Polymeric Semiconductors with a Pre‐Specified Alternation of Conjugated Bonds and Metal Clusters

Summary: In this work the first samples of polymeric semiconductors of a new structure are produced. Their electric conductivity is of the order ∼10⁻² Ohm⁻¹ · cm⁻¹ and it increases with temperature. Their synthesis includes a stage of radiation grafting of a matrix‐type on stretched polyamide films. Conducting molecular circuits in such materials include fragments with conjugated bonds and metal clusters. The alternation of these fragments is determined by the polyamide matrix.

Plot of voltage versus current determined for new polymer semiconducting films where fragments with conjugated bonds alternate with silver clusters.     

Reaction of ω‐carbonyl substituted 1,3,3‐trimethyl‐2‐methyleneindolines with phosphorus(III) halides

The phosphorylation of N‐benzoyl‐2‐(1,3,3‐trimethyl‐2‐methyleneindoline)acetamide ( 2 ) and ω‐(3‐dimethylamino)benzoyl‐1,3,3‐trimethyl‐2‐methyleneindoline ( 6 ) with phosphorus(III) halides resulted in the formation of 2,3‐dihydro‐4H‐1,5,2‐oxazaphosphinin‐4‐one and 1,2‐dihydro‐3H‐phosphindol‐3‐one systems, respectively. The properties of the obtained compounds were studied. Further cyclization of 1,2‐dihydro‐3H‐phosphindol‐3‐one into dihydrophosphindolo[3,2‐c]pyrazole was carried out. © 2003 Wiley Periodicals, Inc. Heteroatom Chem 14:23–28, 2003; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.10060     

Effect of spatial heterogeneity on level of rejuvenation in Ni80P20 metallic glass

Understanding the relation between spatial heterogeneity and structural rejuvenation is one of the hottest topics in the field of metallic glasses (MGs). In this work, molecular dynamics (MD) simulation is implemented to discover the effects of initial spatial heterogeneity on the level of rejuvenation in the Ni$_{80}$P$_{20 }$MGs. For this purpose, the samples are prepared with cooling rates of $10^{10}$ K/s-$10^{12}$ K/s to make glassy alloys with different atomic configurations. Firstly, it is found that the increase in the cooling rate leads the Gaussian-type shear modulus distribution to widen, indicating the aggregations in both elastically soft and hard regions. After the primary evaluations, the elastostatic loading is also used to transform structural rejuvenation into the atomic configurations. The results indicate that the sample with intermediate structural heterogeneity prepared with 10$^{11}$ K/s exhibits the maximum structural rejuvenation which is due to the fact that the atomic configuration in an intermediate structure contains more potential sites for generating the maximum atomic rearrangement and loosely packed regions under an external excitation. The features of atomic rearrangement and structural changes under the rejuvenation process are discussed in detail.     

Kinetic Analysis of Prostate-Specific Antigen Interaction with Monoclonal Antibodies for Development of a Magnetic Immunoassay Based on Nontransparent Fiber Structures

Prostate cancer is the second most common cancer diagnosed in men worldwide. Measuring the prostate-specific antigen (PSA) is regarded as essential during prostate cancer screening. Early diagnosis of this disease relapse after radical prostatectomy requires extremely sensitive methods. This research presents an approach to development of an ultrasensitive magnetic sandwich immunoassay, which demonstrates the limit of PSA detection in human serum of 19 pg/mL at a dynamic range exceeding 3.5 orders of concentration. Such attractive performance stems, inter alia, from the kinetic analysis of monoclonal antibodies (mAbs) against free PSA to select the mAbs exhibiting best kinetic characteristics and specificity. The analysis is carried out with a label-free multiplex spectral-correlation interferometry compatible with inexpensive single-use glass sensor chips. The high sensitivity of developed PSA immunoassay is due to electronic quantification of magnetic nanolabels functionalized by the selected mAbs and three-dimension porous filters used as an extended solid phase. The assay is promising for PSA monitoring after radical prostatectomy. The proposed versatile approach can be applied for the rational design of highly sensitive tests for detection of other analytes in many fields, including in vitro diagnostics, veterinary, food safety, etc.     

Liquid-Crystalline Order in the Phosphorus-Containing DenDrimers

The structure of phosphorus-containing dendrimers has been studied by IR spectroscopy and optical polarization microscopy. The repeating units of dendrimer molecules are mesogens. This property arises from the conjugation of the aromatic ring and the hydrazone group. An analysis of the IR spectra showed that, with an increase in the generation number, the width of the stretching vibration bands ν(PN) and ν(PO) increases. Difficulties in packing molecules of higher generations cause conformational diversity. The shape of the dendrimer molecules was determined by analyzing the increments of dipole moments. Additionally, the modeling of the stacking of repeating links was performed. The spherical model of molecules does not satisfy the experimental dipole moments of the dendrimers. The flat disk model is more suitable for explaining step changes in dipole moments. The liquid-crystalline ordering of dendrimers under the action of applied pressure was found. With simultaneous heating and uniaxial compression, optical anisotropy appears in dendrimers. It is associated with the formation of liquid-crystalline order. However, a thermodynamically stable liquid-crystalline phase is not formed in this case. Dendrimers most likely have disk-shaped molecules.     

Synthesis and structure of a new selenium-bridged tungsten cluster, [W3Se7(S2P(OEt)2)3]Br

[W₃Se₇(S₂P(OEt)₂)₃]Br was prepared by reacting (Et₄N)₂W₃Se₇Br₆ with KS₂P (OEt)₂ in CH₃CN and its crystal structure determined. In the [W₃(μ₃-Se)(μ₂-Se₂)₃]⁴⁺ core the W---W bond length is 2.755(5)-2.764(6) Å and the Se---Se bond length is 2.32(1)- 2.34(4) Å.     

Fluorescence Spectral Properties of Indocyanine Green on a Roughened Platinum Electrode: Metal-Enhanced Fluorescence

The interactions of fluorophores with noble metal particles can modify their emission spectral properties, a relatively new phenomenon in fluorescence. We subsequently examined indocyanine green (ICG), which is widely used in medical testing and imaging, in close proximity to an electrically roughened platinum electrode. The emission intensity and lifetimes were decreased about 2-fold on the roughened surface as compared to a smooth Pt surface, and the photostability about the same. Platinum does not appear promising for metal enhanced fluorescence, at least for long wavelength fluorophores.     

Multiplicity of the ground state of large alternant organic molecules with conjugated bonds

The multiplicity and the full spin of the ground state of large alternate molecules with conjugated bonds are considered. It is strictly shown that if the numbers of starred and unstarred atoms (say, carbon) differ from each other the full spin of the molecule is more than zero. Some possible planar and linear molecules having the full spin to be proportional to their sizes are presented. Particularly, they would be ferromagnets at infinite sizes.