Exploring the Role of Surface States in Emissive Carbon Nanodots: Analysis at Single-Particle Level

Fluorescent carbon nanodots (CDs) have been highlighted as promising semiconducting materials due to their outstanding chemical and optical properties. However, the intrinsic heterogeneity of CDs has impeded a clear understanding of the mechanisms behind their photophysical properties. In this study, as-prepared CDs are fractionated via chromatography to reduce their structural and chemical heterogeneity and analyzed through ensemble and single-particle spectroscopies. Many single particles reveal fluorescence intensity fluctuations between two or more discrete levels with bi-exponential decays. While the intrinsic τ₁ components are uniform among single particles, the τ₂ components from molecule-like emissions spans a wider range of lifetimes, reflecting the inhomogeneity of the surface states. Furthermore, it is concluded that the relative population and chemical states of surface functional groups in CDs have a significant impact on emissive states, brightness, blinking, stability, and lifetime distribution of photoluminescence.     

Detection of a systemic effect of malignancy in vivo by magnetic resonance imaging

In animals bearing tumors prolongation of spin lattice relaxation time (T1) has been detected in vitro in organs not directly affected by the malignancy. This has been termed the "Systemic Effect." In this study the possible existence of such an effect in the liver, muscle and fat of humans with lymphoma has been investigated. In vivo T1 measurements were made using a low field strength (0.08 Tesla) magnetic resonance imager. The mean liver T1 for 19 lymphoma patients with normal liver histology was 206 ms, compared with a mean of 191 ms for 61 volunteers (p less than 0.0001). Among these patients prolongation of liver T1 was related to the extent of disease elsewhere in the body. For 23 patients with Hodgkin's disease (HD) examined at the time of diagnosis, liver T1 was significantly correlated with other known markers of disease extent or activity (alkaline phosphatase level, erythrocyte sedimentation rate and the presence of systemic symptoms). No such correlations were observed among 25 patients with non-Hodgkin's lymphoma (NHL). Muscle and fat T1 was measured in 26 patients with lymphoma, 14 patients with acute leukemia and 88 volunteers. Seven of the patients with lymphoma and 2 of those with leukemia had muscle T1 values above the range observed for volunteers. Similarly, 3 patients with lymphoma and 1 with leukemia had prolonged fat T1. These findings indicate that a systemic effect of malignancy on T1 is detectable in a proportion of humans with lymphoma or leukemia.     

Multivariate Liouville distributions

A random vector (X₁, …, X_n), with positive components, has a Liouville distribution if its joint probability density function is of the formf(x₁ + … + x_n)x₁^a₁.1 … x_n^a_n.1 with thea_i all positive. Examples of these are the Dirichlet and inverted Dirichlet distributions. In this paper, a comprehensive treatment of the Liouville distributions is provided. The results pertain to stochastic representations, transformation properties, complete neutrality, marginal and conditional distributions, regression functions, and total positivity and reverse rule properties. Further, these topics are utilized in various characterizations of the Dirichlet and inverted Dirichlet distributions. Matrix analogs of the Liouville distributions are also treated, and many of the results obtained in the vector setting are extended appropriately.     

Optimization of Biocompatibility for a Hydrophilic Biological Molecule Encapsulation System

Despite considerable advances in recent years, challenges in delivery and storage of biological drugs persist and may delay or prohibit their clinical application. Though nanoparticle-based approaches for small molecule drug encapsulation are mature, encapsulation of proteins remains problematic due to destabilization of the protein. Reverse micelles composed of decylmonoacyl glycerol (10MAG) and lauryldimethylamino-N-oxide (LDAO) in low-viscosity alkanes have been shown to preserve the structure and stability of a wide range of biological macromolecules. Here, we present a first step on developing this system as a future platform for storage and delivery of biological drugs by replacing the non-biocompatible alkane solvent with solvents currently used in small molecule delivery systems. Using a novel screening approach, we performed a comprehensive evaluation of the 10MAG/LDAO system using two preparation methods across seven biocompatible solvents with analysis of toxicity and encapsulation efficiency for each solvent. By using an inexpensive hydrophilic small molecule to test a wide range of conditions, we identify optimal solvent properties for further development. We validate the predictions from this screen with preliminary protein encapsulation tests. The insight provided lays the foundation for further development of this system toward long-term room-temperature storage of biologics or toward water-in-oil-in-water biologic delivery systems.     

Application of the Suzuki reaction to the asymmetric desymmetrisation of 1,2- and 1,3-disubstituted bulky cobalt metallocenes

Reaction of (η⁵-cyclopentadienyl)(η⁴-tetraphenylcyclobutadiene)cobalt with Hg(OAc)₂ (2.3 equiv) in 1:1 MeOH/CH₂Cl₂ followed by the addition of LiCl resulted in the formation of (η⁵-1,2-dichloromercuricyclopentadienyl)(η⁴-tetraphenylcyclobutadiene)cobalt (33%) and its 1,3-isomer (6%). Following conversion into their corresponding diiodides these compounds were desymmetrised by Suzuki reactions with ArB(OH)₂ employing [(R)-BINAP]PdCl₂, with the highest ee of 24% being obtained for (η⁵-1-iodo-3-(2-methoxyphenyl)cyclopentadienyl)(η⁴-tetraphenylcyclobutadiene)cobalt.     

Pattern recognition and massively distributed computing

A feature of Peter Kollman's research was his exploitation of the latest computational techniques to devise novel applications of the free energy perturbation method. He would certainly have seized upon the opportunities offered by massively distributed computing. Here we describe the use of over a million personal computers to perform virtual screening of 3.5 billion druglike molecules against protein targets by pharmacophore pattern matching, together with other applications of pattern recognition such as docking ligands without any a priori knowledge about the binding site location.     

Estimate of the cosmological bispectrum from the MAXIMA-1 cosmic microwave background map

We use the measurement of the cosmic microwave background taken during the MAXIMA-1 flight to estimate the bispectrum of cosmological perturbations. We propose an estimator for the bispectrum that is appropriate in the flat sky approximation, apply it to the MAXIMA-1 data, and evaluate errors using bootstrap methods. We compare the estimated value with what would be expected if the sky signal were Gaussian and find that it is indeed consistent, with a chi(2) per degree of freedom of approximately unity. This measurement places constraints on models of inflation.     

Different auditory filter bandwidth estimates based on profile analysis, notched noise, and hybrid tasks

Auditory filter bandwidths were estimated in three experiments. The first experiment was a profile-analysis experiment. The stimuli were composed of sinusoidal components ranging in frequency from 200 to 5000 Hz. The standard stimulus was the sum of equal-amplitude tones, and the signal stimulus had a power spectrum that varied up-down ... up-down. The number of components ranged from four to 60. Interval-by-interval level randomization prevented the change in level of a single component from reliably indicating the change from standard to signal. The second experiment was a notched-noise experiment in which the 1000-Hz tone to be detected was added to a noise with a notch arithmetically centered at 1000 Hz. Detection thresholds were estimated both in the presence of and in the absence of level randomization. In the third, hybrid, experiment a 1000-Hz tone was to be detected, and the masker was composed of equal-amplitude sinusoidal components ranging in frequency from 200 to 5000 Hz. For this experiment, thresholds were estimated both in the presence and absence of level variation. For both the notched-noise and hybrid experiments, only modest effects of level randomization were obtained. A variant of Durlach et al.'s channel model ["Towards a model for discrimination of broadband signals," J. Acoust. Soc. Am. 80, 63-72 (1986)] was used to estimate auditory filter bandwidths for all three experiments. When a two-parameter roex(p,r) filter weighting function was used to fit the data, bandwidth estimates were approximately two to three times as large for the two detection tasks than for the profile-analysis task.     

Structural changes within the plastic phase of diamantane

Structural changes within the pre-melting plastic phase of diamantane have been revealed from high-temperature X-ray powder diffraction data. A gradual transition to a more disordered state is suggested, and hexagonal symmetry ($\text{a = 14.1}\text{A}\text{?}\text{, c = 11.0}\text{A}\text{?}$) for the plastic phase is firmly established.