Scope and Limitations of 3‐Iodo‐Kdo Fluoride‐Based Glycosylation Chemistry using N‐Acetyl Glucosamine Acceptors

The ketosidic linkage of 3‐deoxy‐d‐manno‐octulosonic acid (Kdo) to lipid A constitutes a general structural feature of the bacterial lipopolysaccharide core. Glycosylation reactions of Kdo donors, however, are challenging due to the absence of a directing group at C‐3 and elimination reactions resulting in low yields and anomeric selectivities of the glycosides. While 3‐iodo‐Kdo fluoride donors showed excellent glycosyl donor properties for the assembly of Kdo oligomers, glycosylation of N‐acetyl‐glucosamine derivatives was not straightforward. Specifically, oxazoline formation of a β‐anomeric methyl glycoside, as well as iodonium ion transfer to an allylic aglycon was found. In addition, dehalogenation of the directing group by hydrogen atom transfer proved to be incompatible with free hydroxyl groups next to benzyl groups. In contrast, glycosylation of a suitably protected methyl 2‐acetamido‐2‐deoxy‐α‐d‐glucopyranoside derivative and subsequent deiodination proceeded in excellent yields and α‐specificity, and allowed for subsequent 4‐O‐phosphorylation. This way, the disaccharides α‐Kdo‐(2→6)‐α‐GlcNAcOMe and α‐Kdo‐(2→6)‐α‐GlcNAcOMe‐4‐phosphate were obtained in good overall yields.     

Synthesis of the Cellulose Model Compound Methyl 4″-O-Methyl-β-D-Cellotrioside

A high-yield synthetic route towards methyl 4″-O-methyl-β-D -cellotrioside ( 17 ) via cellobioside acceptor 8 and glucosyl fluoride donor 15 was established. The former was synthesized from cellobiose peracetate in 7 steps and 21% overall yield, while the latter was obtained from methyl β-D -glucopyranoside in a 6-step-synthesis with 19% yield. Glycosidation afforded 13% of α-compound besides the desired β-isomer (31%). The target compound, being the higher homologue of the recently prepared 4′-O-methyl-β-D -cellobioside ( 1 ), is required to study by solid-state techniques the hydrogen bond network in cellodextrins and cellulose, and its changes upon swelling and dissolution.     

Characterization and Differentiation of Fresh Orange Juice Variety Based on Conventional Physicochemical Parameters,Flavonoids, and Volatile Compounds Using Chemometrics

The present study focused on the possibility of differentiating fresh-unprocessed orange juice according to botanical origin (variety), based on the use of conventional physico-chemical parameters, flavonoids, and volatile compounds, in combination with chemometrics. For this purpose, oranges from seven different varieties were collected during the harvest years of 2013–2014 and 2014–2015 from central and southern Greece. The physico-chemical parameters that were determined included: electrical conductivity, acidity, pH, and total soluble solids. The flavonoids: hesperidin, neohespseridin, quercetin, naringin, and naringenin were determined using high-performance liquid chromatography (HPLC-DAD). Finally, volatile compounds were determined using headspace solid-phase micro-extraction in combination with gas chromatography-mass spectrometry (HS-SPME/GC-MS). Statistical treatment of data by multivariate techniques showed that orange juice variety had a significant (p < 0.05) impact on the above analytical parameters. The classification rate for the differentiation of orange juice according to orange variety using multivariate analysis of variance (MANOVA) and linear discriminant analysis (LDA) was 89.3%, based on the cross-validation method.     

Synthesis of Lipid A and Inner Core LPS ligands containing 4-amino-4-deoxy-l-arabinose units

Attachment of 4-amino-4-deoxy-l-arabinose to phosphates or sugar hydroxyl groups of lipopolysaccharide contributes to bacterial resistance against common antibiotics. For a detailed study of antigenic properties and binding interactions, Ara4N-containing inner core ligands related to Burkholderia and Proteus LPS have been synthesized in good yields. Glycosylation at position 8 of allyl glycosides of oct-2-ulosonic acids (Ko, Kdo) has been accomplished using an N-phenyltrifluoroacetimidate 4-azido-4-deoxy-l-arabinosyl glycosyl donor followed by azide reduction and global deprotection. The β-l-Ara4N-(1→8)-α-Kdo disaccharide was further extended into the branched β-l-Ara4N-(1→8)[α-Kdo-(2→4)]-α-Kdo trisaccharide via a regioselective glycosylation of a protected triol intermediate. Synthesis of Ara4N-modified lipid A - part structure occurring in the LPS of Burkholderia, Pseudomonas and Klebsiellla strains was accomplished using the H-phosphonate approach. The stereocontrolled assembly of the phosphodiester linkage connecting glycosidic centres of two aminosugars was elaborated employing an anomeric H-phosphonate of cyclic silyl-ether protected 4-azido-4-deoxy-β-l-arabinose which was coupled to the hemiacetal of the lipid A GlcN-disaccharide backbone. Conditions for global deprotection which warrant the integrity of "double anomeric" phosphodiester linkage were successfully developed. Introduction of thiol-terminated spacer at the synthetic ligands allows both coupling to BSA and immobilization on gold nanoparticles as well as generation of glycoarrays.     

Supercontinuum extending from > 1000 to 250 nm, generated by focusing ten-fs laser pulses at 805 nm into Ar

Ten femtosecond pulses at 805 nm with energy up to 1 mJ were produced by self-phase modulation of 45-fs pulses in Ar at atmospheric pressure and subsequent compression by chirped mirrors. Focusing part of this radiation again into Ar at atmospheric pressure generates a single filament with broadband emission covering the range from > 1000 to 250 nm. This range extends farther into the UV than previously observed with such low energies, overlapping even the region of the third harmonic. Only a small fraction of the power is contained outside the central spot. Using a simple prism compressor, pulses were obtained with durations of 70 fs and energies of 700 nJ in the range 270–290 nm.This revised version was published online in March 2005. The last name of the corresponding author W. Fuß was corrected.     

Widely tunable ultraviolet sub-30-fs pulses from supercontinuum for transient spectroscopy

Focusing 800-nm pulses of 10–20 fs and ≤0.4 mJ into atmospheric-pressure argon gives rise to a supercontinuum extending down to 250 nm. We show that spectral cuts from this radiation can be shortened by a simple prism compressor down to 30 fs even near the UV cut-off. The resulting pulses have enough energy (several hundred nanojoules) to serve as a simple and rugged broadly tunable pump source in ultra-fast transient spectroscopy. Such an application is demonstrated for the first time, using pulses tuned over 280–320 nm to excite Cr(CO)₆; probing it by intense-field ionization at 800 nm, we determine the lifetime of initially populated states to be as short as 14 fs.PACS 42.65.Jx; 42.65.Ky; 42.65.Re; 42.72.Bj; 82.20.-w; 82.53.-k