Effect of Different Substitutions at the 1,7-Bay Positions of Perylenediimide Dyes on Their Optical and Laser Properties.

Perylenediimide (PDI) compounds are widely used as the active units of thin-film organic lasers. Lately, PDIs bearing two sterically hindering diphenylphenoxy groups at the 1,7-bay positions have received attention because they provide a way to red-shift the emission with respect to bay-unsubstituted PDIs, while maintaining a good amplified spontaneous emission (ASE) performance at high doping rates. Here, we report the synthesis of a series of six PDI derivatives with different aryloxy groups (PDI 6 to PDI 10) or ethoxy groups (PDI 11) at the 1,7 positions of the PDI core, together with a complete characterization of their optical properties, including absorption, photoluminescence, and ASE. We aim to stablish structure-property relationships that help designing compounds with optimized ASE performance. Film experiments were accomplished at low PDI concentrations in the film, to resemble the isolated molecule behaviour, and at a range of increasing doping rates, to investigate concentration quenching effects. Compounds PDI 10 and PDI 7, bearing substituents in the 2' positions of the benzene ring (the one contiguous to the linking oxygen atom) attached to the 1,7 positions of the PDI core, have shown a better threshold performance, which is attributed to conformational (steric) effects. Films containing PDI 11 show dual ASE.

ADAMTS Proteases: Importance in Animal Reproduction.

Many reproductive physiological processes, such as folliculogenesis, ovulation, implantation, and fertilization, require the synthesis, remodeling, and degradation of the extracellular matrix (ECM). The ADAMTS (A Disintegrin and Metalloproteinase with Thrombospondin Motifs) family genes code for key metalloproteinases in the remodeling process of different ECM. Several genes of this family encode for proteins with important functions in reproductive processes; in particular, ADAMTS1, 4, 5 and 9 are genes that are differentially expressed in cell types and the physiological stages of reproductive tissues. ADAMTS enzymes degrade proteoglycans in the ECM of the follicles so that the oocytes can be released and regulate follicle development during folliculogenesis, favoring the action of essential growth factors, such as FGF-2, FGF-7 and GDF-9. The transcriptional regulation of ADAMTS1 and 9 in preovulatory follicles occurs because of the gonadotropin surge in preovulatory follicles, via the progesterone/progesterone receptor complex. In addition, in the case of ADAMTS1, pathways involving protein kinase A (PKA), extracellular signal regulated protein kinase (ERK1/2) and the epidermal growth factor receptor (EGFR) might contribute to ECM regulation. Different Omic studies indicate the importance of genes of the ADAMTS family from a reproductive aspect. ADAMTS genes could serve as biomarkers for genetic improvement and contribute to enhance fertility and animal reproduction; however, more research related to these genes, the synthesis of proteins encoded by these genes, and regulation in farm animals is needed.

Fused Triangulene Dimers: Facile Synthesis by Intramolecular Radical-Radical Coupling and Application for Near-Infrared Lasers.

Large graphene-like molecules with four zigzag edges are ideal gain medium materials for organic near-infrared (NIR) lasers. However, synthesizing them becomes increasingly challenging as the molecular size increases. In this study, we introduce a new intramolecular radical-radical coupling approach and successfully synthesize two fused triangulene dimers (1 a/1 b) efficiently. X-ray crystallographic analysis of 1 a indicates that there is no intermolecular π-π stacking in the solid state. When the more soluble derivative 1 b is dispersed in polystyrene thin films, amplified spontaneous emission in the NIR region is observed. Using 1 b as the active gain material, we fabricate solution-processed distributed feedback lasers that exhibit a narrow emission linewidth at around 790 nm. The laser devices also exhibit low thresholds with high photostability. Our study provides a new synthetic strategy for extended nanographenes, which have diverse applications in electronics and photonics.

Distributed Feedback Lasers by Thermal Nanoimprint of Perovskites Using Gelatin Gratings.

To date, thermal nanoimprint lithography (NIL) for patterning hybrid perovskites has always involved an intricate etching step of a hard stamp material or its master. Here, we demonstrate for the first time the successful nanopatterning of a perovskite film by NIL with a low-cost polymeric stamp. The stamp consists of a dichromated gelatin grating structured by holographic lithography. The one-dimensional grating is imprinted into a perovskite film at 95 °C and 90 MPa for 10 min, resulting in a high quality second-order distributed feedback (DFB) laser. The laser exhibits an excellent performance with a threshold of 81 µJ/cm2, a line width of 0.32 nm, and a pronounced linear polarization. This novel approach enables cost-effective fabrication of high-quality DFB lasers compatible with different perovskite compositions and photonic nanostructures for a wide range of applications.

A variant associated to IGF-1 mRNA and protein expression in sheep.

The insulin-like growth factor-1 (IGF-1), a key hormone in muscle development was investigated for single-nucleotide polymorphisms (SNPs) upstream of the IGF-1 gene and their effects upon its cognate mRNA and hormone levels in sheep. A 70 d feeding trial was conducted with 22 F1 (Dorper × Pelibuey) lambs, individually allocated and fed a diet with a forage-to-concentrate ratio of 36:64 and 17% crude protein. Sequence analyses of 265 bp upstream the IGF-1 gene revealed the variant NC_040254.1:g.[184028491G > C;184028493G > A]. These SNPs generate alleles A and B, with frequencies of 0.66 and 0.34 in F1 lambs and of 0.73 and 0.27 in 81 pure Dorper lambs, respectively. Females were grouped by genotype AA, AB and BB (n = 3). IGF-1 hormone concentrations at 14, 42 and 70 d were higher (p < 0.05) in AA lambs compared to AB + BB lambs. The IGF-1 mRNA level was 2.6-fold higher in AA animals (n = 5, p < 0.05) than in AB + BB lambs (n = 7). A DNA binding site for the Inhibitor of Growth family member 4 (ING4) was found in allele B but not in allele A, which could explain the lower mRNA and hormone expression levels for AB + BB animals. The variant reported here appears to function as an eQTL with a negative effect on the level of IGF-1.

Excited states engineering enables efficient near-infrared lasing in nanographenes.

The spectral overlap between stimulated emission (SE) and absorption from dark states (i.e. charges and triplets) especially in the near-infrared (NIR), represents one of the most effective gain loss channels in organic semiconductors. Recently, bottom-up synthesis of atomically precise graphene nanostructures, or nanographenes (NGs), has opened a new route for the development of environmentally and chemically stable materials with optical gain properties. However, also in this case, the interplay between gain and absorption losses has hindered the attainment of efficient lasing action in the NIR. Here, we demonstrate that the introduction of two fluoranthene imide groups to the NG core leads to a more red-shifted emission than the precursor NG molecule (685 vs. 615 nm) and also with a larger Stokes shift (45 nm vs. 2 nm, 1026 cm-1vs. 53 cm-1, respectively). Photophysical results indicate that, besides the minimisation of ground state absorption losses, such substitution permits to suppress the detrimental excited state absorption in the NIR, which likely arises from a dark state with charge-transfer character and triplets. This has enabled NIR lasing (720 nm) from all-solution processed distributed feedback devices with one order of magnitude lower thresholds than those of previously reported NIR-emitting NGs. This study represents an advance in the field of NGs and, in general, organic semiconductor photonics, towards the development of cheap and stable NIR lasers.

N,N'-Bis(3-methylphenyl)-N,N'-dyphenylbenzidine Based Distributed Feedback Lasers with Holographically Fabricated Polymeric Resonators.

The molecule N,N'-bis(3-methylphenyl)-N,N'-dyphenylbenzidine (TPD) has been widely used in optoelectronic applications, mainly for its hole-transporting properties, but also for its capability to emit blue light and amplified spontaneous emission, which is important for the development of organic lasers. Here, we report deep-blue-emitting distributed feedback (DFB) lasers based on TPD dispersed in polystyrene (PS), as active media, and dichromated gelatin layers with holographically engraved relief gratings, as laser resonators. The effect of the device architecture (with the resonator located below or on top of the active layer) is investigated with a dye (TPD) that can be doped into PS at higher rates (up to 60 wt%), than with previously used dyes (<5 wt%). This has enabled changing the index contrast between film and resonator, which has an important effect on the laser performance. With regards to thresholds, both architectures behave similarly for TPD concentrations above 20 wt%, while for lower concentrations, top-layer resonator devices show lower values (around half). Remarkably, the operational durability of top-layer resonator devices is larger (in a factor of around 2), independently of the TPD concentration. This is a consequence of the protection offered by the resonator against dye photo-oxidation when the device is illuminated with pulsed UV light.

Simultaneous Determination of Refractive Index and Thickness of Submicron Optical Polymer Films from Transmission Spectra.

High-transparency polymers, called optical polymers (OPs), are used in many thin-film devices, for which the knowledge of film thickness (h) and refractive index (n) is generally required. Spectrophotometry is a cost-effective, simple and fast non-destructive method often used to determine these parameters simultaneously, but its application is limited to films where h > 500 nm. Here, a simple spectrophotometric method is reported to obtain simultaneously the n and h of a sub-micron OP film (down to values of a few tenths of a nm) from its transmission spectrum. The method is valid for any OP where the n dispersion curve follows a two-coefficient Cauchy function and complies with a certain equation involving n at two different wavelengths. Remarkably, such an equation is determined through the analysis of n data for a wide set of commercial OPs, and its general validity is demonstrated. Films of various OPs (pristine or doped with fluorescent compounds), typically used in applications such as thin-film organic lasers, are prepared, and n and h are simultaneously determined with the proposed procedure. The success of the method is confirmed with variable-angle spectroscopic ellipsometry.

Dual Amplified Spontaneous Emission and Lasing from Nanographene Films.

Chemically synthesized zigzag-edged nanographenes (NG) have recently demonstrated great success as the active laser units in solution-processed organic distributed feedback (DFB) lasers. Here, we report the first observation of dual amplified spontaneous emission (ASE) from a large-size NG derivative (with 12 benzenoid rings) dispersed in a polystyrene film. ASE is observed simultaneously at the 685 and 739 nm wavelengths, which correspond to different transitions of the photoluminescence spectrum. Ultrafast pump-probe spectroscopy has been used to ascertain the underlying photophysical processes taking place in the films. DFB lasers, based on these materials and top-layer nanostructured polymeric resonators (i.e., one or two-dimensional surface relief gratings), have been fabricated and characterized. Lasers emitting close to either one of the two possible ASE wavelengths, or simultaneously at both of them, have been prepared by proper selection of the resonator parameters.

Perylene-Fused, Aggregation-Free Polycyclic Aromatic Hydrocarbons for Solution-Processed Distributed Feedback Lasers.

Perylene-fused, aggregation-free polycyclic aromatic hydrocarbons with partial zigzag periphery (ZY-01, ZY-02, and ZY-03) were synthesized. X-ray crystallographic analysis reveals that there is no intermolecular π-π stacking in any of the three molecules, and as a result, they show moderate-to-high photoluminescence quantum yield in both solution and in the solid state. They also display the characteristic absorption and emission spectra of perylene dyes. ZY-01 and ZY-02 with a nearly planar π-conjugated skeleton exhibit amplified spontaneous emission (ASE) when dispersed in polystyrene thin films. Solution-processed distributed feedback lasers have been fabricated using ZY-01 and ZY-02 as active gain materials, both showing narrow emission linewidth (<0.4 nm) at wavelengths around 515 and 570 nm, respectively. In contrast, ZY-03 did not show ASE and lasing, presumably due to its highly twisted backbone, which facilitates nonradiative internal conversion and intersystem crossing.

Controlling the emission properties of solution-processed organic distributed feedback lasers through resonator design.

Surface-emitting distributed feedback (DFB) lasers with both, resonator and active material based on solution-processable polymers, are attractive light sources for a variety of low-cost applications. Besides, the lasers should have competitive characteristics compared to devices based on high-quality inorganic resonators. Here, we report high performing all-solution-processed organic DFB lasers, consisting of water-processed photoresist layers with surface relief gratings located over the active films, whose emission properties can be finely tuned through resonator design. Their laser threshold and efficiency are simultaneously optimized by proper selection of residual resist thickness and grating depth, d. Lowest thresholds and largest efficiencies are obtained when there is no residual layer, while a trade-off between threshold and efficiency is found in relation to d, because both parameters decrease with decreasing d. This behaviour is successfully explained in terms of an overlap factor r, defined to quantify the interaction strength between the grating and the light emitted by the active film and traveling along it, via the evanescent field. It is found that optimal grating depths are in the range 100-130 nm (r ~ 0.5-0.4). Overall, this study provides comprehensive design rules towards an accurate control of the emission properties of the reported lasers.

Solution-processed nanographene distributed feedback lasers.

The chemical synthesis of nanographene molecules constitutes the bottom-up approach toward graphene, simultaneously providing rational chemical design, structure-property control and exploitation of their semiconducting and luminescence properties. Here, we report nanographene-based lasers from three zigzag-edged polycyclic aromatics. The devices consist of a passive polymer film hosting the nanographenes and a top-layer polymeric distributed feedback resonator. Both the active material and the laser resonator are processed from solution, key for the purpose of obtaining low-cost devices with mechanical flexibility. The prepared lasers show narrow linewidth ( < 0.13 nm) emission at different spectral regions covering a large segment of the visible spectrum, and up to the vicinity of the near-infrared. They show outstandingly long operational lifetimes (above 105 pump pulses) and very low thresholds. These results represent a significant step forward in the field of graphene and broaden its versatility in low-cost devices implying light emission, such as lasers.

The glyceraldehyde-3-phosphate dehydrogenase of the shrimp Litopenaeus vannamei: Molecular cloning, characterization and expression during hypoxia.

Some marine crustaceans like the white shrimp Litopenaeus vannamei are tolerant to environmental hypoxia. Under oxygen deprivation, shrimp tissues obtain energy by enhancing anaerobic glycolysis. In mammals, hypoxia increases the expression of the glycolytic enzyme glyceraldehyde-3-phosphate dehydrogenase (GAPDH), which has been shown a "moonlighting" role in cells. However, the effect of hypoxia on the GAPDH expression has not been studied in crustaceans. In the present work, we obtained a 2744 bp gene sequence with a 999 bp ORF split by a single intron. The deduced protein is 332 amino acids and corresponds to the L. vannamei GAPDH (LvGAPDH), which is highly similar in sequence and structure to other animal GAPDHs. During hypoxia, LvGAPDH expression is significantly induced in gills but not in hepatopancreas, suggesting that it may play a role in the molecular and cellular response of shrimp to hypoxia.

Hypoxia drives apoptosis independently of p53 and metallothionein transcript levels in hemocytes of the whiteleg shrimp Litopenaeus vannamei.

The cellular mechanisms used by the shrimp Litopenaeus vannamei to respond to hypoxia have been studied from the energetic metabolism and antioxidant angles. We herein investigated the participation of p53 and metallothionein (MT) in the apoptotic process in response to hypoxia in shrimp hemocytes. The Lvp53 or LvMT genes were efficiently silenced by injection of double stranded RNA for p53 or MT. The effects of silencing on apoptosis were measured as caspase-3 activity and flow cytometry in hemocytes after 24 and 48 h of hypoxia (1.5 mg DO L(-1)). Hemocytes from unsilenced animals had significantly higher apoptosis levels upon both times of hypoxia. The apoptotic levels were diminished but not suppressed in dsp53-silenced but not dsMT-silenced hemocytes after 24 h of hypoxia, indicating a contribution of Lvp53 to apoptosis. Apoptosis in normoxia was significantly higher in dsp53-and dsMT-silenced animals compared to the unsilenced controls, pointing to a possible cytoprotective role of LvMT and Lvp53 during the basal apoptotic program in normoxia. Overall, these results indicate that hypoxia augments apoptosis in shrimp hemocytes and high mRNA levels of Lvp53 and LvMT are not necessary for this response.

A novel functional glucose transporter in the white shrimp Litopenaeus vannamei -LvGLUT2- is up-regulated during hypoxia in hepatopancreas.

In hypoxia conditions, the white shrimp Litopenaeus vannamei shifts its energetic metabolism from aerobic to anaerobic, requiring more glucose uptake into the cells by GLUT proteins. We here report a novel glucose transporter in shrimp. The Lvglut2 cDNA is 2473 bp-long containing an ORF of 1458 bp encoding 486 amino acid residues. The deduced protein has the features of a facilitative sugar transporter. The Lvglut2 gene product tagged with GFP was expressed in the cell membrane of Xenopus oocytes. In the same expression system, untagged LvGLUT2 resulted to be a bidirectional glucose transporter that functions moving glucose down its concentration gradient in and out of the cell. Lvglut2 mRNA is expressed in hepatopancreas while in muscle and gills it was not detected. Hypoxia up-regulates the expression of Lvglut2 transcripts in hepatopancreas. These results provide a better understanding of facilitative glucose transporters and gene regulation during hypoxia in crustaceans.

Carbon-bridged oligo(p-phenylenevinylene)s for photostable and broadly tunable, solution-processable thin film organic lasers.

Thin film organic lasers represent a new generation of inexpensive, mechanically flexible devices for spectroscopy, optical communications and sensing. For this purpose, it is desired to develop highly efficient, stable, wavelength-tunable and solution-processable organic laser materials. Here we report that carbon-bridged oligo(p-phenylenevinylene)s serve as optimal materials combining all these properties simultaneously at the level required for applications by demonstrating amplified spontaneous emission and distributed feedback laser devices. A series of six compounds, with the repeating unit from 1 to 6, doped into polystyrene films undergo amplified spontaneous emission from 385 to 585 nm with remarkably low threshold and high net gain coefficients, as well as high photostability. The fabricated lasers show narrow linewidth (<0.13 nm) single mode emission at very low thresholds (0.7 kW cm(-2)), long operational lifetimes (>10(5) pump pulses for oligomers with three to six repeating units) and wavelength tunability across the visible spectrum (408-591 nm).

Expression of fructose 1,6-bisphosphatase and phosphofructokinase is induced in hepatopancreas of the white shrimp Litopenaeus vannamei by hypoxia.

Marine organisms are exposed to hypoxia in natural ecosystems and during farming. In these circumstances marine shrimp survive and synthesize ATP by anaerobic metabolism. Phosphofructokinase (PFK) and fructose 1,6-bisphosphatase (FBP) are key enzymes in carbohydrate metabolism. Here we report the cDNA of FBP from the shrimp Litopenaeus vannamei hepatopancreas and expression of PFK and FBP under normoxia and hypoxia. Hypoxia induces PFK and FBP expression in hepatopancreas but not in gills and muscle. Induction in hepatopancreas of the glycolytic and gluconeogenic key enzymes, PFK and FBP, suggests that PFK could be a key factor for increasing anaerobic rate, while FBP is probably involved in the activation of gluconeogenesis or the pentose-phosphates pathway during hypoxia in the highly active metabolism of hepatopancreas.

The metallothionein gene from the white shrimp Litopenaeus vannamei: characterization and expression in response to hypoxia.

Aquatic animals encounter variation in oxygen tension that leads to the accumulation of reactive oxygen species (ROS) that can harm the organisms. Under these circumstances some organisms have evolved to tolerate hypoxia. In mammals, metallothioneins (MTs) protect against hypoxia-generated ROS. Here we report the MT gene from the shrimp Litopenaeus vannamei (LvMT). LvMT is differentially expressed in hemocytes, intestine, gills, pleopods, heart, hepatopancreas and muscle, with the highest levels in hepatopancreas and heart. LvMT mRNA increases during hypoxia in hepatopancreas and gills after 3 h at 1.5 mg L(-1) dissolved oxygen (DO). This gene structure resembles the homologs from invertebrates and vertebrates possessing three exons, two introns and response elements for metal response transcription factor 1 (MTF-1), hypoxia-inducible factor 1 (HIF-1) and p53 in the promoter region. During hypoxia, HIF-1/MTF-1 might participate inducing MT to contribute towards the tolerance to ROS toxicity. MT importance in aquatic organisms may include also ROS-detoxifying processes.

The glucose transporter 1 -GLUT1- from the white shrimp Litopenaeus vannamei is up-regulated during hypoxia.

During hypoxia the shrimp Litopenaeus vannamei accelerates anaerobic glycolysis to obtain energy; therefore, a correct supply of glucose to the cells is needed. Facilitated glucose transport across the cells is mediated by a group of membrane embedded integral proteins called GLUT; being GLUT1 the most ubiquitous form. In this work, we report the first cDNA nucleotide and deduced amino acid sequences of a glucose transporter 1 from L. vannamei. A 1619 bp sequence was obtained by RT-PCR and RACE approaches. The 5´ UTR is 161 bp and the poly A tail is exactly after the stop codon in the mRNA. The ORF is 1485 bp and codes for 485 amino acids. The deduced protein sequence has high identity to GLUT1 proteins from several species and contains all the main features of glucose transporter proteins, including twelve transmembrane domains, the conserved motives and amino acids involved in transport activity, ligands binding and membrane anchor. Therefore, we decided to name this sequence, glucose transporter 1 of L. vannamei (LvGLUT1). A partial gene sequence of 8.87 Kbp was also obtained; it contains the complete coding sequence divided in 10 exons. LvGlut1 expression was detected in hemocytes, hepatopancreas, intestine gills, muscle and pleopods. The higher relative expression was found in gills and the lower in hemocytes. This indicates that LvGlut1 is ubiquitously expressed but its levels are tissue-specific and upon short-term hypoxia, the GLUT1 transcripts increase 3.7-fold in hepatopancreas and gills. To our knowledge, this is the first evidence of expression of GLUT1 in crustaceans.

Blue surface-emitting distributed feedback lasers based on TPD-doped films.

Single-mode second-order distributed feedback (DFB) lasers with low threshold, based on polystyrene films doped with 30 wt. % of the hole-transporting organic molecule N,N'-bis (3-methylphenyl)-N,N'-diphenylbenzidine (TPD) are reported. The laser emission wavelength was tuned between 415 and 427 nm by film thickness variation. The effectiveness of the DFB grating in improving the laser performance is evidenced by the observation of linewidths and laser thresholds lower than those of the amplified spontaneous emission characteristics shown by films without gratings. The use of holographic lithography as the technique for grating recording has allowed us to prepare large samples in a fast, versatile, and simple manner.