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The styrene oxide to styrene carbonate conversion performed in CO2 atmosphere, herein selected as a case study, was implemented in microdroplets (aerosol) reactions at the preparative scale (3.5 mmol of the starting material) and mild conditions (1 atm CO2 pressure), within a custom-made ultrasonic nebulization reactor. Upon opti-mization of the promoter stoichiometry (1 eq of 4.3 TEG/KI ratio) and methanol (MeOH) dilution (7.5 mL of 2.5 v/v MeOH/TEG), performances under mass transfer-limited conditions of this novel methodological paradigm have been compared at 25 degrees C and 50 degrees C with those implemented as: a) no-stirred, b) stirred, and c) sonicated bulk reactions. Complete selectivity and an apparent acceleration factor (AAF) of 1.9 was registered at both temperature for microdroplets reactions in respect with the sonicated counterparts, these latter performing better than the other bulk reactions. These significative efficiency improvements, candidate aerosol reactions as a preferred process intensification approach in the realm of effective CO2-utilization strategies and, in general, in the development and exploitation of gas-liquid two-phase reactions. The present work was supported by the NATO Science for Peace and Security Programme (NATO SPS, Grant No. MYP G5885, project acronym: TANGO). The authors are grateful to the funding agency.

Four novel chitosan hydrogels were successfully synthesized through the cross-linking reaction of chitosan with different concentrations of ethyl 5-(3,5-dihydroxy-1,4-dioxan-2-yl)-2-methylfuran-3-carboxylate. Their structures were confirmed by Fourier transform infrared spectroscopy (FT-IR), 13C Cross polarization magic angle spinning nuclear magnetic resonance spectroscopy (CP/MAS 13C NMR), ultraviolet-visible spectroscopy, thermogravimetric analysis (TGA, DTA), and X-ray diffraction (XRD). Cytotoxicity on hepatocellular carcinoma (HepG-2) cell line and a normal African green monkey kidney (Vero) cell line were studied using the MTT assay. The resultant hydrogels showed a good inhibitory effect comparing to the un-modified parent; the hydrogels with the lowest degree cross-linking (0.125 and 0.25 mol cross-linker per one chitosan residue) showed potent anticancer activity in the HepG2 cells with IC50 of 57.9 and 80.9 μg/ml, respectively. These results show that the newly synthesized cross-linked chitosan derivatives demonstrated more selectivity to the HepG2 than the Vero cells, indicating its potential for Investigation in the cure of hepatocellular carcinoma.

International audience; Tentacle-like polymers decorated with several copies of peptide antigens can be interesting tools to increase the ability to capture circulating antibodies in patient sera, using cooperative effects for stronger avidity. We previously showed that antibodies from multiple sclerosis (MS) patient sera preferentially recognize hyperglucosylated adhesin protein HMW1 of non-typeable Haemophilus influenzae (NTHi) . We selected the C-terminal HMW1(1347-1354) minimal epitope and prepared the diglucosylated analogue Ac-KAN(Glc)VTLN(Glc)TTG-K(N 3 )-NH 2 to graft a 40 kDa dextran scaffold modified with glycidyl-propargyl moieties to perform a copper catalysed alkyne-azide coupling reaction (CuAAC). Quantitative NMR measurements allowed to characterize the peptide loading (19.5%) on the multivalent dextran conjugate. This novel polymeric structure displayed optimal capturing properties of both IgG and, more interestingly, IgM antibodies in MS sera. Specific antibodies from a representative MS serum, were successfully depleted using a sepharose resin bearing the new glucosylated multivalent conjugate, as confirmed by ELISA. These results may offer a promising proof-of-concept for the selective purification of high affinity autoantibodies from sera of patients affected by autoimmune patients, in general, and of specific high affinity antibodies against a minimal glycosylated epitope Asn(Glc) from sera of multiple sclerosis (MS) patients, in particular.

Highly stable gold nanoparticles anchored on propynylcarbamate-functionalized silica (Au/SiO2@Yne) have been efficiently utilized for the heterogeneous hydroamination of phenylacetylene with aniline under different reaction conditions. In order to ascertain the eventual influence of surface silanol groups on the system activity and selectivity tailored modifications of Au/SiO2@Yne catalysts were pursued according to two different strategies, involving respectively functionalization with trimethylethoxysilane (Au/SiO2@Yne-TMS) or post-treatment with triethylamine (Au/SiO2@Yne-NEt3). The prepared materials were analysed by several complementary techniques such as Solid State NMR (SS NMR), Transmission Electron Microscopy (TEM), X-ray Photoelectron Spectroscopy (XPS), X-ray Diffraction (XRD). A comparison of the resulting catalytic activities with that of the pristine Au/SiO2@Yne revealed a significant improvement for Au/SiO2@Yne-NEt3 in terms of both conversion and selectivity. Recycling and stability studies showed a catalytic activity decrease after the first run, due to the formation of polyphenylacetylene (PPhA) oligomers shielding the active sites. PPhA removal by sonication in acetone fully restored the catalytic activity and empowered the system with a good operational stability, a very crucial issue in view of eventual practical applications.

The adopted strategy and the results achieved by the Italian National Research Council within the Knowledge and Innovation Community “Raw Materials” of the European Institute of Innovation and Technology (KIC EIT-RM) are presented in detail. We focus on activities dedicated to education as well as validation and acceleration actions of the EIT-RM. Regarding the former, activities tackling the awareness of citizens on the impact of RMs in our life, guiding pupils towards an informed engagement into RMs university carriers, and lifelong learning of professionals dedicated to methodologies to access, organize, and share scientific literature and data are presented. Regarding the validation and acceleration actions, two main activities are discussed: (1) development of Platinum–Group Metals free catalysts and the corresponding know-how transfer initiative towards East and South East Europe (ESEE) countries; (2) development of novel analytical logging tools and portable devices for real-time compositional analyses based on laser technologies.

The use of microflow reactors enabled dramatic improvements in the apparent rates of photochemical reactions. However, scaling-up of photomicroreactors remains a challenge due to the difficulties of distributing light and flow to all units of photomicroreactors. In this work, the mass and photon transfer limitations of an easily scalable micro-structured reactor, an aerosol photoreactor, was studied. In this reactor concept, each droplet works as a microreactor. The nature of aerosol light interaction enables good light distribution to all the droplets. A singlet oxygen mediated photosulfoxidation reaction was utilized as a model reaction to assess the reactor performance. The light transfer limitations were proven to be overcome in the aerosol photoreactor. The reaction rate constant was calculated as 0.12 s−1. A simple solution of the convection–diffusion equation for a droplet was presented to check for the mass transfer limitations in aerosol reactors. The Sauter mean diameters of the droplets at different pressures varied between 7 and 8 µm. The aerosol photoreactor was proven to overcome the mass transfer limitations at these droplet diameters. In addition, the highest volumetric mass transfer coefficient (kLa) was calculated as 1.2 s−1, which was at the same order of magnitude compared to other intensified photoreactors such as Corning Advanced Flow ReactorsTM or a gas–liquid microreactor. A discussion on increasing the throughput of aerosol photoreactors further is presented. This work paves the way for efficient and scalable photoreactors for industrial use.

A strategy for the immobilization of chiral 2,3-bisaminocyclopropenium salt (pre-catalyst) onto polystyrene and silica supports is presented together with a suitable procedure for the conversion into the corresponding cyclopropenimine superbase catalysts. The activity and recyclability of polystyrene- and silica-supported cyclopropenimines were initially tested under batch conditions in a model Michael addition detecting comparable efficiencies but a superior stability of the latter heterogeneous catalyst (5 cycles, accumulated TON of 27.1). The preferred silica-supported cyclopropenimine behaved very similarly to the soluble counterpart in the reaction of glycine imine with different Michael acceptors (48-92% yield; 60-98% ee) and it could be utilized as packing material for the fabrication of fixed-bed mesoreactors (pressure-resistant stainless-steel columns). Continuous-flow experiments were performed with satisfactory long-term stability (24 h on stream) with unaltered conversion efficiency and enantioselectivity.

We report the structural dependency of long range scalar J-coupling constant across four bonds as function of the dihedral angles Φ1 and Φ3. The calculated homonuclear coupling constants 4 J(H,H ), obtained at a density functional theory level, were measured between C(1)─X(2) and X(2)─C(3) bonds in three-term models, where C, N, O, and S were systematically used as the second atom of the alkyl structures (1-4). The 4 J(H,H) calculated values, tabulated for variation of 30° for both Φ1 and Φ3, have disclosed an unexpected detectable coupling constant (4 J(H,H ) ≥ 1 Hz) across heteroatoms, useful to provide valuable structural information. A 2-methyl-1,3-dithiane sulfide (5) was used as a case study to prove the applicability and reliability of the calculated values to real issues. The 4 J(H,H ) values obtained at density functional theory for the system 4 have reproduced with good accuracy an unexpected experimental 4 J(H2ax-H4ax ) = 1.01 Hz of sulfide molecule (5), suggesting these calculated coupling constant values as a new powerful tool for the organic synthesis and stereochemical analysis.

Nuclear Magnetic Resonance (NMR) is an analytical technique extensively used in almost every chemical laboratory for structural identification. This technique provides statistically equivalent signals in spite of using spectrometer with different hardware features and is successfully used for the traceability and quantification of analytes in food samples. Nevertheless, to date only a few internationally agreed guidelines have been reported on the use of NMR for quantitative analysis. The main goal of the present study is to provide a methodological pipeline to assess the reproducibility of NMR data produced for a given matrix by spectrometers from different manufacturers, with different magnetic field strengths, age and hardware configurations. The results have been analyzed through a sequence of chemometric tests to generate a community-built calibration system which was used to verify the performance of the spectrometers and the reproducibility of the predicted sample concentrations.

Docosahexaenoic acid (DHA) is a semiessential polyunsaturated fatty acid (PUFA) for eukaryotic cells that is found in natural sources such as fish and algal oils and widely used as an ingredient for omega-3 containing foods or supplements. DHA effects are connected to its natural structure with six cis double bonds, but geometrical monotrans isomers can be formed during distillation or deodorization processes, as an unwanted event that alters molecular characteristics and annihilates health benefits. The characterization of the six monotrans DHA regioisomers is an open issue to address for analytical, biological, and nutraceutical applications. Here we report the preparation, separation, and first identification of each isomer by a dual approach consisting of the following: (i) the direct thiyl radical-catalyzed isomerization of cis-DHA methyl ester and (ii) the two-step synthesis from cis-DHA methyl ester via monoepoxides as intermediates, which are separated and identified by nuclear magnetic resonance spectroscopy, followed by elimination for the unequivocal assignment of the double bond position. This monotrans DHA isomer library with NMR and GC analytical characterization was also used to examine the products of thiyl-radical-catalyzed isomerization of a fish oil sample and to evaluate the trans isomer content in omega-3 containing supplements commercially available in Italy and Spain.

We report the structural dependency of long range scalar J-coupling constant across four bonds as function of the dihedral angles Φ1 and Φ3. The calculated homonuclear coupling constants

L'indagine ha lo scopo di comprendere quale valore ha per i professionisti, ricercatori e R&D manager di aziende l'informazione tecnico-scientifica, frutto del lavoro di ricerca, e che uso fanno della documentazione scientifica (esigenze, comportamenti di ricerche, difficoltà di recupero o gestione, ecc.) durante il loro lavoro. La raccolta dati è stata fatta attraverso un questionario online e una serie di interviste semi strutturate e ha coinvolto tre paesi: Italia, Spagna e Finlandia.

Raw Matters Ambassadors at schools 3.0 (RM@Schools) is an innovative program to make science education and careers in raw materials (RM) attractive for youngsters, involving RM experts and teachers (RM Ambassadors). ...

Gold nanoparticles (AuNPs) were anchored on alkynyl carbamate-functionalized support materials having the suitable features for application as catalysts in continuous-flow packed bed reactors. The functionalization step was carried out by grafting with the difunctional organosilane [3-(2-propynylcarbamate)propyl]triethoxysilane (PPTEOS) three commercial micrometer-sized oxide supports, i.e. silica, alumina, and titania. The alkynyl-carbamate moieties were capable of straightforwardly reducing the gold precursor HAuCl4 yielding the supported AuNPs systems Au/SiO2@Yne, Au/Al2O3@Yne, and Au/ TiO2@Yne. A comparison among the three materials revealed that silica allowed the highest organic functionalization (12 wt %) as well as the highest gold loading (3.7 wt %). Moreover, a TEM investigation showed only for Au/SiO2@Yne the presence of homogeneously distributed spherically shaped AuNPs (average diameter 15 nm). Au/ SiO2@Yne is an efficient catalyst, both in batch and flow conditions, in the oxidation of a large variety of alcohols using H2O2 as the oxidizing agent at a temperature of 90 °C. Furthermore, under flow conditions, the catalyst worked for over 50 h without any significant decrease in the catalytic activity. The catalytic activity of the three catalysts was evaluated and compared in the oxidation of 1-phenylethanol as a model substrate. We found that the flow approach plays a strategic role in preserving the physical and chemical integrity of the solid catalysts during its use, with remarkable consequences for the reaction conversion (from 2% in batch to 80% in flow) in the case of Au/TiO2@Yne.

Mesenchymal stem cells (MSC) have the unique ability to home and engraft in tumor stroma. These features render them potentially a very useful tool as targeted delivery vehicles which can deliver therapeutic drugs to the tumor stroma. In the present study, we investigate whether fluorescent core-shell PMMA nanoparticles (FNPs) post-loaded with a photosensitizer, namely meso-tetrakis (4-sulfonatophenyl) porphyrin (TPPS) and uploaded by MSC could trigger osteosarcoma (OS) cell death in vitro upon specific photoactivation. In co-culture studies we demonstrate using laser confocal microscopy and time lapse imaging, that only after laser irradiation MSC loaded with photosensitizer- coated fluorescent NPs (TPPS@FNPs) undergo cell death and release reactive oxygen species (ROS) which are sufficient to trigger cell death of all OS cells in the culture. These results encourage further studies aimed at proving the efficacy of this novel tri-component system for PDT applications. © 2013 Elsevier B.V.

An efficient enantioselective aryloxylation of cyclic β-keto esters with a selection of substituted o-quinones catalyzed by a bifunctional cinchona alkaloid derivative, giving entry to tricyclic dioxin adducts with high enantio- and diastereoselectivity, is described. © Georg Thieme Verlag Stuttgart - New York.

We report a new potent revisited version of a triazole-based inhibitor obtained by structure-based drug design on the human mPGES-1 crystal structure. Moreover, we disclosed the substitution with a halogen atom at position 5 as a new key factor influencing the biological activity on the mPGES-1 enzyme. This journal is

We have developed a multifunctional polymer-based nanoplatform for bimodal cancer phototherapy. It was achieved by electrostatic entangling of two anionic photoactivable components, a commercial porphyrin and a tailored nitro-aniline derivative, within the cationic shell of polymeric nanoparticles (NPs) based on polymethyl methacrylate. The combination of steady-state and time-resolved spectroscopic and photochemical techniques shows that the two photoresponsive agents do not interfere with each other while being in close proximity in the same polymeric scaffold and can thus operate in parallel under the exclusive control of light stimuli. Specifically, visible light triggers satisfactory red fluorescence emission and generation of singlet oxygen (O-1(2)) from one component and release of nitric oxide (NO) from the other. Fluorescence microscopy analysis provides unambiguous evidence for the internalization of the NPs within B78H1 melanoma cells, where they induce amplified mortality due to a combinatory effect of the two photogenerated cytotoxic species.

Herein, the successful utilization of core shell poly-methyl methacrylate nanoparticles (CS-PMMA NPs) as a valuable support for organocatalyst immobilization in aqueous medium is presented along with an unprecedented direct current-based electrochemical method for processing a water colloid of the resulting nano-supported catalyst. The NP coagulation procedure relied on various electrocoagulation techniques and it was achieved through water electrolysis occurring in a dialysis membrane immersed in the colloid. Mass recoveries of up to 95% w/w were obtained for the NPs within 1 h of electrolysis. This was optimized at a constant current of 90 mA or a constant potential of 24 V. The disclosed NP separation procedure was effectively exploited in a continuous-flow reaction/separation/recycle sequence involving the tetraphenylporphyrin tetrasulfonate (TPPS) organo-photocatalyst immobilized on CS-PMMA NPs (NP2s). After an optimization study aimed at maximizing the chemical efficiency of the entire synthetic and purification process, the nano-supported catalyst NP2 (0.05 mol%) efficiently promoted the photo-excitation of triplet oxygen to singlet oxygen for the selective and environmentally benign sulfoxidation of a model sulfide in an aqueous medium.

Capitalizing on an oxidation–alkylation approach, a non-diastereoselective entry into 2′-methyl taxanes was developed. The issue of configurational assignment at the newly formed side-chain quaternary stereocenter was solved and put into a more general context by integrating information from an alternative diastereoselective synthesis of model compounds and from spectroscopic measurements, critically comparing the J -Based and the Universal NMR Database approaches.

The retro-aldol reductive fragmentation of different structural types of 7-hydroxy-9,10-dioxotaxoids was investigated, showing that the reaction is typical of taxanes and requires cerium(III) promotion with NaBH4 in protic medium and alkylboron (aluminium) hydrides in aprotic solvents. The resulting 7,8-seco-taxanes are key intermediates for the synthesis of a novel class of anticancer taxanes endowed with a unique pattern of in vivo biological activity. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

Objectives Percutaneous catheterization of the coronary sinus (CS) to enable the administration of retrograde cardioplegia may play an important role in minimally invasive cardiac surgery. A new specially designed device (ProPlege; Edwards Lifesciences, Irvine, CA) is described that can be placed under transesophageal echocardiography (TEE) and pressure guidance with a high rate of success and low rate of complications. Design Case series. Setting A university-affiliated private hospital. Participants Patients undergoing minimally invasive cardiac surgery. Interventions The ProPlege device was placed under TEE and pressure guidance only. Measurements and Main Results Records of 70 patients managed with ProPlege were reviewed and analyzed. Successful placement was attained in 69 patients (98.6%) as confirmed by the ventricularization of the CS pressure curve and TEE images. Direct imaging of the ProPlege tip was possible in 34 patients (49.2%). The capacity to generate a CS pressure>30 mmHg during retrograde cardioplegia administration at a flow>150 mL/min was obtained in 64 patients; ProPlege displacement occurred in 5 cases (7.2%). Successful retrograde cardioplegia was delivered in 91.4% of cases. No CS perforation or other injuries to the right heart were noted at intraoperative TEE or direct surgical inspection. Conclusions Percutaneous CS catheterization with ProPlege was performed with a high rate of success for positioning and low complication rate using TEE and pressure guidance only. Further studies are needed to more accurately determine complication rates and to establish the possible complementary role of fluoroscopy.

Human mesenchymal stem cells (hMSC) are multipotent cells that display the unique ability to home and engraft in tumor stroma. This remarkable tumor tropic property has generated a great deal of interest in many clinical settings. Recently, we showed that hMSC represent an excellent base for cell-mediated anticancer therapy since they are able to internalize paclitaxel (PTX) and to release it in an amount sufficient to inhibit tumor cell proliferation. In order to shed light on the dynamics of drug uptake and release, in the present paper we describe the synthesis of two novel thiophene-based fluorophore-paclitaxel conjugates, namely PTX-F32 and PTX-F35, as tools for in vitro drug tracking. We aimed to study the ability of these novel derivatives to be efficiently internalized by hMSC and, in a properly engineered coculture assay, to be released in the medium and taken up by tumor cells. In order to ensure better stability of the conjugates toward enzymatic hydrolysis, the selected oligothiophenes were connected to the taxol core at the C7 position through a carbamate linkage between PTX and the diamino linker. Antiproliferative experiments on both tumor cells and stromal cells clearly indicate that, in good correlation with the parent compound, cells are sensitive to nanomolar concentrations of the fluorescent conjugates. Moreover, in the coculture assay we were able to monitor, by fluorescence microscopy, PTX-F32 trafficking from hMSC toward glioblastoma U87 tumor cells. Our work paves the way for novel possibilities to perform extensive and high quality fluorescence-based analysis in order to better understand the cellular mechanisms involved in drug trafficking, such as microvescicle/exosome mediated release, in hMSC vehicle cells. © 2014 American Chemical Society.

[structure: see text] The configuration of the alpha-substituted alpha-hydroxy-beta-aminoester moiety in a series of 2'-substituted taxanes was analyzed according to the recently proposed Universal NMR Database (UDB) approach. A critical analysis of the results showed that modifications regarding chemical shift adjustment (so as to render the shifts virtually connectivity independent) were necessary to get consistent stereoassignments in this set of compounds. On this basis, a modified UDB-based strategy, especially tailored to the configurational assignment of densely substituted diastereomeric fragments, is proposed.

[reaction: see text] L-proline failed to act as an organocatalyst in the homoaldol reaction of ethyl pyruvate; however, it reacted with the ester to give an azomethine ylide that in turn underwent 1,3-dipolar cycloaddition with a second molecule of pyruvate. Direct catalytic homoaldol reaction of ethyl pyruvate was performed using an (S)-(+)-1-(2-pyrrodinylmethyl)pyrrolidine/trifluoroacetic acid combination as organocatalyst. The use of polymer-supported reagents allowed for the lactonization of the aldol and isolation of the isotetronic acid derivative in hydroxy-free form.

Thiazolium salt pre-catalysts have been immobilized on silica and monolithic polystyrene and their activity was tested under batch conditions in three model umpolung reactions, namely the benzoin condensation of benzaldehyde, the acyloin-type condensation of biacetyl, and the Stetter reaction of biacetyl with trans-chalcone. A prerequisite of the study has been the utilization of environmentally benign water and ethanol solvents. After having established the higher performance of polystyrene monolithic thiazolium carbene catalysts, their effectiveness has been tested under the flow regime by fabricating the corresponding monolithic microreactors (pressure-resistant stainless-steel columns). Importantly, it has been demonstrated by a brief substrate scope study that the polymeric matrix and the continuous flow regime synergistically contribute to preserve the activity of the carbene catalysts over time, thus permitting the long-term operation (up to 7 days) of the prepared monolithic reactors for the production of valuable compounds via the umpolung strategy.