Prepregnancy body mass index and gestational weight gain affect the offspring neurobehavioral development at one year of age.

OBJECTIVE: Recent data show that maternal prepregnancy body mass index (BMI) and gestational weight gain (GWG) are associated with offspring neurobehavior in childhood. However, little is known about the effect on infants that less than 20 months of age, and whether this association has sex differences. METHODS: In this birth cohort study, a total of 661 mother-infant pairs were enrolled in Shanghai, China, between February 2017 and April 2019. Maternal prepregnancy BMI was categorized according to the Chinese classification and GWG according to the 2009 Institute of Medicine (IOM). Neurobehavioral development for infants of 12 months of age was assessed by Gesell Developmental Scale (GDS), which contained five subscales of gross motor, fine motor, adaptive behavior, language, and social behavior. RESULTS: Abnormal maternal prepregnancy BMI and excessive GWG were associated with infant birth weight and/or birth length (p < .05), while no influence was found on yearling weight or length. Women who were overweight/obese prior to pregnancy or excessive GWG during pregnancy had infants who were more deficient in neurobehavioral developmental including language (p < .01) and/or social behavior (p < .05). Specifically, excessive GWG was associated with lower language ability in girls but not boys (p < .05). CONCLUSIONS: Aberrant prepregnancy BMI and excessive GWG not only affect the body size of newborn infants, but also impair their neurobehavioral development, suggesting that general guidance to the women should be advised to attain optimal prepregnancy BMI and GWG.

Osteoporotic fractures and persistent non-fusion of the hand epiphyses caused by empty sella syndrome in an adult: a case report.

We report a case of primary empty sella syndrome (ESS) resulting in osteoporotic fractures and persistent non-fusion of the hand epiphyses, and discuss the potential pathogenesis of this disease. A 41-year-old man presented with pain in the right hand and back after a fall. X-radiographs revealed persistent epiphyses and severe osteoporosis. Serum phosphorus and prolactin levels were above normal levels, and free triiodothyronine, free thyroxine and testosterone levels were below normal limits. Magnetic resonance imaging of the head revealed empty sella. A lumbar bone mineral density examination indicated severe osteoporosis. ESS caused a systemic hormone disorder in this patient, resulting in osteoporotic fractures and persistent non-fusion of the hand epiphyses. Possible causes of this anomaly are chronic or congenital abnormities of the pituitary gland.

Super-Poissonian statistics of photon emission from single CdSe-CdS core-shell nanocrystals coupled to metal nanostructures.

We demonstrate that photon antibunching observed for individual nanocrystal quantum dots (NQDs) can be transformed into photon bunching characterized by super-Poissonian statistics when they are coupled to metal nanostructures (MNs). This observation indicates that, while the quantum yield of a biexciton (Q(2X)) is lower than that of a single exciton (Q(1X)) in freestanding NQDs, Q(2X) becomes greater than Q(1X) in NQDs coupled to MNs. This unique phenomenon is attributed to metal-induced quenching with a rate that scales more slowly with exciton multiplicity than the radiative decay rate and dominates over other nonradiative decay channels for both single excitons and biexcitons.

Pump-intensity- and shell-thickness-dependent evolution of photoluminescence blinking in individual core/shell CdSe/CdS nanocrystals.

We report a systematic study of photoluminescence (PL) intensity and lifetime fluctuations in individual CdSe/CdS core/shell nanocrystal quantum dots (NQDs) as a function of shell thickness. We show that while at low pump intensities PL blinking in thin-shell (4-7 monolayers, MLs) NQDs can be described by random switching between two states of high (ON) and low (OFF) emissivities, it changes to the regime with a continuous distribution of ON intensity levels at high pump powers. A similar behavior is observed in samples with a medium shell thickness (10-12 MLs) without, however, the PL intensity ever switching to a complete "OFF" state and maintaining ca. 30% emissivity ("gray" state). Further, our data indicate that highly stable, blinking-free PL of thick-shell (15-19 MLs) NQDs ("giant" or g-NQDs) is characterized by nearly perfect Poisson statistics, corresponding to a narrow, shot-noise limited PL intensity distribution. Interestingly, in this case the PL lifetime shortens with increasing pump power and the PL decay may deviate from monoexponential. However, the PL intensity distribution remains shot-noise limited, indicating the absence of significant quantum yield fluctuations at a given pump power intensity during the experimental time window.

Effect of shell thickness and composition on blinking suppression and the blinking mechanism in 'giant' CdSe/CdS nanocrystal quantum dots.

We recently developed an inorganic shell approach for suppressing blinking in nanocrystal quantum dots (NQDs) that has the potential to dramatically improve the utility of these fluorophores for single-NQD tracking of individual molecules in cell biology. Here, we consider in detail the effect of shell thickness and composition on blinking suppression, focusing on the CdSe/CdS core/shell system. We also discuss the blinking mechanism as understood through profoundly altered blinking statistics. We clarify the dependence of blinking behavior and photostability on shell thickness, as well as on interrogation times. We show that, while the thickest-shell systems afford the greatest advantages in terms of enhanced optical properties, thinner-shell NQDs may be adequate for certain applications requiring relatively shorter interrogation times. Shell thickness also determines the sensitivity of the NQD optical properties to aqueous-phase transfer, a critical step in rendering NQDs compatible with bioimaging applications. Lastly, we provide a proof-of-concept demonstration of the utility of these unique NQDs for fluorescent particle tracking.

Suppressed auger recombination in "giant" nanocrystals boosts optical gain performance.

Many potential applications of semiconductor nanocrystals are hindered by nonradiative Auger recombination wherein the electron-hole (exciton) recombination energy is transferred to a third charge carrier. This process severely limits the lifetime and bandwidth of optical gain, leads to large nonradiative losses in light-emitting diodes and photovoltaic cells, and is believed to be responsible for intermittency ("blinking") of emission from single nanocrystals. The development of nanostructures in which Auger recombination is suppressed has recently been the subject of much research in the colloidal nanocrystal field. Here, we provide direct experimental evidence that so-called "giant" nanocrystals consisting of a small CdSe core and a thick CdS shell exhibit a significant (orders of magnitude) suppression of Auger decay rates. As a consequence, even multiexcitons of a very high order exhibit significant emission efficiencies, which allows us to demonstrate optical amplification with an extraordinarily large bandwidth (>500 meV) and record low excitation thresholds. This demonstration represents an important milestone toward practical lasing technologies utilizing solution-processable colloidal nanoparticles.

'Giant' multishell CdSe nanocrystal quantum dots with suppressed blinking: Novel fluorescent probes for real-time detection of single-molecule events.

We reported for the first time that key nanocrystal quantum dot (NQD) optical properties-quantum yield, photobleaching and blinking-can be rendered independent of NQD surface chemistry and environment by growth of a very thick, defect-free inorganic shell (Chen, et al. J. Am. Chem. Soc. 2008). Here, we show the precise shell-thickness dependence of these effects. We demonstrate that 'giant-shell' NQDs can be largely non-blinking for observation times as long as 54 minutes and that on-time fractions are independent of experimental time-resolution from 1-200 ms. These effects are primarily demonstrated on (CdSe)CdS (core)shell NQDs, but we also show that alloyed shells comprising Cd(x)Zn(1-x)S and terminated with a non-cytotoxic ZnS layer exhibit similar properties. The mechanism for suppressed blinking and dramatically enhanced stability is attributed to both effective isolation of the NQD core excitonic wavefunction from the NQD surface, as well as a quasi-Type II electronic structure. The unusual electronic structure provides for effective spatial separation of the electron and hole into the shell and core, respectively, and, thereby, for reduced efficiencies in non-radiative Auger recombination.

"Giant" multishell CdSe nanocrystal quantum dots with suppressed blinking.

Semiconductor nanocrystal quantum dots (NQDs) comprise an important class of inorganic fluorophores for applications from optoelectronics to biology. Unfortunately, to date, NQD optical properties (e.g., their efficient and particle-size-tunable photoluminescence) have been susceptible to instabilities at the bulk and single-particle levels. Specifically, ensemble quantum yields (QYs) in emission are dependent upon NQD surface chemistry and chemical environment, while at the single-particle level, NQDs are characterized by significant fluorescence intermittency (blinking) that hinders applications as single-photon light sources for quantum informatics and biolabels for real-time monitoring of single biomolecules. Furthermore, while NQDs are significantly more photostable than their organic dye counterparts, traditional NQDs photobleach over periods of seconds to many minutes. Here, we demonstrate for the first time that by encapsulating the NQD core in a sufficiently thick inorganic shell, we are able to divorce NQD function from NQD surface chemistry and chemical environment. We show that our "giant" NQDs (g-NQDs) are functionally distinct from standard core-only, core/shell and even core/multishell NQDs. g-NQDs are substantially less sensitive to changes in surface chemistry. They do not photobleach under continuous laser excitation over periods of several hours repeated over several days, and they exhibit markedly different blinking behavior; >20% of the g-NQDs do not blink, while >40% have on-time fractions of >80%. All of these observations are in stark contrast with control samples comprising core-only and standard, thinner core/multishell NQDs.

Formation of monodisperse and shape-controlled MnO nanocrystals in non-injection synthesis: self-focusing via ripening.

Formation of nearly monodiperse MnO nanocrystals by simple heating of Mn stearate in octadecene was studied systematically and quantitatively as a model for non-injection synthesis of nanocrystals. For controlling the shape of the nanocrystals, that is, rice, rods, peanuts, needles, and dots, either an activation reagent (ocadecanol) or an inhibitor (stearic acid) might be added prior to heating. The quantitative results of this typical non-injection system reveal that the formation of nearly monodisperse nanocrystals did not follow the well-known "focusing of size distribution" mechanism. A new growth mechanism, self-focusing enabled by inter-particle diffusion, is proposed. Different from the traditional "focusing of size distribution", self-focusing not only affects the growth process of the nanocrystals, but may also play a role in controlling nucleation. Because of the simplicity of the reaction system, it was possible to also identify the chemical reactions associated with the growth and ripening of MnO nanocrystals with a variety of shapes. Through a recycling reaction path, water was identified as a decisive component in determining the kinetics for both growth and ripening in this system, although the reaction occurred at around 300 degrees C.

Side reactions in controlling the quality, yield, and stability of high quality colloidal nanocrystals.

Effects of side reactions during the formation of high quality colloidal nanocrystals were studied using ZnO as a model system. In this case, an irreversible side reaction, formation of esters, was identified to accompany formation of ZnO nanocrystals through the chemical reaction between zinc stearate and an excess amount of alcohols in hydrocarbon solvents at elevated temperatures. This irreversible side reaction made the resulting nanocrystals stable and with nearly unity yield regardless of their size, shape, and size/shape distribution. Ostwald ripening and intraparticle ripening were stopped due to the extremely low solubility/stability of the possible monomers because all free ligands in the solution were consumed by the side reaction. However, focusing on size distribution and 1D growth that are needed for the growth of high quality nanocrystals could still occur for high yield reactions. Upon the addition of a small amount of stearic acid or phosphonic acid, immediate partial dissolution of ZnO nanocrystals took place. Although the excess alcohol could not react with the resulting zinc phosphonic acid salt, it could force the newly formed zinc stearate gradually but completely back onto the existing nanocrystals. The results in this report indicate that side reactions are extremely important for the formation of high quality nanocrystals by affecting their quality, yield, and stability under growth conditions. Due to their lack of information in the literature and obvious practical advantages, studies of side reactions accompanying formation of nanocrystals are important for both fundamental science related to crystallization and industrial production of high quality nanocrystals.

Luminescent CdS quantum dots as selective ion probes.

Water-soluble luminescent CdS quantum dots (QDs) capped by polyphosphate, L-cysteine, and thioglycerol were synthesized in aqueous solution. The ligands were found to have a profound effect on the luminesence response of CdS QDs to physiologically important metal cations. Polyphosphate-capped CdS QDs were sensitive to nearly all mono- and divalent cations, showing no ion selectivity. Conversely, thioglycerol-capped CdS QDs were sensitive to only copper and iron ions. Similar concentrations of physiologically relevant cations, such as zinc, sodium, potassium, calcium, and magnesium ions did not affect the luminescence of thioglycerol-capped CdS QDs. On the other hand, L-cysteine-capped CdS QDs were sensitive to zinc ions and insensitive to other physiologically important cations, such as copper, calcium, and magnium ions. To demonstrate the detection capability of these new ion probes, L-cysteine and thioglycerol-capped CdS QDs were used to detect zinc and copper ions in physiological buffer samples. The detection limits were 0.8 microM for zinc (II) and 0.1 microM for copper (II) ions. The emission enhancement of the QDs by zinc (II) is attributed to activation of surface states, whereas the effective reduction of copper (II) to copper (I) may explain the emission decrease of the thioglycerol-capped CdS QDs when charged with copper ions. Unlike organic fluorescent dyes, the thioglycerol-capped luminescent CdS QDs discriminate between copper and zinc ions and are therefore suitable for the analysis of copper ions in biological samples in the presence of physiological concentrations of zinc ions. The interference of iron ions with zinc and copper ion detection is attributed to an inner filter effect, which is eliminated by adding fluoride ions to form the colorless complex FeF6(3-). To the best of our knowledge, this is first use of luminescent semiconductor quantum dots as selective ion probes in aqueous samples.