Nido‐Carboranes: Donors for Thermally Activated Delayed Fluorescence

An approach to the design of nido‐carborane‐based luminescent compounds that can exhibit thermally activated delayed fluorescence (TADF) is proposed. 7,8‐Dicarba‐nido‐undecaboranes (nido‐carboranes) having various 8‐R groups (R=H, Me, i‐Pr, Ph) are appended to the meta or para position of the phenyl ring of the dimesitylphenylborane (PhBMes₂) acceptor, forming donor–acceptor compounds (nido‐ m1 – m4 and nido‐ p1 – p4 ). The bulky 8‐R group and meta substitution of the nido‐carborane are essential to attain a highly twisted arrangement between the donor and acceptor moieties, leading to a very small energy splitting between the singlet and triplet excited states (ΔE_ST <0.05 eV for nido‐ m2 , ‐ m3 , and ‐ p3 ). These compounds exhibit efficient TADF with microsecond‐range lifetimes. In particular, nido‐ m2 and ‐ m3 display aggregation‐induced emission (AIE) with TADF properties.     

Chemoselective reduction of aldehydes and ketones by potassium diisobutyl-t-butoxy aluminum hydride (PDBBA)

t-Butoxy derivatives of DIBALH [lithium diisobutyl-t-butoxyaluminum hydride (LDBBA), sodium diisobutyl-t-butoxyaluminum hydride (SDBBA), and potassium diisobutyl-t-butoxyaluminum hydride (PDBBA)] were examined as chemoselective reducing agents of carbonyl compounds. Among them, PDBBA was found to be the most efficient for the reduction of aldehydes and ketones to the corresponding alcohols in the presence of ester, amide, and nitrile substituents at ambient temperature. In addition, the optimal conditions gave higher chemoselectivity for aldehydes in the presence of ketones.     

Application and exploration of fast gas chromatography-surface acoustic wave sensor to the analysis of thymus species

Fast gas chromatography combined with surface acoustic wave sensor (GC/SAW) has been applied for the detection of volatile aroma compounds emanated from thymus medicinal plants such as T. quinquecostotus (Jeju and Mt. Gaya in South Korea), T. quinquecostotus var. japonica (Ulreung island in South Korea), T. mongolicus (Northeastern Asia), and T. serpyllum (Europe). The GC/SAW involving the fragrance pattern analysis provides a novel analytical method with a very fast separation and characterization of aromas caused by the delicate difference of chemical composition according to botanical and geographical origin. On the comparison of experiments, the characteristic components and analytical tendency for air-dried thymus species detected by GC/SAW appear to be quite similar to those obtained by headspace solid-phase microextraction (HS-SPME)-GC-MS, but the abundance ratios between these two methods are different. In addition to that, the discrimination of various thymus species by using VaporPrint image based on GC/SAW provides a quite reliable result. On the basis of principal component analysis (PCA) results, the ability for classification among species of completely different chemotypes by HS-SPME-GC-MS is good enough, but the classification of same chemotypes species which are from different geographical origin in same country, original species and its variety, an air-drying term for 13 days and 16 months appear much lower than GC/SAW. Interestingly, the present experiment reveals that the air-drying term influences the aroma composition: the concentration of the pharmacologically active species, monoterpene phenol (thymol), reaches its highest concentrations after it was dried for 5 days or 13 days, which is much higher than in fresh or over-dried for a long times.     

Anti-tumor immunostimulatory effect of heat-killed tumor cells

As a part of our ongoing search for a safe and efficient anti-tumor vaccine, we attempted to determine whether the molecular nature of certain tumor antigens would influence immune responses against tumor cells. As compared with freeze-thawed or formaldehyde-fixed tumor antigens, heat-denatured tumor antigens elicited profound anti-tumor immune responses and greatly inhibited the growth of live tumor cells. The heat-denatured tumor antigens induced a substantial increase in the anti-tumor CTL response in the absence of any adjuvant material. This response appears to be initiated by strong activation of the antigen-presenting cells, which may recognize heat-denatured protein antigens. Upon recognition of the heat-denatured tumor antigens, macrophages and dendritic cells were found to acutely upregulate the expression of co-stimulatory molecules such as B7.2, as well as the secretion of inflammatory cytokines such as IL-12 and TNF-alpha. The results of this study indicate that heat-denatured tumor extracts might elicit protective anti-tumor adaptive immune responses and also raise the possibility that a safe and efficient adjuvant-free tumor vaccine might be developed in conjunction with a dendritic cell-based tumor vaccine.     

Spectroscopic observation of atomic hydrogen radicals entrapped in icy hydrogen hydrate

A hydrogen molecule entrapped in the cages of icy hydrogen hydrate is confined in host water framework and thus behaves unlike pure solid or liquid hydrogen. The gamma-irradiated hydrogen radicals are for the first time observed from ESR and solid-state MAS 1H NMR spectra to stably exist in the icy hydrate channels without any collapse of the host framework, confirming the chemical shift consistency of ionized hydrogen derivatives. We discuss the confined icy hydrate channels, which can act as potential storage sites for simultaneously imprisoning both molecular and ionized hydrogen and further as icy nanoreactors.     

Melampolides from the leaves of Smallanthus sonchifolius and their inhibitory activity of lps-induced nitric oxide production

Two new melampolide-type sesquiterpene lactones, 8beta-epoxyangeloyloxy-9alpha-ethoxy-14-oxo-acanthospermolide (1) and 8beta-angeloyloxy-9alpha-ethoxy-14-oxo-acanthospermolide (2), were isolated from the leaves of yacon [Smallanthus sonchifolia (POEPP. et ENDL.) H. Robinson] along with eleven known melampolides, allo-schkuhriolide (3), enhydrin (4), polymatin A (5), fluctuanin (6), 8beta-angeloyloxy-9alpha-acetoxy-14-oxo-acanthospermolide (7), 8beta-angeloyloxy-14-oxo-acanthospermolide (8), 8beta-methacryloyloxymelampolid-14-oic acid methyl ester (9), uvedalin (10), polymatin B (11), 8beta-tigloyloxymelampolid-14-oic acid methyl ester (12), and sonchifolin (13). Their structures were established on the basis of spectroscopic evidence including 1D- and 2D-NMR experiments. All isolates were evaluated for inhibition of LPS-induced nitric oxide production in murine macrophage RAW 264.7 cells.     

Sparse Penalized Forward Selection for Support Vector Classification

We propose a new binary classification and variable selection technique especially designed for high-dimensional predictors. Among many predictors, typically, only a small fraction of them have significant impact on prediction. In such a situation, more interpretable models with better prediction accuracy can be obtained by variable selection along with classification. By adding an ?₁-type penalty to the loss function, common classification methods such as logistic regression or support vector machines (SVM) can perform variable selection. Existing penalized SVM methods all attempt to jointly solve all the parameters involved in the penalization problem altogether. When data dimension is very high, the joint optimization problem is very complex and involves a lot of memory allocation. In this article, we propose a new penalized forward search technique that can reduce high-dimensional optimization problems to one-dimensional optimization by iterating the selection steps. The new algorithm can be regarded as a forward selection version of the penalized SVM and its variants. The advantage of optimizing in one dimension is that the location of the optimum solution can be obtained with intelligent search by exploiting convexity and a piecewise linear or quadratic structure of the criterion function. In each step, the predictor that is most able to predict the outcome is chosen in the model. The search is then repeatedly used in an iterative fashion until convergence occurs. Comparison of our new classification rule with ?₁-SVM and other common methods show very promising performance, in that the proposed method leads to much leaner models without compromising misclassification rates, particularly for high-dimensional predictors.     

Thermally cross-linked superparamagnetic iron oxide nanoparticles: synthesis and application as a dual imaging probe for cancer in vivo

We report the fabrication and characterization of thermally cross-linked superparamagnetic iron oxide nanoparticles (TCL-SPION) and their application to the dual imaging of cancer in vivo. Unlike dextran-coated cross-linked iron oxide nanoparticles, which are prepared by a chemical cross-linking method, TCL-SPION are prepared by a simple, thermal cross-linking method using a Si-OH-containing copolymer. The copolymer, poly(3-(trimethoxysilyl)propyl methacrylate-r-PEG methyl ether methacrylate-r-N-acryloxysuccinimide), was synthesized by radical polymerization and used as a coating material for as-synthesized magnetite (Fe3O4) SPION. The polymer-coated SPION was further heated at 80 degrees C to induce cross-linking between the -Si(OH)3 groups in the polymer chains, which finally generated TCL-SPION bearing a carboxyl group as a surface functional group. The particle size, surface charge, presence of polymer-coating layers, and the extent of thermal cross-linking were characterized and confirmed by various measurements, including dynamic light scattering, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The carboxyl TCL-SPION was converted to amine-modified TCL-SPION and then finally to Cy5.5 dye-conjugated TCL-SPION for use in dual (magnetic resonance/optical) in vivo cancer imaging. When the Cy5.5 TCL-SPION was administered to Lewis lung carcinoma tumor allograft mice by intravenous injection, the tumor was unambiguously detected in T2-weighted magnetic resonance images as a 68% signal drop as well as in optical fluorescence images within 4 h, indicating a high level of accumulation of the nanomagnets within the tumor site. In addition, ex vivo fluorescence images of the harvested tumor and other major organs further confirmed the highest accumulation of the Cy5.5 TCL-SPION within the tumor. It is noteworthy that, despite the fact that TCL-SPION does not bear any targeting ligands on its surface, it was highly effective for tumor detection in vivo by dual imaging.