Ligand-Bound CO2 as a Nonclassical Route toward Efficient Photocatalytic CO2 Reduction with a Ni N-Confused Porphyrin.

Implementing the synergistic effects between the metal and the ligand has successfully streamlined the energetics for CO2 activation and gained high catalytic activities, establishing the important breakthroughs in photocatalytic CO2 reduction. Herein, we describe a Ni(II) N-confused porphyrin complex (NiNCP) featuring an acidic N-H group. It is readily deprotonated and exists in an anion form during catalysis. Owing to this functional site, NiNCP gave rise to an outstanding turnover number (TON) as high as 217,000 with a 98% selectivity for CO2 reduction to CO, while the parent Ni(II) porphyrin (NiTPP) was found to be nearly inactive. Our mechanistic analysis revealed a nonclassical reaction pattern where CO2 was effectively activated via the attack of the Lewis-basic ligand. The resulting ligand-bound CO2 adduct could be further reduced to produce CO. This new metal-ligand synergistic effect is anticipated to inspire the design of highly active catalysts for small molecule activations.

Synergistic Poly(lactic acid) Antibacterial Surface Combining Superhydrophobicity for Antiadhesion and Chlorophyll for Photodynamic Therapy.

The problem of nosocomial infections caused by bacterial growth on material surfaces is an urgent threat to public health. Although numerous materials and methods have been explored to fight against infections, the methods are complicated and the materials are slightly toxic. It is highly desirable to develop an antibacterial strategy that kills bacteria effectively without drug resistance and cytotoxicity. Herein, we present a synergistic antibacterial polylactic acid (PLA) surface with superhydrophobic antibacterial adhesion and photodynamic bactericidal activity. Initially, the surface displayed low-adhesion superhydrophobicity and resisted most bacterial adhesion. Furthermore, completely non-toxic chlorophyll possessed excellent photodynamic bactericidal properties under non-toxic visible light, which was incorporated into micro-/nanoscale PLA surfaces. We achieved efficient antibacterial activity using completely non-toxic materials and a facile non-solvent-induced phase separation process. This non-toxic, simple, good biocompatible, and no drug-resistant strategy has great advantages in combating bacterial infections.

Engineering Functional Interface with Built-in Catalytic and Self-Oxidation Sites for Highly Stable Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries have attracted great attention due to their high theoretical energy density. The rapid redox conversion of lithium polysulfides (LiPS) is effective for solving the serious shuttle effect and improving the utilization of active materials. The functional design of the separator interface with fast charge transfer and active catalytic sites is desirable for accelerating the conversion of intermediates. Herein, a graphene-wrapped MnCO3 nanowire (G@MC) was prepared and utilized to engineer the separator interface. G@MC with active Mn2+ sites can effectively anchor the LiPS by forming the Mn-S chemical bond according to our theoretical calculation results. In addition, the catalytic Mn2+ sites and conductive graphene layer of G@MC could accelerate the reversible conversion of LiPS via the spontaneous "self-redox" reaction and the rapid electron transfer in electrochemical process. As a result, the G@MC-based battery exhibits only 0.038 % capacity decay (per cycle) after 1000 cycles at 2.0 C. This work affords new insights for designing the integrated functional interface for stable Li-S batteries.

Strain-Induced Nucleophilic Ring Opening of Donor-Acceptor Cyclopropenes for Synthesis of Monosubstituted Succinic Acid Derivatives.

1,2,3-Trisubstituted donor-acceptor cyclopropenes (DACPs) generated in situ from enoldiazo compounds react with nucleophiles to form α-substituted succinic acid derivatives in high yields. Initial dirhodium(II) carboxylate catalysis rapidly converts enoldiazo-acetates or -acetamides to DACPs that undergo catalyst-free Favorskii ring opening with amines, and also with anilines, alcohols, and thiols, when facilitated by catalytic amounts of 4-dimethylaminopyridine (DMAP). This methodology provides easy access to mixed esters and amides of monosubstituted succinic acids, including derivatives of naturally occurring compounds. It also affords dihydrazide, dihydroxamic acid, and diamide derivatives, as well as α-substituted tetrahydropyridazine-3,6-diones in high yields. Attempts to generate optically enriched DACPs were not successful because their populations having the R and S configurations formed with a chiral dirhodium catalyst are quite similar, and the loss of enantiocontrol likely originates from the DACP ring forming step which is reversible with its intermediate metal carbene.

Blue Light-Promoted Formal [4+1]-Annulation of Diazoacetates with o-Aminoacetophenones: Synthesis of Polysubstituted Indolines and Computational Study.

A blue light-promoted formal [4+1]-annulation of diazoacetates with o-aminoacetophenones has been reported, which provides an environmentally friendly method for the synthesis of polysubstituted indoline derivatives in moderate to good yields with excellent diastereoselectivities. Detailed mechanistic studies through density functional theory calculations reveal that the (E)-enol species is the key intermediate in this transformation, and the excellent diastereoselectivity is enabled via H-bonding in the intramolecular Aldol-type addition.

Hydrogels as Durable Anti-Icing Coatings Inhibit and Delay Ice Nucleation.

The accumulation of ice on surfaces brings dangerous and costly problems to our daily life. Thus, it would be desirable to design anti-icing coatings for various surfaces. We report a durable anti-icing coating based on mussel-inspired chemistry, which is enabled via fabricating a liquid water layer, achieved by modifying solid substrates with the highly water absorbing property of sodium alginate. Dopamine, the main component of the mussel adhesive protein, is introduced to anchor the sodium alginate in order to render the coating applicable to all types of solid surfaces. Simultaneously, it serves as the cross-linking agent for sodium alginate; thus, the cross-linking degree of the coatings could be easily varied. The non-freezable and freezable water in the coatings with different cross-link degrees all remain liquid-like at subzero conditions and synergistically fulfill the aim of decreasing the temperature of ice nucleation. These anti-icing coatings display excellent stability even under harsh conditions. Furthermore, these coatings can be applied to almost all types of solid surfaces and have great promise in practical applications.

Palliative pain relief and safety of percutaneous radiofrequency ablation combined with cement injection for bone metastasis.

PURPOSE: To investigate the pain relief effect and safety of percutaneous radiofrequency ablation (RFA) with a multitined electrode combined with cement injection in patients with painful metastatic bone tumors. MATERIALS AND METHODS: Sixteen patients with 34 osteolytic metastatic lesions were treated with RFA including 4 males and 12 females (age range 54-84). Thirteen patients with spinal metastases received additional cement injection. Medical imaging, a visual analog scale (VAS) and the EORTC QLQ-C30 were performed to evaluate the metastatic lesion, pain and quality of life, respectively, before and after RFA and at follow-ups. RESULTS: The RFA and/or vertebroplasty with cement injection were successful in all patients (100%). Except for one patient who had cement leakage, no intraprocedural complications occurred. After RFA, severe refractory pain was greatly relieved in all patients, with pretreatment VAS score of 8.1 ± 1.4 significantly reduced to 5.5 ± 1.1 at 24 h, 2.8 ± 0.6 at 1 week and 1.4 ± 0.8 at 6 months (P < 0.01). The EORTC QLQ-C30 scale at 1 month demonstrated significant improvement (P < 0.05) in the physical (P = 0.03) and emotion function (P = 0.003), global health status (P = 0.002), pain (P = 0.001) and insomnia (P = 0.002). The analgesics were reduced after the procedure and stopped 2 months later in all patients, with greatly improved quality of life and no apparent pain. Followed up for 6-12 months, all patients remained alive with no recurrence of pain. Palliative pain relief and safety of percutaneous radiofrequency ablation combined with cement injection for bone metastasis. CONCLUSION: RFA with or without bone cement is safe and effective in the palliative treatment of pain caused by metastatic bone tumors.

Acupuncture for Primary Sjögren Syndrome (pSS) on symptomatic improvements: study protocol for a randomized controlled trial.

BACKGROUND: Currently, feasible medical treatments are hitherto not satisfying to relieve pSS symptoms, which concerns numbers of clinical doctors. Acupuncture seems to be an alternative to treat pSS and conduces to good symptomatic results. However further research is necessary. This trial is to investigate the efficacy of acupuncture on improving the key symptoms of pSS, which are dryness, pain and fatigue (DPF). METHODS & DESIGN: The study is designed as a randomized controlled trial of two arms with a single centre. We compare acupuncture with sham acupuncture on symptomatic improvements of pSS. A total of 120 pSS patients, aged at least 18, with DPF, will be randomly assigned to acupuncture or sham acupuncture groups, where they will have needle intervention for 8 weeks with 16 weeks of follow-up. Subjects will be assessed each time before interventions during the 8-week intervention, in week 8 after all interventions and in week 12, 16, 20 and 24 for follow-up with different measurements. The primary outcome are the proportions of subjects that have 30% or greater reduction in at least 2 out of 3 items of DPF in Numeric Analog Scale (NAS) scores (0 = the best, 10 = the severest), calculated between the baseline and the average scores of week 2 to 8. The secondary outcome are related to individual items of NAS scores, EULAR Sjögren's Syndrome Patient Reported Index (ESSPRI), EULAR Sjögren's Syndrome Disease Activity Index (ESSDAI), Schirmer test score and unstimulated salivary flow, serum Immunoglobulin G, A and M levels, Medical Outcome Study Short Form 36 Short-Form Health Survey (SF-36), Salivary glands ultrasounds, Hospital Anxiety and Depression (HAD) scale score. The secondary outcome scores are to be collected at baseline, in week 8, 16, and 24. Besides, individual items of NAS will also be collected in week 12 and 20. Moreover, subjects' satisfaction and the proportion of the subjects who identified their allocation will also be measured and analyzed. DISCUSSION: This study will be the first randomized and controlled pilot trial of acupuncture on alleviating the symptoms of pSS with relatively long-term follow-up. The result of the study might offer a new option to treat pSS and might be a clinical proof that acupuncture has beneficial effects on pSS. TRIAL REGISTRATION: ClinicalTrials.gov: NCT02691377 (February 20, 2016).

Nonsolvent-assisted fabrication of multi-scaled polylactide as superhydrophobic surfaces.

The solution-processing fabrication of superhydrophobic surfaces is currently intriguing, owing to high-efficiency, low cost, and energy-consuming. Here, a facile nonsolvent-assisted process was proposed for the fabrication of the multi-scaled surface roughness in polylactide (PLA) films, thereby resulting in a significant transformation in the surface wettability from intrinsic hydrophilicity to superhydrophobicity. Moreover, it was found that the surface topographical structure of PLA films can be manipulated by varying the compositions of the PLA solutions. And the samples showed superhydrophobic surfaces as well as high melting enthalpy and crystallinity. In particular, a high contact angle of 155.8° together with a high adhesive force of 184 µN was yielded with the assistance of a multi-nonsolvent system, which contributed to the co-existence of micro-/nano-scale hierarchical structures.

Injectable Conductive Hydrogel with Self-Healing, Motion Monitoring, and Bacteria Theranostics for Bioelectronic Wound Dressing.

Wounds at joints are difficult to treat and tend to recover more slowly due to the frequent motions. When using traditional hydrogel dressings, they are easy to crack and undergo bacterial infection, difficult to match and monitor the irregular wounds. Integrating multiple functions within a hydrogel dressing to achieve intelligent wound monitoring and healing remains a significant challenge. In this research, a multifunctional hydrogel is developed based on polysaccharide biopolymer, poly(vinyl alcohol), and hydroxylated graphene through dynamic borate ester bonding and supramolecular interaction. The prepared hydrogel not only exhibits rapid self-healing (within 60 s), injectable, conductive and motion monitoring properties, but also realizes in situ bacterial sensing and killing functions. It shows excellent bacterial sensitivity (within 15 min) and killing ability via the changes of electrical signals and photothermal therapy, avoiding the emergence of drug-resistant bacteria. In vivo experiments prove that the hydrogel can promote wound healing effectively. In addition, it displays great electromechanical performance to achieve real-time monitoring and prevent re-tearing of the wound at human joints. The injectable pH-responsive hydrogel with good biocompatibility demonstrates considerable potential as multifunctional bioelectronic dressing for the detection, treatment, management, and healing of infected joint wounds.

Tuning ice nucleation with pH-modulated Fe3+ cross-linked hydrogel surfaces.

Ice nucleation plays a vital function in various fields. In this study, we prepared hydrogel surfaces with different cross-linkages by pH-modulating the coordination pattern of Fe3+ and catechol. We found that the ice nucleation temperature decreases with increasing cross-linkages. Further analysis shows that the hydrogel surfaces with different cross-linking degrees could achieve the regulation of ice nucleation by modulating the interfacial water. Our study elucidates the mechanism of ice nucleation regulated by interfacial water in soft matter and proposes a new method for preparing ice nucleation-regulated material.

Stimuli-Responsive Antibacterial Materials: Molecular Structures, Design Principles, and Biomedical Applications.

Infections are regarded as the most severe complication associated with human health, which are urgent to be solved. Stimuli-responsive materials are appealing therapeutic platforms for antibacterial treatments, which provide great potential for accurate theranostics. In this review, the advantages, the response mechanisms, and the key design principles of stimuli-responsive antibacterial materials are highlighted. The biomedical applications, the current challenges, and future directions of stimuli-responsive antibacterial materials are also discussed. First, the categories of stimuli-responsive antibacterial materials are comprehensively itemized based on different sources of stimuli, including external physical environmental stimuli (e.g., temperature, light, electricity, salt, etc.) and bacterial metabolites stimuli (e.g., acid, enzyme, redox, etc.). Second, structural characteristics, design principles, and biomedical applications of the responsive materials are discussed, and the underlying interrelationships are revealed. The molecular structures and design principles are closely related to the sources of stimuli. Finally, the challenging issues of stimuli-responsive materials are proposed. This review will provide scientific guidance to promote the clinical applications of stimuli-responsive antibacterial materials.

An enantioselective four-component reaction via assembling two reaction intermediates.

A reaction intermediate is a key molecular entity that has been used in explaining how starting materials converts into the final products in the reaction, and it is usually unstable, highly reactive, and short-lived. Extensive efforts have been devoted in identifying and characterizing such species via advanced physico-chemical analytical techniques. As an appealing alternative, trapping experiments are powerful tools in this field. This trapping strategy opens an opportunity to discover multicomponent reactions. In this work, we report various highly diastereoselective and enantioselective four-component reactions (containing alcohols, diazoesters, enamines/indoles and aldehydes) which involve the coupling of in situ generated intermediates (iminium and enol). The reaction conditions presented herein to produce over 100 examples of four-component reaction products proceed under mild reaction conditions and show high functional group tolerance to a broad range of substrates. Based on experimental and computational analyses, a plausible mechanism of this multicomponent reaction is proposed.

Modulating residual ammonium in MnO2 for high-rate aqueous zinc-ion batteries.

Manganese dioxide (MnO2), as a promising cathode candidate, has attracted great attention in aqueous zinc ion batteries (ZIBs). However, the undesirable dissolution of Mn2+ and the sluggish kinetic reaction are still two challenges to overcome before achieving good cycling stability and high-rate performance of ZIBs. Herein, ß-MnO2 with chemically residual NH4+ (NMO) was successfully fabricated by controlling the washing condition and utilized as a cathode in a ZIB. Interestingly, NH4+, as a layer pillar in the tunnel structure of NMO, could enhance its conductivity by changing the chemical structure, contributing to accelerating the kinetics of the charge carrier. Moreover, the residual NH4+ in NMO could stabilize the chemical microstructure through the cationic electrostatic shielding effect and the formation of Mn-O⋯H bonds in NMO, promoting the reversible and successive insertion/extraction of H+/Zn2+ in the ZIB. As a result, the Zn/NMO battery exhibits excellent rate performance (up to 8.0 A g-1) and cycling stability (10 000 cycles). This work will pave the way for the design of cathode materials with nonmetallic doping for high-performance ZIB systems.

Intrinsic carbon nanotube liquid crystalline elastomer photoactuators for high-definition biomechanics.

Photoresponsive soft actuators with the unique merits of flexibility, contactless operation, and remote control have huge potential in technological applications of bionic robotics and biomedical devices. Herein, a facile strategy was proposed to prepare an intrinsically-photoresponsive elastomer by chemically grafting carbon nanotubes (CNTs) into a thermally-sensitive liquid-crystalline elastomer (LCE) network. Highly effective dispersion and nematic orientation of CNTs in the intrinsic LCE matrix were observed to yield anchoring energies ranging from 1.65 × 10-5 J m-2 to 5.49 × 10-7 J m-2, which significantly enhanced the mechanical and photothermal properties of the photoresponsive elastomer. When embedding an ultralow loading of CNTs (0.1 wt%), the tensile strength of the LCE increased by 420% to 13.89 MPa (||) and 530% to 3.94 MPa (⊥) and exhibited a stable response to repeated alternating cooling and heating cycles, as well as repeated UV and infrared irradiation. Furthermore, the shape transformation, locomotion, and photo-actuation capabilities allow the CNT/LCE actuator to be applied in high-definition biomechanical applications, such as phototactic flowers, serpentine robots and artificial muscles. This design strategy may provide a promising method to manufacture high-precision, remote-control smart devices.

Efficacy and Safety of Acupuncture on Symptomatic Improvement in Primary Sjögren's Syndrome: A Randomized Controlled Trial.

Aim: We sought to evaluate the efficacy of acupuncture in treating the main symptoms of primary Sjögren's syndrome, specifically dryness, pain, and fatigue. Methods: A total of 120 patients with primary Sjögren's syndrome were randomized in a parallel-group, controlled trial. Participants received acupuncture or sham acupuncture for the first 8 weeks, then were followed for 16 weeks thereafter. The primary outcome was the proportion of participants with a ≥ 30% reduction in ≥ 2 of 3 numeric analog scale scores for dryness, pain, and fatigue. The secondary outcomes included the European League Against Rheumatism (EULAR) Sjögren's Syndrome Patient-reported Index (ESSPRI); the EULAR Sjögren's Syndrome Disease Activity Index; the Schirmer test score; unstimulated saliva flow; serum immunoglobulin G, A, and M concentrations; the Medical Outcome Study Short Form 36 score; salivary gland ultrasound imaging; and the Hospital Anxiety and Depression Scale score. Results: The proportions of patients meeting the primary endpoint were 28.33% (17/60) in the acupuncture group and 31.66% (19/60) in the sham group, without a statistically significant difference (P = 0.705). The IgG concentration at week 16 and the homogeneity in ultrasonography of the salivary glands at week 8 showed significant differences between the 2 groups (P = 0.0490 and P = 0.0334, respectively). No other differences were observed between the 2 groups. ESSPRI and unstimulated saliva flow were improved in both groups compared to baseline, albeit with a significant difference between them. Conclusion: In patients with primary Sjögren's syndrome, acupuncture did not satisfactorily improve symptoms compared to placebo. However, interesting discoveries and possible underlying reasons were demonstrated and discussed, which may be useful to studies in the future. Clinical Trial Registration: [www.ClinicalTrials.gov], identifier [NCT02691377].

Toward Application of Liquid Crystalline Elastomer for Smart Robotics: State of the Art and Challenges.

Liquid crystalline elastomers (LCEs) are lightly crosslinked polymers that combine liquid crystalline order and rubber elasticity. Owing to their unique anisotropic behavior and reversible shape responses to external stimulation (temperature, light, etc.), LCEs have emerged as preferred candidates for actuators, artificial muscles, sensors, smart robots, or other intelligent devices. Herein, we discuss the basic action, control mechanisms, phase transitions, and the structure-property correlation of LCEs; this review provides a comprehensive overview of LCEs for applications in actuators and other smart devices. Furthermore, the synthesis and processing of liquid crystal elastomer are briefly discussed, and the current challenges and future opportunities are prospected. With all recent progress pertaining to material design, sophisticated manipulation, and advanced applications presented, a vision for the application of LCEs in the next generation smart robots or automatic action systems is outlined.

Solution-processed electronics for artificial synapses.

Artificial synaptic devices and systems have become hot topics due to parallel computing, high plasticity, integration of storage, and processing to meet the challenges of the traditional Von Neumann computers. Currently, two-terminal memristors and three-terminal transistors have been mainly developed for high-density storage with high switching speed and high reliability because of the adjustable resistivity, controllable ion migration, and abundant choices of functional materials and fabrication processes. To achieve the low-cost, large-scale, and easy-process fabrication, solution-processed techniques have been extensively employed to develop synaptic electronics towards flexible and highly integrated three-dimensional (3D) neural networks. Herein, we have summarized and discussed solution-processed techniques in the fabrication of two-terminal memristors and three-terminal transistors for the application of artificial synaptic electronics mainly reported in the recent five years from the view of fabrication processes, functional materials, electronic operating mechanisms, and system applications. Furthermore, the challenges and prospects were discussed in depth to promote solution-processed techniques in the future development of artificial synapse with high performance and high integration.

A gold(i)-catalysed chemoselective three-component reaction between phenols, α-diazocarbonyl compounds and allenamides.

Gold(i) catalysts are considered to be efficient in promoting sp2 C-H bond insertion at the para position of unprotected phenols because of the exceptionally chemical reactivity of gold-stabilized carbophilic carbocations. Herein, we present a gold(i)-catalysed three-component reaction between phenols, diazocarbonyl compounds and allenamides, affording the corresponding three-component reaction products with excellent geometric selectivity (E : Z > 20 : 1) in moderate to high yields (up to 90%) under mild conditions. Additionally, a gram-scale transformation and diverse transformations of the resulting product show the high synthetic utility of the present three-component protocol.