| 1. |
|
|
| 2. |
- Bai, Yang, et al.
(author)
-
Geometry design of tethered small-molecule acceptor enables highly stable and efficient polymer solar cells
- 2023
-
In: Nature Communications. - : NATURE PORTFOLIO. - 2041-1723. ; 14:1
-
Journal article (peer-reviewed)abstract
- With the power conversion efficiency of binary polymer solar cells dramatically improved, the thermal stability of the small-molecule acceptors raised the main concerns on the device operating stability. Here, to address this issue, thiophene-dicarboxylate spacer tethered small-molecule acceptors are designed, and their molecular geometries are further regulated via the thiophene-core isomerism engineering, affording dimeric TDY-alpha with a 2, 5-substitution and TDY-beta with 3, 4-substitution on the core. It shows that TDY-alpha processes a higher glass transition temperature, better crystallinity relative to its individual small-molecule acceptor segment and isomeric counterpart of TDY-beta, and amore stablemorphology with the polymer donor. As a result, the TDY-alpha based device delivers a higher device efficiency of 18.1%, and most important, achieves an extrapolated lifetime of about 35000 hours that retaining 80% of their initial efficiency. Our result suggests that with proper geometry design, the tethered small-molecule acceptors can achieve both high device efficiency and operating stability.
|
|
| 3. |
- Hua, Geng, et al.
(author)
-
Anionic polycondensation and equilibrium driven monomer formation of cyclic aliphatic carbonates
- 2018
-
In: RSC Advances. - : ROYAL SOC CHEMISTRY. - 2046-2069. ; 8:68, s. 39022-39028
-
Journal article (peer-reviewed)abstract
- The current work explores the sodium hydride mediated polycondensation of aliphatic diols with diethyl carbonate to produce both aliphatic polycarbonates and cyclic carbonate monomers. The lengths of the diol dictate the outcome of the reaction; for ethylene glycol and seven other 1,3-diols with a wide array of substitution patterns, the corresponding 5-membered and 6-membered cyclic carbonates were synthesized in excellent yield (70-90%) on a 100 gram scale. Diols with longer alkyl chains, under the same conditions, yielded polycarbonates with an M-w ranging from 5000 to 16000. In all cases, the macromolecular architecture revealed that the formed polymer consisted purely of carbonate linkages, without decarboxylation as a side reaction. The synthetic design is completely solvent-free without any additional post purification steps and without the necessity of reactive ring-closing reagents. The results presented within provide a green and scalable approach to synthesize both cyclic carbonate monomers and polycarbonates with possible applications within the entire field of polymer technology.
|
|
| 4. |
- Hua, Geng, et al.
(author)
-
Exploiting Ring-Opening Aminolysis–Condensation as a Polymerization Pathway to Structurally Diverse Biobased Polyamides
- 2018
-
In: Biomacromolecules. - : American Chemical Society (ACS). - 1525-7797 .- 1526-4602.
-
Journal article (peer-reviewed)abstract
- A pathway to biobased polyamides (PAs) via ring-opening aminolysis–condensation (ROAC) under benign conditions with diverse structure was designed. Ethylene brassylate (EB), a plant oil-derived cyclic dilactone, was used in combination with an array of diamines of diverse chemical structure, and ring-opening of the cyclic dilactone EB was revealed as a driving force for the reaction. The ROAC reactions were adjusted, and reaction conditions of 100 °C under atmospheric pressure using 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as a catalyst for 24 h were optimal. The structures of the polyamides were confirmed by mass spectroscopy, FTIR, and NMR, and the PAs had viscosity average molecular weights (Mη) of ∼5–8 kDa. Glassy or semicrystalline PAs with glass transition temperatures between 48 and 55 °C, melting temperatures of 120–200 °C for the semicrystalline PAs, and thermal stabilities above 400 °C were obtained and were comparable to the existing PAs with similar structures. As a proof-of-concept of their usage, one of the PAs was shown to form fibers by electrospinning and films by melt pressing. Compared to conventional methods for PA synthesis, the ROAC route portrayed a reaction temperature at least 60–80 °C lower, could be readily carried out without a low-pressure environment, and eliminated the use of solvents and toxic chemicals. Together with the plant oil-derived monomer (EB), the ROAC route provided a sustainable alternative to design biobased PAs.
|
|
| 5. |
- Hua, Geng, et al.
(author)
-
From Food Additive to High-Performance Heavy Metal Adsorbent : A Versatile and Well-Tuned Design
- 2016
-
In: ACS Sustainable Chemistry and Engineering. - : ACS Publications. - 2168-0485.
-
Journal article (peer-reviewed)abstract
- A biosourced, cross-linked hydrogel-type heavy metal adsorbent is presented. Various factors such as the highly efficient chemical interactions, the various network structures, the decreased energy consumption during cross-linking, and the negligible amount of generated waste are considered when designing the adsorbent. The widely applied, naturally occurring food additive δ-gluconolactone is studied as a building block for the adsorbent. Aminolysis reactions were applied to form linear dimer precursors between diamines and δ-gluconolactones. The abundant hydroxyl groups on the dimers from δ-gluconolactone were fully exploited by using them as the cross-linking sites for reactions with ethylenediaminetetraacetic dianhydride, a well-known metal-chelating moiety. The versatility of the adsorbent and its metal-ion binding capacity is well tuned using dimers with different structures and by controlling the feed ratios of the precursors. Buffers with different pH values were used as the conditioning media to examine the swelling properties and the mechanical properties of the hydrogels, revealing that both properties can be controlled. High heavy metal chelating performance of the adsorbent was determined by isothermal adsorption kinetics, titration, and thermal gravimetric analysis. The adsorbent exhibits an outstanding chelating ability toward the three tested heavy metals (Cu(II), Co(II), Ni(II)), and the maximum adsorption capacity (qm ∼ 121 mg·g–1) is higher than that of the majority of the reported biosourced adsorbents.
|
|
| 6. |
- Hua, Geng, et al.
(author)
-
Isocyanate-Free, UV-Crosslinked Poly(Hydroxyurethane) Networks: A Sustainable Approach toward Highly Functional Antibacterial Gels
- 2017
-
In: Macromolecular Bioscience. - : John Wiley & Sons. - 1616-5187 .- 1616-5195.
-
Journal article (peer-reviewed)abstract
- An increased sustainabile awarness has inspired the development of new polymeric networks in a remarkable way and this strive should be combined with environmentally concerned end-uses. Therefore, a UV-crosslinked polyhydroxyurethane film with antibacterial properties is developed. First, a hydroxyurethane precursor is synthesized using aminolysis condensation, circumventing the use of isocyanates. The films are subsequently crosslinked under solvent-free conditions through a UV-triggered thiol-ene mechanism. The reactions are monitored by 1H nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, and Raman spectroscopy, and the networks have gel contents above 90%, and are transparent, hydrophilic, and highly flexible. Antibacterial properties are achieved by a controlled quaternization of the network's tertiary-amine and methylation of thiol-ether functionality, resulting in quaternary ammonium compounds (QACs) and sulfonium compounds. The antibacterial properties are evaluated against both Escherichia coli and Staphylococcus aureus using the agar plate diffusion and tube shaking methods. The QAC-loaded films exhibit outstanding bactericide properties (>99.9%) and the antibacterial mechanism is demonstrated to be a dual killing mechanism, i.e., diffusion killing and contact active killing.
|
|
| 7. |
- Hua, Geng, et al.
(author)
-
One-pot inimer promoted ROCP synthesis of branched copolyesters using α-hydroxy-γ-butyrolactone as the branching reagent
- 2016
-
In: Journal of Polymer Science Part A. - : John Wiley & Sons. - 0887-624X .- 1099-0518. ; 54:13, s. 1908-1918
-
Journal article (peer-reviewed)abstract
- An array of branched poly(ɛ-caprolactone)s was successfully synthesized using an one-pot inimer promoted ring-opening multibranching copolymerization (ROCP) reaction. The biorenewable, commercially available yet unexploited comonomer and initiator 2-hydroxy-γ-butyrolactone was chosen as the inimer to extend the use of 5-membered lactones to branched structures and simultaneously avoiding the typical tedious work involved in the inimer preparation. Reactions were carried out both in bulk and in solution using stannous octoate (Sn(Oct)2) as the catalyst. Polymerizations with inimer equivalents varying from 0.01 to 0.2 were conducted which resulted in polymers with a degree of branching ranging from 0.049 to 0.124. Detailed ROCP kinetics of different inimer systems were compared to illustrate the branch formation mechanism. The resulting polymer structures were confirmed by 1H, 13C, and 1H-13C HSQC NMR and SEC (RI detector and triple detectors). The thermal properties of polymers with different degree of branching were investigated by DSC, confirming the branch formation. Through this work, we have extended the current use of the non-homopolymerizable γ-butyrolactone to the branched polymers and thoroughly examined its behaviors in ROCP.
|
|
| 8. |
- Hua, Geng, et al.
(author)
-
Phosphazene-Catalyzed Regioselective Ring-Opening Polymerization of rac-1-Methyl Trimethylene Carbonate : Colder and Less is Better
- 2019
-
In: Macromolecules. - : AMER CHEMICAL SOC. - 0024-9297 .- 1520-5835. ; 52:7, s. 2681-2690
-
Journal article (peer-reviewed)abstract
- The regioselective organocatalytic ring-opening polymerization (ROP) of a 6-membered cyclic carbonate, rac-1-methyl trimethylene carbonate, was studied using phosphazene base (t-BuP2) as the principle catalyst. The influence on the reaction kinetics caused by the reaction temperature (-74-60 degrees C), catalyst loading (0.5-2.5%), and reaction solvent (toluene and tetrahydrofuran) was systematically tuned and followed by H-1 NMR. All studied reactions reached close to or above 90% monomer conversion in 3 h, and all exhibited typical equilibrium polymerization behavior that is inherent to 6-membered cyclic carbonates. Good control over the molecular weight and distribution of the polycarbonate product was obtained in most studied conditions, with M-n ranging from similar to 4k to similar to 20k and D < 1.2. The regioregularity (X-reg) of the resulting polycarbonate was thoroughly studied using various NMR techniques, with the highest X-reg obtained being.0.90. The major influence from the reaction conditions on both the ROP kinetics and X-reg are as follows: higher reaction temperature resulted in a decrease of both; higher catalyst loading resulted in a faster ROP reaction but a slight decrease in X-reg; and toluene being a better solvent resulted in both faster reaction and higher X-reg. Throughout this study, we have demonstrated the possibility to synthesize regioregular aliphatic polycarbonate using an organic base as the ROP catalyst, contrary to the existing studies on similar systems where only metal-base catalysts were in focus and our systems showed similar high X-reg of the product.
|
|
| 9. |
|
|
| 10. |
- Klionsky, Daniel J., et al.
(author)
-
Guidelines for the use and interpretation of assays for monitoring autophagy
- 2012
-
In: Autophagy. - : Informa UK Limited. - 1554-8635 .- 1554-8627. ; 8:4, s. 445-544
-
Research review (peer-reviewed)abstract
- In 2008 we published the first set of guidelines for standardizing research in autophagy. Since then, research on this topic has continued to accelerate, and many new scientists have entered the field. Our knowledge base and relevant new technologies have also been expanding. Accordingly, it is important to update these guidelines for monitoring autophagy in different organisms. Various reviews have described the range of assays that have been used for this purpose. Nevertheless, there continues to be confusion regarding acceptable methods to measure autophagy, especially in multicellular eukaryotes. A key point that needs to be emphasized is that there is a difference between measurements that monitor the numbers or volume of autophagic elements (e.g., autophagosomes or autolysosomes) at any stage of the autophagic process vs. those that measure flux through the autophagy pathway (i.e., the complete process); thus, a block in macroautophagy that results in autophagosome accumulation needs to be differentiated from stimuli that result in increased autophagic activity, defined as increased autophagy induction coupled with increased delivery to, and degradation within, lysosomes (in most higher eukaryotes and some protists such as Dictyostelium) or the vacuole (in plants and fungi). In other words, it is especially important that investigators new to the field understand that the appearance of more autophagosomes does not necessarily equate with more autophagy. In fact, in many cases, autophagosomes accumulate because of a block in trafficking to lysosomes without a concomitant change in autophagosome biogenesis, whereas an increase in autolysosomes may reflect a reduction in degradative activity. Here, we present a set of guidelines for the selection and interpretation of methods for use by investigators who aim to examine macroautophagy and related processes, as well as for reviewers who need to provide realistic and reasonable critiques of papers that are focused on these processes. These guidelines are not meant to be a formulaic set of rules, because the appropriate assays depend in part on the question being asked and the system being used. In addition, we emphasize that no individual assay is guaranteed to be the most appropriate one in every situation, and we strongly recommend the use of multiple assays to monitor autophagy. In these guidelines, we consider these various methods of assessing autophagy and what information can, or cannot, be obtained from them. Finally, by discussing the merits and limits of particular autophagy assays, we hope to encourage technical innovation in the field.
|
|
