ACS Publications最新文献

{"title":"Mental Healthcare Providers Understanding and Experiences of Palliative Care: A Qualitative Analysis.","authors":"Tanya Park, Lydia Mutoni, Ramya Sridhar, Kathy Hegadoren, Bernadette Workun","doi":"10.1177/08258597221134865","DOIUrl":"10.1177/08258597221134865","url":null,"abstract":"<p><p><b>Objective:</b> To understand the experiences and perceptions of mental health providers about palliative care. <b>Background:</b> Little attention is paid to the experience of people with chronic persistent mental illness (CPMI) and life-threatening diseases and how their dying experience might differ from those without a CPMI. <b>Methods:</b> Interpretive description informed the project. Sixteen mental health care providers were interviewed using a semi-structured interview template. The interviews were recorded, transcribed, and analyzed using a reflexive, inductive-deductive thematic approach, guided by Braun & Clarke's framework for thematic analysis. <b>Results:</b> Four themes were identified from the data: intersectionality, limited collaboration, misconceptions about palliative care, and relationships. Mental health providers identified gaps in their knowledge of palliative care practices along with their knowledge of death and dying.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":"322-328"},"PeriodicalIF":17.7,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12318162/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"40562849","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"CYCLO70: A New Challenging Pericyclic Benchmarking Set for Kinetics and Thermochemistry Evaluation.","authors":"Javier E Alfonso-Ramos, Carlo Adamo, Éric Brémond, Thijs Stuyver","doi":"10.1021/acs.jctc.5c00925","DOIUrl":"https://doi.org/10.1021/acs.jctc.5c00925","url":null,"abstract":"<p><p>Here, a new challenging benchmarking data set for cycloaddition reactions, CYCLO70, is presented and analyzed. CYCLO70 has been generated with the specific aim of being representative of the most challenging regions of the chemical reaction space surrounding Diels-Alder, dipolar cycloadditions, and (sigmatropic) rearrangement reactions with the help of an active learning approach. Testing 93 different functionals, spanning from spin-local density approximation to the most recent double-hybrid functionals, we observe that the errors on CYCLO70 are significantly bigger than those on the cycloaddition subset of BH9, the most popular benchmarking data set for this reaction class. Furthermore, we observe that the range-separated hybrid ωB97M-V is the best performing functional to model barrier heights and reaction energies, with a deviation closest to the desirable \"chemical accuracy\"; among the double hybrids, PBE-QIDH performs best, and among the fixed-range hybrids, M06-2X and r²SCAN0 emerge as the most balanced in terms of simultaneously reproducing both properties. Next, we perform a principal component analysis on the errors across the data set and demonstrate not only that the errors across different functional approximations correlate to a significant extent (the first two components explain 98% of the variance), but we also observe that functionals belonging to the same rung of Jacob's ladder cluster together in the constructed two-dimensional plot. These results were further validated on a set of Diels-Alder reactions relevant to self-healing polymer design, reinforcing the practical relevance of CYCLO70.</p>","PeriodicalId":45,"journal":{"name":"Journal of Chemical Theory and Computation","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145032326","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Periodic Feature Characterization in Nanostructured Surfaces and Emulsions.","authors":"André Guerra, Ziheng Wang, Samuel Mathews, Alejandro D Rey, Kevin De France","doi":"10.1021/acs.langmuir.5c02320","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c02320","url":null,"abstract":"<p><p>Understanding structure-function relationships is essential to advance the manufacturing of next-generation materials with desired properties and functionalities. Precise and rapid measurement of features like wrinkle size, droplet diameter, and surface roughness is essential to establishing such structure-function relationships. To this end, this work developed feature size and surface morphology characterizations through image analysis in Python and validated them with both synthetic and experimental images. Manual measurements of biobased surfaces resulted in errors between 3.3% (<i>N</i> = 50; visually simple) and 51.2% (<i>N</i> = 100; visually complex) compared to the results of Python analysis. This analysis was also used to accurately distinguish multiple feature size populations in a given image (which were missed entirely in manual measurements) and to determine the skewness and kurtosis of biological surfaces in a surface roughness map. This work contributes to the larger goal of developing a robust and computationally cheap platform to analyze complex materials to accelerate structure-function discovery.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":" ","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145032415","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Modulation of Nanoscale Self-Assembled Structures of Highly Hydrophobic Block Copolymers by Urea, Alkylureas, and Thiourea: Vesicle to Micelle Transition.","authors":"Nitumani Tripathi, Divya Patel, Sapana Sinha, Debes Ray, Vinod K Aswal, Debabrata Seth, Ketan Kuperkar, Pratap Bahadur","doi":"10.1021/acs.jpcb.5c05839","DOIUrl":"https://doi.org/10.1021/acs.jpcb.5c05839","url":null,"abstract":"&lt;p&gt;&lt;p&gt;Self-assembly in poly(ethylene oxide, EO)-poly(propylene oxide, PO)-based highly hydrophobic block copolymer (BCPs) with 10%EO content (L31, L61, L81, L101, and L121) is investigated in the presence of urea, thiourea and alkyl ureas (methyl urea, dimethyl urea, and tetramethyl urea) using clouding, scattering, photophysical and computational simulation approach. This work explores BCPs with significantly lower %EO content, unreported in different areas, that highlight the novelty of our investigation. The results of our study conveyed an increase in the clouding phenomenon, the extent of which was dependent on the molecular characteristics of the BCPs. High-sensitivity differential scanning calorimetry was employed to investigate the thermodynamics of micellization. Fourier Transform Infrared spectral profile presented the involved interactions within the examined copolymeric systems. Two-dimensional nuclear Overhauser effect spectroscopy provided spatial correlation signals, confirming close molecular proximities and specific interactions in the micellar environment. Computational simulations were performed using the DFT/B3LYP method with the 3-21G basis set in Gaussian 5.0.9, and the optimized descriptors were evaluated. Interestingly, urea, thiourea, and alkyl urea, especially tetramethyl urea, significantly impacted the micellar structure, leading to demicellization in some BCPs. Here, the dimension expressed as hydrodynamic diameter (&lt;i&gt;D&lt;/i&gt;&lt;sub&gt;h&lt;/sub&gt;) and micelle size changes in the observed system were monitored using dynamic light scattering analysis with the normalized intensity autocorrelation functions providing complementary information on size-dependent scattering dynamics. Furthermore, small-angle neutron scattering studies revealed that ureas enhance the solubility of the EO segments, inducing the structural transitions from multilamellar vesicles to unilamellar vesicles to spherical or Gaussian chains, attributed to the accumulation of water molecules in the micellar proximity. The effect of varying urea concentrations on the fluorescence behavior of Nile Blue A perchlorate (NBA) dye in 1%w/v L81 vesicles at 30 °C was investigated through absorbance, fluorescence emission, excitation, and lifetime decay measurements. Here, absorbance spectra exhibited a bathochromic shift with increasing urea concentration, indicating a change in micellar polarity. The fluorescence emission also showed bathochromic shift, suggesting the migration of NBA into a more hydrophobic environment within the micellar core as urea disrupted the micelle structure. Fluorescence emission lifetime decay analysis revealed complex decay at low urea concentrations, reflecting a heterogeneous dye environment, which simplified at higher urea concentrations due to micelle collapse or dye aggregation. These findings provide insight into the role of urea in altering micelle behavior and dye aggregation, with implications for micelle-based drug delivery systems","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2025-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145032505","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Vibrational Spectroscopy of C-H Activation Intermediates and Dehydrogenation Products of Sequential Reactions of Niobium Cation with Methane.","authors":"Arnab Das, Joseph R Gerrior, Ricardo B Metz","doi":"10.1021/acs.jpca.5c05156","DOIUrl":"10.1021/acs.jpca.5c05156","url":null,"abstract":"<p><p>Vibrational spectra of NbC_<i>n</i>H_4<i>n</i>⁺ (<i>n</i> = 1-4) and dehydrogenation products NbC₃H₁₀⁺ and NbC₄H₁₂⁺ produced by the reaction of Nb⁺ with methane are measured using photofragment spectroscopy in the C-H and H-H stretching regions (2500-3600 cm^-1). Entrance channel complexes Nb⁺(CH₄)_<i>n</i> are observed with red-shifted vibrations of proximate C-H stretches. Calculations at the B3LYP/aug-cc-pVTZ level of theory assist in identifying the structures of the ions. The hydrogen coordination moves from η³ toward η² as more methanes ligate. Exit channel complexes (H₂)NbCH₂⁺(CH₄)₂(Ar) and (H₂)NbCH₂⁺(CH₄)₃ are also observed, identified based on their characteristic agostic carbene C-H stretch (∼2530 cm^-1) and H-H stretch (∼3500 cm^-1). Although dehydrogenation of methane by Nb⁺ is endothermic, the interaction with multiple methane molecules opens exothermic H₂ loss pathways. The measured spectrum of the two H₂ loss product NbC₄H₁₂⁺ consists of a single peak, confirming it to be Nb(CH₃)₄⁺. This is consistent with the calculations, which predict a preference for species with Nb-CH₃ bonds.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"8407-8418"},"PeriodicalIF":2.8,"publicationDate":"2025-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144936434","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Binary Mixtures of Ionic Liquids to Enhance Dicationic Ionic Liquid Performance: Insights from Molecular Dynamics Simulations and Quantum Mechanics.","authors":"Zahra Ostadsharif Memar, Majid Moosavi, Zahra Keyvanfard","doi":"10.1021/acs.jpcb.5c02254","DOIUrl":"10.1021/acs.jpcb.5c02254","url":null,"abstract":"<p><p>In this work, the effect of adding a monocationic ionic liquid (MIL) on the properties of a dicationic ionic liquid (DIL) was investigated using molecular dynamics (MD) simulations and quantum mechanical (QM) calculations. The binary mixture of [C₆(mim)₂][NTf₂]₂ (DIL) and [P₁EOE][NTf₂] (MIL) was analyzed in terms of thermophysical, structural, and dynamical properties, along with density functional theory (DFT) and atoms-in-molecules (AIM) analyses. These properties were compared to those of the pure DIL system. Structural properties were examined using radial distribution functions (RDFs) and hydrogen-bonding networks, providing insights into ion arrangement, spatial heterogeneity, and interaction strength. RDF analysis revealed that increasing the MIL mole fraction enhances the local density of anions near the ring hydrogen atoms more significantly than the bulk density. Furthermore, the orientation of imidazolium rings suggests that MIL promotes π-π stacking interactions among [C₆(mim)₂]²⁺ cations. Notably, the system with <i>x</i>_MIL = 0.50 exhibited the lowest structural heterogeneity among the investigated mixtures. Dynamical properties, including mean square displacement (MSD), ionic conductivity, and van Hove correlation functions, were also analyzed. The results indicate that adding MIL enhances microheterogeneity and reduces ion cage strength, thereby facilitating ion mobility and increasing ionic conductivity. QM calculations further demonstrate that adding MIL lowers ion interaction energies due to the formation of stronger hydrogen bonds in the mixture. Additionally, AIM analysis reveals that the presence of MIL increases electron density between the dication and anions.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":"9190-9205"},"PeriodicalIF":2.9,"publicationDate":"2025-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144936458","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Effect of Solvents on Lignin-Surface Interactions via Molecular Dynamics Simulations.","authors":"Juriti Rajbangshi, Canan Sener, Reid C Van Lehn","doi":"10.1021/acs.jpcb.5c02943","DOIUrl":"10.1021/acs.jpcb.5c02943","url":null,"abstract":"<p><p>Lignin, an essential building block of lignocellulosic biomass, is a potential abundant source of aromatic monomers for the polymer and chemical industry. Reductive catalytic fractionation (RCF) is one promising process that can produce high yields of phenolic monomers and oligomers from lignin under different catalytic conditions. An important choice in optimizing RCF is the selection of solvent; however, detailed insights into the effects of solvent on lignin behaviors and interactions remain limited. In this work, we perform all-atom molecular dynamics simulations to study the solvation of lignin, solvent-mediated conformational changes, and the interaction of solvated lignin oligomers with model surfaces. We focus on the behavior of an oligomeric lignin model compound in methanol, ethanol, a binary mixture of ethanol and water, and water at both the RCF reaction temperature (473 K) and room temperature. Analysis of structural features of lignin suggests that these three organic solvent systems favorably solvate lignin, resulting in a more extended conformation suitable for catalytic conversion to valuable chemicals. We further introduce model palladium (Pd) and carbon (C) surfaces to understand how solvent choice impacts adsorption onto a representative catalytic surface and support and to quantify the competition among the reactant and solvent molecules for the surface. Unbiased simulations suggest strong adsorption of lignin on both Pd and C surfaces at 473 K, with notable solvent-mediated differences in adsorption energies. Additionally, our findings indicate that lignin adsorption is promoted by the entropy change resulting from the displacement of the solvent molecules from the surface. This study provides a molecular perspective of adsorption of lignin onto varying surfaces, which is a step toward understanding and optimizing the catalytic conversion of lignin into valuable chemicals.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":"9175-9189"},"PeriodicalIF":2.9,"publicationDate":"2025-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144936431","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Water-In-Glass: A Self-Supporting Inorganic Aqueous Electrolyte.","authors":"Sinorul Haque, Indrajeet Mandal, K Jayanthi, Prabir Pal, Prince Sen, Bijay Laxmi Pradhan, Krishna K Dey, Manasi Ghosh, Nitya Nand Gosvami, N M Anoop Krishnan, Mir Wasim Raja, Amarnath R Allu","doi":"10.1021/acs.jpcb.5c04789","DOIUrl":"10.1021/acs.jpcb.5c04789","url":null,"abstract":"<p><p>Aqueous rechargeable sodium-ion batteries (ARNIBs) are emerging as cost-effective and safe candidates for large-scale energy storage applications. However, their advancement has been constrained by the narrow electrochemical stability window (ESW) of conventional aqueous electrolytes (1.23 V). Here, we present a transformative approach using an inexpensive and rapidly dissolvable inorganic glass material, water glass (W-glass), to significantly enhance the ESW and enable the development of solid-state, self-supporting aqueous film (SSA film) electrolytes. These SSA film electrolytes exhibit an extended ESW of up to 3.5 V and a conductivity of ∼10^-4 S/cm at room temperature. Structural analysis using magic-angle spinning nuclear magnetic resonance (NMR) and solution-state NMR reveals that the dissolution of W-glass in water is driven by the interdependent hydrolysis of P-O-P linkages and Na⁺-H⁺ ion exchange. This work offers a cost-effective and scalable solution for advancing high-performance ARNIB technology, addressing critical barriers to commercial adoption.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":"9240-9248"},"PeriodicalIF":2.9,"publicationDate":"2025-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144936075","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Enhanced Mechanophore Activation in Hydrogel Networks Driven by Swollen Network Pretension.","authors":"Meytal Forer, Alessio Maselli, Yifan Liao, Adan Hijaze, Thekra Msarwe, Joshua M Grolman","doi":"10.1021/acs.jpcb.5c02492","DOIUrl":"10.1021/acs.jpcb.5c02492","url":null,"abstract":"<p><p>There is often a discrepancy between the strain required to activate mechanophores and incorporation in bulk materials, inhibiting these force sensors from many practical, commercial, and biological uses. The difference is particularly pronounced for biomimetic networks such as viscoelastic hydrogels, in which the distribution of strain is unclear due to dissipation. Here, we show that the activation of spiropyran mechanophores in alginate networks is related to cross-linking characteristics by comparing ionic and covalent bonds. Through a simple shear force setup using syringes and Bernoulli's principle, we observe higher activation of spiropyran in ionic gels, regardless of mechanical versus ultraviolet light stimulus. This may be predominantly driven by differences in network pretension due to swelling, as the ring-closing reaction of merocyanine to spiropyran was similarly affected. These insights shed new light on understanding force propagation in complex networks, leading to higher mechanophore sensitivities in biologically similar materials.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":"9249-9255"},"PeriodicalIF":2.9,"publicationDate":"2025-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144936384","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Drug Loading and Release: Development and Characterization of a Novel Therapeutic Agent-Nanographene Conjugate.","authors":"Kaiyue Hu, Agnese Pavan, Alessandro Semeraro, Alberto Ongaro, Luigi Brambilla, Maria Cristina De Rosa, Matteo Tommasini, Chiara Castiglioni, Michele Maggini","doi":"10.1021/acs.jpcb.5c04238","DOIUrl":"10.1021/acs.jpcb.5c04238","url":null,"abstract":"<p><p>Compound <b>8</b>, (5<i>Z</i>)-2-hydroxy-4-methyl-6-oxo-5-[(5-phenylfuran-2-yl)methylidene]-5,6-dihydropyridine-3-carbonitrile, is an effective NEK6 kinase inhibitor with demonstrated anticancer and neuroprotective activity. However, its poor aqueous solubility (3 μg/mL) presents a significant barrier to therapeutic development. To address this limitation, we developed a graphene-based nanocarrier system by conjugating compound <b>8</b> and its fluorinated derivatives (<b>8-F</b> and <b>8-CF</b>_<b>3</b>) onto structurally uniform few-layer graphene nanoparticles (GNPs) obtained via ball-milling and liquid-phase exfoliation (B60). The resulting conjugates (<b>8</b>@B60, <b>8-F</b>@B60, and <b>8-CF</b>_<b>3</b>@B60) were thoroughly characterized by UV-vis, IR, and Raman spectroscopy, as well as by TEM and STEM-EDX analysis. Spectroscopic and elemental data confirmed effective drug loading and structural preservation of the B60 nanocarriers. Drug release experiments further confirmed thermally triggered desorption of <b>8</b> from the GNPs surface in aqueous conditions, highlighting the potential of B60-based conjugates as controlled release systems. A key finding of this work is the reversible hydration of compound <b>8</b> in aqueous solution, resulting in a colorless, nonconjugated species. Detailed spectroscopic and computational studies revealed that this hydrated form likely represents the dominant species under physiological conditions. Crucially, molecular docking and molecular dynamics simulations demonstrated that hydration does not compromise the binding affinity of compound <b>8</b> for the NEK6 active site. These insights provide a molecular-level rationale for the design and evaluation of drug delivery systems based on nanographene platforms in aqueous environments.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":"9097-9112"},"PeriodicalIF":2.9,"publicationDate":"2025-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144936466","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}