Synthesis of β-cyclodextrin-lysozyme conjugates and their physicochemical and biochemical properties

Recently a great interest in the field of protein engineering and the design of innovative drug delivery systems employing specific ligands such as cyclodextrins is observed. The paper reports the solid state, thermal method for protein coupling with β-cyclodextrin and the physicochemical and biological properties of the obtained conjugates. The structure of the obtained conjugates was investigated via liquid chromatography-mass spectrometry, dynamic light scattering and circular dichroism analysis. The presented conjugates were biologically active and covalently bound β-cyclodextrin preserved the ability to form inclusion complexes with the model compound. This report demonstrates the great potential of cyclodextrin as a modifying unit that can be used to modulate the properties of therapeutic proteins, additionally giving such conjugates the possibility to transport many therapeutic substances in the form of inclusion complexes. In addition, the paper presents the potential of protein-cyclodextrin conjugates to construct innovative bioactive molecules for biological and medical applications.     

Design,synthesis and application of new bile acid ligands with 1,2,3-triazole ring

New dimers have been obtained from propargyl ester of bile acids and α,α′-diazide-m-xylene by intermolecular 1,3-dipolar cycloaddition. These compounds have been used as ligands to form intermolecular hydrogen bonds with various aromatic acids. The structures of all products were confirmed by spectroscopic (¹H NMR, ¹³C NMR and FT-IR) analysis, mass spectrometry (ESI, MALDI) and PM5 semiempirical methods.     

$$\varvec{L^p}$$-norm estimate of the Bergman projection on Hartogs triangle

Let \({\mathcal {S}}\) denote the set of positive integers that may appear as the strong symmetric genus of a finite abelian group. We obtain a set of (simple) necessary and sufficient conditions for an integer g to belong to \({\mathcal {S}}\). We also prove that the set \({\mathcal {S}}\) has an asymptotic density and approximate its value.     

An engineering theory of soil behaviour in unloading and reloading

Summary A constitutive law is proposed for describing the stress-strain characteristic of soils in unloading-reloading. The constitutive equations are valid piecewisely between subsequent, appropriately formulated, stress reversal loci. The stress-strain relationships are formulated in terms of generalized stress and strain differences referred to the last stress reversal point and connected through a variable compliance tensor. The shear compaction effect is modelled by a suitable formulation of the compliance tensor.Specialization to conventional triaxial condition is given. As well as fitting available experimental data in unloading-reloading of normally consolidated and overconsolidated clays, the proposed constitutive relation can model the dependence on OCR of the shape of the undrained effective stress paths, the phenomenon of cyclic mobility of clay in undrained compression and the unloading-reloading stress paths in the oedometer. The theory requires the identification of only three material constants in addition to those pertinent to the usual elastoplastic theory of soil with which it may be easily combined.

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Sommario Si propone una legge costitutiva per descrivere il legame sforzi-deformazioni dei terreni sottoposti a processi di scarico e ricarico. Le equazioni costitutive sono formulate a tratti e definite su un dominio limitato dai luoghi di inversione di carico. Nella formulazione della legge costituitiva verranno introdotte delle variabili generalizzate di sforzo riferite all'ultimo punto di inversione di carico. Queste variabili sono legate alle deformazioni, riferite anche esse allo stato relativo all'ultimo punto di inversione di carico, da un tensore di cedevolezza variabile. Un'adeguata formulazione di questo tensore permette di modellare l'efferio di densificazione sotto carico deviatorico ciclico.Questa legge costitutiva interpreta bene i risultati sperimentali su argille normalmente consolidate e sovraconsolidate. La teoria permette anche di descrivere la dipendenza del percorso degli sforzi efficaci in condizioni non drenate dal grado di sovraconsolidazione, la mobilità ciclica dell'argilla in condizioni non drenate e il percorso degli sforzi efficaci in un processo di scarico e ricarico in un edometro.Per identificare il modello sono necessari solo tre parametri oltre a quelli necessari per identificare il comportamento del terreno vergine.

     

The effect of points fattening on Hirzebruch surfaces

The purpose of this note is to study initial sequences of 0–dimensional subschemes of Hirzebruch surfaces and classify subschemes whose initial sequence has the minimal possible growth.     

Photophysics,Excited‐state Double‐Proton Transfer and Hydrogen‐bonding Properties of 5‐Deazaalloxazines

The photophysical properties of 5‐deazaalloxazine and 1,3‐dimethyl‐5‐deazaalloxazine were studied in different solvents. These compounds have higher values of fluorescence quantum yields and longer fluorescence lifetimes, compared to those obtained for their alloxazine analogs. Electronic structure and S₀–S_i transitions were investigated using the ab initio methods [MP2, CIS(D), EOM‐CCSD] with the correlation‐consistent basis sets. Also the time‐dependent density functional theory (TD‐DFT) has been employed. The lowest singlet excited states of 5‐deazaalloxazine and 1,3‐dimethyl‐5‐deazaalloxazine are predicted to have the π, π* character, whereas similar alloxazines have two close‐lying π, π* and n, π* transitions. Experimental steady‐state and time‐resolved spectral studies indicate formation of an isoalloxazinic excited state via excited‐state double‐proton transfer (ESDPT) catalyzed by an acetic acid molecule that forms a hydrogen bond complex with the 5‐deazaalloxazine molecule. Solvatochromism of both 5‐deazaalloxazine and its 1,3‐dimethyl substituted derivative was analyzed using the Kamlet–Taft scale and four‐parameter Catalán solvent scale. The most significant result of our studies is that the both scales show a strong influence of solvent acidity (hydrogen bond donating ability) on the emission properties of these compounds, indicating the importance of intermolecular solute–solvent hydrogen‐bonding interactions in their excited state.     

Enantioselective addition of phenylacetylene to aldehydes catalyzed by a d-glucosamine-derived sulfonamide-titanium complex

We present the synthesis of β-hydroxy sulfonamides derived from d-glucosamine and their application as ligands in titanium tetraisopropoxide promoted enantioselective addition of phenylacetylene to benzaldehyde and selected aromatic and aliphatic aldehydes. The N-3,5-bis(trifluoromethyl)benzenesulfonamido-d-glucosamine derivative was chosen as the most efficient ligand for this addition. The reaction is highly enantioselective for several aromatic aldehydes and enantiomeric excesses up to 92% were obtained.     

Photophysical properties and photocytotoxicity of novel phthalocyanines - potentially useful for their application in photodynamic therapy

Two novel zinc(II) phthalocyanines bearing non-peripheral ester-alkyloxy substituents (Pc-4 and Pc-5) were synthesized, by a two-step procedure starting from 2,3-dicyanohydroquinone. Both sensitizers show promising photophysical properties, including solvatochromic study, qualitative evaluation of emission, aggregation behavior and singlet oxygen generation. It was proven that the photodynamic activity of the compounds studied depends on the molecular oxygen level. Comparison of the quantum yields of singlet oxygen generation as well as the oxidation rate constants using 1,3-diphenylisobenzofurane before and after deaeration proved the photodynamic effect of Pc-4 and Pc-5 to be governed by the photosensitization mechanism II. Changes in the quantities of the compounds exposed to irradiation were also estimated. Upon their exposure to light the changes in intensity of the Q band were monitored. The photodecomposition of Pc-4 and Pc-5 in DMSO or DMF solutions was found to proceed according to the first order kinetic reaction in two stages.The photosensitizing effect of Pc-4 in HSC-3 cells was significantly lower than that of ZnPc. Pc-4 was ineffective at 0.1 μM, while a low, approx. 15% photocytotoxicity was observed at 5 μM, at a distance of 5 and 10 cm. The efficacy of Pc-4 in photokilling of cultured cells is affected by hydrophobicity and the aggregation status of the photosensitizer.     

Synthesis,molecular characterisation,and in vivo study of platinum(IV) coordination compounds against B16 mouse melanoma tumours

A novel platinum(IV) coordination compound with 6-mercaptopurine (6-Hmp) has been synthesised and characterised by IR and NMR spectroscopy. Spectroscopic parameters indicate the presence of two chelate (S-6, N-7) monodeprotonated ligands and two chloride ions in the coordination sphere of [PtCl₂(6-mp)₂] · H₂O (I). Two Pt(IV) coordination compounds, [PtCl₂(6-mp)₂] · H₂O (I) and [PtCl₄(dbtp)₂] (II), were used in the in vivo test against B16 mouse melanoma tumours. Cytotoxic activity of compound II against the tumour cells was found to be high (LC₁₀ = 2.6 μM, LC₅₀ = 17.0 μM, LC₉₀ = 58.0 μM) compared to that of cisplatin.