Ligand Steric Profile Tunes the Reactivity of Indium Phosphide Clusters.

Indium phosphide quantum dots have become an industrially relevant material for solid-state lighting and wide color gamut displays. The synthesis of indium phosphide quantum dots from indium carboxylates and tris(trimethylsilyl)phosphine (P(SiMe3)3) is understood to proceed through the formation of magic-sized clusters, with In37P20(O2CR)51 being the key isolable intermediate. The reactivity of the In37P20(O2CR)51 cluster is a vital parameter in controlling the conversion to quantum dots. Herein, we report structural perturbations of In37P20(O2CR)51 clusters induced by tuning the steric properties of a series of substituted phenylacetate ligands. This approach allows for control over reactivity with P(SiMe3)3, where meta-substituents enhance the susceptibility to ligand displacement, and para-substituents hinder phosphine diffusion to the core. Thermolysis studies show that with complete cluster dissolution, steric profile can modulate the nucleation period, resulting in a nanocrystal size dependence on ligand steric profile. The enhanced stability from ligand engineering also allows for the isolation and structural characterization by single-crystal X-ray diffraction of a new III-V magic-sized cluster with the formula In26P13(O2CR)39. This intermediate precedes the In37P20(O2CR)51 cluster on the InP QD reaction coordinate. The physical and electronic structure of this cluster are analyzed, providing new insight into previously unrecognized relationships between II-VI and III-V materials and the discrete growth of III-V cluster intermediates.

Survival implications of postoperative restricted diffusion in high-grade glioma and limitations of intraoperative MRI detection.

PURPOSE: Here we assess whether the volume of cerebral ischemia induced during glioma surgery may negatively impact survival independently of neurological function. We also evaluate the sensitivity of intraoperative MRI (iMRI) in detecting cerebral ischemia during surgery. METHODS: We retrospectively reviewed 361 cranial surgeries that used a 3 Tesla iMRI. 165 patients met all inclusion criteria and were included in the final analysis. Diffusion weighted imaging (DWI) obtained during iMRI was compared to postoperative DWI obtained within 7 days of the operation in cases where no further resection occurred after the iMRI. RESULTS: 42 of 165 patients (25%) showed at least some evidence of restricted diffusion on postoperative (poMRI). 37 of these 42 (88%) cases lacked evidence of restricted diffusion on iMRI, meaning iMRI had a false-negative rate of 88% and a sensitivity of 12% in assessing the extent of ischemic brain after surgery. In high-grade gliomas, the volume of restricted diffusion on poMRI was predictive of overall survival, independent of new functional deficits acquired during surgery (p = 0.011). CONCLUSION: This study presents the largest case series to date analyzing the sensitivity of iMRI in detecting surgical ischemia. In high-grade gliomas, increased volume of ischemia correlated with worsening median overall survival (OS) irrespective of postoperative neurologic deficits. Future work will focus on improving intraoperative detection of ischemia during the hyperacute phase when interventions such as blood pressure modulation or direct application of vasodilator agents may be effective.

Consistent predictors of microbial community composition across spatial scales in grasslands reveal low context-dependency.

Environmental circumstances shaping soil microbial communities have been studied extensively. However, due to disparate study designs, it has been difficult to resolve whether a globally consistent set of predictors exists, or context-dependency prevails. Here, we used a network of 18 grassland sites (11 of those containing regional plant productivity gradients) to examine (i) if similar abiotic or biotic factors predict both large-scale (across sites) and regional-scale (within sites) patterns in bacterial and fungal community composition, and (ii) if microbial community composition differs consistently at two levels of regional plant productivity (low vs. high). Our results revealed that bacteria were associated with particular soil properties (such as base saturation) and both bacteria and fungi were associated with plant community composition across sites and within the majority of sites. Moreover, a discernible microbial community signal emerged, clearly distinguishing high and low-productivity soils across different grasslands independent of their location in the world. Hence, regional productivity differences may be typified by characteristic soil microbial communities across the grassland biome. These results could encourage future research aiming to predict the general effects of global changes on soil microbial community composition in grasslands and to discriminate fertile from infertile systems using generally applicable microbial indicators.

Factors Associated With Neuroradiologic Diagnostic Errors at a Large Tertiary-Care Academic Medical Center: A Case-Control Study.

BACKGROUND. Numerous studies have explored factors associated with diagnostic errors in neuroradiology; however, large-scale multivariable analyses are lacking. OBJECTIVE. The purpose of this study was to evaluate associations of interpretation time, shift volume, care setting, day of week, and trainee participation with diagnostic errors by neuroradiologists at a large academic medical center. METHODS. This retrospective case-control study using a large tertiary-care academic medical center's neuroradiology quality assurance database evaluated CT and MRI examinations for which neuroradiologists had assigned RADPEER scores. The database was searched from January 2014 through March 2020 for examinations without (RADPEER score of 1) or with (RADPEER scores of 2a, 2b, 3a, 3b, or 4) diagnostic error. For each examination with error, two examinations without error were randomly selected (unless only one examination could be identified) and matched by interpreting radiologist and examination type to form case and control groups. Marginal mixed-effects logistic regression models were used to assess associations of diagnostic error with interpretation time (number of minutes since the immediately preceding report's completion), shift volume (number of examinations interpreted during the shift), emergency/inpatient setting, weekend interpretation, and trainee participation in interpretation. RESULTS. The case group included 564 examinations in 564 patients (mean age, 50.0 ± 25.0 [SD] years; 309 men, 255 women); the control group included 1019 examinations in 1019 patients (mean age, 52.5 ± 23.2 years; 540 men, 479 women). In the case versus control group, mean interpretation time was 16.3 ± 17.2 [SD] minutes versus 14.8 ± 16.7 minutes; mean shift volume was 50.0 ± 22.1 [SD] examinations versus 45.4 ± 22.9 examinations. In univariable models, diagnostic error was associated with shift volume (OR = 1.22, p < .001) and weekend interpretation (OR = 1.60, p < .001) but not interpretation time, emergency/inpatient setting, or trainee participation (p > .05). However, in multivariable models, diagnostic error was independently associated with interpretation time (OR = 1.18, p = .003), shift volume (OR = 1.27, p < .001), and weekend interpretation (OR = 1.69, p = .02). In subanalysis, diagnostic error showed independent associations on weekdays with interpretation time (OR = 1.18, p = .003) and shift volume (OR = 1.27, p < .001); such associations were not observed on weekends (interpretation time: p = .62; shift volume: p = .58). CONCLUSION. Diagnostic errors in neuroradiology were associated with longer interpretation times, higher shift volumes, and weekend interpretation. CLINICAL IMPACT. These findings should be considered when designing work-flow-related interventions seeking to reduce neuroradiology interpretation errors.

Colloidal, Room-Temperature Growth of Metal Oxide Shells on InP Quantum Dots.

We demonstrate colloidal, layer-by-layer growth of metal oxide shells on InP quantum dots (QDs) at room temperature. We show with computational modeling that native InP QD surface oxides give rise to nonradiative pathways due to the presence of surface-localized dark states near the band edges. Replacing surface indium with zinc to form a ZnO shell results in reduced nonradiative decay and a density of states at the valence band edge that resembles defect-free, stoichiometric InP. We then developed a synthetic strategy using stoichiometric amounts of common atomic layer deposition precursors in alternating cycles to achieve layer-by-layer growth. Metal-oxide-shelled InP QDs show bulk and local structural perturbations as determined by X-ray diffraction and extended X-ray absorption fine structure spectroscopy. Upon growing ZnSe shells of varying thickness on the oxide-shelled QDs, we observe increased photoluminescence (PL) quantum yields and narrowing of the emission linewidths that we attribute to decreased ion diffusion to the shell, as supported by phosphorus X-ray emission spectroscopy. These results present a versatile strategy to control QD interfaces for novel heterostructure design by leveraging surface oxides. This work also contributes to our understanding of the connections between structural complexity and PL properties in technologically relevant colloidal optoelectronic materials.

Role of Advanced MR Imaging in Diagnosis of Neurological Malignancies: Current Status and Future Perspective.

Lesions of the central nervous system (CNS) can present with numerous and overlapping radiographical and clinical features that make diagnosis difficult based exclusively on history, physical examination, and traditional imaging modalities. Given that there are significant differences in optimal treatment protocols for these various CNS lesions, rapid and non-invasive diagnosis could lead to improved patient care. Recently, various advanced magnetic resonance imaging (MRI) techniques showed promising methods to differentiate between various tumors and lesions that conventional MRI cannot define by comparing their physiologic characteristics, such as vascularity, permeability, oxygenation, and metabolism. These advanced MRI techniques include dynamic susceptibility contrast MRI (DSC), diffusion-weighted imaging (DWI), dynamic contrast-enhanced (DCE) MRI, Golden-Angle Radial Sparse Parallel imaging (GRASP), Blood oxygen level-dependent functional MRI (BOLD fMRI), and arterial spin labeling (ASL) MRI. In this article, a narrative review is used to discuss the current trends in advanced MRI techniques and potential future applications in identifying difficult-to-distinguish CNS lesions. Advanced MRI techniques were found to be promising non-invasive modalities to differentiate between paraganglioma, schwannoma, and meningioma. They are also considered promising methods to differentiate gliomas from lymphoma, post-radiation changes, pseudoprogression, demyelination, and metastasis. Advanced MRI techniques allow clinicians to take advantage of intrinsic biological differences in CNS lesions to better identify the etiology of these lesions, potentially leading to more effective patient care and a decrease in unnecessary invasive procedures. More clinical studies with larger sample sizes should be encouraged to assess the significance of each advanced MRI technique and the specificity and sensitivity of each radiologic parameter.

Tuning the interfacial stoichiometry of InP core and InP/ZnSe core/shell quantum dots.

We demonstrate fine-tuning of the atomic composition of InP/ZnSe quantum dots (QDs) at the core/shell interface. Specifically, we control the stoichiometry of both anions (P, As, S, and Se) and cations (In and Zn) at the InP/ZnSe core/shell interface and correlate these changes with the resultant steady-state and time-resolved optical properties of the nanocrystals. The use of reactive trimethylsilyl reagents results in surface-limited reactions that shift the nanocrystal stoichiometry to anion-rich and improve epitaxial growth of the shell layer. In general, anion deposition on the InP QD surface results in a redshift in the absorption, quenching of the excitonic photoluminescence, and a relative increase in the intensity of broad trap-based photoluminescence, consistent with delocalization of the exciton wavefunction and relaxation of exciton confinement. Time-resolved photoluminescence data for the resulting InP/ZnSe QDs show an overall small change in the decay dynamics on the ns timescale, suggesting that the relatively low photoluminescence quantum yields may be attributed to the creation of new thermally activated charge trap states and likely a dark population that is inseparable from the emissive QDs. Cluster-model density functional theory calculations show that the presence of core/shell interface anions gives rise to electronic defects contributing to the redshift in the absorption. These results highlight a general strategy to atomistically tune the interfacial stoichiometry of InP QDs using surface-limited reaction chemistry allowing for precise correlations with the electronic structure and photophysical properties.

Isolated IgG4-related Infundibulo-hypophysitis.

A 72-year-old man presented with several months of weakness, poor appetite, and depressed moods. Laboratory tests indicated central hypocortisolism, hypothyroidism and hypogonadism, and mild hyperprolactinemia. Imaging indicated a homogenously enhancing solid suprasellar mass inseparable from the hypothalamus and contiguous with a thickened proximal infundibulum. Neuro-ophthalmological evaluation was normal. Symptoms improved with hydrocortisone, levothyroxine, and testosterone replacement. After 6 months, transsphenoidal biopsy was performed due to mass enlargement and revealed fibrosis, lymphoplasmacytic infiltration, and CD138 and IgG4 staining. The levels of serum IgG4, complement, inflammatory markers, protein electrophoresis, amylase, and lipase and imaging of the chest, abdomen, and thyroid were unremarkable. After 1 month of prednisone therapy (starting dose 40 mg/day), the mass significantly involuted and remained stable afterward. Prednisone was gradually tapered to 5 mg daily over 10 weeks. During 22 months of follow-up, no systemic IgG4 disease was detected. Glucocorticoid, thyroid, and testosterone replacement was continued. This case of isolated IgG4-related hypophysitis illustrates the variable presentation that may not entail vasopressin deficiency or clinical mass effect. This entity should be considered in the differential diagnosis of suprasellar masses even in the absence of IgG4 systemic disease or characteristic serology. Management entails multidisciplinary collaboration and long-term follow-up.

Shift Volume Directly Impacts Neuroradiology Error Rate at a Large Academic Medical Center: The Case for Volume Limits.

BACKGROUND AND PURPOSE: Unlike in Europe and Japan, guidelines or recommendations from specialized radiological societies on workflow management and adaptive intervention to reduce error rates are currently lacking in the United States. This study of neuroradiologic reads at a large US academic medical center, which may hopefully contribute to this discussion, found a direct relationship between error rate and shift volume. MATERIALS AND METHODS: CT and MR imaging reports from our institution's Neuroradiology Quality Assurance database (years 2014-2020) were searched for attending physician errors. Data were collected on shift volume specific error rates per 1000 interpreted studies and RADPEER scores. Optimal cutoff points for 2, 3 and 4 groups of shift volumes were computed along with subgroups' error rates. RESULTS: A total of 643 errors were found, 91.7% of which were clinically significant (RADPEER 2b, 3b). The overall error rate (errors/1000 examinations) was 2.36. The best single shift volume cutoff point generated 2 groups: ≤ 26 studies (error rate 1.59) and > 26 studies (2.58; OR: 1.63, P < .001). The best 2 shift volume cutoff points generated 3 shift volume groups: ≤ 19 (1.34), 20-28 (1.88; OR: 1.4, P = .1) and ≥ 29 (2.6; OR: 1.94, P < .001). The best 3 shift volume cutoff points generated 4 groups: ≤ 24 (1.59), 25-66 (2.44; OR: 1.54, P < .001), 67-90 (3.03; OR: 1.91, P < .001), and ≥ 91 (2.07; OR: 1.30, P = .25). The group with shift volume ≥ 91 had a limited sample size. CONCLUSIONS: Lower shift volumes yielded significantly lower error rates. The lowest error rates were observed with shift volumes that were limited to 19-26 studies. Error rates at shift volumes between 67-90 studies were 226% higher, compared with the error rate at shift volumes of ≤ 19 studies.

Synthesis and Single Crystal X-ray Diffraction Structure of an Indium Arsenide Nanocluster.

The discovery of magic-sized clusters as intermediates in the synthesis of colloidal quantum dots has allowed for insight into formation pathways and provided atomically precise molecular platforms for studying the structure and surface chemistry of those materials. The synthesis of monodisperse InAs quantum dots has been developed through the use of indium carboxylate and As(SiMe3)3 as precursors and documented to proceed through the formation of magic-sized intermediates. Herein, we report the synthesis, isolation, and single-crystal X-ray diffraction structure of an InAs nanocluster that is ubiquitous across reports of InAs quantum dot synthesis. The structure, In26As18(O2CR)24(PR'3)3, differs substantially from previously reported semiconductor nanocluster structures even within the III-V family. However, it can be structurally linked to III-V and II-VI cluster structures through the anion sublattice. Further analysis using variable temperature absorbance spectroscopy and support from computation deepen our understanding of the reported structure and InAs nanomaterials as a whole.

Electronic Structures and Spectroscopic Signatures of Noble-Gas-Doped Nanodiamonds.

Fluorescent nanodiamonds, that is, those containing optically active defects, have attracted interest for their ability to be used as qubits; for in vivo imaging; and as sensors for spin, stress, and temperature. One of the most commonly studied nanodiamond color centers is the nitrogen vacancy. However, there is strong interest in discovering other impurity centers that provide localized midband gap transitions. Noble gas atoms have garnered attention since they have been discovered within nanodiamonds produced through high-pressure-high-temperature laser-heated diamond anvil cell synthesis methods, where they are commonly used as hydrostatic pressure media. Noble gas atoms that exist in macrosized natural or synthetic diamonds have been shown to be able to form color centers. This research uses ab initio density functional theory and cluster models to systematically study the localized electronic structure for group VIII impurities of nanodiamond, including helium, neon, argon, krypton, and xenon. An in-depth examination of the interaction between the noble gas atom and diamond lattice has been carried out. The changes to the vibrational and UV/vis absorption spectra have been analyzed. It was determined that the energetically preferred geometry is dependent on the atom size. Most noble gas defects are stabilized within the nanodiamond lattice and exist in tetrahedral interstitial positions, except for the largest noble gas studied in this work, Xe, which was determined to prefer a substitutional configuration. Both Kr and Xe are expected to be able to manifest visible/near-IR optical responses when included in the diamond lattice.

Enhanced Charge Transfer from Coinage Metal Doped InP Quantum Dots.

This paper describes coinage-metal-doped InP quantum dots (QDs) as a platform for enhanced electron transfer to molecular acceptors relative to undoped QDs. A synthetic strategy is developed to prepare doped InP/ZnSe QDs. First-principles DFT calculations show that Ag+ and Cu+ dopants localize photoexcited holes while leaving electrons delocalized. This charge carrier wave function modulation is leveraged to enhance electron transfer to molecular acceptors by up to an order of magnitude. Examination of photoluminescence quenching data suggests that larger electron acceptors, such as anthraquinone and methyl viologen, bind to the QD surface in two ways: by direct adsorption to the surface and by adsorption following displacement of a weakly bound surface cation-ligand complex. Reactions with larger acceptors show the greatest increases in electron transfer between doped and undoped quantum dots, while smaller acceptors show smaller enhancements. Specifically, benzoquinone shows the smallest, followed by naphthoquinone and then methyl viologen and anthraquinone. These results demonstrate the benefits of dopant-induced excited-state carrier localization on photoinduced charge transfer and highlight design principles for improved implementation of quantum dots in photoredox catalysis.

Autoimmune diseases of the spine and spinal cord.

Magnetic resonance imaging (MRI) and clinicopathological tools have led to the identification of a wide spectrum of autoimmune entities that involve the spine. A clearer understanding of the unique imaging features of these disorders, along with their clinical presentations, will prove invaluable to clinicians and potentially limit the need for more invasive procedures such as tissue biopsies. Here, we review various autoimmune diseases affecting the spine and highlight salient imaging features that distinguish them radiologically from other disease entities.

Magnetic resonance imaging-derived relative cerebral blood volume characteristics in a case of pathologically confirmed neurocysticercosis: illustrative case.

BACKGROUND: Neurocysticercosis (NCC) is a parasitic infection of the brain caused by ingesting water or food contaminated with tapeworm eggs. When it presents as a solitary mass, differentiation from a primary brain tumor on imaging can be difficult. Magnetic resonance imaging (MRI)-derived relative cerebral blood volume (rCBV) is a newer imaging technique used to identify areas of neovascularization in tumors, which may advance the differential diagnosis. OBSERVATIONS: A 25-year-old male presented after a seizure. Computed tomography (CT) and MRI demonstrated a partially enhancing lesion with microcalcifications and vasogenic edema. Follow-up rCBV assessment demonstrated mild hyperperfusion and/or small vessels at the lesional margins consistent with either an intermediate grade glioma or infection. Given the radiological equipoise, surgical accessibility, and differential diagnosis including primary neoplasm, metastatic disease, NCC, and abscess, resection was pursued. The calcified mass was excised en bloc and was confirmed as larval-stage NCC. LESSONS: CT or MRI may not always provide sufficient information to distinguish NCC from brain tumors. Although reports have suggested that rCBV may aid in identifying NCC, here the authors describe a case of pathologically confirmed NCC in which preoperative, qualitative, standardized rCBV findings raised concern for a primary neoplasm. This case documents the first standardized rCBV values reported in a pathologically confirmed case of NCC in the United States.

Posterior arm compartment syndrome after a combined supracondylar humeral and capitellar fractures in an adolescent: a case report.

BACKGROUND: Supracondylar humeral fractures in children are common, with associated bony injuries typically being fractures of the forearm or distal radius. To our knowledge, a combined supracondylar humeral fracture associated with a Hahn-Steinthal capitellar fracture has not been reported earlier. Similarly, posterior arm compartment syndrome is extremely rare, with most instances having occurred after chronic compression and bleeding into the compartments from anticoagulation, direct trauma including crush, or tendon ruptures. Only 2 cases have been reported after a fracture of the humerus. One of these described fractures was localized to a distal shaft and the other involved the surgical neck. No cases have been reported in children, nor have any been reported after a supracondylar humeral fracture. METHODS: In this case report, we describe a patient who presented with an ipsilateral Wilkins type-3A supracondylar humeral fracture, Hahn-Steinthal capitellar fracture, Salter-Harris II distal radius fracture, and posterior arm compartment syndrome. RESULTS: The patient was taken to the operative room for closed reduction and percutaneous pinning of the radius fracture with open reduction, internal fixation of the distal humeral fractures. Elevated compartment pressure measurements were anticipated because of the nature of the injuries. After fixation of the fractures, the mobile wad, volar, and dorsal compartments measured 9, 9, and 8 mm Hg, respectively. The absolute pressure in the posterior arm compartment was measured multiple times in different locations ranging from 34 to 39 mm Hg. The patient's blood pressure throughout the case averaged 115/65 mm Hg. A diagnosis of posterior arm compartment syndrome was confirmed and the fascia was released. CONCLUSIONS: Our patient ultimately suffered 2 uncommon injuries involving the arm. She sustained a complex fracture of the distal humerus with an extension type supracondylar fracture, a separate Hahn-Steinthal capitellar fracture, and isolated posterior arm compartment syndrome. This is an unusual case that required specialized care and follow-up. LEVEL OF EVIDENCE: Level IV.

A comparison of the pain perceived during intravenous catheter insertion after injection with various local anesthetics.

This study compared 4 local anesthetics, 1% lidocaine, 1% lidocaine with sodium bicarbonate, 2% chloroprocaine, and 0.5% bupivacaine, in a double-blinded manner for pain on intradermal injection and pain during subsequent intravenous (IV) cannulation with an 18-gauge catheter. The subjects rated their pain, using 100-mm visual analog scales, related to the local injection itself and again after the IV catheter was inserted. No statistical differences were noted in pain scores after the injection of the local anesthetic (P = . 134) or on insertion of the IV catheter itself (P = .394). However, there was a low correlation between the pain perceived during the injection of local anesthetic and insertion of the IV catheter (r = 0.483; P = .001). We found that there were no differences in pain produced by 1% lidocaine, 1% lidocaine with sodium bicarbonate, 2% chloroprocaine, and 0.5% bupivacaine during intradermal injection. There were also no differences in pain produced by an 18-gauge IV catheter being inserted after administration of any of these local anesthetics. Thus, any of these 4 local anesthetics may be used, and the choice may be based on other factors such as price and convenience.

Defect-Induced Magnetic Skyrmion in a Two-Dimensional Chromium Triiodide Monolayer.

Chromium iodide monolayers, which have different magnetic properties in comparison to the bulk chromium iodide, have been shown to form skyrmionic states in applied electromagnetic fields or in Janus-layer devices. In this work, we demonstrate that spin-canted solutions can be induced into monolayer chromium iodide by select substitution of iodide atoms with isovalent impurities. Several concentrations and spatial configurations of halide substitutional defects are selected to probe the coupling between the local defect-induced geometric distortions and orientation of chromium magnetic moments. This work provides atomic-level insight into how atomically precise chemical doping can be used to create and control complex magnetic patterns in chromium iodide layers and lays out the foundation for investigating the field- and geometric-dependent magnetic properties in similar two-dimensional materials.

Simulating Magnetic Circular Dichroism Spectra with Real-Time Time-Dependent Density Functional Theory in Gauge Including Atomic Orbitals.

Magnetic circular dichroism (MCD) spectra are able to provide insights into the geometric, electronic, and magnetic properties of chemical systems. However, they can be challenging to understand and simulate given the need to simultaneously treat both the finite magnetic and optical fields. Thus, efficient simulations are desired to understand the spectra and resolve the molecular electronic states. Real-time dynamics are used widely in the simulation of electronic spectroscopies such as absorption as well as electronic circular dichroism, but simulating MCD with real-time dynamics is technically and theoretically challenging. In this work, we introduce a real-time dynamics-based ab initio method with a nonperturbative treatment of a static magnetic field with London orbitals for simulating the MCD spectra of closed shell systems. Effects of a magnetic field are included variationally in the spin-free nonrelativistic Hamiltonian. Real-time time-dependent density functional theory dynamics are then performed, from which we compute the response function in the presence of the external magnetic field, giving the MCD spectrum. The method developed in this paper is applied to simulate the MCD spectra for pyrimidine, pyrazine, and 1,4-naphthoquinone. Results are discussed and compared to the experiment.

Carboxylate Anchors Act as Exciton Reporters in 1.3 nm Indium Phosphide Nanoclusters.

Developing interfacial probes of ligand-nanocluster interactions is crucial for understanding and tailoring the optoelectronic properties of these emerging nanomaterials. Using transient IR spectroscopy, we demonstrate that ligand vibrational modes of oleate-capped 1.3 nm InP nanoclusters report on the photogenerated exciton. The exciton induces an intensity change in the asymmetric carboxylate stretching mode by 57% while generating no appreciable shift in frequency. Thus, the observed difference signal is attributed to an exciton-induced change in the dipole magnitude of the asymmetric carboxylate stretching mode. Additionally, the transient IR data reveal that the infrared dipole change is dependent on the geometry of the ligand bound to the nanocluster. The experimental results are interpreted using TDDFT calculations, which identify how the spatial dependence of an exciton-induced electron density shift affects the vibrational motion of the carboxylate anchors. More broadly, this work demonstrates transient IR spectroscopy as a useful method for characterizing ligand-nanocluster coupling interactions.