arXiv subjects

Alexandre Poirier

Publications and source records attributed to Alexandre Poirier.

At least 19 recordsLinked to original sources

arXiv2026

Assessing Sensitivity to IV Exclusion and Exogeneity without First Stage Monotonicity

Exclusion and exogeneity are core assumptions in instrumental variable (IV) analyses, but their empirical validity is often debated. This paper develops new sensitivity analyses for these assumptions. Our results accommodate arbitrary heterogeneity in treatment effects and do not impose any monotonicity requirements on the first stage. Specifically, we derive identified sets for the marginal distributions of potential outcomes and their functionals, like average treatment effects, under a broad class of nonparametric relaxations of the exclusion and exogeneity assumptions. These identified sets are characterized as solutions to linear programs and have desirable theoretical properties. We explain how to estimate these solutions using computationally tractable methods even when the linear program is infinite-dimensional. We illustrate these methods with an empirical application to peer effects in movie viewership, using weather as a potentially imperfect instrument.

econ.EM↗

arXiv2025

An Axiomatic Approach to Comparing Sensitivity Parameters

Many methods are available for assessing the importance of omitted variables in linear regression. These methods typically make different, non-falsifiable assumptions. Hence the data alone cannot tell us which method is most appropriate. Since it is unreasonable to expect results to be robust against all possible robustness checks, researchers often use methods deemed ``interpretable,'' a subjective criterion with no formal definition. In contrast, we develop the first formal, axiomatic framework for comparing and selecting among these methods. Our framework is analogous to the standard approach for comparing estimators based on their sampling distributions. We propose that sensitivity parameters be selected based on their covariate sampling distributions, a design distribution of parameter values induced by an assumption on how covariates are assigned to be observed or unobserved. Using this idea, we define new concepts of parameter consistency and monotonicity, and argue that a reasonable sensitivity parameter should satisfy both properties. We prove that the literature's most popular approach is inconsistent and non-monotonic, while several alternatives satisfy both.

econ.EM↗

arXiv2025

A General Approach to Relaxing Unconfoundedness

This paper defines a general class of relaxations of the unconfoundedness assumption. This class includes several previous approaches as special cases, including the marginal sensitivity model of Tan (2006). This class therefore allows us to precisely compare and contrast these previously disparate relaxations. We use this class to derive a variety of new identification results which can be used to assess sensitivity to unconfoundedness. In particular, the prior literature focuses on average parameters, like the average treatment effect (ATE). We move beyond averages by providing sharp bounds for a large class of parameters, including both the quantile treatment effect (QTE) and the distribution of treatment effects (DTE), results which were previously unknown even for the marginal sensitivity model.

econ.EM↗

arXiv2024

Quantifying the Internal Validity of Weighted Estimands

In this paper we study a class of weighted estimands, which we define as parameters that can be expressed as weighted averages of the underlying heterogeneous treatment effects. The popular ordinary least squares (OLS), two-stage least squares (2SLS), and two-way fixed effects (TWFE) estimands are all special cases within our framework. Our focus is on answering two questions concerning weighted estimands. First, under what conditions can they be interpreted as the average treatment effect for some (possibly latent) subpopulation? Second, when these conditions are satisfied, what is the upper bound on the size of that subpopulation, either in absolute terms or relative to a target population of interest? We argue that this upper bound provides a valuable diagnostic for empirical research. When a given weighted estimand corresponds to the average treatment effect for a small subset of the population of interest, we say its internal validity is low. Our paper develops practical tools to quantify the internal validity of weighted estimands. We also implement these tools in our companion Stata package causalrep and use them to revisit four prominent empirical studies.

econ.EM↗

arXiv2023

Aqueous self-assembly of a wide range of sophorolipid and glucolipid microbial bioamphiphiles (biosurfactants): considerations on the structure-properties relationship

Sophorolipids are well-known scaled-up microbial glycolipid biosurfactants with a strong potential for commercialization due to their biological origin and mildness in contact with the skin and the environment compared to classical surfactants. However, their association properties in water are still poorly understood, they cannot be predicted and their behavior in solution challenges half a century of knowledge generated in the field of surfactant science. By studying forty different types of sophorolipids and sophorosides in water using small angle X-ray scattering, and optical and cryogenic transmission electron microscopy, this work provides better understanding of their structure-property relationship and identifies which chemical groups in their molecular structure have a critical influence on their self-assembly properties. Structural features like the number of sugar headgroups, acetylation, end-chain functional group, (un)saturation, lactonization and length of chain are adjusted to both rationalize their impact and understand their effect on self-assembly. The number of sugar groups, pH, (un)saturation and lactonization were found to have a critical impact on sophorolipid self-assembly. The chemical nature of the end-chain functional group and chain length were also found to have a possibly critical impact, depending on the specific type of chemical function (COOH and long chains are critical). Mono- and diacetylation, as well as the position of sophorose in the fatty acid ($\omega$, $\omega$-1), are not critical, i.e., they did not significantly influence sophorolipid self-assembly.

cond-mat.soft↗

arXiv2023

Self-Assembly of Rhamnolipids Bioamphiphiles: Understanding Structure-Properties Relationship using Small-Angle X-Ray Scattering

The structure-properties relationship of rhamnolipids, RLs, well known microbial bioamphiphiles (biosurfactants), is exlored in detail by coupling cryogenic transmission electron microscopy (cryo-TEM) and both ex situ and in situ small angle X-ray scattering (SAXS). The self-assembly of three RLs with reasoned variation of their molecular structure (RhaC10, RhaC10C10 and RhaRhaC10C10) and a rhamnose-free C10C10 fatty acid is studied in water as a function of pH. It is found that RhaC10 and RhaRhaC10C10 form micelles in a broad pH range and RhaC10C10 undergoes a micelle-to-vesicle transition from basic to acid pH occurring at pH 6.5. Modelling coupled to fitting SAXS data allows a good estimation of the hydrophobic core radius (or length), the hydrophilic shell thickness, the aggregation number and the surface area per RL. The essentially micellar morphology found for RhaC10 and

cond-mat.mtrl-sci↗

arXiv2022

Shear recovery and temperature stability of Ca2+ and Ag+ glycolipid fibrillar metallogels with unusual $\beta$-sheet-like domains

Low-molecular weight gelators (LMWG) are small molecules (Mw < ~1 kDa), which form self-assembled fibrillar networks (SAFiN) hydrogels in water. The great majority of SAFiN gels is described by an entangled network of self-assembled fibers, in analogy to a polymer in a good solvent. Here, fibrillation of a biobased glycolipid bolaamphiphile is triggered by Ca2+ or Ag+ ions, added to its diluted micellar phase. The resulting SAFiN, which forms hydrogel above 0.5 wt%, has a ``nano-fishnet'' structure, characterized by a fibrous network of both entangled fibers and $\beta$-sheets-like rafts, generally observed for silk fibroin, actin hydrogels or mineral imogolite nanotubes, but generally not known for SAFiN. This work focuses on the strength of the SAFIN gels, their fast recovery after applying a mechanical stimulus (strain) and their unusual resistance to temperature, studied by coupling rheology to small angle X-ray scattering (rheo-SAXS) using synchrotron radiation. The Ca2+-based hydrogel keeps its properties up to 55{\textdegree}C, while the Ag+-based gel shows a constant elastic modulus up to 70{\textdegree}C, without appearance of any gel-to-sol transition temperature. Furthermore, the glycolipid is obtained by fermentation from natural resources (glucose, rapeseed oil), thus showing that naturally-engineered compounds can have unprecedented properties, when compared to the wide range of chemically derived amphiphiles.

cond-mat.soft↗

arXiv2022

In situ stimulation of self-assembly tunes the elastic properties of interpenetrated glycolipid-biopolymer biobased hydrogels

Hydrogels are widespread soft materials, which can serve a wide range of applications. The control over the viscoelastic properties of the gel is of paramount importance. Ongoing environmental issues have raised the consumer's concern towards the use of more sustainable materials, including hydrogels. However, are greener materials compatible with high functionality? In a safe-by-design approach, this work demonstrates that functional hydrogels with in situ responsivity of their elastic properties by external stimuli can be developed from entirely ``sustainable'' components, a biobased amphiphile and biopolymers (gelatin, chitosan and alginate). The bioamphiphile is a stimuli-responsive glycolipid obtained by microbial fermentation, which can self-assemble into fibers, but also micelles or vesicles, in water under high dilution and by a rapid variation of the stimuli. The elastic properties of the bioamphiphile/biopolymer interpenetrated hydrogels can be modulated by selectively triggering the phase transition of the glycolipid and/or the biopolymer inside the gel by mean of temperature or pH.

cond-mat.soft↗

arXiv2022

Interpenetrated biosurfactant-biopolymer orthogonal hydrogels: the biosurfactant's phase controls the hydrogel's mechanics

Controlling the viscoelastic properties of hydrogels is a challenge for many applications. Low molecular weight gelators (LMWG) like bile salts and glycolipids, and biopolymers like chitosan and alginate, are good candidates for developing fully biobased hybrid hydrogels that combine the advantages of both components. Biopolymers lead to enhanced mechanics while LMWG add functionality. In this work, hybrid hydrogels are composed of biopolymers (gelatin, chitosan, alginate) and microbial glycolipid bioamphiphiles, known as biosurfactants. Besides their biocompatibility and natural origin, bioamphiphiles can present chameleonic behavior, as pH and ions control their phase diagram in water around neutrality under strongly diluted conditions (< 5 wt%). The glycolipid used in this work behaves like a surfactant (micellar phase) at high pH or like a phospholipid (vesicle phase) at low pH. Moreover, at neutral-to-alkaline pH in the presence of calcium, it behaves like a gelator (fiber phase). The impact of each of these phases on the elastic properties of biopolymers is explored by means of oscillatory rheology, while the hybrid structure is studied by small angle X-ray scattering. The micellar and vesicular phase reduce the elastic properties of the hydrogels, while the fiber phase has the opposite effect, it enhances the hydrogel's strength by forming an interpenetrated biopolymer-LMWG network.

cond-mat.soft↗

arXiv2022

The Effect of Omitted Variables on the Sign of Regression Coefficients

We show that, depending on how the impact of omitted variables is measured, it can be substantially easier for omitted variables to flip coefficient signs than to drive them to zero. This behavior occurs with "Oster's delta" (Oster 2019), a widely reported robustness measure. Consequently, any time this measure is large -- suggesting that omitted variables may be unimportant -- a much smaller value reverses the sign of the parameter of interest. We propose a modified measure of robustness to address this concern. We illustrate our results in four empirical applications and two meta-analyses. We implement our methods in the companion Stata module regsensitivity.

econ.EM↗

arXiv2022

Energy Landscape of Sugar Conformation Controls the Sol-to-Gel Transition in Self-assembled Bola Glycolipid Hydrogels

Self-assembled fibrillar network (SAFIN) hydrogels and organogels are commonly obtained by a crystallization process into fibers induced by external stimuli like temperature or pH. The gel-to-sol-to-gel transition is generally readily reversible and the change rate of the stimulus determines the fiber homogeneity and eventual elastic properties of the gels. However, recent work shows that in some specific cases, fibrillation occurs for a given molecular conformation and the sol-to-gel transition depends on the relative energetic stability of one conformation over the other, and not on the rate of change of the stimuli. We observe such a phenomenon on a class of bolaform glycolipids, sophorosides, similar to the well-known sophorolipid biosurfactants, but composed of two symmetric sophorose units. A combination of oscillatory rheology, small-angle X-ray scattering (SAXS) cryogenic transmission electron microscopy (cryo-TEM) and in situ rheo-SAXS using synchrotron radiation shows that below 14$^\circ$C, twisted nanofibers are the thermodynamic phase. Between 14$^\circ$C and about 33$^\circ$C, nanofibers coexist with micelles and a strong hydrogel forms, the sol-to-gel transition being readily reversible in this temperature range. However, above the annealing temperature of about 40$^\circ$C, the micelle morphology becomes kinetically-trapped over hours, even upon cooling, whichever the rate, to 4$^\circ$C. A combination of solution and solid-state nuclear magnetic resonance (NMR) suggests two different conformations of the 1'', 1' and 2' carbon stereocenters of sophorose, precisely at the $\beta(1,2)$ glycosidic bond, for which several combinations of the dihedral angles are known to provide at least three energetic minima of comparable magnitude and each corresponding to a given sophorose conformation.

cond-mat.mtrl-sci↗

arXiv2022

Assessing Omitted Variable Bias when the Controls are Endogenous

Omitted variables are one of the most important threats to the identification of causal effects. Several widely used methods assess the impact of omitted variables on empirical conclusions by comparing measures of selection on observables with measures of selection on unobservables. The recent literature has discussed various limitations of these existing methods, however. This includes challenges that arise when the omitted variables are endogenous, meaning that they are correlated with the included controls. We develop a new approach to regression sensitivity analysis that avoids those limitations, while still allowing researchers to calibrate sensitivity parameters by comparing the magnitude of selection on observables with the magnitude of selection on unobservables as in previous methods. We illustrate our results in an empirical study of the effect of historical American frontier life on modern cultural beliefs. Finally, we implement these methods in the companion Stata module regsensitivity for easy use in practice.

econ.EM↗

arXiv2022

Choosing Exogeneity Assumptions in Potential Outcome Models

There are many kinds of exogeneity assumptions. How should researchers choose among them? When exogeneity is imposed on an unobservable like a potential outcome, we argue that the form of exogeneity should be chosen based on the kind of selection on unobservables it allows. Consequently, researchers can assess the plausibility of any exogeneity assumption by studying the distributions of treatment given the unobservables that are consistent with that assumption. We use this approach to study two common exogeneity assumptions: quantile and mean independence. We show that both assumptions require a kind of non-monotonic relationship between treatment and the potential outcomes. We discuss how to assess the plausibility of this kind of treatment selection. We also show how to define a new and weaker version of quantile independence that allows for monotonic treatment selection. We then show the implications of the choice of exogeneity assumption for identification. We apply these results in an empirical illustration of the effect of child soldiering on wages.

econ.EM↗

arXiv2021

Identification and Estimation of Partial Effects in Nonlinear Semiparametric Panel Models

Average partial effects (APEs) are often not point identified in panel models with unrestricted unobserved individual heterogeneity, such as a binary response panel model with fixed effects and logistic errors as a special case. This lack of point identification occurs despite the identification of these models' common coefficients. We provide a unified framework to establish the point identification of various partial effects in a wide class of nonlinear semiparametric models under an index sufficiency assumption on the unobserved heterogeneity, even when the error distribution is unspecified and non-stationary. This assumption does not impose parametric restrictions on the unobserved heterogeneity and idiosyncratic errors. We also present partial identification results when the support condition fails. We then propose three-step semiparametric estimators for APEs, average structural functions, and average marginal effects, and show their consistency and asymptotic normality. Finally, we illustrate our approach in a study of determinants of married women's labor supply.

econ.EM↗

arXiv2021

pH Switchable Pickering Emulsions Stabilized by Polyelectrolyte Biosurfactant Complex Coacervate Colloids

Polyelectrolyte-surfactant complexes (PESCs) have long been employed as oil-in-water (o/w) emulsions stabilizers, but never in the structure of colloidal complex coacervates providing a Pickering effect. The complexed state of PESCs could make them unsuitable o/w Pickering emulsifiers, which instead require a balance between colloidal structure and stability, amphiphilicity and wettability. Here we hypothesize that PESCs coacervates are efficient Pickering stabilizers. Instead of classical surfactants, we employ sophorolipid (SL) biosurfactants, atypical anionic/neutral stimuli-responsive biosurfactants. Despite their tunable charge and mild amphiphilic character, they can be used in combination with cationic/neutral polyelectrolytes (chitosan, CHL, or poly-L-lysine, PLL) to form PESC coacervates for the development of biobased, but also pH-switchable, Pickering emulsions.Aqueous solutions of SL-CHL (or SL-PLL) complex coacervates are emulsified with dodecane. Confocal laser scanning microscopy (CLSM) and scanning electron microscopy under cryogenic conditions (cryo-SEM) demonstrate the Pickering effect, while optical microscopy and oscillatory rheology respectively assess the emulsion formation and relative viscoelastic properties.Both SL-CHL and SL-PLL PESCs stabilize o/w emulsions up to $\Phi$oil of 0.7 only in the pH region of complex coacervation (6 < pH < 9): outside this range, phase separation occurs. Rheology shows a typical solid-like response and mechanical recovery upon applying large deformations. CLSM and cryo-SEM highlight a colloidal structure, associated to the complex coacervates, of the oil/water interface and suggest a Pickering effect. These findings demonstrate the Pickering effect from PESC coacervates and the possibility to use biobased and biocompatible components, with application potential in cosmetics, food science, or oil recovery.

cond-mat.soft↗

arXiv2021

Self-Assembly, Interfacial Properties, Interactions with Macromolecules and Molecular Modelling and Simulation of Microbial Bio-based Amphiphiles (Biosurfactants). A Tutorial Review

Chemical surfactants are omnipresent in consumers' products but they suffer from environmental concerns. For this reason, complete replacement of petrochemical surfactants by biosurfactants constitute a holy grail but this is far from occurring any soon. If the "biosurfactants revolution" has not occurred, yet, mainly due to the higher cost and lower availability of biosurfactants, another reason explains this fact: the poor knowledge of their properties in solution. This tutorial review aims at reviewing the self-assembly properties and phase behavior, experimental (sections 2.3 and 2.4) and from molecular modelling (section 5), in water of the most important microbial biosurfactants (sophorolipids, rhamnolipids, surfacting, cellobioselipids, glucolipids) as well as their major derivatives. A critical discussion of such properties in light of the well-known packing parameter of surfactants is also provided (section 2.5). The relationship between the nanoscale self-assembly and macroscopic materials properties, including hydrogelling, solid foaming, templating or encapsulation is specifically discussed (section 2.7). We also present their self-assembly and adsorption at flat and complex air/liquid (e.g., foams), air/solid (adhesion), liquid/solid (nanoparticles) and liquid/liquid (e.g., emulsions) interfaces (section 3). A critical discussion on the use of biosurfactants as capping agents for the development of stable nanoparticles is specifically provided (section 3.2.4). Finally, we discuss the major findings involving biosurfactants and macromolecules, including proteins, enzymes, polymers and polyelectrolytes.

cond-mat.soft↗

arXiv2020

Assessing Sensitivity to Unconfoundedness: Estimation and Inference

This paper provides a set of methods for quantifying the robustness of treatment effects estimated using the unconfoundedness assumption (also known as selection on observables or conditional independence). Specifically, we estimate and do inference on bounds on various treatment effect parameters, like the average treatment effect (ATE) and the average effect of treatment on the treated (ATT), under nonparametric relaxations of the unconfoundedness assumption indexed by a scalar sensitivity parameter c. These relaxations allow for limited selection on unobservables, depending on the value of c. For large enough c, these bounds equal the no assumptions bounds. Using a non-standard bootstrap method, we show how to construct confidence bands for these bound functions which are uniform over all values of c. We illustrate these methods with an empirical application to effects of the National Supported Work Demonstration program. We implement these methods in a companion Stata module for easy use in practice.

econ.EM↗

arXiv2020

Synthesis and self-assembly of aminyl and alkynyl substituted sophorolipids

Sophorolipids are one of the most important microbial biosurfactants, because of their large-scale production and applications developed so far in the fields of detergency, microbiology, cosmetics or environmental science. However, the structural variety of native sophorolipids is limited/restricted, a limiting fact for the development of new properties and their potential applications. In their open acidic form, C18:1 sophorolipids (SL) are classically composed of a sophorose headgroup and a carboxylic acid (COOH) end-group. The carboxyl group gives them unique pH-responsive properties, but they are a poorly-reactive group and their charge can only be negative. To develop a new generation of pH-responsive, positively-charged, SL and to improve their reactivity for further functionalization, we develop here SLs with an amine (-NH2) or terminal alkyne (-C$\not\equiv$CH) end-group analogues. The amine group generates positively-charged SL and is more reactive than carboxylic acids, e.g. towards aldehydes; the alkyne group provides access to copper-based click chemistry. In this work, we synthesize (C18:1) and (C18:0) --NH2 and (C18:1) -C$\not\equiv$CH sophorolipid derivatives and we study their self-assembly properties in response to pH and/or temperature changes by means of static and dynamic light scattering, small angle (X-ray, neutron) scattering and cryogenic electron microscopy. Monounsaturated aminyl SL-C18:1-NH2 sophorolipids form a micellar phase in their neutral form at high pH and a mixed micellar-bilayer phase in their positively-charged form at low pH. Saturated aminyl SL-C18:0-NH2 sophorolipids form a micellar phase in their charged form at low pH and a twisted ribbon phase in their neutral form at high pH and monounsaturated alkynyl SL-C18:1-C$\not\equiv$CH sophorolipids form a main micellar phase at T> 51.8{\textdegree}C and a twisted ribbon phase at T< 51.8 {\textdegree}C.

cond-mat.soft↗