A Ligand System for the Flexible Functionalization of Quantum Dots via Click Chemistry

We present a novel ligand, 5‐norbornene‐2‐nonanoic acid, which can be directly added during established quantum dot (QD) syntheses in organic solvents to generate “clickable” QDs at a few hundred nmol scale. This ligand has a carboxyl group at one terminus to bind to the surface of QDs and a norbornene group at the opposite end that enables straightforward phase transfer of QDs into aqueous solutions via efficient norbornene/tetrazine click chemistry. Our ligand system removes the traditional ligand‐exchange step and can produce water‐soluble QDs with a high quantum yield and a small hydrodynamic diameter of approximately 12 nm at an order of magnitude higher scale than previous methods. We demonstrate the effectiveness of our approach by incubating azido‐functionalized CdSe/CdS QDs with 4T1 cancer cells that are metabolically labeled with a dibenzocyclooctyne‐bearing unnatural sugar. The QDs exhibit high targeting efficiency and minimal nonspecific binding.     

Artificial atom solids based on metal nanocrystals: Formation and electrical properties

Metal nanocrystals can behave as “artificial atoms” due to their diameter-dependent single electron charging energy. Organically passivated nanocrystals with narrow size distributions can self-assemble into ordered arrays, offering the possibility of artificial atom solids with unique collective electronic properties, derived from both the size-dependent electronic properties of the individual nanocrystal cores and the inter-nanocrystal electronic coupling mechanisms. We review our recent progress on probing the electronic properties of artificial atom solids via variable temperature charge transport measurements on laterally contacted arrays of metal nanocrystals, together with development of combined synthesis and processing routes to manipulate these properties.     

The mixing advantage is less than 2

Corresponding to n independent non-negative random variables X ₁,...,X _n , are values M ₁,...,M _n , where each M _i is the expected value of the maximum of n independent copies of X _i . We obtain an upper bound for the expected value of the maximum of X ₁,...,X _n in terms of M ₁,...,M _n . This inequality is sharp in the sense that the random variables can be chosen so that the bound is approached arbitrarily closely. We also present related comparison results.      

Structural Tunability and Diversity of Two-Dimensional Lead Halide Benzenethiolate

Two-dimensional (2D) organic-inorganic hybrid materials are currently of great interest for applications in electronics and optoelectronics. Here, the synthesis and optical properties of a new type of halide-organothiolate-mixed 2D hybrid material, Pb₂X(S-C₆H₅)₃, are reported, in which X is a halide (I, Br, or Cl). Different from conventional lead-based 2D layered materials, these compounds feature unusual five-coordinated lead centers with a stereochemically active electron lone pair on the lead atoms and four-coordinated iodine atoms. The Pb₂X(S-C₆H₅)₃ materials feature an indirect bandgap, strongly emissive long-lived self-trap states, and an extremely large Stokes shift. Interestingly, the optical bandgap of the materials can be tuned through variation of the halides; however, the photoluminescence is less sensitive to the composition and is more likely dominated by lead-sulfur lattice interactions or the lead lone-pair electrons. Our results support that a halide–organothiolate mixed anion hybrid structure offers a unique platform for discovering new exciting 2D electronic materials.     

Investigation of the influence of high-risk human papillomavirus on the biochemical composition of cervical cancer cells using vibrational spectroscopy

The main aetiology of cervical cancer is infection with high-risk human papillomavirus (HPV). Cervical cancer is almost 100% curable if detected in the early stages. Thus, information about the presence and levels of HPV in patient samples has high clinical value. As current screening methods, such as the Pap smear test, are highly subjective and in many cases show low sensitivity and specificity, new supportive techniques are desirable to improve the quality of cervical cancer screening. In this study, vibrational spectroscopic techniques (Raman and Fourier Transform Infra Red absorption) have been applied to the investigation of four cervical cancer cell lines: HPV negative C33A, HPV-18 positive HeLa with 20-50 integrated HPV copies per cell, HPV-16 positive SiHa with 1-2 integrated HPV strands per cell and HPV-16 positive CaSki containing 60-600 integrated HPV copies per cell. Results show that vibrational spectroscopic techniques can discriminate between the cell lines and elucidate cellular differences originating from proteins, nucleic acids and lipids. Similarities between C33A and SiHa cells were exhibited in the Raman and infrared spectra and were confirmed by Principal Component Analysis (PCA). Analysis of the biochemical composition of the investigated cells, with the aid of PCA, showed a clear discrimination between the C33A-SiHa group and HeLa and CaSki cell lines indicating the potential of vibrational spectroscopic techniques as a support to current methods for cervical cancer screening.     

Investigating the spectrum of biological activity of ring-substituted salicylanilides and carbamoylphenylcarbamates

In this study, a series of twelve ring-substituted salicylanilides and carbamoylphenylcarbamates were prepared and characterized. The compounds were analyzed using RP-HPLC to determine lipophilicity. They were tested for their activity related to the inhibition of photosynthetic electron transport (PET) in spinach (Spinacia oleracea L.) chloroplasts. Moreover, their site of action in the photosynthetic apparatus was determined. Primary in vitro screening of the synthesized compounds was also performed against mycobacterial, bacterial and fungal strains. Several compounds showed biological activity comparable with or higher than the standards 3-(3,4-dichlorophenyl)-1,1-dimethylurea, isoniazid, penicillin G, ciprofloxacin or fluconazole. The most active compounds showed minimal anti-proliferative activity against human cells in culture, indicating they would have low cytotoxicity. For all compounds, the relationships between lipophilicity and the chemical structure are discussed.     

The putative use of alpha-1-acid glycoprotein as a non-invasive marker of fibrosis

The acute phase response to injury or infection results in alterations in the expression of the plasma proteins produced by the liver. Many of these biomolecules are glycosylated with oligosaccharide chains covalently attached to the polypeptide backbone and the extent and composition of this glycosylation can be altered in a disease-dependent manner. Of particular interest is the observation that the acute phase glycoprotein, alpha-1-acid glycoprotein (AGP) has altered glycosylation in several physiological and pathological conditions. It is posited that changes induced in liver diseases may reflect disease severity and may therefore act as a non-invasive marker of fibrosis. This study has investigated the glycosylation of AGP in the plasma of people with varying degrees of cirrhosis and fibrosis. Hyperfucosylation was observed in all disease samples in comparison to normal plasma and was significantly increased in cirrhosis. Both sialic acid and N-acetylgalactosamine (GalNAc) were negatively associated with fibrosis. Two samples were found to express GalNAc, which as a constituent of the glycosylation of serum proteins is rare. In conclusion, fucose, sialic acid and other aspects of the glycosylation of AGP are influenced by the degree of fibrosis and as such may prove a valuable prognostic indicator of the development of cirrhosis.     

The Effect of a Hydrogen Bonding Environment (Dimethyl Sulfoxide) on the Ionisation and Redox Properties of the Thiol Group in Cysteine and a Protein Disulfide Isomerase Mimic (Vectrase)

Increasing enrichment of dimethyl sulfoxide, DMSO, in DMSO-water mixtures causes a reversal in the thermodynamic dissociation constants, pK _as, and has a marked effect on the redox potentails of the thiolic and amino groups in cysteine and the protein disulfide isomerase (PDI) mimic BMC, Vectrase. This paper illustrates the effect of a hydrogen-bonding environment on the ionisation and redox properties of thiol groups in amino acids. A combination of potentiometry and Raman spectroscopy was applied to rationalise the observations. Intracellular environments are full of hydrophobic, hydrogen-bonding environments. The results illustrate the profound effects of the local environment on the thiol group.     

The power of programmed grammars with graphs from various classes

Programmed grammars, one of the most important and well investigated classes of grammars with context-free rules and a mechanism controlling the application of the rules, can be described by graphs. We investigate whether or not the restriction to special classes of graphs restricts the generative power of programmed grammars with erasing rules and without appearance checking, too. We obtain that Eulerian, Hamiltonian, planar and bipartite graphs and regular graphs of degree at least three are pr-universal in that sense that any language which can be generated by programmed grammars (with erasing rules and without appearance checking) can be obtained by programmed grammars where the underlying graph belongs to the given special class of graphs, whereas complete graphs, regular graphs of degree 2 and backbone graphs lead to proper subfamilies of the family of programmed languages.