Formation Of Structure Research Articles

Enhanced early galaxy formation in JWST from axion dark matter?

We demonstrate that enhanced early galaxy formation can generically arise in axion-like particle (ALP) dark matter (DM) models with a delayed onset of axion field oscillation. In these models, the formation of localized massive objects enhances structure formation, potentially addressing the excess recently observed by the James Webb Space Telescope (JWST), while remaining consistent with existing constraints. We identify viable parameter space with the ALP mass in the range of 10−22eV<ma<10−19eV. In addition, we show that the ALP parameter regions of interest can lead to intriguing complementary signatures in the small scale structure of DM halos and existing experimental searches for ALPs.

Tertiary lymphoid structure formation: A matter of tumor-immune co-evolution

The immune make-up of human tumors is dynamic over the course of cancer progression. However, what factors drive spatiotemporal changes in the tumor-immune landscape is not well-known. In issue 3 of Cell Reports Medicine, Liu, You, Lan and Ren et al. demonstrate that the development of tertiary lymphoid structures (TLSs) is a stepwise process that co-occurs with tumor progression in patients with lung adenocarcinoma (LUAD).

Tandem Solid‐Solution Phase Post‐Synthetic Modification of Porous Molecular Crystals for In‐Situ Generation of Fluorophores

AbstractConventional synthetic methods of organic luminescent molecules often involve labor‐intensive solution‐phase organic synthesis, which violate the principles of atom‐economic transformation. Post‐synthetic modification (PSM) offers a promising alternative, allowing direct transformation from one fluorophore to another. Although PSM is commonly implemented in extended frameworks, its application in porous molecular crystals remains challenging. Herein, we focus on utilizing porous molecular crystals, specifically tetraphenylethylene‐cored frameworks, as versatile platforms for tandem PSM reactions to customize organic fluorophores. The tailored skeleton design ensures both the formation of porous structures and the occurrence of tandem solid‐solution phase reactions while maintaining the solid state of reactants and products in each step. The inherent non‐covalent bonding nature of the frameworks facilitates processing and characterization, offering unparalleled advantages for porous networks. The accompanying solid‐state fluorescence transition from green to blue and then to green (or yellow) enables real‐time monitoring of tandem reactions and provides intuitive mechanistic insights. This phenomenon is exploited for the facile construction of a dynamic information encryption system using fluorescent quick response codes.

Investigation of electrical, dielectric, magnetic and electrochemical characteristics of a BaFe12O19/Co0.5Zn0.5Fe2O4 nanocomposite

BaFe12O19 (barium ferrite, i.e., BaF) nanoparticles, Co0.5Zn0.5Fe2O4 (cobalt zinc ferrite, i.e, CZF) nanoparticles and their nanocomposite were synthesized for the investigation of electrical, magnetic, dielectric, and electrochemical properties. The X-ray diffraction (XRD) pattern revealed the formation of hexagonal structure for BaF nanoparticles and cubic structure for CZF nanoparticles with crystallite size of 32.44 nm and 31.30 nm, respectively. Whereas, for nanocomposite, the crystallite size obtained is 34.21 nm were shifting of peaks revealed the formation of nanocomposite. The Fourier transform Infrared (FTIR) spectra revealed the presence of metal-oxygen vibrational peaks for all the samples. The dielectric data revealed the increase in dielectric constant of nanocomposite as compared to pristine CZF whereas, loss reduced for nanocomposite significantly. Single semicircle in Nyquist plot for all the samples revealed the contribution of grain resistance in impedance. The hysteresis loop showed the increase in specific saturation magnetization from 16.963 emu/g to 21.305 emu/g for nanocomposite when compared with pristine BaF. Whereas specific remnant magnetization increased to 10.305 emu/g for nanocomposites. The electrochemical properties presented by Cyclic voltammetry showed the presence of cathodic and anodic peaks which revealed the presence of redox reaction in all samples. The specific capacitance calculated for all samples at different scan rate revealed that a nanocomposite showed highest Cs value 16.43 F/g at 25 mV, whereas it increased to 27.01 F/g, 35.93 F/g and 38.87 F/g with the increase in scan rate to 50 mV, 75 mV and 100 mV, respectively.

Supramolecular Reconstruction of Self-Assembling Photosensitizers for Enhanced Photocatalytic Hydrogen Evolution.

Natural photosynthetic systems require spatiotemporal organization to optimize photosensitized reactions and maintain overall efficiency, involving the hierarchical self-assembly of photosynthetic components and their stabilization through synergistic interactions. However, replicating this level of organization is challenging due to the difficulty in efficiently communicating supramolecular nano-assemblies with nanoparticles or biological architectures, owing to their dynamic instability. Herein, we demonstrate that the supramolecular reconstruction of self-assembled amphiphilic rhodamine B nanospheres (RN) through treatment with metal-phenolic coordination complexes results in the formation of a stable hybrid structure. This reconstructed structure enhances electron transfer efficiency, leading to improved photocatalytic performance. Due to the photoluminescence quenching property of RN and its electronic synergy with tannic acid (T) and zirconium (Z), the supramolecular complexes of hybrid nanospheres (RNTxZy) with Pt nanoparticles or a biological workhorse, Shewanella oneidensis MR-1, showed marked improvement in photocatalytic hydrogen production. The supramolecular hybrid particles with a metal-phenolic coordination layer showed 5.6- and 4.0-fold increases, respectively, in the productivities of hydrogen evolution catalyzed by Pt (Pt/RNTxZy) and MR-1 (M/RNTxZy), respectively. These results highlight the potential for further advancements in the structural and photochemical control of supramolecular nanomaterials for energy harvesting and bio-hybrid systems.

Optimization Study on Nozzle Selection Based on the Influence of Nozzle Parameters on Jet Flow Field Structure

Currently, the primary method for controlling red tides in the ocean involves spraying water solutions with special chemicals as solutes. High-pressure spraying results in the formation of typical jet structures. In this study, numerical simulation methods are employed to investigate the velocity variations, turbulent characteristics, and gas content distribution of jet flow fields under different initial jet flow pressures, cone angles, and nozzle diameters. Based on practical application scenarios, cluster analysis is used to explore the similarities and differences in jet equivalent diameters under different parameter conditions. The research findings indicate the following. (1) The difference of jet velocity distribution at the far field exit will be enlarged with the increase in the nozzle cone angle. When the nozzle cone angle is 4 mm, the velocity uniformity at the outlet is the best. (2) The TKE of the flow field has no consistent change law along the central axis. At the jet exit, the TKE shows an obvious multi-peak structure. (3) The gas content demonstrates a typical “double-valley” feature at the jet outlet cross-section. Increasing the initial pressure leads to a decrease in the gas content within the jet due to reduced entrainment, while the entrainment range remains largely constant. (4) Cluster analysis reveals that the similarity of jet flow width when it reaches the water surface is minimal compared to other operating conditions when the initial pressure is 0.36 MPa, the cone angle is 115°, and the nozzle diameter is 2 mm. All conditions can be categorized into two or three groups to ensure jet effectiveness. The study results provide scientific guidance for selecting spray devices for controlling red tides in the ocean.

Supramolecular Reconstruction of Self‐Assembling Photosensitizers for Enhanced Photocatalytic Hydrogen Evolution

Natural photosynthetic systems require spatiotemporal organization to optimize photosensitized reactions and maintain overall efficiency, involving the hierarchical self‐assembly of photosynthetic components and their stabilization through synergistic interactions. However, replicating this level of organization is challenging due to the difficulty in efficiently communicating supramolecular nano‐assemblies with nanoparticles or biological architectures, owing to their dynamic instability. Herein, we demonstrate that the supramolecular reconstruction of self‐assembled amphiphilic rhodamine B nanospheres (RN) through treatment with metal‐phenolic coordination complexes results in the formation of a stable hybrid structure. This reconstructed structure enhances electron transfer efficiency, leading to improved photocatalytic performance. Due to the photoluminescence quenching property of RN and its electronic synergy with tannic acid (T) and zirconium (Z), the supramolecular complexes of hybrid nanospheres (RNTxZy) with Pt nanoparticles or a biological workhorse, Shewanella oneidensis MR‐1, showed marked improvement in photocatalytic hydrogen production. The supramolecular hybrid particles with a metal‐phenolic coordination layer showed 5.6‐ and 4.0‐fold increases, respectively, in the productivities of hydrogen evolution catalyzed by Pt (Pt/RNTxZy) and MR‐1 (M/RNTxZy), respectively. These results highlight the potential for further advancements in the structural and photochemical control of supramolecular nanomaterials for energy harvesting and bio‐hybrid systems.

Influence of the shock wave-turbulence interaction on the swirl distortion in hypersonic inlet

This study uses the Large Eddy Simulation (LES) technique to conduct an exhaustive analysis of the flow characteristics within the Rectangular-to-Elliptical shape Transition (REST) inlet under Mach 6 conditions. It mainly focuses on investigating the influence of the shock wave-turbulence interaction on the swirl distortion at the inlet exit. At the design condition, characterized by 0° Attack and 0° Sideslip, the incident shock wave at the inlet lip undergoes multiple reflections within the boundary layer of the domain wall, culminating in the formation of turbulent structures. The first reflected shock wave has the highest energy, exerting a significant impact on the boundary layer and the exit swirl distortion. On the contrary, the energy of the incident shock wave is progressively reduced due to repeated reflections, which results in reducing the exit swirl distortion. Under off-design conditions, characterized by 6° Attack and 0° Sideslip as well as 6° Attack with 6° Sideslip, variations in the incoming flow make the incident shock wave move inward, decreasing the frequency of shock wave reflections and even significantly reducing the reflected shock waves under conditions of 6° Attack and 6° Sideslip. However, this results in significantly increasing the exit swirl angle and distortion intensity. The obtained results demonstrate that changes in the incoming flow conditions significantly affect the level of exit swirl distortion by modulating the shock wave-turbulence interaction, especially in terms of the positioning of the incident shock wave and the quantity of reflected shock waves. In addition, this paper studies the wall heat transfer coefficient of the inlet. The obtained results show that the interaction between shock waves and the boundary layer significantly affects the heat transfer coefficient. This study provides a foundation for the comprehension and prediction of the performance of hypersonic inlets across a spectrum of flight conditions, and for the guidance of the design and optimization of such inlets.

Effect of metakaolin and lime addition on geopolymerization of construction and demolition waste.

Construction and demolition waste generates the largest amount of waste by volume, which threatens sustainable development and adversely affects the environment. These wastes contain a significant amount of aluminosilicates that have the potential to be used as building materials for value-added applications applicable to alternative construction materials. This study aims to synthesize geopolymers from brick powder using metakaolin/lime as additives and compare their physico-mechanical properties. The compressive strengths of the geopolymer products GP-1, GP-2, and GP-3 developed at 28days from brick powder and metakaolin/lime with the activator solution were found to be 8.35, 21.30, and 25.0MPa respectively, 2.55 and 2.99 times higher when metakaolin and lime were added. FTIR spectra and SEM-EDX micrographs of the reaction products showed structural changes and formation of aluminosilicate hydrate and calcium silicate hydrate gel with Al2O3/Na2O ratios of 0.75, 1.67, and 1.98 respectively. The reaction products containing SiO2/(SiO2 + Al2O3 + Fe2O3) ratios of 0.70 and 0.76 were found to be desirable. The geopolymer product GP-3 was found to have a higher bulk density and mechanical strength than those of GP-1 and GP-2. These products are found to be very hard, with potential applications in construction industries to conserve the environment.

Hydrogen‐Bonded Cyclic Tetramer Formation of a Pyridylethynylimidazole‐Based Fluorophore

AbstractSupramolecular have promising application prospects owing to their catalytic, self‐healing, and stimulus‐responsive functions. Pyridylethynylimidazole‐based supramolecular synthons with fluorescent properties have been developed. 4‐(2‐Pyridylethynyl)‐5‐arylethynyl‐1H‐imidazole derivatives 1 with different substituents at the 4‐ and 5‐positions of the imidazole skeleton were prepared using a step‐by‐step Sonogashira coupling reaction. The fluorescence maxima of phenyl‐ and methoxyphenyl‐substituted derivatives 1a and 1c were independent of solvent polarity. On the other hand, ester‐ and cyano‐substituted 1b and 1d showed bathochromically shifted fluorescence maxima in highly polar solvents. In crystals, the 4‐(2‐pyridylethynyl)‐5‐arylethynyl‐1H‐imidazole derivatives formed a supramolecular cyclic tetramer structure via two hydrogen bonds: one was between N─H in imidazole and N in pyridine, and the other was between C─H in imidazole and N in imidazole. Introducing the pyridine ring as a hydrogen bond acceptor, in addition to the imidazole ring, promoted the unique cyclic tetramer structure formation.

Porous Metal Phosphonate Frameworks: Construction and Physical Properties.

ConspectusPorous metal phosphonate frameworks (PMPFs) as a subclass of metal-organic frameworks (MOFs) have promising applications in the fields of gas adsorption and separation, ion exchange and storage, catalysis, sensing, etc. Compared to the typical carboxylate-based MOFs, PMPFs exhibit higher thermal and water stability due to the strong coordination ability of the phosphonate ligands. Despite their robust frameworks, PMPFs account for less than 0.51% of the porous MOFs reported so far. This is because metal phosphonates are highly susceptible to the formation of dense layered or pillared-layered structures, and they precipitate easily and are difficult to crystallize. There is a tendency to use phosphonate ligands containing multiple phosphonate groups and large organic spacers to prevent the formation of dense structures and generate open frameworks with permanent porosity. Thus, many PMPFs are composed of chains or clusters of inorganic metal phosphonates interconnected by organic spacers. Using this feature, a wide range of metal ions and organic components can be selected, and their physical properties can be modulated. However, limited by the small number of PMPFs, there are still relatively few studies on the physical properties of PMPFs, some of which merely remain in the description of the phenomena and lack in-depth elaboration of the structure-property relationship. In this Account, we review the strategies for constructing PMPFs and their physical properties, primarily based on our own research. The construction strategies are categorized according to the number (n = 1-4) of phosphonate groups in the ligand. The physical properties include proton conduction, electrical conduction, magnetism, and photoluminescence properties. Proton conductivity of PMPFs can be enhanced by increasing the proton carrier concentration and mobility. The former can be achieved by adding acidic groups such as -POH and/or introducing acidic guests in the hydrophilic channels. The latter can be attained by introducing conjugate acid-base pairs or elevating the temperature. Semiconducting PMPFs, on the other hand, can be obtained by constructing highly conjugated networks of coordination bonds or introducing large conjugated organic linkers π-π stacked in the lattice. In the case of magnetic PMPFs, long-range magnetic ordering occurs at very low temperatures due to very weak magnetic exchange couplings propagated via O-P-O and/or O(P) units. However, lanthanide compounds may be interesting candidates for single-molecule magnets because of the strong single-ion magnetic anisotropy arising from the spin-orbit coupling and large magnetic moments of lanthanide ions. The luminescent properties of PMPFs depend on the metal ions and/or organic ligands. Emissive PMPFs containing lanthanides and/or uranyl ions are promising for sensing and photonic applications. We conclude with an outlook on the opportunities and challenges for the future development of this promising field.

Synthesis of Amorphous Nickel-Cobalt Hydroxides for Ni-Zn Batteries.

In this work we developed a hydrothermal method for synthesizing amorphous Ni-Co hydroxide (NC(OH)) and in the subsequent step crystalline NiCo2O4 (NCO) has been produced using water as the solvent. For nickel-zinc batteries, NC(OH) was found to have superior performance to its NCO prepared by two-step process. The thermal stability analysis exhibited the optimum temperature to obtain the NC(OH), and NCO electrode materials. The XRD pattern showed mixed phases containing both Ni and Co hydroxides (during the initial step) and in the subsequent step (calcined) the formation of cubic spinel structure was noticed. For NC(OH), aggregated particles with irregular morphology were observed while clustered nanorod-like shapes were noticed for NCO samples. To be noted, that the nanorod morphology was obtained through a facile approach without employing any structure-directing agent. Both NC(OH) and NCO were employed as cathodes for Ni-Zn battery studies against Zn foil anode with a polyamide-based separator soaked in 6 M KOH saturated with ZnO additive was used as electrolyte. The Ni-Zn cell was fabricated in CR2032 coin cell configuration. The electrochemical studies such as cyclic voltammetry (CV) showed the characteristic redox peaks for NC(OH) sample exhibiting high peak current compared to its NCO counterpart. The NC(OH) had a capacity of 268 mAh g-1 against 120 mAh g-1 for NCO at a current density of 1 Ag-1. The cell was able to retain 85 % of the capacity at the end of 500 cycles and showed remarkable rate capability. The Ni-Zn battery presents energy and power densities of 428.8 Wh Kg-1 and 2.68 kW Kg-1, respectively surpassing the normal values reported for aqueous rechargeable batteries. Owing to the presence of Ni and Co in hydroxide form (reduced crystallinity) the NC(OH) sample showed improved electrochemical activity. This work provides a facile approach and effective strategy for developing bimetallic hydroxides for optimal energy storage performance.

Photocatalytic Tricyclization of Enediynes for the Synthesis of Chromenoquinolines in Continuous Flow.

A photocatalyzed radical-initiated tricyclization of enediynes was developed to synthesize a range of hitherto unknown sulfonated chromenoquinolines with moderate to excellent yields under continuous operational conditions. The reaction mechanism involves a complex series of steps including alkyl radical capture by sulfur dioxide (SO2), radical addition, 6-exo-dig/6-exo-dig/6-endo-trig tricyclization, and single electron transfer (SET). This cascade of reactions results in the direct formation of a pentacyclic framework structure, along with the creation of up to three new rings and five chemical bonds in a single step. This photocatalytic protocol exhibits a diverse substrate scope, remarkable tolerance to functional groups, and scalable adaptability.

Hypoxia-Induced Inflammation in In Vitro Model of Human Blood-Brain Barrier: Modulatory Effects of the Olfactory Ensheathing Cell-Conditioned Medium.

Hypoxia compromises the integrity of the blood-brain barrier (BBB) and increases its permeability, thereby inducing inflammation. Olfactory ensheathing cells (OECs) garnered considerable interest due to their neuroregenerative and anti-inflammatory properties. Here, we aimed to investigate the potential modulatory effects of OEC-conditioned medium (OEC-CM) on the response of human brain microvascular endothelial cells (HBMECs), constituting the BBB, when exposed to hypoxia. HBMECs were utilized to establish the in vitro BBB model. OECs were isolated from mouse olfactory bulbs, and OEC-CM was collected after 48h of culture. The effect of OEC-CM treatment on the HBMEC viability was evaluated under both normoxic and hypoxic conditions at 6h, 24h, and 30h. Western blot and immunostaining techniques were employed to assess NF-κB/phospho-NF-κB expression. HIF-1α, VEGF-A, and cPLA2 mRNA expression levels were quantified using digital PCR. ELISA assays were performed to measure PGE2, VEGF-A, IL-8 secretion, and cPLA2 specific activity. The in vitro formation of HBMEC capillary-like structures was examined using a three-dimensional matrix system. OEC-CM attenuated pro-inflammatory responses and mitigated the HIF-1α/VEGFA signaling pathway activation in HBMECs under hypoxic condition. Hypoxia-induced damage of the BBB can be mitigated by novel therapeutic strategies harnessing OEC potential.

Flame Front Model with the Clusters Condensation

The processes model in a flame during the n-alkanes air mixture combustion initiation is proposed, taking into account the supramolecular structures formation possibility in the peroxide clusters form. This approach is justified by the n-alkanes melting temperatures correlation with their autoignition temperatures and anti-knock indexes. The condensation possibility is provided for such high molecular structures. Boiling temperatures values at flame front pressures characteristic were evaluated. To predict the peroxide clusters melting temperatures, a formula developed earlier for the hydrocarbons condensed state was used, which takes into account the length and molecular weight of modeled clusters. Expected peroxide clusters melting temperatures were predicted for conditions of dimeric and tetrameric structures. A linear dependence was used to recalculation the obtained values in boiling temperatures. It is shown that the calculated clusters phase transitions characteristic temperatures can be realized in the flame front preparatory zone. Based on the condensation theory, the flame front thickness and the minimum non-extinguishing sphere radius during ignition were estimated: the obtained data closely coincide with these parameters known values.

Wax crystal dynamics and viscosity abnormal reduction in asphaltene-containing waxy oil at low temperatures

A micro-rheological integration experiment was conducted on model oils without asphaltene and with 0.05 wt% asphaltene. The study examined the viscosity-temperature characteristics of both model oils under different cooling rates and shear rates. Significant changes were observed in the viscosity-temperature curve of the asphaltene-containing model oil. At low shear rates, a distinct wavelet peak was identified in the temperature range of 37-30 °C, where viscosity initially increased, then decreased, and subsequently increased again. This wavelet peak diminished with the increasing shear rate, eventually forming a “buffer platform”. The underlying mechanism was attributed to asphaltene altering the wax crystal behavior from “uniform precipitation network structure formation” to “formation of unstable large aggregates - dissociation into multiple small stable aggregates - growth into larger stable aggregates.” In addition, the wax precipitation rate remained constant in the model oil without asphaltene, while in the asphaltene-containing model oil, the rate significantly accelerated between 34.5 °C and 32.5 °C. And the asphaltenes promoted the formation of small wax crystal particles but inhibited the growth of wax crystal particles.

Low temperature powder bed fusion of polyamide 6: transient process characteristics and process-dependent part properties

AbstractThe powder-based additive manufacturing of high-melting polyamides is impeded by unfavorable fracture properties and oxidation tendencies, limiting the technical applicability and the reuse of unfused powder. Overcoming these limitations through new processing strategies provides the opportunity for significantly extending the range of materials applicable for powder bed fusion processes. Based on fractal, locally quasi-simultaneous exposure strategies, a mesoscale compensation of thermal and crystallization-induced shrinkage is obtained, enabling the non-isothermal processing and stable layer formation of polyamide 6 at powder bed temperatures of 25 °C, 50 °C, and 75 °C. Thermographic in situ investigations reveal the layerwise quenching of discrete layers, leading to cooling rates exceeding − 250 K s−1 at 130 °C. Based on microscopic, mechanical, thermal, and spectroscopic investigations, insights into the structure formation and corresponding mechanical properties can be obtained, yielding reduced fractions of α-PA6 while increasing the elongation at break. The inherent layerwise quenching promotes the formation of microspherulitic morphologies while minimizing oxidation-induced material degradation, reflected in infrared spectroscopic material characteristics. Relying on obtained findings, process optimization strategies can be derived that enable the processability of high-melting polyamides at reduced temperatures, reducing the energy consumption of the build process while adapting underlying material characteristics based on accelerated intermediate cooling conditions.

An updated method for identifying the formative factors in soil structure

AbstractSoil structure is a standard component of pedon descriptions collected to characterize the nature and function of soils as a natural body. Soil structure is an important indicator of soil development and a predictor of water, air, and root movement throughout the profile. However, inconsistencies exist within the current standardized methodologies used to describe soil structure in the field, making soil structure data difficult to use and often confusing to students encountering these concepts for the first time. Therefore, we propose an updated method of soil structure description to add an interpretive component that clearly distinguishes geogenic, pedogenic, and human‐induced structures. This method employs terminology that communicates both observable morphology and the mechanism of formation. The updated method herein differentiates three classes of structure: (a) geogenic structural formation (GS), (b) natural pedological structural formation (current nomenclature), and (c) significant human‐induced structure changes from natural pedological structure. This updated approach improves the documentation of scientifically relevant soil morphology and communicates the processes involved in the formation of all forms of soil structure. As a result, this change eases description challenges around soil structure and interpretations common in soil science classes, including soil judging.

Reactions of Tetracyanoethylene with Aliphatic and Aromatic Amines and Hydrazines and Chemical Transformations of Tetracyanoethylene Derivatives

The significant synthetic potential and reactivity of tetracyanoethylene (TCNE) have captured the interest of numerous chemical communities. One of the most promising, readily achievable, yet least explored pathways for the reactivity of TCNE involves its interaction with arylamines. Typically, the reaction proceeds via tricyanovinylation (TCV); however, deviations from the standard chemical process have been observed in some instances. These include the formation of heterocyclic structures through tricyanovinyl intermediates, aliphatic dicarbonitriles through the cleavage of the C–C bond of a tetracyanoethyl substituent, complexation, and various pericyclic reactions. Therefore, the objective of this study is to review the diverse modes of interaction of TCNE with aromatic nitrogen-containing compounds and to focus the attention of the chemical community on the synthetic capabilities of this reagent, as well as the various biological and optical activities of the structures synthesized based on TCNE.

Ligand-Induced Folding in a Dopamine-Binding DNA Aptamer.

Aptamers are often employed as molecular recognition elements in the development of different types of biosensors. Many of these biosensors take advantage of the aptamer having a ligand-induced structure-formation binding mechanism. However, this binding mechanism is poorly understood. Here we use isothermal titration calorimetry, circular dichroism spectroscopy and NMR spectroscopy to study the binding and ligand-induced structural change exhibited by a dopamine-binding DNA aptamer. We analysed a series of aptamers where we shorten the terminal stem that contains the 5´and 3´termini of the aptamer sequence. All aptamers bind dopamine in an enthalpically driven process coupled with an unfavorable entropy. A general trend of the aptamer having a weaker binding affinity is observed as the terminal stem is shortened. For all aptamers studied, numerous signals appear in the imino region of the1H NMR spectrum indicating that new structure forms with ligand binding. However, it is only when this region of structure formation in the aptamer is brought close to the sensor surface that we obtain a functional electrochemical aptamer-based biosensor.