Spectroscopic characterization of core and shell regions in monolayer protected gold nanoparticles

We report studies on the structure of the metallic core and the alkyl cap layer in monolayer protected gold nanoparticles having sizes down to 1.6 nm. These particles are obtained by laser ablating gold targets in alkane-thiol solutions at different concentrations. The electronic structure of gold core and the vibrational properties of the capping hydrocarbon chains reveal effects connected with the nanosized nature of the particles.     

Immunodetection by quartz crystal microbalance

Biodetection is one of the most important challenges for the twenty-first century: many fields are concerned, mainly environmental and medical. The quartz crystal microbalance (QCM) may offer great possibilities for this purpose: a direct response signal, which characterizes the binding event between a sensitive layer, immobilized onto the surface transducer, and the analyte to be detected, can be obtained. However, for the detection of small biomolecules such as antigens, it is quite difficult to obtain an observable signal that corresponds directly to the binding event. In general, this is owing to the lack of mass sensitivity of the commonly used QCM, with 5- to 10-MHz quartz crystals. For improving this mass sensitivity, a 27-MHz quartz resonator was developed and incorporated in a flow-through microcell. Two biospecies, IgG rabbit and peroxidase enzyme, were studied with this ultra-sensitive QCM in terms of specificity, detection limit, and calibration curve.     

Bidimensional mixtures of polyglutamic and myristic acid

Summary Monolayers of polyglutamic acid and of its mixtures with myristic acid at the water/air interface on subphase composed of solutions of hydrochloric acid only and solutions containing CaCl₂ and hydrochloric acid were studied. The comparison of the experimental data with the bidimensional state equation deduced theoretically is in agreement with the presence of the rigid macromolecular form of alpha helix type in the bidimensional state, as shown by other authors. So far as the mixtures are concerned, on both the support solutions the two components are miscible between one another in all the molar ratios considered. On the support solution free of Ca⁺⁺ ions, the bidimensional mixtures are more stable than either of the components. In particular at a 1/1 molar ratio a sharp minimum of the free surface energy of mixing is found. On support solutions containing Ca⁺⁺ ions, the mixtures especially those containing higher concentrations of myristic acid, are thermodynamically less stable than the components themselves.

---

Zusammenfassung Es werden an der Grenzfläche Wasser/Luft Monoschichten von Polyglutaminsäure und deren Mischungen mit Miristinsäure auf Unterlagen, die nur Salzsäutelösungen oder auch Ca⁺⁺ enthalten, studiert. Für die Polyglutaminsäure ist der Vergleich der experimentellen Daten mit den theoretischen Gleichungen des bidimensionalen Zustand übereinstimmend mit dem Vorhandensein in bidimensionalem Zustand einer makromolekularen starren Form des-Helixtyps, wie schon von anderen Autoren festgestellt wurde.Was die Mischungen betrifft, sind auf beiden Unterlagen die Komponenten miteinander mischbar in sämtlichen Verhältnissen, die in Betracht gezogen wurden. Auf einer Unterlage ohne Calciumionen sind die bidimensionalen Mischungen stabiler als die Komponenten allein. Insbesondere dem Verhältnis 1/1 entspricht ein ausgesprochenes Minimum der Freien Oberflächenenergie der Mischungen. Auf einer Unterlage, die Calciumionen enthält, insbesondere wenn die Mischungen reich an Miristinsäure sind, erweisen sie sich als thermodynamisch weniger stabil als die Komponenten.

---

---

With 4 figures and 1 table     

Enzymatic hydrolysis reaction of phospholipids in monolayers

The hydrolysis reaction of , and , -dipalmitoylphosphatidylcholine (DPPC) catalized by bee venom phospholipase A₂ was studied in spreading monolayer at the water/air interface. DPPC and the hydrolysis products, palmitic acid and -lysophosphatidylcholine, palmitoyl were characterized at the interface by means of surface pressure, surface potential and ellipsometric measurements. Furthermore, mixed monolayers of reagents and products were investigated to ascertain their miscibility. The results show that the hydrolysis reaction can be followed by the decrease of surface pressure with time on subphases containing β-cyclodextrin, a well-known complexing agent of many amphiphilic compounds. The order of the reaction, the kinetic constant and other kinetic parameters are deduced.     

Addition reactions to cyclopolyolefin transition metal π complexes

The non-coordinated double bonds of (η⁴-1,2,3,4-cycloheptatriene)Fe(CO)₃ and (η⁴-1,2,5,6-cyclooctatetraene)Co(η⁵-C₅H₅) add methylene generated from the Simmons-Smith reaction to yield (η⁴-2,3,4,5-bicyclo[5.1.0]octa-2,4-diene)Fe(CO)₃ and (η⁴-2,3,7,8-tricyclo[7.1.0.0^4,6]deca-2,7-diene)Co(η⁵-C₅H₅). An analogous reaction of (η⁴-1,2,3,4-cyclooctatetraene)Fe(CO)₃ yields (η⁴-6,7,8,9-tricyclo[8.1.0.0^3,5]undeca-6,8-diene)Fe(CO)₃, a product of the addition of three equivalents of methylene in which a cyclopropyl ring opening is proposed to occur. Dichlorocatbene, generated from C₆H₅HgCCl₂Br, would not react in a similar fashion. A BH₃ · THF solution would react with these starting materials but unusual products were produced.     

Diterpenoids from cultured Erythropodium caribaeorum

The known antimitotic agent eleutherobin and the briarane diterpenoids erythrolides A and B have been isolated from cultured specimens of Erythropodium caribaeorum in amounts comparable to those reported from wild-harvested reef animals. The novel diterpenoid aquariolide A, having an unprecedented highly rearranged carbon skeleton (named aquariane), has also been found. The aquariane skeleton can be formally derived from the briarane skeleton by sequential di-pi-methane and vinyl-cyclopropane rearrangements. [structure: see text]     

The fragmentation of 5- and 3-substituted thiophene-2-carboxamides under electron impact

The 70 eV electron impact mass spectra of twelve 5- and 3-substituted thiophene-2-carboxamides are discussed with the aid of exact mass measurements and labelling experiments. All mass spectra exhibit pronounced molecular ions. Some isomeric 5- and 3-substituted title compounds can be differentiated by mass spectrometry. The fragmentation is influenced by a strong ‘ortho-effect’ which activates the NH₃ elimination. In the other cases the most important fragmentation is NH₂˙ loss, followed by CO elimination.     

Thermodynamic and spectroscopic properties of mixtures of β-lactoglobulin and dioleylphosphatidylcholine

 The behavior of the single spreading monolayers of β-lacto-globulin (β-LG) and dioleyl-phosphatidylcholine (DOPC), as well as their mixtures, has been studied on subphases containing Na⁺ or Ca⁺⁺ ions. The results show an influence of temperature and subphase on the studied systems. The behavior of the areas as a function of the weight fraction of the two components shows significative and prevalently positive deviations from the additivity and their bidimensional miscibility. The variation of ΔG ^ex, ΔH ^ex and ΔS ^ex calculated for the DOPC–β-LG mixture having maximum deviation on two different supports allows to deduce that the interactions are prevalently repulsive. FTIR–ATR spectra of transferred plurilayers show that DOPC has a surface orientation which can originate the miscibility between the protein and DOPC. Received: 3 February 1997 Accepted: 3 June 1997     

Monolayers of methacrylic polymers containing aromatic groups

Monolayers of poly-methacrylates containing either aromatic or linear side groups were studied at the air-water interface. The aim of the work is to define the role of the aromatic group in determining the interfacial distribution and orientation of these polymers. Surface pressure measurements show that all the polymers give stable expanded monomolecular films between 288 K and 308 K temperature range.Surface potential and ellipsometric measurements show that both aromatic and aliphatic polymers are in an almost horizontal conformation at the liquid-air interface. From a comparison of the experimental isotherms with Huggins' theory, it was deduced that no preferential interactions exist between benzene rings in the film. In contrast, preferential attractive energies are observed for n-alkylmethacrylates.Further information on the state of the collapsed film was obtained from electron scanning micrographs.     

Conjugated Azoalkenesi Part III. Synthesis of Sone Phosphorous Azoalkenes

Recently, some of us reviewed the synthes is and chemical reactions of conjugated azoalkenes.¹ Emphasis was placed on the fact that these derivatives represent at the same time interesting products and useful intermediates in organic chemistry. In fact, conjugated azoolefins undergo a wide range of 1,4-additions, (3+2)- and (4+2)-cycloadditions allowing various functionalizations of the carbon atom adjacent to the carbonyl group, and the construction of many types of interesting five - and six-membered heterocycles, such as widely substituted pyrrole and pyridazine rings. These relevant synthetic objectives appear not to be smoothly obtained by other procedures. In addition, many of the compounds produced from conjugated azoalkenes can profitably be employed in the preparation of natural, pharmaceutical, and phytopharmaceutical products.¹