Photon Upconversion in Small Molecules

Upconversion (UC) is a process that describes the emission of shorter-wavelength light compared to that of the excitation source. Thus, UC is also referred to as anti-Stokes emission because the excitation wavelength is longer than the emission wavelength. UC materials are used in many fields, from electronics to medicine. The objective of using UC in medical research is to synthesize upconversion nanoparticles (UCNPs) composed of a lanthanide core with a coating of adsorbed dye that will generate fluorescence after excitation with near-infrared light to illuminate deep tissue. Emission occurs in the visible and UV range, and excitation mainly in the near-infrared spectrum. UC is observed for lanthanide ions due to the arrangement of their energy levels resulting from f-f electronic transitions. Organic compounds and transition metal ions are also able to form the UC process. Biocompatible UCNPs are designed to absorb infrared light and emit visible light in the UC process. Fluorescent dyes are adsorbed to UCNPs and employed in PDT to achieve deeper tissue effects upon irradiation with infrared light. Fluorescent UCNPs afford selectivity as they may be activated only by illumination of an area of diseased tissue, such as a tumor, with infrared light and are by themselves atoxic in the absence of infrared light. UCNP constructs can be monitored as to their location in the body and uptake by cancer cells, aiding in evaluation of exact doses required to treat the targeted cancer. In this paper, we review current research in UC studies and UCNP development.     

Polyphenols Content,Antioxidant Properties and Allergenic Potency of Organic and Conventional Blue Honeysuckle Berries

Blue honeysuckle berries are a rich source of polyphenols with strong antioxidant properties. The purpose of this research was to determine the effect of organic and conventional cultivation on the polyphenols, antioxidant and allergenic potency of blue honeysuckle berry cultivars: ‘No 30’, ‘Jolanta’ and ‘Indygo’ in two growing seasons. Identification of individual polyphenols was performed using the HPLC method; the total polyphenols content and antioxidant activity were determined by spectrophotometric methods. The determination of allergic potency was tested by ELISA. In the second year of the study the total polyphenols were significantly higher in organic blue honeysuckle than in the conventional blue honeysuckle. In both growing seasons, the ‘Indygo’ cv. was characterized by the highest concentration of all bioactive compounds 3241.9 mg and 3787.2 mg per 100 g⁻¹ D.W. A strong correlation was found between the polyphenol content and the antioxidant activity for organic fruit in both years, as well as for allergenic potency. Contrary to the best bioactive properties was ‘Indigo’ cv., with the highest allergenic potency (108.9 and 139.2 ng g⁻¹ D.W.). The lowest content of specific allergens was found in the ‘No 30’ cv. Since honeysuckle is still a new cultivated plant, information about its allergenic potency is insufficient.     

Computational Bioprospecting Guggulsterone against ADP Ribose Phosphatase of SARS-CoV-2

Coronavirus Disease-2019 (COVID-19) is a highly contagious disease caused by Severe Acute Respiratory Syndrome-Coronavirus-2 (SARS-CoV-2). The World Health Organization (WHO) classified the disease a as global public health hazard on 11 March 2020. Currently, there are no adequate measures to combat viral infections, including COVID-19, and the medication guidelines for the management of COVID-19 are dependent on previous findings from SARS-CoV and MERS-CoV research. Natural products have achieved widespread acceptance around the world as a means of enhancing healthcare and disease prevention. Plants are a potential source of antiviral factors such as flavonoids, phenolic acids, terpenoids, and others. Some of these agents exhibit a broad spectrum of antiviral activity. This study aimed to screen herbal leads for possible inhibitors of the SARS-CoV-2 ADP Ribose Phosphatase enzyme (ARP). Guggulsterone was found to be highly stabilized within the active site of the viral ARP enzyme by molecular dynamic simulation with very little fluctuation throughout the simulation timeframe of 100 ns. Thus, guggulsterone can be further used to develop a safe and competent medication for evolving therapy against SARS-CoV-2 in post-preclinical and clinical trials.     

Using self-assembled monolayers for controlled electrodeposition of copper into submicrometer size surface features/decrements

This work presents the application of alkanethiols for selectively masking the main surface of copper-seed-layer-covered silicon wafer, as used for the microprocessor production. The target of the investigation was to deposit copper only in the trenches and vias (channels of various shape) of micrometer size and not over the entire surface as in the presently used methods. The procedure developed starts with filling the trenches and vias with water, which is followed by dipping the wafers in a hexane solution containing dissolved dodekanetiol. Alkanetiol adsorbs and self-organizes on copper not protected with water and blocks the electroreduction of copper ions from the bath. The trenches and vias are free from adsorbed alkanetiols due to their very limited solubility in water. The surface-blocking process works very well and may effectively simplify the copper electrodeposition for microelectronic applications. The selective electrodeposition of copper accomplished by the proposed method significantly reduces the problems associated with the removal of excess of copper from the processed circuit elements.     

On the graph labellings arising from phylogenetics

We study semigroups of labellings associated to a graph. These generalise the Jukes-Cantor model and phylogenetic toric varieties defined in [Buczynska W., Phylogenetic toric varieties on graphs, J. Algebraic Combin., 2012, 35(3), 421–460]. Our main theorem bounds the degree of the generators of the semigroup by g + 1 when the graph has first Betti number g. Also, we provide a series of examples where the bound is sharp.     

Photoinduced electron transfer from tryptophan to Ru(II)TAP complexes: the primary process for photo-cross-linking with oligopeptides

The photoreaction mechanism of [Ru(TAP)(2)(phen)](2+) and [Ru(TAP)(3)](2+) (TAP = 1,4,5,8-tetraazaphenanthrene) with tryptophan (Trp), N-acetyl-Trp, and Lys-Trp-Lys is examined. The existence of a photoelectron-transfer process from the amino acid unit is demonstrated by laser flash photolysis experiments. The back electron transfer (BET) from the reduced complex to the oxidized amino acid, occurring at the microsecond time scale, corresponds approximately to an equimolecular-bimolecular process; however, it is disturbed by another reaction, originating from the oxidized Trp. Moreover, in competition with the BET, the reduced and oxidized intermediates give rise to an adduct. The latter is clearly detected by gel electrophoresis experiments in denaturing conditions, with a system composed of an oligonucleotide derivatized at the 3' end by the Ru(II)TAP complex and hybridized with the complementary sequence functionalized at the 5' end by the tripeptide Lys-Trp-Lys. Thus, upon illumination, a cross-linking between the two strands is observed, which originates from the presence of a Trp residue.     

Higher Sucrose Analogs: Homologation of a Glucose Unit of Sucrose by Two Carbon Atoms

Abstract

The primary hydroxyl groups (at C-6 and C-6′) in 2,3,4,3′4′-penta-O-benzyl-l′-O-methoxymethyl sucrose (2) can be reactively differentiated with tert-butyldiphenylsilyl chloride. Reaction of 2 with TBDPSCl afforded only one monosilylated product protected at C-6′ (6). The regioisomeric monoprotected sucrose 8 was prepared by selective deprotection of the double silylated derivative 7. Compound 6 was converted into 2,3,4,3′,4′-penta-O-benzyl-6-carbomethoxymethylidene-1′-O-methoxymethylsucrose 10 in three steps. Osmylation of the double bond in 10 afforded stereoisomeric homologated sucroses: 11a [6(S),7(R)] and 11b [6(R),7(S)] in the ratio 3:2. A large downfield shift of the H-1 (up to 0.5 ppm) was observed for 6′-silylated derivatives.     

Synthesis and Structural Analysis of Higher Analogs of Sucrose

ABSTRACT

Three sucrose monoalcohols with free hydroxyl groups at C-1', C-6, and C-6' (1, 4, and 6) were prepared selectively and in good yield from 2,3,3',4,4'-penta-O-benzylsucrose. These compounds were oxidized to aldehydes and reacted with stabilized ylide, Ph₃P=CHCO₂Me to afford appropriate α,β-unsaturated esters 10, 11, and 12. Each olefin was cis-hydroxylated with OsO₄/NMO to stereoisomeric diols 13/14, 15/16, and 17/18, configurations of which were assigned by chemical correlation and CD evaluation. Stereoselectivity of the osmylation reaction was surprisingly low (ca 3:2), especially as compared to a similar process performed on simple derivatives of 6,7-unsaturated methyl glycosides for which the ratio of isomeric diols was assigned as 10:1. The osmylation of 11 (derivative homologated by a C₂-unit at the glucose part) did not obey Kishi's rule. Horner-Emmons reaction of sucrose aldehyde 7 with a sugar-derived phosphonate 22 afforded α,β-unsaturated derivative 24, homologated by a C₇-unit at the glucose end.