Metal-Organic Framework as a New Type of Magnetothermally-Triggered On-Demand Release Carrier.

The development of external stimuli-controlled payload systems has been sought after with increasing interest toward magnetothermally-triggered drug release (MTDR) carriers due to their non-invasive features. However, current MTDR carriers present several limitations, such as poor heating efficiency caused by the aggregation of iron oxide nanoparticles (IONPs) or the presence of antiferromagnetic phases which affect their efficiency. Herein, a novel MTDR carrier is developed using a controlled encapsulation method that fully fixes and confines IONPs of various sizes within the metal-organic frameworks (MOFs). This novel carrier preserves the MOF's morphology, porosity, and IONP segregation, while enhances heating efficiency through the oxidation of antiferromagnetic phases in IONPs during encapsulation. It also features a magnetothermally-responsive nanobrush that is stimulated by an alternating magnetic field to enable on-demand drug release. The novel carrier shows improved heating, which has potential applications as contrast agents and for combined chemo and magnetic hyperthermia therapy. It holds a great promise for magneto-thermally modulated drug dosing at tumor sites, making it an exciting avenue for cancer treatment.

Mimicking Enzymatic Non-Covalent Interactions with Functionalized Covalent Organic Frameworks for Improved Adsorption and Hydrolysis of Cellobiose.

Tuning catalytic centers in heterogeneous catalyst, both in a chemical and a spatial manner, is a powerful approach to improve the stability and the efficiency of catalysts. While the chemical aspects are largely understood, the spatial interactions around active sites, comprised of non-covalent interactions, are difficult to maintain and challenging to study. Herein, the unique properties of covalent organic frameworks (COFs) are utilized to establish an ideal reaction environment for the hydrolysis of cellobiose and other common disaccharides in mild, metal-free, and neutral aqueous conditions. The chosen COF, HCl-PSA-IM-COF-OMe ("HCl" for hydrochloric acid, "PSA" for propyl sulfonic acid, "IM" for imidazole, and "OMe" for methoxy), is modified to be ultra-stable in aqueous conditions and possesses sulfonic acid groups for general acid catalysis and for enhanced hydrogen bonding with reactants as well as intraporous chloride anions for oxocarbenium intermediate stabilization. In addition, the system also relies on the differences in adsorptive binding behavior, Kads , of the reactants and the products to the functionalized framework and benefits from a separate physical, kinetic process to boost the catalytic cycle. Due to its stability in aqueous conditions, HCl-PSA-IM-COF-OMe can be recycled and maintains its hydrolytic properties for five cycles before regeneration is needed.

First complete mitochondrial genomes of Ototretinae (Coleoptera, Lampyridae) with evolutionary insights into the gene rearrangement.

The subfamily Ototretinae represents an important and unusual lineage of fireflies. Here, we sequenced and annotated three mitogenomes for this subfamily, with two Stenocladius species and one Drilaster species as representatives. The mitogenome of Stenocladius exhibits a rearranged gene order between trnC and trnW caused by transposition, which is a novel finding in Lampyridae. Meanwhile, a long intergenic space (241 to 376 bp) exists between the two rearranged genes, and some remnants (23 bp) of trnW are present within this non-coding region. Moreover, phylogenetic analyses did not recover the monophyly of Ototretinae, in which Drilaster is shown at a basal lineage in Lampyridae, but Stenocladius seems more related to Luciolinae. Therefore, the gene rearrangement in Stenocladius is presumed to result from independent evolutionary events, suggesting that this genus should be placed in a separate lineage. Nevertheless, more representative mitogenomes from different groups are required to verify the present results.

Mitochondrial genomes of Sternochetus species (Coleoptera: Curculionidae) and the phylogenetic implications.

The three weevil species, Sternochetus gravis, S. mangiferae, and S. olivieri, have all been reported to be serious pests of mango fruits. Morphology, biology, and various management approaches of these economically important weevils have been well studied. However, no mitochondrial genomes have been reported from the genus Sternochetus. Herein, we assembled mitogenomes of all the three Sternochetus species to reveal their mitogenomic characteristics. A DNA library of 350 bp insert size was constructed and sequenced in Illumina's HiSeq 6000 platform with a pair-end 150 bp sequencing strategy by Novogene. The sequence reads were assembled using GetOrganelle v1.7.1 and the genes were annotated by Geneious Prime 2021.0.3 and MITOS Web Server. Coupled with 61 published mitogenomes from 13 subfamilies of Curculionidae, we reconstructed phylogenetic trees to resolve evolutionary relationships of these closely related species and also examined subfamily-level classification among Curculionidae. All three mitogenomes are double-stranded circular molecules with 22 transfer RNA genes, 13 protein-coding genes (PCGs), 2 ribosomal RNA genes, and 1 noncoding control region as in other insects. Higher interspecific nucleotide divergence (about 10%) of 13 PCGs indicated these three Sternochetus species diverged a long time ago. Phylogenetic analyses using both maximum likelihood and Bayesian inference methods showed that Sternochetus falls into the basal clade of Cryptorhynchini, a tribe in the subfamily Molytinae. The relationship of S. olivieri as a sister species to S. gravis + S. mangiferae was strongly supported. The monophyly of Cryptorhynchini was also well supported whereas Molytinae was suggested to be a polyphyletic group.

Efficient Electron Transfer from Electron-Sponge Polyoxometalate to Single-Metal Site Metal-Organic Frameworks for Highly Selective Electroreduction of Carbon Dioxide.

In this work, by combining the superiority of polyoxometalates (POMs) and catalytic single-metal site Co of metalloporphyrin, a series of mixed-valence POM-based metal-organic frameworks (MOFs) composites is synthesized by a post-modification method. The electron-transfer property of POM@PCN-222(Co) composite is significantly enhanced owing to the directional electron-transfer from POM to single-metal site Co in PCN-222(Co). In particular, H-POM@PCN-222(Co) gives a high Faradaic efficiency of 96.2% for electroreduction of CO2 into CO and good stability over 10 h. DFT calculations confirm that the directional electron transfer, which accelerates the multi-electron transfer from the electrode to active single-metal site Co, enriches the electron density of the Co center, and ultimately reduces the energy of the rate-determining step, thus increasing the catalytic activity of CO2 reduction reaction (CO2 RR). This work therefore suggests some new insight for the design of efficient electrocatalysts for CO2 RR.

A Mysterious Asian Firefly Genus, Oculogryphus Jeng, Engel & Yang (Coleoptera, Lampyridae): The First Complete Mitochondrial Genome and Its Phylogenetic Implications.

The firefly genus Oculogryphus Jeng, Engel & Yang, 2007 is a rare-species group endemic to Asia. Since its establishment, its position has been controversial but never rigorously tested. To address this perplexing issue, we are the first to present the complete mitochondrial sequence of Oculogryphus, using the material of O. chenghoiyanae Yiu & Jeng, 2018 determined through a comprehensive morphological identification. Our analyses demonstrate that its mitogenome exhibits similar characteristics to that of Stenocladius, including a rearranged gene order between trnC and trnW, and a long intergenic spacer (702 bp) between the two rearranged genes, within which six remnants (29 bp) of trnW were identified. Further, we incorporated this sequence into phylogenetic analyses of Lampyridae based on different molecular markers and datasets using ML and BI analyses. The results consistently place Oculogryphus within the same clade as Stenocladius in all topologies, and the gene rearrangement is a synapomorphy for this clade. It suggests that Oculogryphus should be classified together with Stenocladius in the subfamily Ototretinae at the moment. This study provides molecular evidence confirming the close relationship between Oculogryphus and Stenocladius and discovers a new phylogenetic marker helpful in clarifying the monophyly of Ototretinae, which also sheds a new light on firefly evolution.

Novel platinum therapeutics induce rapid cancer cell death through triggering intracellular ROS storm.

Induction of reactive oxygen species (ROS) production in cancer cells plays a critical role for cancer treatment. However, therapeutic efficiency remains challenging due to insufficient ROS production of current ROS inducers. We designed a novel platinum (Pt)-based drug named "carrier-platin" that integrates ultrasmall Pt-based nanoparticles uniformly confined within a poly(amino acids) carrier. Carrier-platin dramatically triggered a burst of ROS in cancer cells, leading to cancer cell death as quick as 30 min. Unlike traditional Pt-based drugs which induce cell apoptosis through DNA intercalation, carrier-platin with superior ROS catalytic activities induces a unique pattern of cancer cell death that is neither apoptosis nor ferroptosis and operates independently of DNA damage. Importantly, carrier-platin demonstrates superior anti-tumor efficacy against a broad spectrum of cancers, particularly those with multidrug resistance, while maintaining minimal systemic toxicity. Our findings reveal a distinct mechanism of action of Pt in cancer cell eradication, positioning carrier-platin as a novel category of anti-cancer chemotherapeutics.

Naringin@Metal-Organic Framework as a Multifunctional Bioplatform.

Naringin, a natural product, can be used as a therapeutic agent due to its low systemic toxicity and negligible adverse effect. However, due to its hydrophobic nature and thereby low solubility, high-dose treatment is required when used for human therapy. Herein, we demonstrate the employment of a metal-organic framework (MOF) as a nontoxic loading carrier to encapsulate naringin, and the afforded nairngin@MOF composite can serve as a multifunctional bioplatform capable of treating Gram-positive bacteria and certain cancers by slowly and progressively releasing the encapsulated naringin as well as improving and modulating immune system functions through synergy between naringin and the MOF.

Recent development of metal-organic framework nanocomposites for biomedical applications.

Albeit metal-organic framework (MOF) composites have been extensively explored, reducing the size and dimensions of various contents within the composition, to the nanoscale regime, has recently presented unique opportunities for enhanced properties with the formation of MOF-based nanocomposites. Many distinctive strategies have been used to fabricate these nanocomposites such as through the introduction of nanoparticles (NPs) into a MOF precursor solution or vice versa to achieve a core-shell or heterostructure configuration. As such, MOF-based nanocomposites offer seemingly limitless possibilities and promising solutions for the vast range of applications across biomedical disciplines especially for improving in vivo implementation. In this review, we focus on the recent development of MOF-based nanocomposites, outline their classification according to the type of integrations (NPs, coating materials, and different MOF-derived nanocomposites), and direct special attention towards the various approaches and strategies employed to construct these nanocomposites for their prospective utilization in biomedical applications including biomimetic enzymes and photo, chemo, sonodynamic, starvation and hyperthermia therapies. Lastly, our work aims to highlight the exciting potential as well as the challenges of MOF-based nanocomposites to help guide future research as well as to contribute to the progress of MOF-based nanotechnology in biomedicine.

Research progress on immunotherapy in triple­negative breast cancer (Review).

Triple­negative breast cancer (TNBC) is a highly heterogeneous and aggressive malignancy. Due to the absence of estrogen receptors and progesterone receptors and the lack of overexpression of human epidermal growth factor receptor 2, TNBC responds poorly to endocrine and targeted therapies. As a neoadjuvant therapy, chemotherapy is usually the only option for TNBC; however, chemotherapy may induce tumor resistance. The emergence of immunotherapy as an adjuvant therapy is expected to make up for the deficiency of chemotherapy. Most of the research on immunotherapies has been performed on advanced metastatic TNBC, which has provided significant clinical benefits. In the present review, possible immunotherapy targets and ongoing immunotherapy strategies were discussed. In addition, progress in research on immune checkpoint inhibitors in early TNBC was outlined.

A Mitochondrial Genome Phylogeny of Cleridae (Coleoptera, Cleroidea).

The predaceous beetle family Cleridae includes a large and widely distributed rapid radiation, which is vital for the ecosystem. Despite its important role, a number of problems remain to be solved regarding the phylogenetic inter-relationships, the timing of divergence, and the mitochondrial biology. Mitochondrial genomes have been widely used to reconstruct phylogenies of various insect groups, but never introduced to Cleridae until now. Here, we generated 18 mitochondrial genomes to address these issues, which are all novel to the family. In addition to phylogenomic analysis, we have leveraged our new sources to study the mitochondrial biology in terms of nucleotide composition, codon usage and substitutional rate, to understand how these vital cellular components may have contributed to the divergence of the Cleridae. Our results recovered Korynetinae sister to the remaining clerids, and the calde of Clerinae+Hydnocerinae is indicated more related to Tillinae. A time-calibrated phylogeny estimated the earliest divergence time of Cleridae was soon after the origin of the family, not later than 160.18 Mya (95% HPD: 158.18-162.07 Mya) during the mid-Jurassic. This is the first mitochondrial genome-based phylogenetic study of the Cleridae that covers nearly all subfamily members, which provides an alternative evidence for reconstructing the phylogenetic relationships.

Unexpected High Species Diversity of Mesolycus Gorham (Coleoptera, Lycidae) from China, with a Preliminary Investigation on Its Phylogenetic Position Based on Multiple Genes.

The lycid genus Mesolycus Gorham, 1883 is mainly distributed in East Palaearctic and Indochinese regions, but poorly studied in China; moreover, its phylogenetic placement remains controversial but has never been rigorously tested. In this study, Mesolycus was reviewed and its placement within Lycidae was tested based on a multilocus phylogeny (cox1, nad5, cox2 and Lrna) by both ML and BI analyses. The reconstructed phylogenies show that Mesolycus is a consistently recovered sister to Dilophotes Waterhouse, 1879, and they form a monophyletic clade which is well supported. This suggests that Mesolycus definitely belongs to Dilophotini rather than to Macrolycini of Lycinae. Besides, three species originally described or placed in Dilophotes are transferred to Mesolycus, including M. atricollis (Pic, 1926) comb. n., M. particularis (Pic, 1928) comb. n. and M. pacholatkoi (Bic, 2002) comb. n. Four new species are discovered in China, including M. shaanxiensis sp. n., M. dentatus sp. n., M. breviplatus sp. n. and M. varus sp. n. Two species, M. murzini Kazantsev, 2004 and M. rubromarginatus Kazantsev, 2013, are recorded from China for the first time. A key for the identification of all Mesolycus species is provided. China was revealed as the region with the highest species diversity of this genus.

First Complete Mitochondrial Genome of Melyridae (Coleoptera, Cleroidea): Genome Description and Phylogenetic Implications.

To explore the characteristics of the mitogenome of Melyridae and reveal phylogenetic relationships, the mitogenome of Cordylepherus sp. was sequenced and annotated. This is the first time a complete mitochondrial genome has beengenerated in this family. Consistent with previous observations of Cleroidea species, the mitogenome of Cordylepherus sp. is highly conserved in gene size, organization and codon usage, and secondary structures oftRNAs. All protein-coding genes(PCGs) initiate withthe standard start codon ATN,except ND1, which starts with TTG, and terminate with the complete stop codons of TAA and TAG, or incomplete forms, TA- and T-. MosttRNAs have the typical clover-leaf structure, except trnS1 (Ser, AGN), whose dihydrouridine (DHU) armis reduced. In the A+T-rich region, three types of tandem repeat sequence units are found, including a 115 bp sequence tandemly repeated twice, a 16 bp sequence tandemly repeated three timeswith a partial third repeat and a 10 bp sequence tandemly repeated seven times. Phylogenetic analyses based on 13 protein-coding genes by both Bayesian inference (BI) and maximum likelihood (ML) methods suggest that Melyridae sensu lato is polyphyletic, and Dasytinae and Malchiinae are supported as independent families.

Characterization of the First Complete Mitochondrial Genome of Cyphonocerinae (Coleoptera: Lampyridae) with Implications for Phylogeny and Evolution of Fireflies.

Complete mitochondrial genomes are valuable resources for phylogenetics in insects. The Cyphonoceridae represents an important lineage of fireflies. However, no complete mitogenome is available until now. Here, the first complete mitochondrial genome from this subfamily was reported, with Cyphonocerus sanguineus klapperichi as a representative. The mitogenome of C. sanguineus klapperichi was conserved in the structure and comparable to that of others in size and A+T content. Nucleotide composition was A+T-biased, and all genes exhibited a positive AT-skew and negative GC-skew. Two types of tandem repeat sequence units were present in the control region (136 bp × 2; 171 bp × 2 + 9 bp). For reconstruction of Lampyridae's phylogeny, three different datasets were analyzed by both maximum likelihood (ML) and Bayesian inference (BI) methods. As a result, the same topology was produced by both ML analysis of 13 protein-coding genes and 2rRNA and BI analysis of 37 genes. The results indicated that Lampyridae, Lampyrinae, Luciolinae (excluding Emeia) were monophyletic, but Ototretinae was paraphyletic, of which Stenocladius was recovered as the sister taxon to all others, while Drilaster was more closely related to Cyphonocerinae; Phturinae + Emeia were included in a monophyletic clade, which comprised sister groups with Lampyridae. Vesta was deeply rooted in the Luciolinae.

The correlation between phase transition and photoluminescence properties of CsPbX3 (X= Cl, Br, I) perovskite nanocrystals.

We report a correlation between the structural phase transition of CsPbX3 (X=Cl, Br, I) nanocrystals (NCs) and their temperature dependent steady-state photoluminescence (PL) and time-resolved PL (TRPL). In constrast to CsPbBr3 and CsPbI3 NCs which exhibited a continuous blue shift in their bandgap with increasing temperature, the CsPbCl3 exhibited a blue shift until ~193 K, followed by a red shift until room temperature. We attribute this change from a blue to a red shift to a structural phase transtion in CsPbCl3, which also manifested in the temperature dependent TRPL. Notably, the exciton recombination lifetimes showed a similar reverse trend due to the phase transition in CsPbCl3, which has not been reported previously.

The complete mitochondrial genome sequence and phylogenetic analysis of Lycocerus asperipennis (Coleoptera, Cantharidae).

The complete mitochondrial genome of a common Chinese soldier beetle was sequenced, Lycocerus asperipennis (Coleoptera, Cantharidae, Cantharinae). The mitogenome is a double-stranded circular molecule, and the obtained sequence with 13 protein-coding genes (PCGs), 22 tRNA genes, 2 rRNA subunits, and an AT-rich region, as in other insects. Total length of this mitogenome is 16162 bp and the composition of each base is A (41.5%), T (37.7%), C (12.4%), G (8.4%), respectively. The phylogenetic tree analysis using 16 species of Elateriformia shows that L. asperipennis is closest to Chauliognathus opacus, which belongs to the subfamily Chauliognathinae of Cantharidae.

The complete mitogenome of Lycostomus sp. (Elateroidea: Lycidae).

The complete mitochondrial genome of a net-winged beetle was sequenced, Lycostomus sp. (Coleoptera: Lycidae). The total length of this mitogenome is 16096 bp and the composition of each base is A (41.1%), T (31.9%), C (17.1%), G (9.9%), respectively. The gene arrangement of this beetle mt genome is the same as other insects. The phylogenetic tree shows that Lycostomus sp. is closest to Platerodrilus sp. with robust statistical support, which confirms the monophyly of Lycidae.