A high temperature in situ optical probe for colloidal nanocrystal synthesis.

We report on the fabrication and utilization of a robust high-temperature (>300 °C), adjustable-path-length, vacuum-tolerant, configurable, in situ optical probe, which interfaces with widely used chemical glassware via a 14/20 ground glass joint. This probe allows for high-speed reaction monitoring of colloidal semiconductor nanocrystal solutions at temperatures that were previously inaccessible. We demonstrate this capability by monitoring the hot-injection synthesis of CdSe quantum dots via UV-Vis absorption spectroscopy at 380 °C with a time resolution of ∼10 ms, with the primary limitation being the acquisition and data saving rate of the commercial spectrometer used. We further demonstrate that this probe can also be used for in situ photoluminescence measurements. This system is generally applicable to harsh solution environments where optical monitoring of reaction progress is desirable and/or necessary.

Colloidal Multi-Dot Nanorods.

Colloidal nanorod heterostructures consisting of multiple quantum dots within a nanorod (n-DNRs, where n is the number of quantum dots within a nanorod) are synthesized with alternating segments of CdSe "dot" and CdS "rod" via solution heteroepitaxy. The reaction temperature, time dependent ripening, and asymmetry of the wurtzite lattice and the resulting anisotropy of surface ligand steric hindrance are exploited to vary the morphology of the growing quantum dot segments. The alternating CdSe and CdS growth steps can be easily repeated to increment the dot number in unidirectional or bidirectional growth regimes. As an initial exploration of electron occupation effects on their optical properties, asymmetric 2-DNRs consisting of two dots of different lengths and diameters are synthesized and are shown to exhibit a change in color and an unusual photoluminescence quantum yield increase upon photochemical doping.

pH Tunable Patterning of Quantum Dots.

Patterning of quantum dots (QDs) is essential for many, especially high-tech, applications. Here, pH tunable assembly of QDs over functional patterns prepared by electrohydrodynamic jet printing of poly(2-vinylpyridine) is presented. The selective adsorption of QDs from water dispersions is mediated by the electrostatic interaction between the ligand composed of 3-mercaptopropionic acid and patterned poly(2-vinylpyridine). The pH of the dispersion provides tunability at two levels. First, the adsorption density of QDs and fluorescence from the patterns can be modulated for pH > ≈4. Second, patterned features show unique type of disintegration resulting in randomly positioned features within areas defined by the printing for pH ≤ ≈4. The first capability is useful for deterministic patterning of QDs, whereas the second one enables hierarchically structured encoding of information by generating stochastic features of QDs within areas defined by the printing. This second capability is exploited for generating addressable security labels based on unclonable features. Through image analysis and feature matching algorithms, it is demonstrated that such patterns are unclonable in nature and provide a suitable platform for anti-counterfeiting applications. Collectively, the presented approach not only enables effective patterning of QDs, but also establishes key guidelines for addressable assembly of colloidal nanomaterials.

Improving photovoltaic performance of light-responsive double-heterojunction nanorod light-emitting diodes.

Double heterojunction nanorods enable both electroluminescence and light harvesting capabilities within the same device structure, providing a promising platform for energy-scavenging displays and related applications. However, the efficiency of the photovoltaic mode remains modest for useful power conversion and may be challenging to improve without sacrificing performance in electroluminescence. Through a facile on-film partial ligand exchange with benzenethiol integrated into the device fabrication step, we achieve an average of more than threefold increase in power conversion efficiency while maintaining the maximum external quantum efficiency and the maximum luminance in the LED mode. The improved photovoltaic performance is mainly due to the increase in the short circuit current, which we attribute to the enhanced charge separation afforded by the partial ligand exchange. The recovery of the photoluminescence lifetime under the forward bias suggests that the hole traps introduced by benzenethiols are filled prior to reaching the voltage at which light emission begins, allowing LED performance to be maintained and possibly improved.

Charging and Charged Species in Quantum Dot Light-Emitting Diodes.

Despite recent rapid advances in improving quantum dot light-emitting diodes, many fundamental aspects of the device operating mechanism remain unresolved. Through transient electroluminescence and time-resolved photoluminescence measurements, the effects of offset voltage on charging and charge transport are examined. First, capacitive charging occurs with a time constant of ∼500 ns, followed by electron transport through quantum dots with a mobility of ∼10-5 cm2 V-1 s-1. Hole injection then initiates an electroluminescence rise that is independent of offset voltage. The photoluminescence lifetime is also unaffected by the offset voltage, indicating no injection of charges into the quantum dots or on their surfaces prior to the voltage pulse. A slower equilibration to steady-state electroluminescence is dependent on the offset voltage, indicative of another charging process. Elemental mapping shows that ZnO deposition from solution can lead to the diffusion of charged species into the quantum dot layer, which may cause the slower process.

Local field potential decoding of the onset and intensity of acute pain in rats.

Pain is a complex sensory and affective experience. The current definition for pain relies on verbal reports in clinical settings and behavioral assays in animal models. These definitions can be subjective and do not take into consideration signals in the neural system. Local field potentials (LFPs) represent summed electrical currents from multiple neurons in a defined brain area. Although single neuronal spike activity has been shown to modulate the acute pain, it is not yet clear how ensemble activities in the form of LFPs can be used to decode the precise timing and intensity of pain. The anterior cingulate cortex (ACC) is known to play a role in the affective-aversive component of pain in human and animal studies. Few studies, however, have examined how neural activities in the ACC can be used to interpret or predict acute noxious inputs. Here, we recorded in vivo extracellular activity in the ACC from freely behaving rats after stimulus with non-noxious, low-intensity noxious, and high-intensity noxious stimuli, both in the absence and chronic pain. Using a supervised machine learning classifier with selected LFP features, we predicted the intensity and the onset of acute nociceptive signals with high degree of precision. These results suggest the potential to use LFPs to decode acute pain.

A Practical Approach to Managing Transcatheter Aortic Valve Replacement With Sedation.

Transcatheter aortic valve replacement is increasingly performed as a minimally invasive treatment option for aortic valve disease. The typical anesthetic management for this procedure was traditionally similar to surgical aortic valve replacement and involved general anesthesia and transesophageal echocardiography. In this review, we discuss the technological advances in transcatheter valve systems that have improved outcomes and allow for use of sedation instead of general anesthesia. We describe an anesthetic protocol that avoids general anesthesia and utilizes transthoracic echocardiography for procedural guidance.

Novel 5' untranslated region directed blockers of iron-regulatory protein-1 dependent amyloid precursor protein translation: implications for down syndrome and Alzheimer's disease.

We reported that iron influx drives the translational expression of the neuronal amyloid precursor protein (APP), which has a role in iron efflux. This is via a classic release of repressor interaction of APP mRNA with iron-regulatory protein-1 (IRP1) whereas IRP2 controls the mRNAs encoding the L- and H-subunits of the iron storage protein, ferritin. Here, we identified thirteen potent APP translation blockers that acted selectively towards the uniquely configured iron-responsive element (IRE) RNA stem loop in the 5' untranslated region (UTR) of APP mRNA. These agents were 10-fold less inhibitory of 5'UTR sequences of the related prion protein (PrP) mRNA. Western blotting confirmed that the 'ninth' small molecule in the series selectively reduced neural APP production in SH-SY5Y cells at picomolar concentrations without affecting viability or the expression of α-synuclein and ferritin. APP blocker-9 (JTR-009), a benzimidazole, reduced the production of toxic Aß in SH-SY5Y neuronal cells to a greater extent than other well tolerated APP 5'UTR-directed translation blockers, including posiphen, that were shown to limit amyloid burden in mouse models of Alzheimer's disease (AD). RNA binding assays demonstrated that JTR-009 operated by preventing IRP1 from binding to the IRE in APP mRNA, while maintaining IRP1 interaction with the H-ferritin IRE RNA stem loop. Thus, JTR-009 constitutively repressed translation driven by APP 5'UTR sequences. Calcein staining showed that JTR-009 did not indirectly change iron uptake in neuronal cells suggesting a direct interaction with the APP 5'UTR. These studies provide key data to develop small molecules that selectively reduce neural APP and Aß production at 10-fold lower concentrations than related previously characterized translation blockers. Our data evidenced a novel therapeutic strategy of potential impact for people with trisomy of the APP gene on chromosome 21, which is a phenotype long associated with Down syndrome (DS) that can also cause familial Alzheimer's disease.