyst platform containing patterned interdigitated arrays of Au and Pt microelectrodes was further assessed using scanning electrochemical microscopy (SECM), demonstrating the successful use of AS-ALD to enable local reaction selectivity in a dual-reaction-site (photo)electrocatalytic system. Finally, interdigitated microelectrodes having independent potential control were used to show that selectively deposited TiO 2 coatings can suppress the rate of back reactions on neighboring active sites by an order of magnitude compared with uncoated control samples.

08 HYDROGEN↗
DOE OSTI2025

Crystalline 1D Coordination Polymer Inhibitor Layer Leads to Vertical Sidewalls in Selectively Deposited ZnO on Nanoscale Patterns

Area-selective atomic layer deposition (AS-ALD) is a promising technique for the fabrication of next-generation nanoelectronics. There are two main challenges in AS-ALD: (1) achieving high selectivity of deposition on the growth regions, and (2) preventing mushrooming of the growth material onto the nongrowth regions and achieving well-defined interfaces. In this work, we use benzenethiol (BT) as an inhibitor in the selective deposition of ZnO on SiO 2 in the presence of copper with and without a native oxide (Cu/CuO x ). We observe that BT forms a monolayer on the Cu surface and a Cu-thiolate multilayer structure on CuO x . Using grazing incidence X-ray diffraction combined with simulations, we find that the multilayer structure is crystalline and composed of 1D coordination polymers of Cu-thiolate. Here, using ellipsometry and X-ray photoelectron spectroscopy, we show that the BT consumes the entirety of the CuO x during multilayer formation, allowing the multilayer thickness to be tuned by the thickness of the original oxide. Both the monolayer BT and the multilayer BT prove to be effective inhibitors of ZnO ALD, blocking nearly 500 ALD cycles, which is more than twice that achieved with other thiol inhibitors. Finally, we demonstrate that the multilayer structure can prevent mushrooming of the ALD material onto the nongrowth surface of nanoscale patterns, creating vertical sidewalls with well-defined material interfaces and providing excellent pattern transfer, even for a relatively thick deposited film. As such, these results demonstrate that BT is not only an effective inhibitor but also that its ability to form tunable multilayers makes it well-suited for highly precise nanopatterning applications.

Layers↗
DOE OSTI2025

Tunable and Degradable Dynamic Thermosets from Compatibilized Polyhydroxyalkanoate Blends

Polyhydroxyalkanoates (PHAs) are versatile, biobased polyesters that are often targeted for use as degradable thermoplastic replacements for polyolefins. Given the substantial chemical diversity of PHA, their potential as cross-linked polymers could also enable similar platforms for reversible, degradable thermosets. In this work, we genetically engineered Pseudomonas putida KT2440 to synthesize poly(3-hydroxybutyrate-co-3-hydroxyundecenoate) (PHBU), which contains both 3-hydroxybutyrate and unsaturated 3-hydroxyundecenoate components. To reduce the brittleness of this polymer, we physically blended PHBU with the soft copolymer poly(3-hydroxydecanonate-co-3-hydroxyundecenoate) in mass ratios of 1:3, 1:1, and 3:1. Upon observing varying degrees of immiscibility by scanning electron microscopy, we installed dynamic boronic ester cross-links via thiol–ene click chemistry, which resulted in compatibilized dynamic thermoset blends ranging in hard, medium, and soft rubber or elastomer thermomechanical profiles. These dynamic thermoset blends were subjected to controlled biological degradation experiments in freshwater conditions, achieving timely mass loss despite the cross-linked architectures. Overall, this work highlights a two-component platform for the production of degradable and reprocessable dynamic thermoset blends suitable for several classes of cross-linked polymer technologies from tailored, biological PHA copolymers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Examining Mechanisms of Groundwater Hg(II) Treatment by Reactive Materials: An EXAFS Study

Laboratory batch experiments were conducted to examine mechanisms of Hg(II) removal by reactive materials proposed for groundwater treatment. These materials included granular iron filings (GIF), 1:1 (w/w) mixtures of metallurgical granular Fe powder + elemental S (MGI+S) and elemental Cu + elemental S (Cu+S), granular activated carbon (GAC), attapulgite clay (ATP), ATP treated with 2-amino-5-thiol-1,3,4-thiadiazole (ATP-a), and ATP treated with 2,5-dimercapto-1,3,4-thiadiazole (ATP-d). Following treatment of simulated groundwater containing 4 mg L{sup -1} Hg for 8 or 16 days, the solution pH values ranged from 6.8 to 8.8 and Eh values ranged from +400 to -400 mV. Large decreases in aqueous Hg concentrations were observed for ATP-d (>99%), GIF (95%), MGI+S (94%), and Cu+S (90%). Treatment of Hg was less effective using ATP (29%), ATP-a (69%), and GAC (78%). Extended X-ray absorption fine structure (EXAFS) spectra of Hg on GIF, MGI+S, and GAC indicated the presence of an Hg-O bond at 2.04-2.07 {angstrom}, suggesting that Hg was bound to GIF corrosion products or to oxygen complexes associated with water sorbed to activated carbon. In contrast, bond lengths ranging from 2.35 to 2.48 {angstrom} were observed for Hg in Cu+S, ATP-a, and ATP-d treatments, suggesting the formation of Hg-S bonds.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Cyclopropenylidenes as Strong Carbene Anchoring Groups on Au Surfaces

The creation of stable molecular monolayers on metallic surfaces is a fundamental challenge of surface chemistry. N-Heterocyclic carbenes (NHCs) were recently shown to form self-assembled monolayers that are significantly more stable than the traditional thiols on Au system. In this study, we theoretically and experimentally demonstrate that the smallest cyclic carbene, cyclopropenylidene, binds even more strongly than NHCs to Au surfaces without altering the surface structure. We deposit bis(diisopropylamino)cyclopropenylidene (BAC) on Au(111) using the molecular adduct BAC–CO 2 as a precursor and determine the structure, geometry, and behavior of the surface-bound molecules through high-resolution X-ray photoelectron spectroscopy, atomic force microscopy, and scanning tunneling microscopy. Our experiments are supported by density functional theory calculations of the molecular binding energy of BAC on Au(111) and its electronic structure. Our work is the first demonstration of surface modification with a stable carbene other than NHC; more broadly, it drives further exploration of various carbenes on metal surfaces.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2024

Ultradynamic Isoreticularly Expanded Porous Organic Crystals

Porous organic materials showcasing large framework dynamics present new paths for adsorption and separation with enhanced capacity and selectivity beyond the size-sieving limits, which is attributed to their guest-responsive sorption behaviors. Porous hydrogen-bonded crosslinked organic frameworks (H C OFs) are attractive for their remarkable ability to undergo guest-triggered expansion and contraction facilitated by their flexible covalent crosslinkages. However, the voids of H C OFs remain limited, which restrains the extent of the framework dynamics. Here in this work, we synthesized a series of H C OFs characterized by unprecedented size expansion capabilities induced by solvents. These H C OFs were constructed by isoreticularly co-crystallizing two complementary sets of hydrogen bonding building blocks to generate porous molecular crystals, which were crosslinked through thiol–ene/yne single-crystal-to-single-crystal transformations. The generated H C OFs exhibit enhanced chemical durability, high crystallinity, and extraordinary framework dynamics. For instance, H C OF-104 crystals featuring a pore diameter of 13.6 Å expanded in DMF to 300 ± 10% of their original lengths within just 1 min. This expansion allows the HCOFs to adsorb guest molecules that are significantly larger than the pore sizes of their crystalline states. Through methanol-induced contraction, these large guests were encapsulated in the fast-contracted H C OFs. These advancements in porous framework dynamics pave the way for new methods of encapsulating guests for targeted delivery.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Enantioselective Hydrodifluoroalkylation of Alkenes with Conformationally Tuned Peptidyl Hydrogen Atom Transfer Catalysts

Here, we report the enantioselective hydrodifluoroalkylation of alkenes proceeding via an asymmetric hydrogen atom transfer (HAT) event catalyzed by thiol-containing tetrapeptides. Photocatalytic generation of a difluoroacetyl radical followed by carbon–carbon bond formation results in a prochiral carbon-centered radical that engages with the chiral catalyst. A trialkylamine reductant is proposed to turn over the catalyst in this net-reductive transformation. Notably, incorporating an (S)-β-methyl-substituted cysteine as the N-terminal residue improved selectivity relative to that of the native N-terminal cysteine (Cys) residue, and X-ray crystallographic analysis supports the conformational underpinning of this effect. A range of enantioenriched γ-substituted amides were synthesized in up to a 96:4 enantiomeric ratio, demonstrating the broad functional group tolerance of this method. Models accounting for asymmetric induction are proposed with supporting DFT calculations.

08 HYDROGEN↗
DOE OSTI2016

Identification of a catalytic iron-hydride at the H-cluster of [FeFe]-hydrogenase

Hydrogenases couple electrochemical potential to the reversible chemical transformation of H 2 and protons, yet the reaction mechanism and composition of intermediates are not fully understood. In this Communication we describe the biophysical properties of a hydride-bound state (H hyd ) of the [FeFe]-hydrogenase from Chlamydomonas reinhardtii . The catalytic H-cluster of [FeFe]-hydrogenase consists of a [4Fe-4S] subcluster ([4Fe-4S] H ) linked by a cysteine thiol to an azadithiolate-bridged 2Fe subcluster ([2Fe] H ) with CO and CN- ligands. Mossbauer analysis and density functional theory (DFT) calculations show that H hyd consists of a reduced [4Fe-4S] H + coupled to a diferrous [2Fe] H with a terminally bound Fe-hydride. The existence of the Fe-hydride in Hhyd was demonstrated by an unusually low Mossbauer isomer shift of the distal Fe of the [2Fe] H subcluster. As a result, a DFT model of H hyd shows that the Fe-hydride is part of a H-bonding network with the nearby bridging azadithiolate to facilitate fast proton exchange and catalytic turnover.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Modulating nanoparticle superlattice structure using proteins with tunable bond distributions

Here, we investigate the use of proteins with tunable DNA modification distributions to modulate nanoparticle superlattice structure. Using Beta-galactosidase (βgal) as a model system, we have employed the orthogonal chemical reactivities of surface amines and thiols to synthesize protein-DNA conjugates with 36 evenly distributed or 8 specifically positioned oligonucleotides. When assembled into crystalline superlattices with AuNPs, we find that the distribution of DNA modifications modulates the favored structure: βgal with uniformly distributed DNA bonding elements results in body-centered cubic crystals, whereas DNA functionalization of cysteines results in AB 2 packing. We probe the role of protein oligonucleotide number and conjugate size on this observation, which revealed the importance of oligonucleotide distribution and number in this observed assembly behavior. These results indicate that proteins with defined DNA-modification patterns are powerful tools to control the nanoparticle superlattices architecture, and establish the importance of oligonucleotide distribution in the assembly behavior of protein-DNA conjugates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗