α-Dimethylaminomethylenation-induced Houben-Hoesch-type cyclization of cyanoacetanilides: a practical synthesis of 3-formyl-4-hydroxyquinolin-2(1H)-ones

The tandem reaction of cyanoacetanilides with triflic anhydride in DMF proceeded at room temperature to afford 3-formyl-4-hydroxyquinolin-2(1H)-ones in good to high yields. A detailed mechanistic study revealed that the tandem reaction proceeded via α-dimethylaminomethylenation, which promoted the subsequent Houben-Hoesch-type cyclization. Both α-functionalization and the cyclization steps were optimized, and a multi-gram scale synthesis of 3-formyl-4-hydroxyquinolin-2(1H)-one was achieved.     

Solid phase total synthesis of callipeltin E isolated from marine sponge Latrunculia sp.

Solid phase total synthesis of callipeltin E (1), truncated linear peptide isolated from marine sponge, Latrunculia sp. was achieved. Our strategy based on traditional Fmoc-SPPS was in common use TFA-treatment final deprotection to reach callipeltin E (1) contained acid-sensitive βMeOTyr.     

Measurements of arsenite and arsenate contained in mining river waters and leached from contaminated sediments by sequential hydride generation flow injection analysis

In this work, a new analytical method for gasifiable compounds based on sequential hydride generation flow injection analysis (SHGFIA) was applied to water analysis and leaching investigation. For water analysis, it was confirmed that 1 μg L⁻¹ As(III) and As(V) were stable for a few days when EDTA was added in the sample waters. Dissolved As(III) and total arsenic (As(III) + As(V)) were converted to AsH₃ in neutral and acidic medium, respectively, to transfer to a miniature gas scrubber (100 μL in absorber volume). The collected arsenic was successively measured by flow analysis based on molybdenum blue chemistry. With this system, changes in As(III) and As(V) concentrations of water placed with arsenic-contaminated-sediment was monitored in near real time. From these data, kinetic analyses were carried out and kinetic constant was obtained from plot of ln{(C^∞ − C)/C^∞} where C and C^∞ were leached arsenic concentration and its final concentration, respectively. It was found that rate of As(III) leaching was much faster than that of As(V) while As(V) leached more in amount compared to As(III). In this work, it was demonstrated that kinetic investigation is also one of the important application of flow analysis. The SHGFIA system showed excellent performance for leaching analysis of arsenic with discrimination of As(III) and As(V).     

Quantitative SENSE-MRSI of the human brain

Purpose

To develop a method for estimating metabolite concentrations using phased-array coils and sensitivity-encoded (SENSE) magnetic resonance spectroscopic images (MRSI) of the human brain.

Materials and Methods

The method is based on the phantom replacement technique and uses receive coil sensitivity maps and body-coil loading factors to account for receive B₁ inhomogeneity and variable coil loading, respectively. Corrections for cerebrospinal fluid content from the MRSI voxel were also applied, and the total protocol scan time was less than 15 min. The method was applied to 10 normal human volunteers using a multislice 2D-MRSI sequence at 3 T, and seven different brain regions were quantified.

Results

N-Acetyl aspartate (NAA) concentrations varied from 9.7 to 14.7 mM, creatine (Cr) varied from 6.6 to 10.6 mM and choline (Cho) varied from 1.6 to 3.0 mM, in good general agreement with prior literature values.

Conclusions

Quantitative SENSE-MRSI of the human brain is routinely possible using an adapted phantom-replacement technique. The method may also be applied to other MRSI techniques, including conventional phase encoding, with phased-array receiver coils, provided that coil sensitivity profiles can be measured.     

Constraints on low energy QCD parameters from $$\eta \rightarrow 3\pi $$ and $$\pi \pi $$ππ scattering

The \(\eta \,\rightarrow \,3\pi \) decays are a valuable source of information on low energy QCD. Yet they were not used for an extraction of the three flavor chiral symmetry breaking order parameters until now. We use a Bayesian approach in the framework of resummed chiral perturbation theory to obtain constraints on the quark condensate and pseudoscalar decay constant in the chiral limit. We compare our results with recent CHPT and lattice QCD fits and find some tension, as the \(\eta \,\rightarrow \,3\pi \) data seem to prefer a larger ratio of the chiral order parameters. The results also disfavor a very large value of the pseudoscalar decay constant in the chiral limit, which was found by some recent work. In addition, we present results of a combined analysis including \(\eta \,\rightarrow \,3\pi \) decays and \(\pi \pi \) scattering and though the picture does not changed appreciably, we find some tension between the data we use. We also try to extract information on the mass difference of the light quarks, but the uncertainties prove to be large.     

Soft Communities in Similarity Space

The \(\mathbb {S}^1\) model has been central in the development of the field of network geometry. It places nodes in a similarity space and connects them with a likelihood depending on an effective distance which combines similarity and popularity dimensions, with popularity directly related to the degrees of the nodes. The \(\mathbb {S}^1\) model has been mainly studied in its homogeneous regime, in which angular coordinates are independently and uniformly scattered on the circle. We now investigate if the model can generate networks with targeted topological features and soft communities, that is, inhomogeneous angular distributions. To that end, hidden degrees must depend on angular coordinates, and we propose a method to estimate them. We conclude that the model can be topologically invariant with respect to the soft-community structure. Our results expand the scope of the model beyond the independent hidden variables limit and can have an important impact in the embedding of real-world networks.     

Superconformal Invariance and the Geography¶of Four-Manifolds

The correlation functions of supersymmetric gauge theories on a four-manifold X can sometimes be expressed in terms of topological invariants of X. We show how the existence of superconformal fixed points in the gauge theory can provide nontrivial information about four-manifold topology. In particular, in the example of gauge group SU(2) with one doublet hypermultiplet, we derive a theorem relating classical topological invariants such as the Euler character and signature to sum rules for Seiberg–Witten invariants. A short account of this paper can be found in [1]. Received: 19 December 1998 / Accepted: 7 March 1999     

Nanostructured Heterogeneous Catalysts for Bioorthogonal Reactions

Bioorthogonal chemistry has inspired a new subarea of chemistry providing a powerful tool to perform novel biocompatible chemospecific reactions in living systems. Following the premise that they do not interfere with biological functions, bioorthogonal reactions are increasingly applied in biomedical research, particularly with respect to genetic encoding systems, fluorogenic reactions for bioimaging, and cancer therapy. This Minireview compiles recent advances in the use of heterogeneous catalysts for bioorthogonal reactions. The synthetic strategies of Pd-, Au-, and Cu-based materials, their applicability in the activation of caged fluorophores and prodrugs, and the possibilities of using external stimuli to release therapeutic substances at a specific location in a diseased tissue are discussed. Finally, we highlight frontiers in the field, identifying challenges, and propose directions for future development in this emerging field.     

Thermal polymerizations of alkali 4-(1-bromoethyl)benzoates

Thermal reactions of alkali salts of 4-(1-bromoethyl)benzoic acid in bulk were investigated. These reactions were found to produce unexpectedly the graft copolymer, poly(4-vinylbenzoate)-graft-oligo(oxycarbonyl-1,4-phenylenethylidene) ( 1 ). The relative reactivity of the oligocondensation as well as the vinyl polymerization of the salts decreased in the following order: K > Na > Li. The reaction polymerization rate proceeded rapidly during the initial 15 min, and then slowed down.     

Tailorable and Biocompatible Supramolecular-Based Hydrogels Featuring two Dynamic Covalent Chemistries

Dynamic covalent chemistry (DCC) has proven to be a valuable tool in creating fascinating molecules, structures, and emergent properties in fully synthetic systems. Here we report a system that uses two dynamic covalent bonds in tandem, namely disulfides and hydrazones, for the formation of hydrogels containing biologically relevant ligands. The reversibility of disulfide bonds allows fiber formation upon oxidation of dithiol-peptide building block, while the reaction between NH−NH₂ functionalized C-terminus and aldehyde cross-linkers results in a gel. The same bond-forming reaction was exploited for the “decoration” of the supramolecular assemblies by cell-adhesion-promoting sequences (RGD and LDV). Fast triggered gelation, cytocompatibility and ability to “on-demand” chemically customize fibrillar scaffold offer potential for applying these systems as a bioactive platform for cell culture and tissue engineering.