Changes In Molecular Volume Research Articles

DFT study of lithium adsorption on silicon quantum dots for battery applications

Understanding lithium (Li) adsorption in silicon quantum dots (SiQDs) is crucial for optimizing Li-ion battery (LIB) anode materials. We systematically investigated Li adsorption in ten hydrogenated SiQDs (Si10H16, Si14H20, Si18H24, Si22H28, Si26H30, Si30H34, Si35H36, Si39H40, Si44H42, and Si48H46) across five adsorption sites (bridge(B), on-top(T), hollow-tetrahedral inner(Tdinner), hollow-tetrahedral surface(Tdsurface), and hollow-hexagonal(Hex)), utilizing density functional theory (DFT) with the M06–2X hybrid functional and 6-31G+(d) basis set. Findings identify Tdinner as the most favorable adsorption site, with a binding energy (Ebind) of 0.80–1.00 eV, dependent on SiQD size. The adsorption site exerts a more pronounced impact on Ebind than the cluster size. Multiple adsorptions in SiQDs show increased Ebind per Li atom with Li atom number. Molecular volume changes, independent of Li atom number but site-dependent, exhibit a maximum of 2.51 %. SiQD energy gap, influencing conductivity, varies with size, larger SiQDs being more conductive, especially with Li adsorption. Conclusively, our study recommends large-sized SiQDs as optimal LIB anode materials, offering high capacity, minimal volume expansion, and reasonable conductivity. This research addresses a theoretical gap, illuminating the impact of Li adsorption on SiQD molecular volumes and electronic structures, aiding in the design of enhanced capacity silicon anodes for LIB.

Biomimetic Sequence-Templating Approach toward a Multiscale Modulation of Chromogenic Polymer Properties.

Precision control via molecular structure over adaptive conjugated polymer properties in aqueous environments is critical for realizing their biomedical applications. Here, we unravel the dependence of amphiphilic peptide-polydiacetylene (PDA) conjugate properties on the characteristic steric and hydrophobic contributions within peptide segments that serve as a biomimetic template for diacetylene polymerization in water. We investigated the functional impacts of molecular volume and polarity changes brought by dipeptide substitution domains on the following peptide-PDA material properties at multiple length scales: supramolecular assembly behavior, chain conformation-dependent photophysical properties, cell-material interfacing, and for the first time, bulk electrical properties of their films processed in water. A library of peptide-PDAs with systematically varied sequences show that the contributions of steric effects predominantly influence the electronic structure and resulting trends in photophysical properties, while the interplay between size and hydrophobicity of individual residues becomes more significant for higher-order assemblies affecting bulk properties. This work demonstrates sequence-tunable molecular volume and polarity as synthetic handles to rationally modulate PDA material properties across length scales, providing insights into the programmability of biomimetic conjugated polymers with adaptive functionalities.

A molecular rotor FLIM probe reveals dynamic coupling between mitochondrial inner membrane fluidity and cellular respiration

The inner mitochondrial membrane (IMM), housing components of the electron transport chain (ETC), is the site for respiration. The ETC relies on mobile carriers; therefore, it has long been argued that the fluidity of the densely packed IMM can potentially influence ETC flux and cell physiology. However, it is unclear if cells temporally modulate IMM fluidity upon metabolic or other stimulation. Using a photostable, red-shifted, cell-permeable molecular-rotor, Mitorotor-1, we present a multiplexed approach for quantitatively mapping IMM fluidity in living cells. This reveals IMM fluidity to be linked to cellular-respiration and responsive to stimuli. Multiple approaches combining invitro experiments and live-cell fluorescence (FLIM) lifetime imaging microscopy (FLIM) show Mitorotor-1 to robustly report IMM 'microviscosity'/fluidity through changes in molecular free volume. Interestingly, external osmotic stimuli cause controlled swelling/compaction of mitochondria, thereby revealing a graded Mitorotor-1 response to IMM microviscosity. Lateral diffusion measurements of IMM correlate with microviscosity reported via Mitorotor-1 FLIM-lifetime, showing convergence of independent approaches for measuring IMM local-order. Mitorotor-1 FLIM reveals mitochondrial heterogeneity in IMM fluidity; between-and-within cells and across single mitochondrion. Multiplexed FLIM lifetime imaging of Mitorotor-1 and NADH autofluorescence reveals that IMM fluidity positively correlates with respiration, across individual cells. Remarkably, we find that stimulating respiration, through nutrient deprivation or chemically, also leads to increase in IMM fluidity. These data suggest that modulating IMM fluidity supports enhanced respiratory flux. Our study presents a robust method for measuring IMM fluidity and suggests a dynamic regulatory paradigm of modulating IMM local order on changing metabolic demand.

G-quadruplex-hemin DNAzyme functionalized nanopipettes: Fabrication and sensing application

Solid-nanopores/nanopipettes have the exquisite ability to reveal the changes in molecular volume due to the advantages of adjustable size, good rigidity and low noise. Herein, a new platform for sensing application was established based on G-quadruplex-hemin DNAzyme (GQH) functionalized gold-coated nanopipettes. In this method, GQH was immobilized on gold-coated nanopipette, which could be used as a catalyst for the reaction of H2O2 with 2,2′-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS) to promote the conversion of ABTS to ABTS+ ions inside gold-coated nanopipette, and the change of transmembrane ion current could be monitored in real time. At the optimal conditions, there was a correlation between the ion current and the concentration of H2O2 in a certain range, which could be used for the hydrogen peroxide sensing. The GQH immobilized nanopipette provides a useful platform to investigate enzymatic catalysis in confined environment, which can be used in electrocatalysis, sensing and fundamental electrochemistry.

Placing CF2 in the Center: Major Physicochemical Changes Upon a Minor Structural Alteration in Gem-Difunctional Compounds.

Fluorine atoms play an important role in all branches of chemistry and accordingly, it is very important to study their unique and varied effects systematically, in particular, the structure-physicochemical properties relationship. The present study describes exceptional physicochemical effects resulting from a H/F exchange at the methylene bridge of gem-difunctional compounds. The Δlog P(CF2-CH2) values, that is, the change in lipophilicity, observed for the CH2 /CF2 replacement in various α,α-phenoxy- and thiophenoxy-esters/amides, diketones, benzodioxoles and more, fall in the range of 0.6-1.4 units, which for most cases, is far above the values expected for such a replacement. Moreover, for compounds holding more than one such gem-difunctional moiety, the effect is nearly additive, so one can switch from a hydrophilic compound to a lipophilic one in a limited number of H/F exchanges. DFT studies of some of these systems revealed that polarity, conformational preference as well as charge distributions are strongly affected by such hydrogen to fluorine atom substitution. The pronounced effects described, are a result of the interplay between changes in polarity, H-bond basicity and molecular volume, which were obtained with a very low 'cost' in terms of molecular weight or steric effects and may have a great potential for implementation in various fields of chemical sciences.

Theoretical investigation of entropic barocaloric effect in spin-crossover systems

We report a theoretical investigation of the entropic barocaloric effect in a spin crossover system. From our model Hamiltonian, the total entropy, which includes the contributions from the lattice (vibrational), magnetic and configurational entropies, was obtained and worked out for a systematic study of the barocaloric effect. The barocaloric effect was parametrically investigated in three scenarios: second order, threshold of second-first order and first order phase transition. Besides, a procedure for obtaining the molecular volume change during the low spin to high spin phase transition conversion was proposed, through the entropic barocaloric measurements.

Molecular and Brain Volume Changes Following Aerobic Exercise, Cognitive and Combined Training in Physically Inactive Healthy Late-Middle-Aged Adults: The Projecte Moviment Randomized Controlled Trial.

Behavioral interventions have shown promising neuroprotective effects, but the cascade of molecular, brain and behavioral changes involved in these benefits remains poorly understood. Projecte Moviment is a 12-week (5 days per week—45 min per day) multi-domain, single-blind, proof-of-concept randomized controlled trial examining the cognitive effect and underlying mechanisms of an aerobic exercise (AE), computerized cognitive training (CCT) and a combined (COMB) groups compared to a waitlist control group. Adherence was > 80% for 82/109 participants recruited (62% female; age = 58.38 ± 5.47). In this study we report intervention-related changes in plasma biomarkers (BDNF, TNF-α, HGF, ICAM-1, SDF1-α) and structural-MRI (brain volume) and how they related to changes in physical activity and individual variables (age and sex) and their potential role as mediators in the cognitive changes. Our results show that although there were no significant changes in molecular biomarker concentrations in any intervention group, changes in ICAM-1 and SDF1-α were negatively associated with changes in physical activity outcomes in AE and COMB groups. Brain volume changes were found in the CCT showing a significant increase in precuneus volume. Sex moderated the brain volume change in the AE and COMB groups, suggesting that men may benefit more than women. Changes in molecular biomarkers and brain volumes did not significantly mediate the cognitive-related benefits found previously for any group. This study shows crucial initial molecular and brain volume changes related to lifestyle interventions at early stages and highlights the value of examining activity parameters, individual difference characteristics and using a multi-level analysis approach to address these questions.

18F]-Fluorodeoxyglucose Positron Emission Tomography/CT to Assess the Early Metabolic Response in Patients with Hormone Receptor-Positive HER2-Negative Metastasized Breast Cancer Treated with Cyclin-Dependent 4/6 Kinase Inhibitors

Introduction: Addition of cyclin-dependent 4/6 kinase (CDK4/6) inhibitors to endocrine therapy is standard of care in the treatment of women with advanced hormone receptor-positive HER2-negative breast cancer. However, the predictive factors for the treatment response to CDK4/6 inhibitor therapy are poorly elucidated. Early changes in the by [¹⁸F]-fluorodeoxyglucose positron emission tomography (FDG-PET) uptake of tumors receiving different kinds of therapy have proven to reliably predict treatment outcomes in a variety of malignancies. Therefore, the feasibility of early metabolic response assessment to predict the long-term treatment response to CDK4/6 inhibitor therapy was evaluated in the present study. Methods: Eight patients underwent FDG-PET/CT before and after the initiation of CDK4/6 inhibitor therapy (ribociclib, palbociclib or abemcaciclib). CDK4/6 inhibitor therapy was combined with either aromatase inhibition or fulvestrant. The median interval between the treatment start (including baseline PET) and the follow-up PET examination was 14 days. Conventional radiographic staging was performed 3 months after the start of CDK4/6 inhibitor therapy. The percentual changes in molecular tumor volume, SUV_peak, the summed SUV_peak of up to 5 metastases (PERCIST-5), and total lesion glycolysis (TLG) were calculated for each patient. Results: Three patients showed progressive disease after 3 months of CDK4/6 inhibitor therapy, whereas 5 patients showed disease control (3 stable disease and 2 partial remission). Disease control was maintained in these patients (follow-up range 7–22 months). Patients with disease control had a significantly greater decline in TLG (–55.3 vs. 16.7%; p < 0.05). The same was true for the PERCIST-5 (–21.9 vs. 11.3%, p < 0.05). All patients with progressive TLG showed treatment failure and/or a poor outcome. Conclusion: Elevated TLG on early FDG-PET seems to be associated with long-term treatment failure and a poor outcome in patients undergoing CDK4/6 inhibitor therapy for metastatic breast cancer. Early findings indicate a potential prognostic value of early FDG-PET in this setting and warrant a prospective evaluation.

Structural insights revealed by two novel THRB mutations.

Among the inheritable forms of impaired sensitivity to thyroid hormone, resistance to thyroid hormone (RTH) due to mutations in the thyroid hormone receptor beta gene (THRB) is the first and best known described defect, revealing a wide phenotypic variability with an incompletely understood physiopathology. The objective of this study was to evaluate two novel mutations in THRB, N331H and L346R, in an attempt to provide a rational understanding of the harmful effects caused by them. The mutations of two patients with RTHβ were reproduced for analysis of gene transactivation by dual-luciferase reporter assay, and for molecular modeling for crystallography-based structural assessment. Serum measurements of TSH and FT4 were performed to compare the thyrotrophic resistance to thyroid hormone between RTHβ patients and controls. Both mutants showed impaired gene transactivation, with greater damage in L346R. Molecular modeling suggested that the damage occurring in N331H is primarily due to reduced strength of the hydrogen bonds that stabilize T3 in its ligand-binding cavity (LBC), whereas in L346R, the damage is more marked and is mainly due to changes in hydrophobicity and molecular volume inside the LBC. Hormonal dosages indicated that the L346R mutant exhibited greater thyrotrophic resistance than N331H. This study provides a rational understanding of the effects of mutations, indicating deleterious structural changes in the LBC in both THR, and discloses that not only the position of the mutation but, notably, the nature of the amino acid exchange, has a cardinal role in the functional damage of the receptor.

First indirect experimental evidence and theoretical discussion of giant refrigeration capacity through the reversible pressure induced spin-crossover phase transition

We report on the giant barocaloric effect and refrigerant capacity in the [Fe(pzt)6](PF6)2 (pzt = 1-propyltetrazole) spin-crossover material. The refrigerant capacity in [Fe(pzt)6](PF6)2 is RC = 1380 J kg−1, 5 times higher than the big value reported in (NH4)2SO4, upon pressure variation ΔP = 1 kbar. This huge caloric effect is ascribed to the coupling interactions between the crystal lattice (phonons) and the order parameter (γHS) that describes the molar fraction of high spin molecules (Fe+2N6)-(t2g4eg2) in [Fe(pzt)6](PF6)2. Our theoretical entropy includes the lattice, electronic and configurational coupled-contributions and was obtained from a microscopic model. A new methodology to obtain the barocaloric effect potentials is presented using a proper thermodynamic Maxwell relation for spin-crossover systems. The experimental results, for the isothermal entropy change, were calculated from the pressure dependence of γHS data. Besides, the determination of molecular volume change between high and low spin states through caloric measurements was discussed.

Evaluation of molecular volume change of block copolymer depending on temperature: A SANS study

Amphiphilic Pluronic triblock copolymers form various self-assembled structures such as sphere, cylinder, lamellae and so on, depending on temperature, leading to the increase of hydrophobicity of block copolymers. However, the effective molecular volume change of the block copolymer has not been fully exploited yet, when temperature increases. Here, we have investigated the effective molecular volume change of the block copolymer upon heating by using the contrast variation small angle neutron scattering. The scattering length densities (SLDs) of the block copolymer were experimentally obtained from the neutron scattering contrast variation method between the solvent and the block copolymer at varying temperature. Even though the SLD, which is the intrinsic property of the material, should not be changed by temperature elevation, it was dependent on temperature, indicating that the molecular volume is changed. Therefore, we obtained the increase rate of the molecular volume change of the block copolymer (the effective molecular volume change) from the comparison of the calculated SLD and the standard SLD, which is evaluated by plotting the SANS intensity at the first order Bragg peak as the function of temperature at each volume fraction of D2O and H2O that is about 25.5%–51.3% depending on temperature.

Asymmetric Nanochannel-Ionchannel Hybrid for Ultrasensitive and Label-Free Detection of Copper Ions in Blood.

Nanochannel/nanopre based analysis methods have attracted increasing interest in recent years due to their exquisite ability to reveal changes in molecular volume. In this work, a highly asymmetric nanochannel-ionchannel hybrid coupled with an electrochemical technique was developed for copper ion (Cu2+) detection. Polyglutamic acid (PGA) was modified in a nanochannel array of porous anodic alumina (PAA). When different concentrations of Cu2+ were introduced into the nanochannel-ionchannel hybrid in a neutral environment, a Cu2+-PGA chelation reaction occurs, resulting in varied current-potential (I-V) properties of the nanochannel-ionchannel hybrid. When PAA was immersed in a low pH solution, the Cu2+-PGA complex dissociated. On the basis of the change in ionic current, a label-free assay for Cu2+ was achieved along with the ability to regenerate and reuse the constructed platform. Because of the unique mass transfer property of the nanochannel-ionchannel hybrid combined with the highly amplified ionic current magnitude of the nanochannel array, significantly increased assay sensitivity was achieved, as expected. To evaluate the applicability of the present methodology for detecting Cu2+ in a real sample, the Cu2+ content in real blood samples was analyzed. The results demonstrate that the present method shows excellent selectivity with high sensitivity toward Cu2+ detection in real blood samples.

Correction to "Photocycle of Photoactive Yellow Protein in Cell-Mimetic Environments: Molecular Volume Changes and Kinetics".

ADVERTISEMENT RETURN TO ISSUEPREVAddition/CorrectionNEXTORIGINAL ARTICLEThis notice is a correctionCorrection to “Photocycle of Photoactive Yellow Protein in Cell-Mimetic Environments: Molecular Volume Changes and Kinetics”Cheolhee Yang, Seong Ok Kim, Yonggwan Kim, So Ri Yun, Jungkweon Choi*, and Hyotcherl Ihee*Cite this: J. Phys. Chem. B 2017, 121, 21, 5461Publication Date (Web):May 17, 2017Publication History Published online17 May 2017Published inissue 1 June 2017https://doi.org/10.1021/acs.jpcb.7b04090Copyright © 2017 American Chemical SocietyRIGHTS & PERMISSIONSArticle Views305Altmetric-Citations-LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (134 KB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

Photocycle of Photoactive Yellow Protein in Cell-Mimetic Environments: Molecular Volume Changes and Kinetics.

Using various spectroscopic techniques such as UV-visible spectroscopy, circular dichroism spectroscopy, NMR spectroscopy, small-angle X-ray scattering, transient grating, and transient absorption techniques, we investigated how cell-mimetic environments made by crowding influence the photocycle of photoactive yellow protein (PYP) in terms of the molecular volume change and kinetics. Upon addition of molecular crowding agents, the ratio of the diffusion coefficient of the blue-shifted intermediate (pB) to that of the ground species (pG) significantly changes from 0.92 and approaches 1.0. This result indicates that the molecular volume change accompanied by the photocycle of PYP in molecularly crowded environments is much smaller than that which occurs in vitro and that the pB intermediate under crowded environments favors a compact conformation due to the excluded volume effect. The kinetics of the photocycle of PYP in cell-mimetic environments is greatly decelerated by the dehydration, owing to the interaction between the protein and small crowding agents, but is barely affected by the excluded volume effect. The results lead to the inference that the signaling transducer of PYP may not necessarily utilize the conformational change of PYP to sense the signaling state.

Wetting-induced layer contraction in illite and mica-family relatives

When dry illite is wetted, its layer structure contracts along the c-axis by up to 0.2Å. This behavior contrasts with that of smectite which shows interlayer swelling on wetting. Layer contraction has also been found to occur in glauconite and celadonite that are structurally more disordered than illite, as well as with phengite and artificially degraded hydromuscovite. In contrast, muscovite proper does not show contraction. The contraction is ascribed to the deprotonation of hydronium ions (H3O+→H2O+H+) occupying interlayer K+ positions. The hydronium ion is approximately 5% larger than the neutral water molecule. This difference in size is proportional to the magnitude of contraction. The change in molecular volume and interlayer separation of illite particles may explain the anomalous decrease in density after dehydration under pressure. This paper reports on wetting-induced contraction in illite and related layer silicates, using humidity-controlled X-ray diffraction.

Performance analysis of pure paraffin wax as RFID tag substrate

AbstractThe article presents an investigation of the performance of the Paraplast, a kind of pure paraffin wax, used as a substrate of RFID tag antennas operating at UHF RFID band. To achieve this purpose, two similar RFID tag antennas with same dimensions have been simulated, fabricated and tested. These include a simple dipole tag on a Rogers RT/Duroid 5880 substrate and on pure paraffin substrate. Because of the relatively close dielectric constant values, paraffin substrate is compared with Duroid RT5880. Paraffin wax can be considered as a low cost and low loss substrate. The main purpose in the future will be using paraffin as a passive temperature sensor, by exploiting the changes in molecular structure, volume and dielectric properties with temperature, especially near its melting point. © 2011 Wiley Periodicals, Inc. Microwave Opt Technol Lett 54:442–446, 2012; View this article online at wileyonlinelibrary.com. DOI 10.1002/mop.26592

Absorption, Fluorescence and Resonance Rayleigh Scattering Spectra of Interaction of Papain with Calf Thymus DNA

In weak acidic medium, interaction between papain and calf thymus DNA (ctDNA) resulted in absorption spectral change, fluorescence quenching of papain and remarkable enhancement of resonance Rayleigh scattering (RRS). The interaction types and binding modes were discussed by characteristics of RRS, absorption, fluorescence and circular dichroism spectra combining thermodynamic data. Four interaction types include electrostatic attraction, hydrophobic force, hydrogen bonding and aromatic stacking interaction. Papain interacted with the major groove of ctDNA. Aromatic stacking interaction is the main reason of change of absorption spectrum and fluorescence quenching of papain. Surface enhanced scattering effect, resonance energy transfer effect, increase of molecular volume and conformational change make contribution to RRS enhancement. The enhanced RRS intensity (ΔI) is directly proportional to the concentration of ctDNA or papain. The detection limit (3σ) is 5.2 ng·mL−1 for ctDNA and 5.6 ng·mL−1 for papain. This creates conditions for determination of papain and ctDNA.

660 Discovery of a novel series of indoleamine 2,3-dioxygenase 2 (IDO2) selective inhibitors for probing IDO2 function in cancer

Binding of nucleic acid aptamers to specific targets and detection with fluorescence anisotropy (FA) or fluorescence polarization (FP) take advantage of the complementary features of aptamers and the fluorescence techniques. We review recent advances in affinity binding assays using aptamers and FA/FP, with an emphasis on studies of molecular interactions and identification of binding sites. Aptamers provide several benefits, including the ease of labelling fluorophores on specific sites, binding-induced changes in aptamer structures, hybridization of the aptamers to complementary sequences, changes in molecular volume upon binding of the aptamer to its target, and adsorption of aptamers onto nanomaterials. Some of these benefits have been utilized for FA/FP assays. Once the aptamer binds to its target, the resulting changes in molecular volume (size), structure, local rotation of the fluorophore, and/or the fluorescence lifetime influence changes to the FA/FP values. Measurements of these fluorescence anisotropy/polarization changes have provided insights into the molecular interactions, such as the binding affinity and the site of binding. Studies of molecular interactions conducted in homogeneous solutions, as well as those with separations, e.g., capillary electrophoresis, have been summarized in this review. Studies on mapping the position of binding in aptamers at the single nucleotide level have demonstrated a unique benefit of the FA/FP techniques and pointed to an exciting direction for future research.

Methodology of Pulsed Photoacoustics and Its Application to Probe Photosystems and Receptors

We review recent advances in the methodology of pulsed time-resolved photoacoustics and its application to studies of photosynthetic reaction centers and membrane receptors such as the G protein-coupled receptor rhodopsin. The experimental parameters accessible to photoacoustics include molecular volume change and photoreaction enthalpy change. Light-driven volume change secondary to protein conformational changes or electrostriction is directly related to the photoreaction and thus can be a useful measurement of activity and function. The enthalpy changes of the photochemical reactions observed can be measured directly by photoacoustics. With the measurement of enthalpy change, the reaction entropy can also be calculated when free energy is known. Dissecting the free energy of a photoreaction into enthalpic and entropic components may provide critical information about photoactivation mechanisms of photosystems and photoreceptors. The potential limitations and future applications of time-resolved photoacoustics are also discussed.

High-Pressure SANS and NSE Experiments in Microemulsion Systems

Small-angle neutron scattering (SANS) and neutron spin echo (NSE) spectroscopy have been used to elucidate static and dynamic structures of a microemulsion system composed of a nonionic surfactant, water, and oil. Using the contrast variation neutron scattering technique, static structure parameters are evaluated, and the molecular volume change with pressure is calculated. The bending elastic modulus increases with increasing pressure. This tendency is similar to the microemulsion system composed of anionic surfactant, water, and oil. Therefore, a universal feature of the surfactant membrane as a response to pressure is clarified, that is, the surfactant membrane becomes rigid at high pressure due to the increase of density of the hydrophobic tail of surfactant molecules and their aggregates.