Mechanism of monovalent and divalent ion mobility in Nafion membrane: An atomistic simulation study.

Polymer cation exchange membranes (CEMs) are widely used in water treatment processes. The fundamental factors that control the separation and selectivity of cations with different valences in CEMs are not fully understood. In this study, we use atomistic molecular dynamics simulations to investigate the underlying molecular mechanisms that control the mobility of cations with different valences in Nafion membranes. Our results indicate structural differences in binding of monovalent and divalent cations, which gives rise to differences in ion diffusion in Nafion. Monovalent cations are shown to be "territorially" bound, i.e., bound while partially hydrated, to the fixed charge groups whereas divalent cations are shown to be "site" bound, i.e., bound while fully dehydrated, to the charge groups on the polymer. This difference in binding structure gives rise to differences in transport characteristics of cations in Nafion.

Prediction of alkaline earth metal ion adsorption on goethite for various background electrolytes with the CD-MUSIC model.

As water scarcity drives the use of more saline water sources, contaminant fate and transport models must capture the impact of high concentrations of alkaline earth metal ions (AEMs) and background electrolytes in these more complex waters. By utilizing macroscopic adsorption data from various electrolyte systems, a Charge Distribution - Multisite Complexation (CD-MUSIC) model, capable of incorporating electrolyte adsorption, was able to accurately simulate the adsorption behavior of alkaline earth metal ions onto goethite. The modeling effort was guided by previous spectroscopic and surface complexation modeling of alkaline earth metal adsorption and built on previous CD-MUSIC modeling that accounted for changes in crystal face contributions to the surface site density as a function of specific surface area. The model was constrained to consider only two dominant surface complex species for each metal ion adsorption reaction. These two species were selected from 44 possible species through objective curve fitting of single-solute macroscopic adsorption data. While most of the alkaline earth metal surface complexes formed outer-sphere complexes at the goethite surface, an inner-sphere species was utilized for Mg2+. With the surface complex species and equilibrium constants obtained from this study, the calibrated model successfully predicted alkaline earth metal ion adsorption over a wide range of solution and surface conditions; the model predictions encompassed a wide range of pH (5-11), solute/solid ratio (1.37 × 10-5- 8.33 × 10-4 mol-solute/g-solid), ionic strengths (0.01 M - 0.7 M), and background electrolytes (Na+, Cs+, Rb+, Cl-, and NO3-) using the same crystal face contribution methodology for site density, capacitance values, and surface acidity constants adopted for proton and cadmium adsorption in previous work (Han and Katz, 2019). Model simulations for a range of background water chemistries demonstrated the potential for Mg2+ to reduce Cd2+ adsorption to goethite in model seawater and oil- and gas-produced waters.

Oxide- and Silicate-Water Interfaces and Their Roles in Technology and the Environment.

Interfacial reactions drive all elemental cycling on Earth and play pivotal roles in human activities such as agriculture, water purification, energy production and storage, environmental contaminant remediation, and nuclear waste repository management. The onset of the 21st century marked the beginning of a more detailed understanding of mineral aqueous interfaces enabled by advances in techniques that use tunable high-flux focused ultrafast laser and X-ray sources to provide near-atomic measurement resolution, as well as by nanofabrication approaches that enable transmission electron microscopy in a liquid cell. This leap into atomic- and nanometer-scale measurements has uncovered scale-dependent phenomena whose reaction thermodynamics, kinetics, and pathways deviate from previous observations made on larger systems. A second key advance is new experimental evidence for what scientists hypothesized but could not test previously, namely, interfacial chemical reactions are frequently driven by "anomalies" or "non-idealities" such as defects, nanoconfinement, and other nontypical chemical structures. Third, progress in computational chemistry has yielded new insights that allow a move beyond simple schematics, leading to a molecular model of these complex interfaces. In combination with surface-sensitive measurements, we have gained knowledge of the interfacial structure and dynamics, including the underlying solid surface and the immediately adjacent water and aqueous ions, enabling a better definition of what constitutes the oxide- and silicate-water interfaces. This critical review discusses how science progresses from understanding ideal solid-water interfaces to more realistic systems, focusing on accomplishments in the last 20 years and identifying challenges and future opportunities for the community to address. We anticipate that the next 20 years will focus on understanding and predicting dynamic transient and reactive structures over greater spatial and temporal ranges as well as systems of greater structural and chemical complexity. Closer collaborations of theoretical and experimental experts across disciplines will continue to be critical to achieving this great aspiration.

Preliminary Evaluation of the Effectiveness of Perinatal Mindfulness-Based Well-Being and Parenting Programs for Low-Income New Mothers.

Objectives: This study examined specificity in the effects of three perinatal mindfulness-based prevention programs that differed in their timing (prenatal, postpartum) and target (maternal well-being, parenting). Effects on maternal mental health (depression, anxiety, resilience), mindfulness, and observed parenting, as well as observed, physiological, and mother-report indicators of infant self-regulation, were examined. Methods: The programs were evaluated in a racially and ethnically diverse sample of first-time mothers (n = 188) living in low-income contexts using intention-to-treat analysis. Mothers were assigned to a prenatal well-being, postpartum well-being, parenting, or book control group. Multi-method assessments that included questionnaire, observational, and physiological measures were conducted at four time points: during pregnancy (T1) and when infants were 2-4 months (T2), 4-6 months (T3), and 10-12 months. Results: Compared to the postpartum intervention and control groups, the 6-week prenatal well-being intervention was related to decreases in depressive symptoms during pregnancy but not postpartum, higher maternal baseline respiratory sinus arrhythmia (RSA), fewer intrusive control behaviors, and lower infant cortisol levels in the early postpartum period. Compared to all other groups, the postpartum parenting intervention was related to decreases in maternal anxiety and increases in responsive parenting. Some differential effects across programs might be due to differences in attendance rates in the prenatal (62%) vs. postpartum (35%) groups. Conclusions: The findings suggest that brief mindfulness-based well-being and parenting preventive interventions can promote maternal and infant mental health in families living in low-income, high-stress settings, particularly if accessibility can be enhanced. Preregistration: This study is not preregistered.

Caregiver emotion regulation predicts trajectories of psychopathology during pediatric cancer treatment.

Elevated child and caregiver psychopathology are observed in families of children with cancer, with a subset developing clinically significant symptoms. This study examines whether caregivers' resting respiratory sinus arrhythmia (RSA) and observed emotion regulation (ER) are protective against caregiver and child psychopathology during the first year of pediatric cancer treatment. Primary caregivers of children recently diagnosed with cancer (N = 159; child Mage = 5.6 years; children 48% male, 52% female) completed 12 monthly questionnaires. At Month 3, primary caregivers were interviewed about their experiences of emotions, and their resting RSA was measured. Data were analyzed using multilevel models. Observed ER was associated with lower caregiver anxiety, depression, and posttraumatic stress symptoms (PTSS) 1 year postdiagnosis but was not associated with children's symptoms. Resting RSA had a significant positive association with child depression/anxiety at the start of treatment and Month 12 child PTSS. Findings suggest that caregivers would benefit from interventions to manage their negative emotions at the start of cancer treatment. Additionally, caregivers who are more physiologically regulated may be more attuned to their children's negative emotions. Our findings highlight the importance of taking a multimethod approach to understanding how ER impacts functioning. (PsycInfo Database Record (c) 2023 APA, all rights reserved).

Accounting for Ion Pairing Effects on Sulfate Salt Sorption in Cation Exchange Membranes.

Ion exchange membranes (IEMs) are frequently used in water treatment and electrochemical applications, with their ion separation properties largely governed by equilibrium ion partitioning between a membrane and contiguous solution. Despite an expansive literature on IEMs, the influence of electrolyte association (i.e., ion pairing) on ion sorption remains relatively unexplored. In this study, salt sorption in two commercial cation exchange membranes equilibrated with 0.01-1.0 M MgSO4 and Na2SO4 is investigated experimentally and theoretically. Association measurements of salt solutions using conductometric experiments and the Stokes-Einstein approximation show significant concentrations of ion pairs in MgSO4 and Na2SO4 relative to those in simple electrolytes (i.e., NaCl), which is consistent with prior studies of sulfate salts. The Manning/Donnan model, developed and validated for halide salts in previous studies, substantially underpredicts sulfate sorption measurements, presumably due to ion pairing effects not accounted for in this established theory. These findings suggest that ion pairing can enhance salt sorption in IEMs due to partitioning of reduced valence species. By reformulating the Donnan and Manning models, a theoretical framework for predicting salt sorption in IEMs that explicitly considers electrolyte association is developed. Remarkably, theoretical predictions of sulfate sorption are improved by over an order of magnitude by accounting for ion speciation. In some cases, good quantitative agreement is observed between theoretical and experimental values for external salt concentrations between 0.1 and 1.0 M using no adjustable parameters.

Asthma exacerbations during the pandemic: Time to rethink clinical markers.

Background: Reductions in asthma exacerbations during the coronavirus disease 2019 (COVID-19) pandemic may have an impact on clinical trial enrollment and outcomes. Objective: Our aim was to review clinical studies and reports evaluating asthma exacerbations before and during the COVID-19 pandemic. Methods: We reviewed clinical studies conducted with biologics over the past decade that evaluated asthma exacerbations as the primary end point. We also reviewed recent clinical reports evaluating asthma exacerbations during the COVID-19 pandemic. Results: We showed that studies requiring at least 2 exacerbations in the prior year resulted in a higher number of exacerbations on study in the placebo arm, and conversely, those studies in which exacerbations were not required for entering the study failed to meet the primary end point. This result confirmed that history of prior exacerbations is a good maker to predict future exacerbations. In addition, a review of the literature confirmed a reduction of asthma exacerbations during the COVID-19 pandemic. The data presented are descriptive; no formal statistics were used. Conclusion: Because of the COVID-19 pandemic, historical exacerbations may no longer be the best predictor for exacerbations in a clinical trial or clinical practice. Other clinical markers associated with exacerbations, such as blood eosinophil count and fractional exhaled nitric oxide level, should be considered for enrollment in clinical studies assessing asthma exacerbations.

Apparent Reactivity of Bromine in Bromochloramine Depends on Synthesis Method: Implicating Bromine Chloride and Molecular Bromine as Important Bromine Species.

The chloramination of bromide containing waters results in the formation of bromine containing haloamines: monobromamine (NH2Br), dibromamine (NHBr2), and bromochloramine (NHBrCl). Many studies have directly shown that bromamines are more reactive than chloramines in oxidation and substitution reactions with organic water constituents because the bromine atom in oxidants is more labile than the chlorine atom. However, similar studies have not been performed with NHBrCl. It has been assumed that NHBrCl has similar reactivity as bromamines with organic constituents in both oxidation and substitution reactions because NHBrCl, like bromamines, rapidly oxidizes N,N-diethyl-p-phenylenediamine. In this study, we examined the reactivity of NHBrCl with phenol red to determine if NHBrCl reacts as readily as bromamines in an isolated substitution reaction. NHBrCl was synthesized two ways to assess whether NHBrCl or the highly reactive intermediates, bromine chloride (BrCl) and molecular bromine (Br2), were responsible for bromine substitution of phenol red. NHBrCl was found to be much less reactive than bromamines with phenol red and that BrCl and Br2 appeared to be the true brominating agents in solutions where NHBrCl is formed. This work highlights the need to reexamine what the true brominating agents are in chloraminated waters containing bromide.

The Donnan potential revealed.

Selective transport of solutes across a membrane is critical for many biological, water treatment and energy conversion and storage systems. When a charged membrane is equilibrated with an electrolyte, an unequal distribution of ions arises between phases, generating the so-called Donnan electrical potential at the solution/membrane interface. The Donnan potential results in the partial exclusion of co-ion, providing the basis of permselectivity. Although there are well-established ways to indirectly estimate the Donnan potential, it has been widely reported that it cannot be measured directly. Here we report the first direct measurement of the Donnan potential of an ion exchange membrane equilibrated with salt solutions. Our results highlight the dependence of the Donnan potential on external salt concentration and counter-ion valence, and show a reasonable agreement with current theoretical models of IEMs, which incorporate ion activity coefficients. By directly measuring the Donnan potential, we eliminate ambiguities that arise from limitations inherent in current models.

Effect of Dielectric Saturation on Ion Activity Coefficients in Ion Exchange Membranes.

Polymeric ion exchange membranes are used in water purification processes to separate ions from water. The distribution and transport of ionic species through these membranes depend on a variety of factors, including membrane charge density, morphology, chemical structure, and the specific ionic species present in the fluid. The electrical potential distribution between membranes and solutions is typically described using models based on Donnan theory. An extension of the original theory is proposed to account for the nonideal behavior of ions both in the fluid and in the membrane as well to provide a more robust description of interactions of solutes with fixed charge groups on the polymer backbone. In this study, the variation in dielectric permittivity in the membrane medium with electric field strength is taken into account in a model based on Gouy-Chapman double-layer theory to provide a more accurate description of ion activity coefficients in an ion exchange membrane. A semianalytical model is presented that accounts for the variation in dielectric permittivity of water in a charged polymer membrane. A comparison of this model with Manning's counterion condensation model clearly demonstrates that by incorporating changes in water dielectric permittivity with electric field strength, much better agreement with experiments can be obtained over a range of salt concentrations for different ions.

Fate of pyrene on mineral surfaces during thermal remediation as a function of temperature.

There is evidence that contaminants can transform at the elevated temperatures of thermal remediation; however, the contribution of redox active minerals to transformation has not been investigated. Three redox active minerals (i.e., birnessite (MnO2), magnetite (Fe3O4), and hematite (Fe2O3)) and one redox inactive mineral (Ottawa sand (SiO2)) were spiked with pyrene and thermally treated. Under dry, anoxic conditions, 100%, 75% ± 3%, 70% ± 15%, and 14% ± 28% of the initial pyrene mass was removed with birnessite, magnetite, hematite, and Ottawa sand, respectively, after treatment at 250 °C for 30 min. Under wet, oxic conditions, 92% ± 8%, 86% ± 12%, 79% ± 4%, and 42% ± 7% was removed for the same minerals, respectively, after treatment at only 150 °C for 30 min. Baseline studies with Ottawa sand resulted in volatilization alone of pyrene with no transformation observed. Increased pyrene loading was used to evaluate potential transformation pathways based on identified by-products, demonstrating that both oxidative and reductive pathways were operative depending on the conditions. Reaction products in the presence of redox active minerals indicate transformation was dominated by reduction via hydrogenation in dry experiments, and by oxidation via hydroxyl radicals in wet experiments. The latter was unexpected, because only low hydroxyl radical concentrations have been detected in mineral-water systems at ambient temperature. These results indicate that understanding dominant reaction pathways and products is advantageous for the design of efficient and safe thermally enhanced treatment systems.

Caregiver perceived financial strain during pediatric cancer treatment: Longitudinal predictors and outcomes.

OBJECTIVE: Previous work has examined family income and material hardship in pediatric cancer. However, few studies have focused on perceived financial strain (PFS), or the extent to which caregivers perceive financial stress and worry related to their child's cancer. The current study addresses this gap by a) describing the trajectory of perceived financial strain over the first year of pediatric cancer treatment; b) examining sociodemographic predictors of that trajectory; and c) examining associations between PFS and caregiver and child psychological adjustment. METHOD: Primary caregivers of children (Mage = 6.31) recently diagnosed with cancer provided 12 monthly reports of their own perceived financial strain and depression, anxiety, and posttraumatic stress symptoms, as well as their child's internalizing and externalizing symptoms. Data were analyzed using multilevel models. RESULTS: Caregiver PFS decreased over the first year of treatment. Nonmarried caregivers and those with lower income reported higher levels of PFS over time. Caregivers with higher PFS relative to other caregivers and relative to their own average PFS in a given month experienced psychological maladjustment. PFS was not associated with child adjustment. CONCLUSIONS: On average caregivers perceive less financial strain over the first year of treatment; however, nonmarried caregivers and those with lower income are at risk for higher PFS over time, and PFS may contribute to psychological maladjustment in caregivers. Caregivers may benefit from psychosocial support focused on managing financial strain. (PsycInfo Database Record (c) 2022 APA, all rights reserved).

Inverse Design of Pore Wall Chemistry To Control Solute Transport and Selectivity.

Next-generation membranes for purification and reuse of highly contaminated water require materials with precisely tuned functionality to address key challenges, including the removal of small, charge-neutral solutes. Bioinspired multifunctional membrane surfaces enhance transport properties, but the combinatorically large chemical space is difficult to navigate through trial and error. Here, we demonstrate a computational inverse design approach to efficiently identify promising materials and elucidate design rules. We develop a combined evolutionary optimization, machine learning, and molecular simulation workflow to spatially design chemical functional group patterning in a model nanopore that enhances transport of water relative to solutes. The genetic optimization discovers nonintuitive functionalization strategies that hinder the transport of solutes through the pore, simply by patterning hydrophobic methyl and hydrophilic hydroxyl functional groups. Examining these patterns, we demonstrate that they exploit an unexpected diffusive solute hopping mechanism. This inverse design procedure and the identification of novel molecular mechanisms for pore chemical heterogeneity to impact solute selectivity demonstrate new routes to the design of membrane materials with novel functionalities. More broadly, this work illustrates how chemical design is a powerful strategy to modulate water-mediated surface-solute interactions in complex, soft material systems that are relevant to diverse technologies.

The role of parental emotion reactivity and regulation in child maltreatment and maltreatment risk: A meta-analytic review.

The prevalence and impact of child maltreatment make the scientific investigation of this phenomenon a matter of vital importance. Prior research has examined associations between problematic patterns of parents' emotion reactivity and regulation and child maltreatment and maltreatment risk. However, the strength and specificity of these relationships is not yet clear. To address this, we conducted a systematic literature search of four databases from inception through February 2021 to identify studies that reported these relationships. Our resulting meta-analysis of maltreatment involved parents of children who are up to 18 years of age (k = 46, encompassing 6669 parents). Our focus was the magnitude of the difference in levels of emotion reactivity and regulation between parents who maltreat or are at risk of maltreating and parents who do not maltreat their children or are not at risk of maltreating their children. As expected, results from meta-analyses using robust variance estimation indicated significantly higher problems with reactivity and regulation in maltreating parents / parents at risk (r = 0.40, k = 140; 95% CI [0.34, 0.45]), indicating that maltreating / at risk parents were more likely to have overall worse measures of reactivity and regulation. In comparison to non-maltreating parents, maltreating / at risk parents experience more negative emotions, display more negative emotion behavior, and are more dysregulated. These effects were fairly stable with little to no remaining heterogeneity. The current review concludes with a theoretical framework outlining the role of emotion reactivity and regulation in multiple risk factors of maltreatment, aiming to guide future study in this area.

Human-Infrastructure Interactions during the COVID-19 Pandemic: Understanding Water and Electricity Demand Profiles at the Building Level.

When engineers design and manage a building's water and electricity utilities, they must make assumptions about resource use. These assumptions are often challenged when unexpected changes in demand occur, such as the spatial and temporal changes observed during the coronavirus (COVID-19) pandemic. Social distancing policies (SDPs) enacted led many universities to close their campuses and implement remote learning, impacting utility consumption patterns. Yet, little is known about how consumption changed at the building level. Here, we aim to understand how water and electricity consumption changed during the pandemic by identifying characteristic weekly demand profiles and understanding how these changes were related to regulatory and social systems. We performed k-means clustering on utility demand data measured before and as the pandemic evolved from five buildings of different types at the University of Texas at Austin. As expected, after SDPs were enacted both water and electricity use shifted, with most buildings seeing a sharp initial decline that remained low until the university partially reopened. In contrast to electricity use, we found that water use was tightly coupled with SDPs. Our study provides actionable information for managers to mitigate negative impacts (e.g., water stagnation) and capitalize on opportunities to minimize resource use.

Stress and psychological adjustment in caregivers of children with cancer.

OBJECTIVE: To examine effects of stress on caregiver psychological adjustment during the first year of pediatric cancer. METHOD: Caregivers (N = 159) of children with cancer completed monthly questionnaires assessing domains of caregiver psychological adjustment (depression, anxiety, and posttraumatic stress symptoms) and stress (general life stress, treatment-related stress, caregiver perceptions of treatment intensity and life threat). Effects of stress were assessed at two levels to examine whether within-person changes in stress predicted concurrent changes in caregiver adjustment and whether average stress was associated with between-person differences in caregiver adjustment trajectories. RESULTS: Overall, higher levels of stress factors were associated with poorer caregiver adjustment at both the between- and within-person levels, with high average levels of treatment-related stress and general life stress emerging as leading predictors of worse adjustment. CONCLUSIONS: Both types of stressors, those directly related as well as unrelated to a child's cancer, contribute uniquely to caregiver distress. Caregiver distress is impacted by both overall levels of stress over time as well as month-to-month changes in stress. Implications for informing care for at-risk caregivers are discussed. (PsycInfo Database Record (c) 2021 APA, all rights reserved).

Primary and secondary caregiver depressive symptoms and family functioning following a pediatric cancer diagnosis: an exploration of the buffering hypothesis.

OBJECTIVE: After diagnosis, caregivers of children with cancer, particularly mothers or primary caregivers (PCs), often show elevated depressive symptoms which may negatively impact family functioning. We tested PC and secondary caregiver (SC) depressive symptoms as predictors of family, co-parenting, and marital functioning and whether having a non-depressed SC buffers against potential negative effects of PC depressive symptoms. METHODS: Families (N = 137) were recruited from two major children's hospitals following a diagnosis of pediatric cancer. Caregivers completed self-report measures of depressive symptoms (Center for Epidemiological Studies-Depression Scale; Depression, Anxiety, and Stress Scale) and marital functioning (Dyadic Adjustment Scale) at 1-month post-diagnosis. A subset of families (n = 75) completed videotaped interaction tasks at approximately 3-months post-diagnosis that were coded for family and co-parenting interactions. RESULTS: Higher PC depressive symptoms at 1-month post-diagnosis was associated with higher adaptability and lower conflict in family functioning. PC depressive symptoms were also associated lower dyadic consensus and lower dyadic satisfaction. SC depressive symptoms were not significantly associated with any family/co-parenting/marital functioning variables. Significant interaction analyses suggested that SC depressive symptoms moderated the effect of PC depressive symptoms on family cohesion, withdrawn parenting, and affective expression in the marriage, such that the relationship between PC depressive symptoms and poorer functioning was attenuated when SC depressive symptoms were at low or average levels. CONCLUSIONS: Having a nondepressed SC buffered against negative effects of PC depressive symptoms on certain domains of family, coparenting, and marital functioning. SCs may play a protective role for families of children with cancer.

Creating a Pathway for Psychosocial Support in Siblings of Youth with a Chronic Illness: Findings from an International Summit.

OBJECTIVE: Serious childhood illnesses such as cancer affect all family members. Siblings experience strong emotions and disruptions to their routines as families reorganize to confront the disease and manage treatment. Addressing siblings' psychosocial needs is a standard of care in pediatric oncology, but siblings' needs are rarely met because of systematic barriers in our health care system. Thus, we aimed to re-envision sibling care. We used an appreciative inquiry approach to inform systematic screening of siblings' psychosocial risk and unmet needs as a first step toward providing appropriate support. METHOD: Sibling-focused researchers, clinicians, policymakers, advocates, and families of youth with cancer (N = 29) convened for a 2-day community stakeholder-centered international summit to create a vision for standardizing and optimizing sibling-focused psychosocial screening and assessment as a pathway to care, including crafting a research agenda and articulating best clinical practices. RESULTS: Summit attendees created a detailed framework for best practices in universal sibling psychosocial screening and pathways to support. The framework emphasizes links between hospital- and community-based care. It highlights the need to prepare systems to feasibly and effectively attend to siblings' needs and recommends incorporating siblings into family-based psychosocial screening at cancer diagnosis, systematically conducting sibling-focused psychosocial screening during and after cancer treatment, and connecting siblings with community-based resources. CONCLUSION: A systematic approach to sibling psychosocial services expands the idea of family-centered care to include siblings and ensures that siblings' needs are adequately recognized and met. This framework was created in the context of cancer but is applicable across illness groups.

Affinity of small-molecule solutes to hydrophobic, hydrophilic, and chemically patterned interfaces in aqueous solution.

Performance of membranes for water purification is highly influenced by the interactions of solvated species with membrane surfaces, including surface adsorption of solutes upon fouling. Current efforts toward fouling-resistant membranes often pursue surface hydrophilization, frequently motivated by macroscopic measures of hydrophilicity, because hydrophobicity is thought to increase solute-surface affinity. While this heuristic has driven diverse membrane functionalization strategies, here we build on advances in the theory of hydrophobicity to critically examine the relevance of macroscopic characterizations of solute-surface affinity. Specifically, we use molecular simulations to quantify the affinities to model hydroxyl- and methyl-functionalized surfaces of small, chemically diverse, charge-neutral solutes represented in produced water. We show that surface affinities correlate poorly with two conventional measures of solute hydrophobicity, gas-phase water solubility and oil-water partitioning. Moreover, we find that all solutes show attraction to the hydrophobic surface and most to the hydrophilic one, in contrast to macroscopically based hydrophobicity heuristics. We explain these results by decomposing affinities into direct solute interaction energies (which dominate on hydroxyl surfaces) and water restructuring penalties (which dominate on methyl surfaces). Finally, we use an inverse design algorithm to show how heterogeneous surfaces, with multiple functional groups, can be patterned to manipulate solute affinity and selectivity. These findings, importantly based on a range of solute and surface chemistries, illustrate that conventional macroscopic hydrophobicity metrics can fail to predict solute-surface affinity, and that molecular-scale surface chemical patterning significantly influences affinity-suggesting design opportunities for water purification membranes and other engineered interfaces involving aqueous solute-surface interactions.