Synthesis and properties of novel macrocycles and related chromophoric benzenoid compounds

The synthesis and properties of some macrocyclic compounds of interest are presented. Resorcinarenes with functionalized conjugated rigid rods made of oligo-p-phenylenes would lead to an entirely new class of functional, soluble, well-defined architectures impacting a variety of multidisciplinary research efforts. The general synthetic design described in this document could be readly extrapolated to include other electronic systems such as heteroaromatics and polyenes. An extensive collaborative study of chromophore formation in resorcinarene solutions is also described here. The study reveals that upon oxidation, the reversible conversion to acyclic precursors occur first, and then these precursors undergo oxidation to quinoid-type compounds (xanthenes). The understanding of the mechanism of chromophore formation allowed us to design selective receptors for carbohydrates and the development of post-column selective reagents for the detection of mono- and oligosaccharides. This latter work is still in progress and the preliminary studies are described here. In another study involving macrocyclic architectures, tiliacorinine, an alkaloid, which consists of five rings forming a macrocycle exhibits a rare H-H spin coupling in its 1H NMR. Molecular modeling was used to determine the spatial relationship between the protons involved. Fluorinated [2,2]p-cyclophanes have been attracting increased attention. Poly(p-xylylene) polymers are materials of current technological interest. An obstacle to the commercialization of these polymers is the multistep syntheses required to obtain the fluorinated monomers. We describe a two-step synthesis of the tetrafluoro[2,2]p-cyclophanes. Another family of compounds, the fullerenes, was studied. Authors of a recent communication about the isolation and characterization of what was called the missing isomer of C60O postulated that this isomer could be present during the epoxidation of C60. Our HPLC and 1H NMR studies of the epoxidation of C60 revealed that there is no other isomer besides the epoxide in the photooxigenation of C60

Detecting Specific Saccharides via a Single Indicator

An improved synthesis of a rhodamine boronic acid indicator is reported. This compound is used in an optimized data collection protocol for wavelength- and time-dependent selectivity of sugars such as fructose and ribose derivatives. One indicator is thus used to selectively distinguish structurally related sugar analytes

Из опыта работы кафедры по организации учебной и воспитательной работы с иностранными студентами

Одна из ярких черт современного высшего образования - его интернационализация. Для Брестского государственного университета имени А.С. Пушкина в процессе интернационализации одним из новых, но перспективных её направлений является экспорт образовательных услуг. Появление в университете данной категории обучающихся (с 2007 г.) внесло коррективы и в организацию учебного процесса, и во внеучебную деятельность

Varied Length Stokes Shift BODIPY-Based Fluorophores for Multicolor Microscopy

Multicolor microscopy tools necessary to localize and visualize the complexity of subcellular systems are limited by current fluorophore technology. While commercial fluorophores cover spectral space from the ultraviolet to the near infrared region and are optimized for conventional bandpass based fluorescence microscopy, they are not ideal for highly multiplexed fluorescence microscopy as they tend to have short Stokes shifts, restricting the number of fluorophores that can be detected in a single sample to four to five. Herein, we synthesized a library of 95 novel boron-dipyrromethene (BODIPY)- based fluorophores and screened their photophysical, optical and spectral properties for their utility in multicolor microscopy. A subset of our BODIPY-based fluorophores yielded varied length Stokes shifts probes, which were used to create a five-color image using a single excitation with confocal laser scanning microscopy for the first time. Combining these novel fluorophores with conventional fluorophores could facilitate imaging in up to nine to ten colors using linear unmixing based microscopy approaches

pH-Dependent Fluorescent Probe That Can Be Tuned for Cysteine or Homocysteine

The very close structural similarities between cysteine and homocysteine present a great challenge to achieve their selective detection using regular fluorescent probes, limiting the biological and pathological studies of these two amino thiols. A coumarin-based fluorescent probe was designed featuring pH-promoted distinct turn-on followed by ratiometric fluorescence responses for Cys and turn-on fluorescence response for Hcy through two different reaction paths. These specific responses demonstrate the activity differences between Cys and Hcy qualitatively for the first time. The probe could also be used for Cys and Hcy imaging in living cells

E‑Cigarette Airflow Rate Modulates Toxicant Profiles and Can Lead to Concerning Levels of Solvent Consumption

Electronic cigarettes enabling enhanced airflow have grown in popularity in recent years. The objective of this study is to show that flow rates modulate the levels of specific aerosol toxicants produced in electronic cigarettes. Flow rates used in various laboratory investigations involving e-cigarettes have varied widely to date, and can thus promote interlaboratory variability in aerosol product profiles. The thermal decomposition of hydroxyacetone and glycolaldehyde is less favorable at lower temperatures, supporting the observations of these products at higher flow rates/lower heating coil temperatures. Higher temperatures promote the formation of acetaldehyde from hydroxyacetone and formaldehyde from both hydroxyacetone and glycolaldehyde. A separate finding is that greater airflow can also expose users to concerning levels of e-liquid solvents. Under the modest conditions studied, propylene glycol aerosol levels are found at above the acceptable inhalation levels defined by NASA, and in range of the generally recognized as safe levels for daily ingestion

Seminaphthofluorones are a family of water-soluble, low molecular weight, NIR-emitting fluorophores

A readily accessible new class of near infrared (NIR) molecular probes has been synthesized and evaluated. Specific fluorophores in this unique xanthene based regioisomeric seminaphthofluorone dye series exhibit a combination of desirable characteristics including (i) low molecular weight (339 amu), (ii) aqueous solubility, and (iii) dual excitation and emission from their fluorescent neutral and anionic forms. Importantly, systematic changes in the regiochemistry of benzannulation and the ionizable moieties afford (iv) tunable deep-red to NIR emission from anionic species and (v) enhanced Stokes shifts. Anionic SNAFR-6, exhibiting an unusually large Stokes shift of ≈200 nm (5,014 cm−1) in aqueous buffer, embodies an unprecedented fluorophore that emits NIR fluorescence when excited in the blue/green wavelength region. The successful use of SNAFR-6 in cellular imaging studies demonstrates proof-of-concept that this class of dyes possesses photophysical characteristics that allow their use in practical applications. Notably, each of the new fluorophores described is a minimal template structure for evaluation of their basic spectral properties, which may be further functionalized and optimized yielding concomitant improvements in their photophysical properties

Tailoring Three-Point Functions and Integrability II. Weak/strong coupling match

We compute three-point functions of single trace operators in planar N=4 SYM. We consider the limit where one of the operators is much smaller than the other two. We find a precise match between weak and strong coupling in the Frolov-Tseytlin classical limit for a very general class of classical solutions. To achieve this match we clarify the issue of back-reaction and identify precisely which three-point functions are captured by a classical computation.Comment: 36 pages. v2: figure added, references adde

Genome-wide trans-ancestry meta-analysis provides insight into the genetic architecture of type 2 diabetes susceptibility.

To further understanding of the genetic basis of type 2 diabetes (T2D) susceptibility, we aggregated published meta-analyses of genome-wide association studies (GWAS), including 26,488 cases and 83,964 controls of European, east Asian, south Asian and Mexican and Mexican American ancestry. We observed a significant excess in the directional consistency of T2D risk alleles across ancestry groups, even at SNPs demonstrating only weak evidence of association. By following up the strongest signals of association from the trans-ethnic meta-analysis in an additional 21,491 cases and 55,647 controls of European ancestry, we identified seven new T2D susceptibility loci. Furthermore, we observed considerable improvements in the fine-mapping resolution of common variant association signals at several T2D susceptibility loci. These observations highlight the benefits of trans-ethnic GWAS for the discovery and characterization of complex trait loci and emphasize an exciting opportunity to extend insight into the genetic architecture and pathogenesis of human diseases across populations of diverse ancestry