Practical Synthesis of (20S)‐10‐(3‐Aminopropyloxy)‐7‐ethylcamptothecin,a Water‐Soluble Analogue of Camptothecin

A robust, practical synthesis of (20S)‐10‐(3‐aminopropyloxy)‐7‐ethylcamptothecin (T‐2513, 5 ), which is a water‐soluble analogue of camptothecin, has been developed. The key step in this synthesis is a highly diastereoselective ethylation at the C20 position by using N‐arylsulfonyl‐(R)‐1,2,3,4‐tetrahydroisoquinoline‐3‐carboxylic acid ester as a chiral auxiliary, which affords the key intermediate ethyl‐(S)‐2‐acyloxy‐2‐(6‐cyano‐5‐oxo‐1,2,3,5‐tetrahydroindolizin‐7‐yl)butanoate ( 8 k ) in 93 % yield and 87 % de. Optically pure compound 8 k was obtained by a single recrystallization from acetone and its further elaboration through Friedlander condensation afforded compound 5 . This synthesis does not require any chromatographic purification steps and can provide compound 5 on a multi‐gram scale in 6.3 % overall yield (16 steps).     

Design and synthesis of 2-(1,3-dialkoxy-2-methylpropan-2-yl)-1,3-diarylpropanes as tethering units for folded H-stacking polymers

1,3-Diarylpropenes 9 having a 1,3-dialkoxy-2-methylpropan-2-yl group were designed as tethering monomers for folded H-stacking polymers, and were readily synthesized from 2-ethoxymethylidene malonate in four- or five-steps, including a facile sequential addition–elimination–addition reaction of benzyl zinc reagents. The preference for the closed (stacked) conformation in the resulting 2-substituted 1,3-diarylpropanes 9 was evaluated using MM2 calculations, ¹H NMR analyses, and fluorescence measurements. Copolymerization of the resulting monomers 9 with compounds containing π-units provided polymers with blue-shifted UV-absorptions both in solution and as films, compared with that of a model compound containing a single π-unit. This optical property is unique to H-aggregated π-units.     

Uncovering the Stoichiometry of Pyrococcus furiosus RNase P,a Multi‐Subunit Catalytic Ribonucleoprotein Complex,by Surface‐Induced Dissociation and Ion Mobility Mass Spectrometry

We demonstrate that surface‐induced dissociation (SID) coupled with ion mobility mass spectrometry (IM‐MS) is a powerful tool for determining the stoichiometry of a multi‐subunit ribonucleoprotein (RNP) complex assembled in a solution containing Mg²⁺. We investigated Pyrococcus furiosus (Pfu) RNase P, an archaeal RNP that catalyzes tRNA 5′ maturation. Previous step‐wise, Mg²⁺‐dependent reconstitutions of Pfu RNase P with its catalytic RNA subunit and two interacting protein cofactor pairs (RPP21⋅RPP29 and POP5⋅RPP30) revealed functional RNP intermediates en route to the RNase P enzyme, but provided no information on subunit stoichiometry. Our native MS studies with the proteins showed RPP21⋅RPP29 and (POP5⋅RPP30)₂ complexes, but indicated a 1:1 composition for all subunits when either one or both protein complexes bind the cognate RNA. These results highlight the utility of SID and IM‐MS in resolving conformational heterogeneity and yielding insights on RNP assembly.     

Development of a fluoride-responsive amide bond cleavage device that is potentially applicable to a traceable linker

A fluoride-responsive (FR) amino acid that induces amide bond cleavage upon the addition of a fluoride was developed, and it was applied to an FR traceable linker. By the use of an alkyne-containing peptide as a model of an alkynylated target protein of a bioactive compound, introduction of the FR traceable linker onto the peptide was achieved. Subsequent fluoride-induced cleavage of the linker followed by labeling of the released peptide derivative was also conducted to examine the potential applicability of the FR traceable linker to the enrichment and labeling of alkynylated target molecules.     

Total Diet Study: Mg and Mn content estimation of a Market Basket of São Paulo state (Brazil) by Instrumental Neutron Activation

Total Diet Studies (TDS) have been carried out to estimate dietary intakes of the essential and toxic elements for a large-scale population over a specific period of time. In this study, the TDS was based on the evaluation of food representing a Market Basket (MB), which reflected the dietary habits of the São Paulo State population, corresponding to 72 % of the average food consumption for the state of São Paulo. In the present Total Diet Study, magnesium and manganese concentrations were determined in 30 of the most consumed food groups of a MB of São Paulo State, Brazil. Instrumental Neutron Activation Analysis (INAA) has been successfully used on a regularly basis in several areas of nutrition and foodstuffs. Element concentrations were determined by INAA in freeze-dried samples and ranged in mg kg^?1. Mg 41.4 (fats)–5287 (coffee) and Mn 0.12 (prime grade beef)–32.9 (coffee). The average daily Mg and Mn intake was calculated by multiplying the concentration of each element in each table-ready food group by the respective weight (g day^?1) of the food group in the MB and adding the products from all food groups. The results of daily dietary intakes in this study were: Mg 174.8 and Mn 1.34 mg day^?1. Theses values were lower than the adequate intake (AI) proposed by the Food and Nutrition Board of the Institute of Medicine (USA National Academy) for adults. The low levels of Mg and Mn intakes presented in this TDS are probably due to the fact that MB of this study represented only 72 % of the weight of the most consumed household foods of São Paulo State.     

Evaluation of As,Se and Zn in octopus samples in different points of sales of the distribution chain in Brazil

Three CRMs of different matrix composition were analysed, representing an environmental matrix sample (BCR–320R Channel Sediment), a botanical matrix sample (SRM 1547 Peach Leaves) and a zoological matrix sample (SRM 1566b Oyster Tissue). The element mass fractions were obtained using the KayWin program. Analytical measurement uncertainty was determined by two approaches: (1) the routine procedure applying combination of the overall uncertainty u(m) = 3.5 % and statistical uncertainty of the peak area determination and (2) the procedure applying the dedicated ERON program for calculating uncertainty. Performance of altogether 31 certified values was tested by means of calculating E _n numbers. For the remaining 52 non-certified values, comparison between uncertainties obtained by the two approaches was made. When using the first approach, the E _n number showed satisfactory performance in 28 cases; by using the second approach, the E _n number showed satisfactory performance in 27 cases. None of the unsatisfactory performances (E _n  > 1) appeared to be of systematic nature. The uncertainties obtained by applying the two approaches revealed a big extent of consistency. As the present nuclear database lacks lot of data that serve as input to the ERON program, in particular uncertainties of Q ₀ factors, estimates need to be introduced for the missing values, emphasising the urgent need to upgrade the database with missing data.     

Use of neutron activation analysis and LC–ICP-MS in the development of candidate reference materials for As species determination

Arsenic (As) is widely found in marine organisms, mainly as organic arsenical compounds. With the introduction of regulations for As species in foodstuffs and for environmental control, it has become more important to quantify the amount of arsenic species present. To address this concern new reference materials (RMs) for validation and quality assurance of As speciation measurements are being developed, including a tuna fish tissue and a robalo liver tissue. Instrumental neutron activation analysis (INAA) is used in this work as a proven analytical tool for As determinations and for validating the As mass fraction determined by liquid chromatography coupled to inductively coupled mass spectrometry (LC–ICP-MS) in extracts of the candidate RMs and other fish samples including certified RMs. Various methods for the extraction of water-soluble As species were evaluated. The best results were acquired after methanol/acetone/water extraction yielding in 93 % extractable As in the tuna RM. This procedure was used for the LC–ICP-MS studies. The results demonstrate that INAA can account for 100 % of the distribution of As species in analytical processes. It complements LC–ICP-MS for the validation of the characterization of As species in the development of RMs for such species. Excellent agreement of measured results in certified RMs with the reported values confirms the validity of the applied procedures.     

A Dual Functional-Group Derivatization Liquid Chromatography–Tandem Mass Spectrometry Method: Application for Quantification of Human Insulin

Chromatographia - Recently, we developed a sensitive and accurate quantification method for short-chain peptides using dual functional-group derivatization. Sensitive and accurate quantification...     

Quantum transport of massless Dirac fermions

Motivated by recent graphene transport experiments, we undertake a numerical study of the conductivity of disordered two-dimensional massless Dirac fermions. Our results reveal distinct differences between the cases of short-range and Coulomb randomly distributed scatterers. We speculate that this behavior is related to the Boltzmann transport theory prediction of dirty-limit behavior for Coulomb scatterers.     

Object recognition by use of polarimetric phase-shifting digital holography

Pattern recognition by use of polarimetric phase-shifting digital holography is presented. Using holography, the amplitude distribution and phase difference distribution between two orthogonal polarizations of three-dimensional (3D) or two-dimensional phase objects are obtained. This information contains both complex amplitude and polarimetric characteristics of the object, and it can be used for improving the discrimination capability of object recognition. Experimental results are presented to demonstrate the idea. To the best of our knowledge, this is the first report on 3D polarimetric recognition of objects using digital holography.