Mass spectral studies of 1-(2-chloroethoxy)-2-[(2-chloroethyl)thio]ethane and related compounds using gas chromatography–mass spectrometry (GC-MS) and gas chromatography–triple quad mass spectrometry (GC-QQQ)

The electron impact and collision-ion-dissociation mass spectra of 1-(2-chloroethoxy)-2-[(2-chloroethyl) thio]ethane (1) and 10 related molecules were obtained using gas chromatography–mass spectrometry and gas chromatography–triple quad mass spectrometry. These mass spectral studies were performed to facilitate the development of a spectral database of mustard-related compounds for verification purposes of the Chemical Weapons Convention. The proposed fragmentation pathways of each individual molecule (1–11) are reported along with rationalizations for the most characteristic ions.     

Two-dimensional densely packed DNA nanostructure derived from DNA complexation with a low-generation poly(amidoamine) dendrimer

One of the keys for using deoxyribonucleic acid (DNA) as a nanomaterial relies on how the individual DNA chain can be aligned and how a multitude of DNA chains can be packed into ordered nanostructures. Here we present a simple method for constructing a 2-D densely packed DNA nanostructure using the electrostatic complex of DNA with a poly(amidoamine) (PAMAM) dendrimer of generation two. Ordered DNA arrays are formed by drop-casting an aqueous solution containing positively overcharged complexes onto mica followed by a prolonged incubation. During the incubation, the complexes tend to adsorb onto the negatively charged mica surface through electrostatic attraction. The rodlike complexes organize to form ordered arrays to increase the surface density of the adsorbed complexes and hence the attractive free energy of adsorption. The densely packed nanostructure obtained here is distinguished from the previously reported spheroid or toroid structure derived from DNA complexations with the higher-generation dendrimers.     

Deliberate design of a 3D homochiral Cu(II)/l-met/Ag(I) coordination network based on the distinct soft-hard recognition principle

A homochiral amino acid coordination network [{Ag3Cu3(l-methioninato)6(NO3)3(H2O)3}.7H2O]n, self-assembled from CuII, AgI, and l-methionine via a distinct soft-hard recognition process, shows interesting characteristics, in that it is constructed from 1D helical building blocks and contains homochiral channels in which 1D water chains are hosted. This result provides an effective and controllable strategy for the preparation of enantiopure heterometallic supramolecular structures that are relevant to biopolymers.     

Structural characterization of phosphatidyl-<Emphasis Type="Italic">myo</Emphasis>-inositol mannosides from <Emphasis Type="Italic">Mycobacterium bovis</Emphasis> bacillus calmette gúerin by multiple-stage quadrupole ion-trap mass spectrometry with electrospray ionization. II. Monoacyl- and diacyl-PIMs

The multiple-stage ion-trap mass spectrometric approaches towards to the structural characterization of the monoacyl-PIM (triacylated PIM) and the diacyl-PIM (tetracylated PIM), namely, the PIM (diacylated PIM) consisting of one or two additional fatty acid substituents attached to the glycoside, respectively, were described. While the assignment and confirmation of the fatty acid substituents on the glycerol backbone can be easily achieved by the methods described in the previous article, the identity of the glycoside moiety and its acylation state can be determined by the observation of a prominent acylglycoside ion arising from cleavage of the diacylglycerol moiety ([M - H - diacylglycerol](-)) in the MS(2)-spectra of monoacyl-PIM and diacyl-PIM. The distinction of the fatty acid substituents on the 2-O-mannoside (i.e., R(3)CO(2)H) from that on the inositol (i.e., R(4)CO(2)H) is based on the findings that the MS(3)-spectrum of [M - H - diacylglycerol](-) contains a prominent ion arising from further loss of the fatty acid at the 2-O-mannoside (i.e., the [M - H - diacylglycerol - R(3)CO(2)H](-) ion), while the ion arising from loss of the fatty acid substituent at the inositol (i.e., the [M - H - diacylglycerol - R(4)CO(2)H](-) ion) is of low abundance. The fatty acyl moiety on the inositol can also be identified by the product-ion spectrum from MS(4) of the [M - H - diacylglycerol - R(3)CO(2)H](-) ion, which gives rise to a prominent ion corresponding to loss of R(4)CO(2)H. An [M - H - acylmannose](-) ion was also observed in the MS(2)-spectra and, thus, the identity of the fatty acid substituent attached to 2-O-mannoside can be confirmed. The combined information obtained from the multiple-stage product-ion spectra from MS(2), MS(3), and MS(4) permit the assignment of the complex structures of monoacyl-PIMs and diacyl-PIMs in a mixture isolated from M. bovis Bacillus Calmette Guérin.     

Excited-state dynamics of trans,trans-distyrylbenzene: transient anisotropy and excitation energy dependence

We report a study of excited-state dynamics of trans,trans-distyrylbenzene in hexane solution with femtosecond two-color transient absorption spectroscopy. A consistent model of two distinct excited states, S1 and X, connected by the 10 ps dynamics is proposed with the support from the analysis of excited-state anisotropy. An investigation on the 10 ps dynamics with varying excitation energy has been also conducted. In the assumption of fast intramolecular vibrational redistribution, a dependence of this nonradiative 10 ps process on intramolecular temperature in the S1 state has been analyzed. We have found that an effective mode of approximately 1270 cm-1 is responsible for the 10 ps dynamics. The analysis of both anisotropy and pump-dependent results further implies that a distribution of rotamers may exist in the X state. The result indicates a drastic different excited-state relaxation pathway than that of trans-stilbene.     

Applications of Hyaluronic Acid in Ophthalmology and Contact Lenses

Hyaluronic acid (HA) is a glycosaminoglycan that was first isolated and identified from the vitreous body of a bull’s eye. HA is ubiquitous in the soft connective tissues of animals and therefore has high tissue compatibility for use in medication. Because of HA’s biological safety and water retention properties, it has many ophthalmology-related applications, such as in intravitreal injection, dry eye treatment, and contact lenses. Due to its broad range of applications, the identification and quantification of HA is a critical topic. This review article discusses current methods for analyzing HA. Contact lenses have become a widely used medical device, with HA commonly used as an additive to their production material, surface coating, and multipurpose solution. HA molecules on contact lenses retain moisture and increase the wearer’s comfort. HA absorbed by contact lenses can also gradually release to the anterior segment of the eyes to treat dry eye. This review discusses applications of HA in ophthalmology.     

Amino acid derivatized carbon dots with tunable selectivity as logic gates for fluorescent sensing of metal cations

Carbon dots (CDs) modified with ethylene diamine (EDA) and the amino acids (AAs) Cys, His, Lys or Arg were synthesized, and their structures were confirmed by high resolution transmission electron microscopy, Raman spectrometry and X-ray photoelectron spectrometry. It is found that derivatization of the CDs with various AAs systemically modulates their electronic properties, and this results in a tunable selectivity in detection of metal cations via fluorescence quenching. The probes can be performed in aqueous solutions around pH 7. CDs can be excited under 345 nm excitation at room temperature and exhibit fluorescent peak at 450 nm. The decreasing fluorescence intensity is directly proportional to the concentration of metal cations. The limits of detection is 8.8 μg L^?1 for Pb(II), 20 μg L^?1 for Hg(II), 3.7 μg L^?1 for Cu(II), 5.3 μg L^?1 for Zn(II), 16 μg L^?1 for Fe(III), and 7.2 μg L^?1 for Cr(III), respectively. The different fluorescence response of the AA-modified CDs can be converted to logic gates and applied to photoelectronic nanoprobes by using microprocessors. In our perception, this assay has a large potential in terms of high-throughput screening for trace amounts of metal ions.

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Graphical abstract Amino acid derivatized carbon dots with tunable selectivity were synthesized by a one pot method for fluorescent sensing of metal cations. The sensing events can be directly converted into different logic gates.

     

Synthesis of γ-sulfonyl δ-lactones and β-sulfonyl styrenes

A facile route to the synthesis of γ-sulfonyl lactones 5 and β-sulfonyl styrenes 6 has been developed, achieving moderate to good yields via the (1) NaH mediated Michael addition of β-ketosulfones 3 and methyl acrylate in refluxing THF and (2) NaBH₄ mediated stereoselective reduction/lactonization of δ-ketoesters 4 in boiling MeOH, or (3) boron trifluoride etherate mediated ring-opening of lactones 5 in MeOH at reflux.     

Widely tunable asymmetric long-period fiber grating with high sensitivity using optical polymer on laser-ablated cladding

We demonstrate high-efficiency, wideband-tunable, laser-ablated long-period fiber gratings that use an optical polymer overlay. Portions of the fiber cladding are periodically removed by CO(2) laser pulses to induce periodic index changes for coupling the core mode into cladding modes. An optical polymer with a high thermo-optic coefficient with a dispersion distinct from that of silica is used on a deep-ablated cladding structure so that the effective indices of cladding modes become dispersive and the resonant wavelengths can be efficiently tuned. The tuning efficiency can be as high as 15.8 nm/ degrees C, and the tuning range can be wider than 105 nm (1545-1650 nm).     

Cell migration rate on poly(epsilon-caprolactone)/poly(ethylene glycol) diblock copolymers and correlation with the material sliding angle

The nanostructure of a biomaterial surface has strong influence on cell behavior. The migration of cells on nanostructured surfaces, however, has not been investigated so far. In this study, we used PCL/PEG diblock copolymers as model surfaces to examine the effect of nanoislands on migration of different cells, including fibroblasts and endothelial cells. The water sliding angle of the substrates was measured. The cell migration rate was examined under a real-time optical microscope. It was found that a greater cell migration rate correlated with the smaller sliding angle of the substrate.