Harnessing Endogenous Formate for Antibacterial Prodrug Activation by in cellulo Ruthenium-Mediated Transfer Hydrogenation Reaction

The abundance and evolving pathogenic behavior of bacterial microorganisms give rise to antibiotic tolerance and resistance which pose a danger to global public health. New therapeutic strategies are needed to keep pace with this growing threat. We propose a novel approach for targeting bacteria by harnessing formate, a cell metabolite found only in particular bacterial species, to activate an antibacterial prodrug and selectively inhibit their growth. This strategy is premised on transfer hydrogenation reaction on a biorthogonal substrate utilizing native formate as the hydride source as a means of uncaging an antibacterial prodrug. Using coordination-directed 3-component assembly to prepare a library of 768 unique Ru–Arene Schiff-base complexes, we identified several candidates that efficiently reduced sulfonyl azide functional group in the presence of formate. This strategy paves the way for a new approach of targeted antibacterial therapy by exploiting unique bacterial metabolites.     

Vocal Fold Paralysis Following Radiotherapy for Nasopharyngeal Carcinoma: Laryngeal Electromyography Findings

Laryngeal electromyography was used to study the pattern of neurological injury in three patients with unilateral vocal fold paralysis following radiotherapy for nasopharyngeal carcinoma. The thyroarytenoid and cricothyroid muscles were assessed to give an indication of recurrent and superior laryngeal nerve function. Two patients demonstrated both recurrent and superior laryngeal neuropathy suggesting injury at the skull base. The other patient had only recurrent laryngeal neuropathy indicating more distal involvement. Subclinical neuropathic changes were seen in two cases on the side contralateral to the vocal fold paralysis. These patients may be at increased risk of developing bilateral vocal fold paralysis and potentially life-threatening airway obstruction. Long-term follow-up is recommended for such patients, especially if medialization thyroplasty is being considered. This is the first report describing the use of electromyography to determine the pattern of nerve injury in patients with vocal fold paralysis following head and neck radiotherapy.     

Shorter identity-based encryption via asymmetric pairings

We present efficient identity-based encryption (IBE) under the symmetric external Diffie–Hellman (SXDH) assumption in bilinear groups; our scheme also achieves anonymity. In our IBE scheme, all parameters have constant numbers of group elements, and are shorter than those of previous constructions based on decisional linear (DLIN) assumption. Our construction uses both dual system encryption (Waters, CRYPTO 2009) and dual pairing vector spaces (Okamoto and Takashima, Pairing 2008; ASIACRYPT 2009). Specifically, we show how to adapt the recent DLIN-based instantiation of Lewko (EUROCRYPT 2012) to the SXDH assumption. To our knowledge, this is the first work to instantiate either dual system encryption or dual pairing vector spaces under the SXDH assumption. Furthermore, our work could be extended to many other functional encryption. In Particular, we show how to instantiate our framework to inner product encryption and key-policy functional encryption. All parameters of our constructions are shorter than those of DLIN-based constructions.     

Effects of intermolecular interaction on the energy distribution of valance electronic states of a carbazole-based material in amorphous thin films

Effects of intermolecular interactions on the occupied electronic structure of amorphous solid of a carbazole-based material were investigated under an assumption that the organic solid consists of randomly oriented assemblies of dimers. The electronic energy states were calculated on the ensemble of large number of random dimers, of which geometries are relaxed using semiempirical van der Waals density functional theory. Intermolecular interactions result in splitting of energy level, and further disorders occur by aggregation of randomly orientated molecules. As a result, frontier occupied energy states can be represented by a superposition of Gaussian distributions, including (i) a main distribution with full width at half maximum of 80-110 meV, depending on the methods of relaxation and (ii) shoulders separated from the center of the main distribution with a value as large as 150 meV. A possible origin for the appearance of these shoulders was ascribed to the presence of molecular assemblies consisting of more tightly bound dimers compared with the others.     

A NAA collaborative study in white rice performed in seven Asian countries

Since 2000, collaborative studies for applying NAA have been performed through the Forum for Nuclear Cooperation in Asia (FNCA) sponsored by the Japanese Government. White rice is a main food for Asians and thus was selected as a common target sample for a collaborative study in 2008. Seven Asian countries including China, Indonesia, Japan, Korea, Malaysia, Philippines and Thailand, are greatly concerned about the composition of arsenic, heavy metals, and essential trace elements and took part in this study. Rice samples were purchased and prepared by following a protocol that had been proposed for this study. Samples were analyzed by their own NAA systems. In each country, more than 10 elements were examined and the results were compared. These data will be very useful in the monitoring of the levels of food contamination and to evaluate the nutritional status for people living in Asia.     

Immobilisation of quantum dots by bio-orthogonal PCR amplification and labelling for direct gene detection and quantitation

A sensitive and versatile detection scheme based on quantum dot immobilisation on a solid support through bio-orthogonal PCR amplification and labelling has been developed for detection and quantification of gene targets in complex DNA mixtures.     

Conformational, steric and electronic effects on the site- and chemoselectivity of the metal-catalyzed reaction of N-bis(trimethylsilyl)methyl, N-(2-indolyl)methyl α-diazoamides

The Rh(II)- and Cu(II)-catalyzed reactions of N-bis(trimethylsilyl)methyl, N-(2-indolyl)methyl α-diazoamides are investigated to delineate how conformational, steric and electronic factors influence the site- and chemoselectivity of the metallocarbenoid reaction. The N-bis(trimethylsilyl)methyl (N-BTMSM) group is found to be essential in promoting the metallocarbenoid reaction at the N-(2-indolyl)methyl moiety as well as providing subtle but effective conformational influence about the amide N-C(α) sigma bond in diazoamides carrying an N-C(α) alkoxymethyl side-chain, to afford excellent site- and chemoselectivity. In general, the metal-catalyzed reactions are found to favor metallocarbenoid addition to the indole C(2)-C(3) double bond over C-H insertion to give cyclopropanated products (tetracyclic γ-lactams); however, chemoselectivity is also affected by steric effects, as revealed in the N-[2-(3-methylindolyl)]methyl diazoamides, and to some extent by the nature of the catalyst employed, as seen in the N-C(α)-alkoxymethyl diazoamides. The tetracyclic γ-lactams are found to rearrange to give good to high yields of the tricyclic indole derivatives under the metallocarbenoid reaction conditions or under acidic conditions. The propensity of the tetracyclic γ-lactams to undergo rearrangement is found to be dependent on the nature of the α-substituent on the original diazo carbon and the indole N-substituent.     

Hydrophilicity Control of Visible‐Light Hydrogen Evolution and Dynamics of the Charge‐Separated State in Dye/TiO2/Pt Hybrid Systems

Visible‐light‐driven H₂ evolution based on Dye/TiO₂/Pt hybrid photocatalysts was investigated for a series of (E)‐3‐(5′‐{4‐[bis(4‐R¹‐phenyl)amino]phenyl}‐4,4′‐(R²)₂‐2,2′‐bithiophen‐5‐yl)‐2‐cyanoacrylic acid dyes. Efficiencies of hydrogen evolution from aqueous suspensions in the presence of ethylenediaminetetraacetic acid as electron donor under illumination at λ>420 nm were found to considerably depend on the hydrophilic character of R¹, varying in the order MOD (R¹=CH₃OCH₂, R²=H)≈ MO4D (R¹=R²=CH₃OCH₂)> HD (R¹=R²=H)> PD (R¹=C₃H₇, R²=H). In the case of MOD /TiO₂/Pt, the apparent quantum yield for photocatalyzed H₂ generation at 436 nm was 0.27±0.03. Transient absorption measurements for MOD ‐ or PD ‐grafted transparent films of TiO₂ nanoparticles dipped into water at pH 3 commonly revealed ultrafast formation (<100 fs) of the dye radical cation (Dye^.+) followed by multicomponent decays, which involve minor fast decays (<5 ps) almost independent of R¹ and major slower decays with significant differences between the two samples: 1) the early decay of the major components for MOD is about 2.5 times slower than that for PD and 2) a redshift of the spectrum occurred for MOD with a time constant of 17 ps, but not for PD . The substituent effects on H₂ generation as well as on transient behavior have been discussed in terms substituent‐dependent charge recombination (CR) of Dye^.+ with electrons in bulk, inner‐trap, and/or interstitial‐trap states, arising from different solvent reorganization.