Comparative genome and transcriptome analyses reveal innate differences in response to host plants by two color forms of the two-spotted spider mite Tetranychus urticae.

BACKGROUND: The two-spotted spider mite, Tetranychus urticae, is a major agricultural pest with a cosmopolitan distribution, and its polyphagous habits provide a model for investigating herbivore-plant interactions. There are two body color forms of T. urticae with a different host preference. Comparative genomics and transcriptomics are used here to investigate differences in responses of the forms to host plants at the molecular level. Biological responses of the two forms sourced from multiple populations are also presented. RESULTS: We carried out principal component analysis of transcription changes in three red and three green T. urticae populations feeding on their original host (common bean), and three hosts to which they were transferred: cotton, cucumber and eggplant. There were differences among the forms in gene expression regardless of their host plant. In addition, different changes in gene expression were evident in the two forms when responding to the same host transfer. We further compared biological performance among populations of the two forms after feeding on each of the four hosts. Fecundity of 2-day-old adult females showed a consistent difference between the forms after feeding on bean. We produced a 90.1-Mb genome of the red form of T. urticae with scaffold N50 of 12.78 Mb. Transcriptional profiles of genes associated with saliva, digestion and detoxification showed form-dependent responses to the same host and these genes also showed host-specific expression effects. CONCLUSIONS: Our research revealed that forms of T. urticae differ in host-determined transcription responses and that there is form-dependent plasticity in the transcriptomic responses. These differences may facilitate the extreme polyphagy shown by spider mites, although fitness differences on hosts are also influenced by population differences unrelated to color form.

Dynamic heterogeneity in homogeneous polymer melts.

Chain entanglement behaviors were studied by 1H Hahn echo nuclear magnetic resonance (NMR) and 1H double-quantum (DQ) NMR experiments. Poly(ethylene oxide) (PEO) was chosen to investigate the chain entanglement behaviors. The 1H Hahn echo NMR results demonstrate that the critical molecular weight of PEO is approximately 6 kg mol-1. Above this critical molecular weight, chain entanglements start to occur in the melts resulting in anisotropic motions of polymer chain. The 1H DQ NMR observations establish that PEO melts with molecular weights above the critical value exhibit dynamical entanglements. The entangled networks, formed by PEO with a molecular weight of 480 kg mol-1 (PEO480), present slow mobility and rather homogeneously distributed chain entanglements, while the entangled networks, formed by PEO with a molecular weight of 255 kg mol-1 (PEO255), present fast mobility and obvious dynamic heterogeneity in the distribution of chain entanglement. Short chain PEOs like that with a molecular weight of 2 kg mol-1 are demonstrated to function like solvents when being added in an appropriate concentration to PEO480, and the dilution effect increases the chain mobility of PEO480. Moreover, properly diluted PEO480 networks exhibit dynamic heterogeneity similar to that observed in PEO255.

THE ENDOPARASITOID Pteromalus puparum INFLUENCES HOST GENE EXPRESSION WITHIN FIRST HOUR OF PARASITIZATION.

The small cabbage butterfly, Pieris rapae, is an important pest of cruciferous corps, and Pteromalus puparum is a predominant pupal endoparasitoid wasp of this butterfly. For successful development of parasitoid offspring, female parasitoids usually introduce one or several kinds of maternal factors into the hemocoels during oviposition to suppress host immunity. To investigate the early changes in host immune-related genes following parasitization, we analyzed transcriptomes of parasitized and unparasitized, control, host pupae. Approximately 17.7 and 19.3 million paired-end reads were generated from nonparasitized and parasitized host pupae, and assembled de novo into 45,639 transcripts and 27,659 nonredundant unigenes. The average unigene length was 790 bp. A total 18,377 of 27,659 unigenes were annotated and we identified 557 differentially expressed unigenes in host pupae at 1 h after parasitization, of which 21 were immune-related. Parasitization led to downregulation of most pattern recognition receptors and upregulation of all serine protease inhibitors. The transcirptomic profile of P. rapae is considerably affected by parasitization. This study provides valuable sources for future investigations of the molecular interaction between P. puparum and its host P. rapae.

A new class of dendritic metallogels with multiple stimuli-responsiveness and as templates for the in situ synthesis of silver nanoparticles.

A new class of poly(aryl ether) dendritic ligands containing a pyridine functionality at the focal point and the corresponding Ag(I) complexes through metal-ligand coordination were designed, synthesized, and fully characterized. Compared with the dendritic ligands, the corresponding dendritic complexes exhibited much better gelation ability for various organic solvents at very low critical gelation concentrations. The gel-sol phase transition temperatures and morphologies could be finely tuned by binding silver ion to the ligand. A preliminary study revealed that multiple noncovalent interactions, such as Ag(I) -pyridine coordination, solvophobic interaction, and π-π stacking, synergistically enable the formation of stable metallogels. Interestingly, these metallogels could intelligently respond to multiple external stimuli including temperature, chemicals, and shear stress, leading to gel-sol phase transitions. In addition, these dendritic metallogels were successfully applied as templates for the in situ formation and stabilization of silver nanoparticles without the use of any chemical reducing/stabilizing agents.

A systematic study of peripherally multiple aromatic ester-functionalized poly(benzyl ether) dendrons for the fabrication of organogels: structure-property relationships and thixotropic property.

A new class of peripherally multiple aromatic ester-functionalized poly(benzyl ether) dendrons and/or dendrimers with different focal point substituents, surface groups, interior structures, as well as different generations have been synthesized and their structure-property relationships with respect to their gelation ability have been investigated systematically. Most of these dendrons are able to gel organic solvents over a wide polarity range. Evident dendritic effects were observed not only in gelation capability but also in thermotropic, morphological, and rheological characterizations. It was disclosed that subtle changes in peripheral ester functionalities and interior dendritic structures affected the gelation behavior of the dendrons significantly. Among all the dendrons studied, the second- and third-generation dendrons G0G2-Me and G0G3-Me with dimethyl isophthalates (DMIP) as peripheral groups exhibited the best capability in gelation, and stable gels were formed in more than 22 aromatic and polar organic solvents. The lowest critical gelation concentration (CGC) reached 2.0 mg mL(-1), indicating that approximately 1.35×10(4) solvent molecules could be entrapped by one dendritic molecule. Further study on driving forces in gel formation was carried out by using a combination of single-crystal/powder X-ray diffraction (XRD) analysis and concentration-dependent (CD)/temperature-dependent (TD) (1)H NMR spectroscopy. The results obtained from these experiments revealed that the multiple π-π stacking of extended π-systems due to the peripheral DMIP rings, cooperatively assisted by non-conventional hydrogen-bonding, is the key contributor in the formation of the highly ordered supramolecular and fibrillar network. In addition, these dendritic organogels exhibited unexpected thixotropic-responsive properties, which make them promising candidates with potential applications in the field of intelligent soft materials.

Relationship between parasitism and morphology of Trichogramma (Hymenoptera: Trichogrammatidae) on Spodoptera frugiperda (Lepidoptera: Noctuidae).

In this study, 5 species of Trichogramma Westwood were evaluated for the biological control of Spodoptera frugiperda (JE Smith), concerning the physical characteristics of female Trichogramma. The results showed that Trichogramma chilonis Ishii, Trichogramma dendrolimi Matsumura, and Trichogramma ostriniae Pang et Chen exhibited high parasitism rates, emergence rates, and offspring numbers, with the highest values observed for T. ostriniae. The ovipositor length of Trichogramma japonicum Ashmead and T. dendrolimi were longer than those of other species, and the hind tibia length was the shortest in Trichogramma cacoeciae Marchal. We further evaluated relationships between the parasitism ability of Trichogramma and various morphological indexes based on Spearman's rank correlation coefficients. A positive correlation was found between the parasitism rate and hind tibia length of T. cacoeciae. In T. dendrolimi, the parasitism rate was negatively correlated with ovipositor width and positively correlated with the length-width ratio of the ovipositor. A significant positive correlation was observed between the proportion of female offspring and the mother's ovipositor length in T. japonicum. However, there were no significant correlations between morphological indexes and indexes of parasitism in T. ostriniae. Overall, the parasitic abilities of T. chilonis on S. frugiperda eggs were significantly correlated with the morphology of the female ovipositors.

Knockdown of vitellogenin receptor based on minute insect RNA interference methods affects the initial mature egg load in the pest natural enemy Trichogramma dendrolimi.

Vitellogenin receptor (VgR) plays a crucial role in oogenesis by mediating endocytosis of vitellogenin and a portion of the yolk proteins in many insect species. However, the function of VgR in minute parasitoid wasps is largely unknown. Here, we applied Trichogramma dendrolimi, a minute egg parasitoid, as a study model to investigate the function of VgR in parasitoids. We developed RNA interference (RNAi) methods based on microinjection of prepupae in T. dendrolimi. RNAi employs nanomaterial branched amphipathic peptide capsules (BAPC) as a carrier for double-stranded RNA (dsRNA), significantly enhancing delivery efficiency. Also, artificial hosts without medium were used to culture the injected prepupae in vitro. Utilizing these methods, we found that ovarian growth was disrupted after knockdown of TdVgR, as manifested by the suppressed development of the ovariole and the inhibition of nurse cell internalization by oocytes. Also, the initial mature egg load in the ovary was significantly reduced. Notably, the parasitic capacity of the female adult with ovarian dysplasia was significantly decreased, possibly resulting from the low availability of mature eggs. Moreover, ovarian dysplasia in T. dendrolimi caused by VgR deficiency are conserved despite feeding on different hosts. The results confirmed a critical role of TdVgR in the reproductive ability of T. dendrolimi and provided a reference for gene functional studies in minute insects.

Extracting Venom from the Parasitoid Wasp Trichogramma dendrolimi using an Artificial Host.

Parasitoid wasps are a diverse group of hymenopteran insects that serve as invaluable resources for pest biocontrol. To ensure successful parasitism, parasitoid wasps inject venom into their hosts to suppress their hosts' immunity, modulate hosts' development, metabolism, and even behavior. With over 600,000 estimated species, the diversity of parasitoid wasps surpasses that of other venomous animals, such as snakes, cone snails, and spiders. Parasitoid wasp venom is an underexplored source of bioactive molecules with potential applications in pest control and medicine. However, collecting parasitoid venom is challenging due to the inability to use direct or electrical stimulation and the difficulty in dissection because of their small size. Trichogramma is a genus of tiny (~0.5 mm) egg parasitoid wasps that are widely used for the biological control of lepidopteran pests in both agriculture and forests. Here, we report a method for extracting venom from T. dendrolimi using artificial hosts. These artificial hosts are created with polyethylene film and amino acid solutions and then inoculated with Trichogramma wasps for parasitism. The venom was subsequently collected and concentrated. This method enables the extraction of large amounts of Trichogramma venom while avoiding contamination from other tissues caused by dissection, a common issue in venom reservoir dissection protocols. This innovative approach facilitates the study of Trichogramma venom, paving the way for new research and potential applications.

Association of biopsy core number and location with pain in patients undergoing a transperineal prostate biopsy under local anaesthesia: a secondary analysis of the APROPOS trial.

BACKGROUND: APROPOS was a multicentre, randomized, blinded trial focus on investigating the perineal nerve block versus the periprostatic block in pain control for men undergoing a transperineal prostate biopsy. In the analysis reported here, the authors aimed to evaluate the association of biopsy core count and location with pain outcomes in patients undergoing a transperineal prostate biopsy under local anesthesia. METHODS: APROPOS was performed at six medical centers in China. Patients with suspected prostate cancer were randomized to receive either a perineal nerve block or a periprostatic block (1:1), followed by a transperineal prostate biopsy. The secondary analysis outcomes were the worst pain experienced during the prostate biopsy and postbiopsy pain at 1,6, and 24 h. RESULTS: Between 12 August 2020 and 20 July 2022, a total of 192 patients were randomized in the original trial, and 188 were involved in this analysis, with 94 patients per group. Participants had a median (IQR) age of 68 (63-72) and a median (IQR) prostate volume of 42.51 (30.04-62.84). The patient population had a median (IQR) number of biopsy cores of 15 (12-17.50), and 26.06% of patients had a biopsy cores count of more than 15. After adjusting the baseline characteristics, the number of biopsy cores was associated with the worst pain during the biopsy procedure in both the perineal nerve block group ( ß 0.19, 95% CI: 0.12-0.26, P <0.001) and the periprostatic block group ( ß 0.16, 95% CI: 0.07-0.24, P <0.001). A similar association was also evident for the postbiopsy pain at 1, 6, and 24 h. A lesser degree of pain in both groups at any time (r range -0.57 to -0.01 for both groups) was associated with biopsy cores from the peripheral zone of the middle gland, while other locations were associated with a higher degree of pain. In addition, the location of the biopsy core had less of an effect on pain during the biopsy (r range -0.01-0.25 for both groups) than it did on postbiopsy pain (r range -0.57-0.60 for both groups). CONCLUSIONS: In this secondary analysis of a randomized trial, biopsy core count and location were associated with pain in patients undergoing a transperineal prostate biopsy under local anesthesia. These results may be helpful for making clinical decisions about the anesthetic approach for scheduled transperineal prostate biopsies.

Early Detection and Identification of Parasitoid Wasps Trichogramma Westwood (Hymenoptera: Trichogrammatidae) in Their Host Eggs Using Polymerase Chain Reaction-Restriction Fragment Length Polymorphism.

Parasitoid wasps are invaluable agents in pest biological control. Early detection and identification of parasitoid immatures are vital in characterizing parasitoid-host interactions and for evaluating parasitism rates accurately in the field. Trichogramma is the most widely used parasitoid wasp, and several studies have been performed for its molecular identification. However, those studies were mainly focused on Trichogramma adults and rarely on immatures. Here, we report a method to detect and identify Trichogramma larvae in their host eggs. We designed a pair of Trichogramma-specific primers that amplified Trichogramma mtCOI sequences from Corcyra cephalonica (Stainton) eggs parasitized by any of eight Trichogramma species tested but not from nonparasitized eggs of four lepidopteran hosts. This PCR method reliably detected Trichogramma immatures in parasitized eggs as early as 1 h after parasitism. We further developed an RFLP (restriction fragment length polymorphism) assay using restriction enzymes SspI and VspI to differentiate eight Trichogramma species at their immature stage. Overall, we developed a sensitive and reliable PCR-RFLP method to detect and identify immature-stage Trichogramma in their lepidopteran hosts. This method shows promise for conveniently identifying Trichogramma in insectaries and accurately evaluating parasitism rates in the field.

Mitochondrial Genomes of Two Asexual Trichogramma (Hymenoptera: Trichogrammatidae) Strains and Comparison with Their Sexual Relatives.

Despite its substantial costs, sexual reproduction dominates in animals. One popular explanation for the paradox of sex is that asexual reproduction is more likely to accumulate deleterious mutations than sexual reproduction. To test this hypothesis, we compared the mitogenomes of two asexual wasp strains, Trichogramma cacoeciae and T. pretiosum, to their sexual relatives. These two asexual strains represent two different transition mechanisms in Trichogramma from sexual to asexual reproduction. Asexual T. pretiosum is induced by Wolbachia, while T. cacoeciae presumably originated from interspecific hybridization. We sequenced and assembled complete mitochondrial genomes of asexual T. cacoeciae and T. pretiosum. Compared to four sexual relatives, we found no evidence of higher mutation accumulation in asexual Trichogramma mitogenomes than in their sexual relatives. We also did not detect any relaxed selection in asexual Trichogramma mitogenomes. In contrast, the intensified selection was detected in Nad1 and Nad4 of the asexual T. pretiosum mitogenome, suggesting more purifying selection. In summary, no higher mitochondrial mutation accumulation was detected in these two asexual Trichogramma strains. This study provides a basis for further investigating mitochondrial evolution and asexual reproduction in Trichogramma.

Quinoline-cored Poly(Aryl Ether) Dendritic Organogels with Multiple Stimuli-Responsive and Adsorptive Properties.

Functional supramolecular gel materials have potential applications in sensors, optical switches, artificial antennae, drug delivery and so on. In this paper, quinoline-cored poly(aryl ether) dendritic organogelators were designed, synthesized and fully characterized. The gelation behaviour of the dendritic organogelator was tested in organic solvents, mixed solvents and ionic liquids. The dendron Q-G1 was found to be an efficient and versatile organogelator toward various apolar and polar organic solvents with the critical gelation concentrations (CGCs) approaching 1.2×10-2  mol/L, indicating one dendritic organogelator could immobilize 1.2×103 solvent molecules in the organogel network. Interestingly, these dendrons exhibited excellent gel formation in ionic liquids. Notably, these dendritic organogels were found to display multiple stimuli-responsive properties toward external stimuli including heat, ultrasound and shear stress, with a reversible sol-gel phase transition. In addition, the dendritic organogel could effectively adsorb heavy metals and organic dyes. The removal rate of Pb2+ was up to 20% and the adsorption rate for Rhodamine B was as high as 89%.

Anti-proliferation effects of Sirolimus sustained delivery film in rabbit glaucoma filtration surgery.

PURPOSE: To investigate the efficacy, safety, and mechanisms of Sirolimus sustained delivery film on prevention of scar formation in a rabbit model of glaucoma filtration surgery. METHODS: Sixty-four New Zealand white rabbits who underwent trabeculectomy in the right eye were randomly allocated to one of the four treatment regimens: Sirolimus sustained delivery film treatment group (Group A), or drug-free film treatment group (Group B), or 30 ng/ml Sirolimus-soaked sponge treatment group (Group C), or no adjunctive treatment group (Group D), and each group consists of 16 rabbits. Intraocular pressure (IOP), morphologic changes of bleb, anterior chamber flare, and corneal endothelial cell count and complications were evaluated over a 28-day period follow-up time. Aqueous humor samples were gathered from Group A, and the concentration of Sirolimus was measured regularly post-operation. Rabbits were sacrificed on the 7th, 14th, and 28th day post-operation separately, and the fibroblast hypertrophy, infiltration of inflammatory, and proliferation of new collagen fiber formation in each group were evaluated with HE and Masson staining. Proliferative cell nuclear antigen (PCNA) and fibroblast apoptosis were evaluated by immunohistochemistry and terminal deoxynucleotidyl transferasemediated dUTP nick end labeling (TUNEL) assay at the 28th day post-operation. RESULTS: Both Sirolimus sustained delivery film (Group A) and Sirolimus alone (Group C) were well tolerated in this model, and significantly prolonged bleb survival compared with no drug treatment group (Group B and D; p<0.001). Group A had the longest bleb survival time in comparison with other groups (p<0.001). There were significant differences in IOP readings between Group A and other groups at the last follow-up (p<0.05). The concentration of Group A maintained stable for over 2 weeks, drops from (10.56 ±0.05) ng/ml at day 3 to (7.74 ±0.05) ng/ml at day 14. The number of corneal endothelial cells of Group A was not statistically significant between pre and post-operation. Histologic examination demonstrated that eyes treated with Sirolimus, especially the Sirolimus sustained delivery film, showed an obvious reduction in subconjunctival fibroblast scar tissue formation compared with no drug treatment groups, and had minimal evidence of inflammatory cell infiltration and new collagen deposition in the subconjunctiva. Immunohistochemistry assay showed that PCNA-expression was lower in the Group A (16.25±3.24%) compared to other groups (p<0.01). TUNEL assay showed a significant increase in the number of apoptotic fibroblasts around the surgical area in Group A and Group C (9.75±1.71% and 8.50±1.92%) compared to the Group B and D (p<0.01). CONCLUSIONS: Sirolimus drug sustained delivery film can inhibit inflammatory cell activity, impede fibroblast proliferation activity, and induce fibroblast apoptosis in the filtration surgery sites in rabbit. The results indicate a safe and effective treatment strategy in anti-scaring treatment in glaucoma surgery.

Transcriptomic analyses of chemosensory genes in Trichogramma japonicum (Hymenoptera: Trichogrammatidae).

Insects perceive dangerous or attractive chemicals in the environment (such as the presence of predators, food or mates) through their olfaction and gustation. This leads to host searching, mate finding and other behaviors that are critical for insect survival. These vital activities are mediated by many chemosensory receptor proteins, including odorant receptors (ORs), gustatory receptors (GRs) and ionotropic receptors (IRs). Trichogramma japonicum Ashmead (Hymenoptera: Trichogrammatidae) is a commonly used egg parasitoid for controlling lepidopteran pests in rice fields. To reveal the roles of its olfactory and gustatory systems in biological control, we systematically analyzed major chemosensory receptor genes from T. japonicum. Through transcriptomic analyses of male and female heads, we found that the differentially expressed genes (DEGs) were mainly related to chemosensory functions, and there were more chemosensory-related genes expressed in female heads than male heads, which may be related to the need for females to search for their hosts or sense male pheromone. Furthermore, we identified 66 chemosensory receptor genes, including 51 ORs, seven IRs and eight GRs, that were most closely relate to those of other hymenopteran species according to the results of both Blast best-hit and phylogenetic analyses. The tissue expression profile showed that 65 of the 66 chemosensory receptors were highly expressed in the heads, suggesting their putative roles in olfaction and gustation. In addition, the sex-specific expression patterns suggested their potential functions in host-seeking or mate sensing behaviors. This study may provide base for further understanding the olfactory and gustatory systems of T. japonicum and increasing its efficiency in pest control in the future.

AIEgen-loaded nanofibrous membrane as photodynamic/photothermal antimicrobial surface for sunlight-triggered bioprotection.

The outbreak of infectious diseases such as COVID-19 causes an urgent need for abundant personal protective equipment (PPE) which leads to a huge shortage of raw materials. Additionally, the inappropriate disposal and sterilization of PPE may result in a high risk of cross-contamination. Therefore, the exploration of antimicrobial materials possessing both microbe interception and self-decontamination effects to develop reusable and easy-to-sterilize PPE is of great importance. Herein, an aggregation-induced emission (AIE)-active luminogen-loaded nanofibrous membrane (TTVB@NM) sharing sunlight-triggered photodynamic/photothermal anti-pathogen functions are prepared using the electrospinning technique. Thanks to its porous nanostructure, TTVB@NM shows excellent interception effects toward ultrafine particles and pathogenic aerosols. Benefiting from the superior photophysical properties of the AIE-active dopants, TTVB@NM exhibits integrated properties of wide absorption in visible light range, efficient ROS generation, and moderate photothermal conversion performance. A series of antimicrobial evaluations reveal that TTVB@NM could effectively inactivate pathogenic aerosols containing bacteria (inhibition rate: >99%), fungi (~88%), and viruses (>99%) within only 10 min sunlight irradiation. This study represents a new strategy to construct reusable and easy-to-sterilize hybrid materials for potential bioprotective applications.

Fabrication of Highly Robust and Conductive Ion Gels Based on the Combined Strategies of Double-Network, Composite, and High-Functionality Cross-Linkers.

A robust hybrid ion gel is fabricated utilizing the combined strategies of double-network (DN), composite, and high-functionality cross-linkers. The charged poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPS) constructs the DN skeleton, with graphene oxide (GO) and N,N'-methylenebisacrylamide (MBA) being the cross-linkers for the first and second networks, respectively. The ionic liquid, either 1-ethyl-3-methylimidazolium dicyanamide ([EMIm][DCA]) or 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF4]), is locked in the network to offer the high conductivity. Compared to the DN PAMPS ion gel without nanoparticles and the hybrid DN ion gel with unconnected silica nanoparticles, the present ion gel exhibits a significantly higher tensile strength (3.2 ± 0.1 MPa) and an excellent compressive strength (26 ± 1 MPa). The [EMIm][DCA] ion gel has a high conductivity close to that of its neat ionic liquids. The conductivity of the gel is sensitive to deformation and temperature, which leads to potential applications in sensing body movements, pulse, and temperature change.

Identification and Comparative Analysis of Venom Proteins in a Pupal Ectoparasitoid, Pachycrepoideus vindemmiae.

Parasitoid wasps inject venom containing complex bioactive compounds to regulate the immune response and development of host arthropods and sometime paralyze host arthropods. Although extensive studies have been conducted on the identification of venom proteins in larval parasitoids, relatively few studies have examined the pupal parasitoids. In our current study, a combination of transcriptomic and proteomic methods was used to identify 64 putative venom proteins from Pachycrepoideus vindemmiae, an ectoparasitoid of Drosophila. Expression analysis revealed that 20 tested venom proteins have 419-fold higher mean expression in the venom apparatus than in other wasp tissues, indicating their specialization to venom. Comparisons of venom proteins from P. vindemmiae and other five species spanning three parasitoid families detected a core set of "ancient" orthologs in Pteromalidae. Thirty-five venom proteins of P. vindemmiae were assigned to the orthologous groups by reciprocal best matches with venoms of other pteromalids, while the remaining 29 were not. Of the 35 categories, twenty-seven have orthologous relationships with Nasonia vitripennis venom proteins and 25 with venoms of Pteromalus puparum. More distant relationships detected that five and two venom proteins of P. vindemmiae are orthologous with venoms of two Figitidae parasitoids and a Braconidae representative, respectively. Moreover, twenty-two venoms unique to P. vindemmiae were also detected, indicating considerable interspecific variation of venom proteins in parasitoids. Phylogenetic reconstruction based on a set of single-copy genes clustered P. vindemmiae with P. puparum, N. vitripennis, and other members of the family Pteromalidae. These findings provide strong evidence that P. vindemmiae venom proteins are well positioned for future functional and evolutionary studies.

Rheological Study on the Thermoreversible Gelation of Stereo-Controlled Poly(N-Isopropylacrylamide) in an Imidazolium Ionic Liquid.

The thermoreversible sol-gel transition for an ionic liquid (IL) solution of isotactic-rich poly (N-isopropylacrylamides) (PNIPAMs) is investigated by rheological technique. The meso-diad content of PNIPAMs ranges between 47% and 79%, and molecular weight (Mn) is ~35,000 and ~70,000 g/mol for two series of samples. PNIPAMs are soluble in 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl) imide ([BMIM][TFSI]) at high temperatures but undergo a gelation with decreasing temperatures. The transition temperature determined from G'-G" crossover increases with isotacticity, consistent with the previous cloud-point result at the same scanning rate, indicating imide groups along the same side of backbones are prone to be aggregated for formation of a gel. The transition point based on Winter-Chambon criterion is on average higher than that of the G'-G" crossover method and is insensitive to tacticity and molecular weight, since it correlates with percolation of globules rather than the further formation of elastic network (G' > G"). For the first time, the phase diagram composed of both G'-G" crossover points for gelation and cloud points is established in PNIPAM/IL mixtures. For low-Mn PNIPAMs, the crossover-point line intersects the cloud-point line. Hence, from solution to opaque gel, the sample will experience two different transitional phases, either clear gel or opaque sol. A clear gel is formed due to partial phase separation of isotactic segments that could act as junctions of network. However, when the partial phase separation is not faster than the formation of globules, an opaque sol will be formed. For high-Mn PNIPAMs, crossover points are below cloud points at all concentrations, so their gelation only follows the opaque sol route. Such phase diagram is attributed to the poorer solubility of high-Mn polymers for entropic reasons. The phase diagram composed of Winter-Chambon melting points, crossover points for melting, and clear points is similar with the gelation phase diagram, confirming the mechanism above.

Rheology of Concentrated Polymer/Ionic Liquid Solutions: An Anomalous Plasticizing Effect and a Universality in Nonlinear Shear Rheology.

An anomalous plasticizing effect was observed in polymer/ionic liquid (IL) solutions by applying broad range of rheological techniques. Poly(ethylene oxide)(PEO)/IL solutions exhibit stronger dynamic temperature dependence than pure PEO, which is in conflict with the knowledge that lower-Tg solvent increases the fractional free volume. For poly(methy methacrylate)(PMMA)/IL solutions, the subtle anomaly was detected from the fact that the effective glass transition temperature Tg,eff of PMMA in IL is higher than the prediction of the self-concentration model, while in conventional polymer solutions, Tg,eff follows the original Fox equation. Observations in both solutions reveal retarded segmental dynamics, consistent with a recent simulation result (Macromolecules, 2018, 51, 5336) that polymer chains wrap the IL cations by hydrogen bonding interactions and the segmental unwrapping delays their relaxation. Start-up shear and nonlinear stress relaxation tests of polymer/IL solutions follow a universal nonlinear rheological behavior as polymer melts and solutions, indicating that the segment-cation interaction is not strong enough to influence the nonlinear chain orientation and stretch. The present work may arouse the further theoretical, experimental, and simulation interests in interpreting the effect of complex polymer-IL interaction on the dynamics of polymer/IL solutions.

Linear and Nonlinear Dynamic Behavior of Polymer Micellar Assemblies Connected by Metallo-Supramolecular Interactions.

The linear and nonlinear rheology of associative colloidal polymer assemblies with metallo-supramolecular interactions is herein studied. Polystyrene-b-poly(tert-butylacrylate) with a terpyridine ligand at the end of the acrylate block is self-assembled into micelles in ethanol, a selective solvent for the latter block, and supramolecularly connected by complexation to divalent metal ions. The dependence of the system elasticity on polymer concentration can be semi-quantitatively understood by a geometrical packing model. For strongly associated (Ni2+, Fe2+) and sufficiently concentrated systems (15 w/v%), any given ligand end-group has a virtually 100% probability of being located in an overlapping hairy region between two micelles. By assuming a 50% probability of intermicellar crosslinks being formed, an excellent prediction of the plateau modulus was achieved and compared with the experimental results. For strongly associated but somewhat more dilute systems (12 w/v%) that still have significant overlap between hairy regions, the experimental modulus was lower than the predicted value, as the effective number of crosslinkers was further reduced along with possible density heterogeneities. The reversible destruction of the network by shear forces can be observed from the strain dependence of the storage and loss moduli. The storage moduli of the Ni2+ and Zn2+ systems at a lower concentration (12 w/v%) showed a rarely observed feature (i.e., a peak at the transition from linear to nonlinear regime). This peak disappeared at a higher concentration (15 w/v%). This behavior can be rationalized based on concentration-dependent network stretchability.