Number Of Repeat Units Research Articles

Rigid Cyclic Polymer in Solution: Cycloamylose Tris(phenylcarbamate) in 1,4-Dioxane and 2-Ethoxyethanol.

Six cyclic amylose tris(phenylcarbamate) (ATPC) samples have been prepared from enzymatically synthesized cyclic amylose ranging in the number of repeat units N from 24 to 290. Synchrotron-radiation small-angle X-ray scattering measurements were made for the samples in 1,4-dioxane (DIOX) and 2-ethoxyethanol (2EE) to determine the z-average radius of gyration ⟨S2⟩z and the particle scattering function P(q). Molar mass dependencies of ⟨S2⟩z in the two solvents were successfully explained by the current theories for the wormlike ring with the same parameters for linear ATPC in the corresponding solvent, that is, the helix pitch h (or contour length) per residue and the Kuhn segment length λ-1 (stiffness parameter, twice the persistence length). The latter parameter λ-1 is 22 and 16 nm in DIOX and 2EE, respectively. Except for the low-q region, P(q) was also explained by the rigid ring having the same contour length Nh as that for linear ATPC. Further, their local conformation estimated from circular dichroism spectra is essentially unaltered from that for linear ATPC at least when N ≥ 24.

A Spectroscopic and DFT Study of the Electronic Properties of Carbazole-Based D–A Type Copolymers

The structural and electronic properties of three carbazole containing copolymers used in organic photovoltaic applications, poly[N-1-octylnonyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)] (PCDTBT), poly[N-1-octylnonyl-2,7-carbazole-alt-4,7-(2′,1′,3′-benzothiadiazole)] (PCBT), and poly[N-1-octylnonyl-2,7-carbazole-alt-4,7-(2′,1′,3′-benzoselenadiazole)] (PCBSe) have been studied using resonance Raman (RR) and transient absorption (TA) spectroscopies and density functional theory (DFT) calculations. Enhancement of Raman modes centered on the acceptor unit when a Raman excitation wavelength is coincident with lowest energy electronic excitation suggests that the excitation involves charge transfer from the carbazole donor to the varying benzodiazole acceptors. The pattern of the enhancement when the excitation wavelength is coincident with the higher energy transition indicates that this transition is π to π* in nature; this is consistent with TD-DFT calculations. Nanosecond transient absorption studies show long-lived excited state signals for PCDTBT (126 ± 4 ns and 1.56 ± 0.1 μs) and PCBSe (1.82 ± 0.1 μs), suggesting that population of the triplet state is appreciable. No transient signal could be detected in PCBT. B3LYP TD-DFT calculations of the monomer through to the hexamer indicate a broadly delocalized excited state orbital for PCDTBT as indicated by the linear decrease in excitation energy with an increased number of repeat units, while for PCBSe and PCBT, the reduction in excitation is sublinear. The highest occupied (HOMO) and lowest unoccupied molecular orbitals (LUMO) of PCBSe and PCBT polymers compared to PCDTBT are similarly diffuse, but the population of higher order orbitals is decreased when compared with PCDTBT. CAM-B3LYP calculations reduce the delocalization of the frontier orbitals and show less reduction in excitation energy with additional repeat units for each polymer.

Dimensionality effects in the electronic structure of organic semiconductors consisting of polar repeat units

In conjugated organic molecules, excitation gaps typically decrease reciprocally with increasing the number of repeat units, n. This usually holds for individual molecules as well as for the corresponding bulk materials. Here, we show using density-functional theory calculations that a qualitatively different evolution is found for layers built from molecules consisting of polar repeat units. Whereas a 1/n-dependence is still observed in the case of isolated polar molecules, the global gap decreases essentially linearly with n in the corresponding 2D-periodic systems and vanishes beyond a certain molecular length, with the frontier states being localized at opposite ends of the layer. The latter is accompanied by a saturation of the dipole moment per molecule, an effect not observed in the isolated polar molecules. Interestingly, in both cases the limit of the gap for long (but finite) molecules differs qualitatively from that of infinite length obtained in 1D-periodic and 3D-periodic calculations, the latter serving as models for polymers and the bulk. We rationalize these dimensionality effects as a consequence of the potential gradient within the finite-length layers. They arise from the collective action of intra-molecular dipoles in the 2D periodic layers and can be traced back to surface effects.

Energy Level Modulation of HOMO, LUMO, and Band‐Gap in Conjugated Polymers for Organic Photovoltaic Applications

AbstractTo devise a reliable strategy for achieving specific HOMO and LUMO energy level modulation via alternating donor‐acceptor monomer units, we investigate a series of conjugated polymers (CPs) in which the electron withdrawing power of the acceptor group is varied, while maintaining the same donor group and the same conjugated chain conformation. Through experiment and DFT calculations, good correlation is identified between the withdrawing strength of the acceptor group, the HOMO and LUMO levels, and the degree of orbital localization, which allows reliable design principles for CPs. Increasing the acceptor strength results in an enhanced charge transfer upon combination with a donor monomer and a more pronounced decrease of the LUMO level. Moreover, while HOMO states remain delocalized along the polymer chain, LUMO states are strongly localized at specific bonds within the acceptor group. The degree of LUMO localization increases with increasing polymer length, which results in a further drop of the LUMO level and converges to its final value when the number of repeat units reaches the characteristic conjugation length. Based on these insights we designed PBT8PT, which exhibits 6.78% power conversion efficiency after device optimization via the additive assisted annealing, demonstrating the effectiveness of our predictive design approach.

Safety Assessment of Alkyl PEG Ethers as Used in Cosmetics

The CIR Expert Panel assessed the safety of Alkyl PEG Ethers as used in cosmetics. These ingredients primarily function in cosmetics as surfactants, and some have additional functions as skin-conditioning agents, fragrance ingredients, and emulsion stabilizers. The Panel reviewed available relevant animal and clinical data, as well as information from previous CIR reports; when data were not available for individual ingredients, the Panel extrapolated from the existing data to support safety. The Panel concluded that the Alkyl PEG ethers are safe as used when formulated to be nonirritating, and the same applies to future alkyl PEG ether cosmetic ingredients that vary from those ingredients recited herein only by the number of ethylene glycol repeat units.

Low numbers of repeat units in variable number of tandem repeats (VNTR) regions of white spot syndrome virus are correlated with disease outbreaks

White spot syndrome virus (WSSV) is the most important pathogen in shrimp farming systems worldwide including the Mekong Delta, Vietnam. The genome of WSSV is characterized by the presence of two major 'indel regions' found at ORF14/15 and ORF23/24 (WSSV-Thailand) and three regions with variable number tandem repeats (VNTR) located in ORF75, ORF94 and ORF125. In the current study, we investigated whether or not the number of repeat units in the VNTRs correlates with virus outbreak status and/or shrimp farming practice. We analysed 662 WSSV samples from individual WSSV-infected Penaeus monodon shrimp from 104 ponds collected from two important shrimp farming regions of the Mekong Delta: Ca Mau and Bac Lieu. Using this large data set and statistical analysis, we found that for ORF94 and ORF125, the mean number of repeat units (RUs) in VNTRs was significantly lower in disease outbreak ponds than in non-outbreak ponds. Although a higher mean RU number was observed in the improved-extensive system than in the rice-shrimp or semi-intensive systems, these differences were not significant. VNTR sequences are thus not only useful markers for studying WSSV genotypes and populations, but specific VNTR variants also correlate with disease outbreaks in shrimp farming systems.

Design strategies for organic semiconductors beyond the molecular formula

Organic semiconducting materials based on polymers and molecular systems containing an electronically delocalized structure are the basis of emerging optoelectronic technologies such as plastic solar cells and flexible transistors. For isolated molecules, guidelines exist that rely on the molecular formula to tailor the frontier (highest occupied or lowest unoccupied) molecular orbital energy levels and optical absorption profiles. Much less control can be achieved over relevant properties, however, as one makes the transition to the ensemble behaviour characteristic of the solid state. Polymeric materials are also challenging owing to the statistical description of the average number of repeat units. Here we draw attention to the limitations of molecular formulae as predictive tools for achieving properties relevant to device performances. Illustrative examples highlight the relevance of organization across multiple length scales, and how device performances--although relevant for practical applications--poorly reflect the success of molecular design.

UbC gene allele frequency in Korean population and novel UbC mosaic repeat unit formation

The genomic structural organization of human UbC CDS repeat units could be representative of concerted evolution. The structure of the UbC gene and its repeat unit number frequency at scales of different human ethnic populations remain to be sufficiently determined. In this study, we performed comparative analysis of UbC CDS regions in genomes from 140 Korean individuals. We found that the UbC gene allele types 9, 8 and 7 are present in the Korean population in proportions of 97.1%, 0.4% and 2.5%, respectively. Interestingly, we discovered that the allele types 7 and 8 harbor the novel UbC gene mosaic repeat units 3∧5 (combined between sequence parts derived from standard repeat units 3 and 5) and 8∧9 (combined between sequence parts derived from standard repeat units 8 and 9) within their sequence structures, respectively. Our analysis showed that the novel mosaic repeat unit 3^5 lacks the highly human-specific amino acid S38, implying a functional consequence. These results suggest that the genomic organization of UbC repeat units is still undergoing dynamic structural changes due to concerted evolution through unequal crossing-over. Our results could represent valuable data for future investigations related to treating genetic diseases caused by UbC gene mutations and variations.

New genotypes of white spot syndrome virus (WSSV) and Taura syndrome virus (TSV) from the Kingdom of Saudi Arabia

White spot syndrome virus (WSSV) and Taura syndrome virus (TSV) are highly pathogenic to penaeid shrimp and have caused significant economic losses in the shrimp culture industry around the world. During 2010 and 2011, both WSSV and TSV were found in Saudi Arabia, where they caused severe mortalities in cultured Indian white shrimp Penaeus indicus. Most outbreaks of shrimp viruses in production facilities can be traced to the importation of infected stocks or commodity shrimp. In an attempt to determine the origins of these viral outbreaks in Saudi Arabia, we performed variable number of tandem repeat (VNTR) analyses for WSSV isolates and a phylogenetic analysis for TSV isolates. From the WSSV genome, the VNTR in open reading frames (ORFs) 125 and 94 were investigated with PCR followed by DNA sequence analysis. The genotypes were categorized as {N125, N94} where N is the number of repeat units in a specific ORF, and the subscript indicates the ORF (i.e. ORFs 125 and 94 in this case). From 15 Saudi Arabia WSSV isolates, we detected 3 genotypes: {6125, 794}, {7125, del94}, and {8125, 1394}. The WSSV genotype of {7125, del94} appears to be a new variant with a 1522 bp deletion encompassing complete coding regions of ORF 94 and ORF 95 and the first 82 bp of ORF 93. For TSV genotyping, we used a phylogenetic analysis based on the amino acid sequence of TSV capsid protein 2 (CP2). We analyzed 8 Saudi Arabian isolates in addition to 36 isolates from other areas: SE Asia, Mexico, Venezuela and Belize. The Saudi Arabian TSV clustered into a new, distinct group. Based on these genotyping analyses, new WSSV and TSV genotypes were found in Saudi Arabia. The data suggest that they have come from wild shrimp Penaeus indicus from the Red Sea that are used for broodstock.

Leucine-Rich Repeat (LRR) Domains Containing Intervening Motifs in Plants.

LRRs (leucine rich repeats) are present in over 14,000 proteins. Non-LRR, island regions (IRs) interrupting LRRs are widely distributed. The present article reviews 19 families of LRR proteins having non-LRR IRs (LRR@IR proteins) from various plant species. The LRR@IR proteins are LRR-containing receptor-like kinases (LRR-RLKs), LRR-containing receptor-like proteins (LRR-RLPs), TONSOKU/BRUSHY1, and MJK13.7; the LRR-RLKs are homologs of TMK1/Rhg4, BRI1, PSKR, PSYR1, Arabidopsis At1g74360, and RPK2, while the LRR-RLPs are those of Cf-9/Cf-4, Cf-2/Cf-5, Ve, HcrVf, RPP27, EIX1, clavata 2, fascinated ear2, RLP2, rice Os10g0479700, and putative soybean disease resistance protein. The LRRs are intersected by single, non-LRR IRs; only the RPK2 homologs have two IRs. In most of the LRR-RLKs and LRR-RLPs, the number of repeat units in the preceding LRR block (N1) is greater than the number of the following block (N2); N1 » N2 in which N1 is variable in the homologs of individual families, while N2 is highly conserved. The five families of the LRR-RLKs except for the RPK2 family show N1 = 8 − 18 and N2 = 3 − 5. The nine families of the LRR-RLPs show N1 = 12 − 33 and N2 = 4; while N1 = 6 and N2 = 4 for the rice Os10g0479700 family and the N1 = 4 − 28 and N2 = 4 for the soybean protein family. The rule of N1 » N2 might play a common, significant role in ligand interaction, dimerization, and/or signal transduction of the LRR-RLKs and the LRR-RLPs. The structure and evolution of the LRR domains with non-LRR IRs and their proteins are also discussed.

Variation in the coding region of the prion protein gene in Slovak cattle

This study was conducted to investigate the presence of single nucleotide polymorphisms (SNPs) in the coding region of the bovine prion protein (PrP) gene among healthy and bovine spongiform encephalopathy (BSE-) affected cattle in Slovakia. Denaturing gradient gel electrophoresis (DGGE) and single-strand conformation polymorphism (SSCP) followed by DNA sequencing were used to identify SNPs and variations in octapeptide repeats. Altogether three single nucleotide polymorphisms (g234a, c339t and c576t) and variations in the number of octapeptide repeat units (5 or 6) were found in the analysed part of the prion protein gene. All single nucleotide polymorphisms were silent, causing no amino acid changes. Significant differences (P < 0.05) in the genotype distribution of g234a polymorphism were observed when the homozygous genotype with a mutated allele (caa/caa) was compared to the heterozygous genotype -/cag among healthy and BSE-affected cattle. The homozygous genotype caa/caa was characteristic of the group of BSE-affected cattle. Additionally, the homozygous genotype caa/caa was significant for the group of Simmental crossbreeds among healthy cattle. The allele and genotype distribution of the other polymorphisms was not significantly different among groups of healthy and BSE-affected cattle. The possible influence of a silent mutation on expression of the gene is not clearly determined and needs further investigations.

The Complete Mitochondrial Genome of the Wild Type of Antheraea pernyi (Lepidoptera: Saturniidae)

Abstract Antheraea pernyi (Guérin-Méneville) (Lepidoptera: Saturniidae), a well-known economically important insect, was domesticated from its wild type. In this study, the complete mitochondrial genome (mitogenome) of the wild type of A. pernyi was determined and compared for nucleotide variation with its domesticated type. The mitogenome of the wild type of A. pernyi is 15,537 bp in size, thus 29 bp smaller than that of the domesticated type. The gene content, order, and orientation of the complete mitogenome of the wild type are identical to those of the domesticated type, as are those of the other completely sequenced lepidopteran mitogenomes. A striking difference between the two mitogenomes was found in the A+T-rich region because of the numbers of tandem repeat units. The wild type has five tandem repeat units, whereas the domesticated type has six. Comparative analysis of the two mitogenomes revealed a relatively lower level of sequence divergence (1.70%). Within the two mitogenomes, there are no significant differences in nucleotide substitution rate for the 13 protein-coding genes except for the nad4L gene, which is different from those differences observed between the domesticated silkmoth Bombyx mori (L.) (Lepidoptera: Bombycidae) and its wild-type ancestor Chinese B. mandarina Moore. The divergence time between the two Antheraea mitochondrias was estimated to be between 0.74 ± 0.13 and 0.97 ± 0.17 million years ago, based on the genes cox1+cox2 sequences. To our knowledge, this is the first report on sequence variation of the complete mitogenomes between the domesticated insect and its wild-type ancestor, within a single species.

A mutant of Leishmania donovani deficient in elongating mannosylphosphoryl transferase activity

Leishmania parasites manipulate essential interactions with its sand fly vector and vertebrate host by expressing developmentally‐regulated forms of its surface lipophosphoglycan (LPG). LPG is a GPI‐anchored polysaccharide consisting of repeating 6Galβ1,4Manα1‐PO4 units. The number of repeat units varies depending on the stage of the life cycle: n~15 in procyclic and n~30 in metacyclic promastigotes; and n=0 in the intracellular amastigote forms.Our work focuses on the family of mannosyl‐phosphate transferases involved in LPG formation. At least two mannosylphosphoryltransferases (MPTs) have been implicated in repeat unit assembly: an “initiation” specific MPT (iMPT) which uses the LPG core as acceptor and an “elongation” specific MPT (eMPT) which uses repeat units as acceptor. We previously identified a chemical mutant of L. donovani that we showed to have only one Gal‐Man‐P unit in its LPG by being deficient in eMPT activity. We are currently examining the mutant for its potential in elucidating further molecular information regarding the critical eMPT that is essential in determining the length of the LPG phosphoglycan.The funding source for this research is NIH grant is RO1‐AI31078 awarded to Salvatore J. Turco.

Excited States of Dicyanovinyl-Substituted Oligothiophenes from Many-Body Green’s Functions Theory

Excited states of dicyanovinyl-substituted oligothiophenes are studied using many-body Green's functions theory within the GW approximation and the Bethe-Salpeter equation. By varying the number of oligomer repeat units, we investigate the effects of resonant-antiresonant transition coupling, dynamical screening, and molecular conformations on calculated excitations. We find that the full dynamically screened Bethe-Salpeter equation yields absorption and emission energies in good agreement with experimental data. The effect of resonant-antiresonant coupling on the first singlet π → π* excitation monotonically decreases with increasing size of the molecule, while dynamical screening effects uniformly lower the excitation energies.

Microevolution of Pandemic Vibrio parahaemolyticus Assessed by the Number of Repeat Units in Short Sequence Tandem Repeat Regions

The emergence of the pandemic strain Vibrio parahaemolyticus O3:K6 in 1996 caused a large increase of diarrhea outbreaks related to seafood consumption in Southeast Asia, and later worldwide. Isolates of this strain constitutes a clonal complex, and their effectual differentiation is possible by comparison of their variable number tandem repeats (VNTRs). The differentiation of the isolates by the differences in VNTRs will allow inferring the population dynamics and microevolution of this strain but this requires knowing the rate and mechanism of VNTRs' variation. Our study of mutants obtained after serial cultivation of clones showed that mutation rates of the six VNTRs examined are on the order of 10−4 mutant per generation and that difference increases by stepwise addition of single mutations. The single stepwise mutation (SSM) was deduced because mutants with 1, 2, 3, or more repeat unit deletions or insertions follow a geometric distribution. Plausible phylogenetic trees are obtained when, according to SSM, the genetic distance between clusters with different number of repeats is assessed by the absolute differences in repeats. Using this approach, mutants originated from different isolates of pandemic V. parahaemolyticus after serial cultivation are clustered with their parental isolates. Additionally, isolates of pandemic V. parahaemolyticus from Southeast Asia, Tokyo, and northern and southern Chile are clustered according their geographical origin. The deepest split in these four populations is observed between the Tokyo and southern Chile populations. We conclude that proper phylogenetic relations and successful tracing of pandemic V. parahaemolyticus requires measuring the differences between isolates by the absolute number of repeats in the VNTRs considered.

Block poly(arylene ether sulfone ketone)s containing densely sulfonated linear hydrophilic segments as proton conductive membranes

Synthesis and properties of aromatic block copolymers composed of highly sulfonated phenylene ether sulfone ketone units as hydrophilic blocks and phenylene ether biphenyene sulfone units as hydrophobic blocks are reported. High molecular weight block copolymers 4 (Mw = 275–362 kDa and Mn = 76–144 kDa) with different compositions (number of repeat unit in the hydrophobic blocks (X) = 15, 30, or 60, and that of hydrophilic blocks (Y) = 4, 8, or 12) were synthesized. Transparent and bendable membranes were obtained by casting from the solution of 4. Due to the rigid rod-like structure of the hydrophilic blocks, the nanophase-separated morphology was not as distinct as that of the conventional sulfonated aromatic block copolymer membranes. Highly sulfonated hydrophilic blocks, which contained phenylene rings with sulfonic acid groups and electron-withdrawing sulfone or ketone groups, contributed to the high proton conductivity and improved oxidative stability of 4 membranes. The 4 (X60Y12) membrane with low IEC (1.18 mequiv g−1) showed comparable or higher conductivity than that of Nafion at >80% relative humidity (RH).

A Meta-Analysis of EST-SSR Sequences in the Genomes of Pine, Poplar and Eucalyptus

Microsatellites are the kinds of sequences in the genome of living organism that have the fastest variation frequency. The variations of numbers of microsatellite repeat units in the structure gene cause frame-shift mutation of the gene, resulting in gene expressing in fully difference or expressing truncated protein. Thus, in the evolutionary process, microsatellite within the gene region would be influenced by a strong selection. In order to study the variations of microsatellite within the of gene s in different tree species, we performed a meta-analysis by using SPUTNIK program to analyze the 30 000 express sequence tag (EST) sequences of pine ( Pinus spp .), Poplar ( Populus spp .) and eucalyptus ( Eucalyptus spp .) downloaded from NCBI database. The results showed that the proportion of EST sequences containing microsatellites was 18.7% in eucalyptus and 15.3% in poplar, whereas only 8.2% occurred in pine tree that exhibited bigger differentiation. The study found that three-base repeat unit was is a major repeat type of microsatellite in the coding sequence of these three tree species. In addition to three-base repeat microsatellite, the abundance of other types of microsatellites in EST sequences of eucalyptus and poplar was decreased with increase of the repeat unit length, but in the pine tree occurring in the opposite situation. It was worth noticeable that the amount of microsatellite with fast frequency of variation of EST sequences in pine (>20 bp) was significantly less than that in eucalyptus and poplar. The study also found that the rate of repeating unit losing or gaining decreased with increases of the repeating units in the microsatellite of three tree species. In this study, we reported the comparative studies of microsatellites within the gene region in different tree species, revealing the similarities and differences in abundance and variation frequency of microsatellites in the EST sequences in pine, poplar and eucalyptus. Microsatellite sequence would have an important influence on the function of the gene containing the microsatellite. The results of this study would provide some parameters for understanding the characteristics of microsatellites with the gene region in the the different species, as well as useful references for developing microsatellite markers with high polymorphism by using the EST sequence of the studying tree species.

Polymorphism in two short tandem repeat loci (R-R and S-Q) linked to tRNA genes in Entamoeba dispar isolates.

In this study, genetic polymorphism of two tRNA-liked short tandem repeat (STR)-containing loci, R-R and S-Q, was analyzed in order to clarify further the genotypic differences among E. dispar isolates. Entamoeba dispar is closely related to the human pathogen E. histolytica, the agent of amebic dysentery and amebic liver abscesses. E. dispar is, to some extent, capable of producing variable focal intestinal lesions in animals and of destroying epithelial cell monolayers in vitro, and some have reported it to be capable of producing amoebic liver abscess in hamsters. However no evidence exists at present to link E. dispar with human disease. A total of 28 E. dispar samples from gastrointestinal disorder patients were characterized using PCR and sequencing. The sequences obtained were edited manually and aligned. Sequence analysis showed 9 and 6 different patterns of units in the repeat-containing region of R-R and S-Q, respectively. The repeat-containing regions of R-R and S-Q loci were found to be extensively polymorphic, varying in size, number and order of repeat units. The results demonstrate extensive genetic variability among Iranian E. dispar clinical isolates. The genetic diversity of tRNA gene-linked STR loci shows them to be suitable for epidemiological studies such as the characterization of the routes of transmission of these parasites in Iran.

Water-mediated structural tunability of an alkyl/siloxane hybrid: from amorphous material to lamellar structure or bilamellar superstructure

Mono-amide cross-linked alkyl/siloxane hybrids (classed as mono-amidosils and represented by the notation m-A(x), where m and A stand for mono and amide, respectively, and x is the number of methylene repeat units) with water-mediated tunable structures have been prepared by means of sol–gel chemistry and self-direct assembly routes from the organosilanes CH3(CH2)x–C(O)NH–(CH2)3–Si–(OCH2CH3)3. The amorphous sample m-A(8) has been produced under the stoichiometric conditions (molar ratio Si : ethanol : water = 1 : 4 : 2) used previously to obtain the lamellar bilayer highly organized m-A(14) hybrid material, showing that the length of the pendant alkyl chains affects the degree of order of the materials. Three structurally ordered samples identified as AC-m-A(8) (1 : y) (where AC represents acid catalysis and y is the number of moles of water per mole of Si) have been obtained using the acid catalyzed hydrolytic route and different water contents (y = 600, 300 and 100). Water plays a unique role in the organized mono-amidosils: it not only reverses the natural tendency of the precursor molecule with x = 8 to yield a disordered material, but it also allows the induction of order, leading to the formation of a lamellar structure exclusively in AC-m-A(8) (1 : 100). The presence of a higher water content promotes extra ordering in AC-m-A(8) (1 : 300) and AC-m-A(8) (1 : 600), where the lamellar structure coexists with a bilamellar superstructure. Upon heating the AC-m-A(8) (1 : 600) sample to 120 °C and then cooling it to room temperature, the lamellar structure remained unaffected, while the superstructure was destroyed. The occurrence of the superstructure, although basically associated with the preferential entrapment of water molecules every two lamellae at the siliceous nanodomains, is also correlated with the amide–amide hydrogen bonded array. The m-A(8) and AC-m-A(8) (1 : 600) hybrids are multi-wavelength emitters under UV/VIS excitation. The emission spectra exhibit a broad band (300–650 nm) resulting from two contributions: a “blue” band, due to electron–hole recombinations in the NH/CO groups of the amide cross-links, and a “purplish-blue” band, due to oxygen-related defects •O–O–Si≡(CO2) in the siliceous nanoclusters. The absolute emission quantum yields determined for m-A(8) and AC-m-A(8) (1 : 600) in the 360–380 nm excitation wavelength range were 0.10 ± 0.01 and 0.15 ± 0.01, respectively. While the lifetime values of the high and low wavelength components of the siliceous-related emission are practically the same for both samples (∼3.5 ms), the lifetime value of the NH/CO component for m-A(8) is higher than that of AC-m-A(8) (1 : 600) (∼292 and ∼156 ms, respectively), suggesting a lower non-radiative transition probability for the former hybrid.

Long-range corrected hybrid functionals for π-conjugated systems: Dependence of the range-separation parameter on conjugation length

Long-range corrected (range-separated hybrid) functionals represent a relatively new class of functionals for generalized Kohn-Sham theory that have proven to be very successful, for instance, when it comes to predicting ionization potentials and energy gaps for a wide range of molecules and solids. The results obtained from long-range corrected density functional theory approaches can be improved dramatically, if the range-separation parameter (ω) is optimized for each system separately. In this work, we have optimized ω for a series of π-conjugated molecular systems of increasing length by forcing the resulting functionals to obey the ionization potential-theorem, i.e., that their highest occupied eigenvalue be equal to the ΔSCF ionization potential. The optimized ω values are observed to vary substantially from their default values for the functionals. For highly conjugated chains such as oligoacenes and polyenes, we find that the characteristic length scale of the range-separation, i.e., 1/ω, grows almost linearly with the number of repeat units, for saturated alkane chains, however, 1/ω quickly saturates after 5-6 repeat units. For oligothiophenes, we find that 1/ω grows linearly for the shorter oligomers but then saturates at around 10 repeat units. Our results point to a close relation between the optimal range-separation parameter and the degree of conjugation in the system.