bluuebunny/crossref_metadata_2025_split huggingface dataset:
Design and Synthesis of BODIPY‐Hetero[5]helicenes as Heavy‐Atom‐Free Triplet Photosensitizers for Photodynamic Therapy of Cancer
Authors: Koli Mrunesh , Gupta Sonali , Chakraborty Saikat , Ghosh Ayan , Ghosh Rajib , Wadawale A. P. , Ghanty Tapan K. , Patro Birija S. , Mula Soumyaditya 
Published: June 2023

AbstractDesigning heavy‐atom‐free triplet photosensitizers (PSs) is a challenge for the efficient photodynamic therapy (PDT) of cancer. Helicenes are twisted polycyclic aromatic hydrocarbons (PAHs) with an efficient intersystem crossing (ISC) that is proportional to their twisting angle. But their difficult syntheses and weak absorption profile in the visible spectral region restrict their use as heavy‐atom‐free triplet PSs for PDT. On the other hand, boron‐containing PAHs, BODIPYs are highly recognized for their outstanding optical properties. However, planar BODIPY dyes has low ISC and thus they are not very effective as PDT agents. We have designed and synthesized fused compounds containing both BODIPY and hetero[5]helicene structures to develop red‐shifted chromophores with efficient ISC. One of the pyrrole units of the BODIPY core was also replaced by a thiazole unit to further enhance the triplet conversion. All the fused compounds have helical structure, and their twisting angles are also increased by substitutions at the boron centre. The helical structures of the BODIPY‐hetero[5]helicenes were confirmed by X‐ray crystallography and DFT structure optimization. The designed BODIPY‐hetero[5]helicenes showed superior optical properties and high ISC with respect to [5]helicene. Interestingly their ISC efficiencies increase proportionally with their twisting angles. This is the first report on the relationship between the twisting angle and the ISC efficiency in twisted BODIPY‐based compounds. Theoretical calculations showed that energy gap of the S1 and T1 states decreases in BODIPY‐hetero[5]helicene as compared to planar BODIPY. This enhances the ISC rate in BODIPY‐hetero[5]helicene, which is responsible for their high generation of singlet oxygen. Finally, their potential applications as PDT agents were investigated, and one BODIPY‐hetero[5]helicene showed efficient cancer cell killing upon photo‐exposure. This new design strategy will be very useful for the future development of heavy‐atom‐free PDT agents.
Macroporous Hydrogels Prepared By Ice Templating: Developments And Challenges†
Authors: Chen Di , Yang Biru , Yang Chen , Wu Jingjun , Zhao Qian 
Published: June 2023

Comprehensive SummaryMacroporous hydrogels are water‐swollen polymer networks with porous structures beyond the mesh size. They provide high specific surface areas and hieratical mass transfer channels which are desired for emerging applications including cell culturing, bio‐separation, and drug delivery. A variety of approaches have been developed to fabricate macroporous hydrogels, including gas foaming, porogen templating, phase separation, 3D printing, etc. Alternatively, ice templating utilizes the crystallization of water as the porogenation mechanism which doesn't need the leaching of porogens. The porous structures can be easily manipulated by controlling the morphology of ice (size, orientation, etc.) upon freezing. In addition, mechanical properties of obtained porous hydrogels are commonly better than those of other macroporous hydrogels since the pore walls are made up of concentrated polymers through the freezing step. These three characteristics, that is, the green process, the highly tunable morphology, and the enhanced mechanical strength make the ice templating a superior porogenation method. This review expects to give an overview on macroporous hydrogels prepared by the ice templating, namely, cryogels. Recent progresses on emerging cryo‐porogenation methods are introduced. Fundamental understanding concerning the behavior of the polymer chains during the formation of ice is proposed. Future opportunities on the application of cryogels are prospected.
Hippocampal CA3 inhibitory neurons receive extensive noncanonical synaptic inputs from CA1 and subicular complex
Authors: Lin Xiaoxiao , Cyrus Neeyaz , Avila Brenda , Holmes Todd C. , Xu Xiangmin 
Published: June 2023

AbstractHippocampal CA3 is traditionally conceptualized as a brain region within a unidirectional feedforward trisynaptic pathway that links major hippocampal subregions. Recent genomic and viral tracing studies indicate that the anatomical connectivity of CA3 and the trisynaptic pathway is more complex than initially expected and suggests that there may be cell type–specific input gradients throughout the three‐dimensional hippocampal structure. In several recent studies using multiple viral tracing approaches, we describe subdivisions of the subiculum complex and ventral hippocampal CA1 that show significant back projections to CA1 and CA3 excitatory neurons. These novel connections form “noncanonical” circuits that run in the opposite direction relative to the well‐characterized feedforward pathway. Diverse subtypes of GABAergic inhibitory neurons participate within the trisynaptic pathway. In the present study, we have applied monosynaptic retrograde viral tracing to examine noncanonical synaptic inputs from CA1 and subicular complex to the inhibitory neuron in hippocampal CA3. We quantitatively mapped synaptic inputs to CA3 inhibitory neurons to understand how they are connected within and beyond the hippocampus formation. Major brain regions that provide typical inputs to CA3 inhibitory neurons include the medial septum, the dentate gyrus, the entorhinal cortex, and CA3. Noncanonical inputs from ventral CA1 and subicular complex to CA3 inhibitory neurons follow a proximodistal topographic gradient with regard to CA3 subregions. We find novel noncanonical circuit connections between inhibitory CA3 neurons and ventral CA1, subiculum complex, and other brain regions. These results provide a new anatomical connectivity basis to further study the function of CA3 inhibitory neurons.
Influence of needle design and irrigation depth in the presence of vapor lock: A computational fluid dynamics analysis in human oval roots with apical ramification
Authors: Loroño G. , Zaldívar J. M. R. , Arias A. , Dorado S. , Jimenez‐Octavio J. R. 
Published: June 2023

AbstractThis paper aims to study the removal of a vapor lock located in the apical ramification of an oval distal root of a human mandibular molar, simulating different needles and irrigation depths with computational fluid dynamic. A geometric reconstruction of the micro‐CT of the molar shaped up to a WaveOne Gold Medium instrument was used. A vapor lock located in the apical 2 mm was incorporated. Geometries with positive pressure needles (side‐vented [SV], flat or front‐vented [FV] and notched [N]) and the EndoVac microcannula (MiC) were created to run the simulations. Irrigation key parameters (flow pattern, irrigant velocity, apical pressure, wall shear stress) and vapor lock removal were compared among the different simulations. Each needle behaved differently that is, FV removed the vapor lock from one ramification and had the highest apical pressure and shear stress values; SV removed the vapor lock in the main root canal but not in the ramification and reached the lowest apical pressure from the positive pressure needles; N was not able to completely remove the vapor lock and showed low apical pressure and shear stress; MiC removed the vapor lock from one ramification, had negative apical pressure and the lowest maximum shear stress. The main conclusion is that none of the needles showed complete removal of vapor lock. MiC, N, and FV were able to partially remove the vapor lock from one out of the three ramifications. However, SV needle was the only simulation that showed high shear stress with low apical pressure.
Gut microbiome influences incidence and outcomes of breast cancer by regulating levels and activity of steroid hormones in women
Authors: Chapadgaonkar Shilpa S. , Bajpai Srashti S. , Godbole Mukul S. 
Published: June 2023

AbstractBackgroundBreast cancer, the leading cancer type in women worldwide, is affected by reproductive and nonreproductive factors. Estrogen and progesterone influence the incidence and progression of breast cancer. The microbiome of the gut, a complex organ that plays a vital role in digestion and homeostasis, enhances availability of estrogen and progesterone in the host. Thus, an altered gut microbiome may influence the hormone‐induced breast cancer incidence. This review describes the current understanding of the roles of gut microbiome in influencing the incidence and progression of breast cancer, with an emphasis on the microbiome‐induced metabolism of estrogen and progesterone.Recent FindingsMicrobiome has been recognized as a promising hallmark of cancer. Next‐generation sequencing technologies have aided in rapid identification of components of the gut microbiome that are capable of metabolizing estrogen and progesterone. Moreover, studies have indicated a wider role of the gut microbiome in metabolizing chemotherapeutic and hormonal therapy agents and reducing their efficacy in patients with breast cancer, with a predominant effect in postmenopausal women.ConclusionThe gut microbiome and variations in its composition significantly alter the incidence and therapy outcomes of patients with breast cancer. Thus, a healthy and diverse microbiome is required for better response to anticancer therapies. Finally, the review emphasizes the requirement of studies to elucidate mechanisms that may aid in improving the gut microbiome composition, and hence, survival outcomes of patients with breast cancer.
Validity of steady Prandtl layer expansions
Authors: Guo Yan , Iyer Sameer 
Published: June 2023

AbstractLet the viscosity for the 2D steady Navier‐Stokes equations in the region and with no slip boundary conditions at . For , we justify the validity of the steady Prandtl layer expansion for scaled Prandtl layers, including the celebrated Blasius boundary layer. Our uniform estimates in ε are achieved through a fixed‐point scheme:
for solving the Navier‐Stokes equations, where are the tangential and normal velocities at , DNS stands for of the vorticity equation for the normal velocity v, and the compatibility ODE for at .
Pharmacokinetics and Bioequivalence of Mirogabalin Orally Disintegrating Tablets and Conventional Tablets in Healthy Japanese Participants
Authors: Toyama Kaoru , Eto Takashi , Suzuki Kanae , Shinohara Sayaka , Yoshiba Satoshi , Yoshihara Kazutaka , Ishizuka Hitoshi 
Published: June 2023

AbstractThis single‐center, randomized, open‐label, single‐dose, 2‐group, 2‐stage crossover trial evaluated the bioequivalence of 15 mg of mirogabalin as orally disintegrating tablets (ODTs) with conventional mirogabalin tablets in healthy Japanese men. The trial involved two studies: in Study 1, the ODT formulation was taken without water, and in Study 2, the ODT formulation was taken with water. The conventional tablet was taken with water in both studies. We investigated the pharmacokinetic parameters and bioequivalence of the 2 formulations, including the maximum plasma concentration and the area under the plasma concentration‐time curve up to the last quantifiable time. The plasma concentrations of mirogabalin were determined by a validated liquid chromatography with tandem mass spectrometry method. A total of 72 participants were enrolled and completed the trial. The geometric least‐squares mean ratios of maximum plasma concentration of the ODT formulation to the conventional formulation were within the prespecified bioequivalence range of 0.80–1.25 (Study 1, 0.995; Study 2, 1.009), as was the area under the plasma concentration‐time curve up to the last quantifiable time (Study 1, 1.023; Study 2, 1.035). No serious adverse events were observed. In conclusion, mirogabalin 15‐mg ODTs, either with or without water, were bioequivalent to conventional 15‐mg tablets.
Synergistically Regulating the Electronic Structure of CoS by Cation and Anion Dual‐Doping for Efficient Overall Water Splitting
Authors: Jiang Ling , Gu Mingzheng , Wang Hao , Huang Xiaomin , Gao An , Sun Ping , Liu Xudong , Zhang Xiaojun 
Published: June 2023

AbstractPrecisely regulating the electronic construction of the reactive center is an essential method to improve the electrocatalysis, but achieving efficient multifunctional characteristics remains a challenge. Herein, CoS sample dual‐doped by Cu and F atoms, as bifunctional electrocatalyst, is designed and synthesized for water electrolysis. According to the experimental results, Cu atom doping can perform primary electronic adjustment and obtain bifunctional properties, and then the electronic structure is adjusted for the second time to achieve an optimal state by introducing F atom. Meanwhile, this dual‐doping strategy will result in lattice distortion and expose more active sites. As expected, dual‐doped Cu−F−CoS show the brilliant electrocatalytic activity, revealing ultralow overpotentials (59 mV for HER, 213 mV for OER) at 10 mA cm−2 in alkaline electrolyte. Besides, it also exhibits distinguished water electrolysis activity with cell voltage as low as 1.52 V at 10 mA cm−2. Our work can provide an atomic‐level perception for adjusting the electronic construction of reactive sites by means of dual‐doping engineering and put forward a contributing path for the electrocatalysts with multifunctional designing.
PD1hi CD200hi CD4+ exhausted T cell increase immunotherapy resistance and tumour progression by promoting epithelial–mesenchymal transition in bladder cancer
Authors: Wu Chun , Duan Lianhui , Li Hongmu , Liu Xuefei , Cai Taonong , Yang Yang , Yin Yuting , Chang Wuguang , Zhong Leqi , Zhang Lin , Cheng Yixin , Qin Haide , Wen Zhesheng , Wang Huiyun , Mai Shijuan 
Published: June 2023

AbstractBackgroundBladder cancer (BLCA) is one of the most diagnosed cancers in humans worldwide. Recently, immunotherapy has become a main treatment option for BC. However, most BLCA patients do not respond to immune checkpoint inhibitors or relapse after immunotherapy. Therefore, it is very important to identify novel biomarkers for the prediction of immunotherapy response in B patients.MethodsPancancer single‐cell RNA sequencing (scRNA‐seq) data were used to identify the clusters of CD4+ T cells in the tumour microenvironment (TME). The clinical significance of key CD4+ T‐cell clusters was evaluated based on the survival data of two independent immunotherapy bladder cancer (BLCA) cohorts. We also investigated the function of key clusters of CD4+ T cell in the TME of BC cells in vitro.ResultsThis study identified two novel exhausted CD4+ T‐cell subpopulations with the expression of PD1hi CD200hi or PD1hi CD200low in BC patients. Moreover, BLCA patients with a high level of PD1hi CD200hi CD4+ exhausted T cell showed immunotherapy resistance. Cell function analysis demonstrated that PD1hi CD200hi CD4+ exhausted T cell can promote epithelial–mesenchymal transition (EMT) and angiogenesis in BLCA cells. In addition, PD1hi CD200hi CD4+ exhausted T cells were shown to communicate with malignant BLCA cells through the GAS6–AXL axis. Finally, we also found that GAS6 expression is upregulated in B cells by METTL3‐mediated m6A modification.ConclusionsPD1hi CD200hi CD4+ exhausted T cell may serve as a novel biomarker for poor prognosis and immunotherapy resistance in B. Targeted inhibitors of PD1hi CD200hi CD4+ exhausted T cells may help improve the efficacy of immunotherapy.
Toward freshwater plant diversity surveys with eDNA barcoding and metabarcoding
Authors: Espinosa Prieto Armando , Beisel Jean‐Nicolas , Verschuren Pieternel , Hardion Laurent 
Published: June 2023

AbstractProviding reliable, cost‐effective data on species distribution is critical to ensuring biodiversity conservation. However, many species may go unrecorded by conventional surveys, especially in aquatic environments. Environmental DNA (eDNA) barcoding and metabarcoding are alternative approaches that could complete biodiversity estimates based on species observations. While eDNA surveys are being standardized for some animal groups (e.g., fish and amphibians), research on eDNA approaches for freshwater plant communities is just starting to bear fruit. Here, we synthesized the 22 studies that used eDNA barcoding and metabarcoding to survey plant biodiversity in freshwater systems. We present evidence that contemporary aquatic plants (macrophytes) and terrestrial plants can be detected in water and surficial sediment eDNA from lakes and rivers. The phenology (e.g., senescence) of the target taxa strongly influences species detection. The main application of eDNA barcoding targets the monitoring of invasive macrophytes, and barcoding assays are available for 14 taxa. The metabarcoding approach shows a range of applications: the detection of rare macrophytes, catchment‐scale floristic inventories, and sediment fingerprinting. Barcodes on the plastid genome (cpDNA) are preferred for both approaches: matK and trnH‐psbA for barcoding, trnL, and rbcL for metabarcoding. The intergenic transcribed spacer 1 (ITS1) from the nuclear ribosomal DNA (nrDNA) was used for designing eDNA barcoding assays on five invasive macrophytes. In contrast, only three metabarcoding studies used the ITS1 or IST2 with newly designed primers. However, metabarcoding applications should routinely use a multi‐locus approach, combining cpDNA and nrDNA barcodes. Barcode combinations and existing primers need further testing on eDNA samples. We recommend using local barcode reference databases (BRDs), ideally self‐made, to circumvent taxonomic gaps and heterogeneous sequences in public BRDs. Finally, new technologies and developments like droplet digital PCR and hybridisation capture offer new perspectives for eDNA‐based biodiversity monitoring approaches.
Forging C−S Bonds on the Azetidine Ring by Continuous Flow Photochemical Addition of Thiols and Disulfides to Azetines
Authors: Colella Marco , Gelato Yuri , Andresini Michael , Graziano Elena , Vilé Gianvito , Degennaro Leonardo , Luisi Renzo 
Published: June 2023

AbstractA strategy for anti‐Markovnikov hydroalkyl/aryl thiolation and disulfidation of 2‐azetines under continuous flow conditions has been developed. Thiyl radicals are generated from thiols or disulfides and subsequently propagate into the azetine unsaturation to forge the C−S bond and shape a secondary radical intermediate. This carbon‐centered radical chain transfers to another thiol via hydrogen atom transfer (HAT) or another disulfide to regenerate the key thiyl radical intermediates. The use of flow technology ensures efficient irradiation of the reaction mixture leading to extremely fast, robust, and scalable protocols. Furthermore, ethyl acetate was adopted as an environmentally responsible solvent.
Aza‐Michael Reaction: A Decade Later – Is the Research Over?
Authors: Yu. Rulev Alexander 
Published: June 2023

AbstractThe 1,4‐conjugated addition of nitrogen centered nucleophiles to electron‐deficient alkenes, historically called the aza‐Michael addition, is one of the most significant and widely used reactions in modern synthetic organic chemistry. In the last decade, great progress has been made in this field namely in the development of various catalytic systems. Fundamental advances involve the use of transition metal catalysts, organocatalysts, enzymes, ionic liquids, Brønsted and Lewis acids and bases. This Review aims to critically analyze the results of research into the reactions of aliphatic and aromatic amines with Michael acceptors.
Transition‐Metal‐Catalyzed Direct Substitution of Alcohols in Aqueous Media
Authors: Ma Xiantao , Yan Xiaoyu , Yu Jing 
Published: June 2023

AbstractThe direct use of alcohols as the much greener and more sustainable alkylated reagents in substitution reactions is one of the emerging areas in green chemisty. However, owing to the poor leaving character of OH group, the direct substitution of alcohols is not an easy thing. Transition metal (TM) catalysis such as Pd‐catalyzed allylic/benzyl substitution and Ir‐catalyzed borrowing hydrogen provides efficient protocols for the direct substitution of alcohols, however, an organic solvent and servely anhydrous conditions are generally required. In recent decade, TM‐catalyzed direct substitution of alcohols in aqueous media was developed as a much greener alternative. In this review, the recent develpoments of this area are summarized. The activation mechanism of alcohols in aqueous reactions are emphatically discussed.
QoS‐aware web service recommendation via exploring the users' personalized diversity preferences
Authors: Kang Guosheng , Liang Bowen , Ding Linghang , Liu Jianxun , Cao Buqing , Kang Yun 
Published: June 2023

AbstractWith the popularity and wide adoption of SOA (service‐oriented architecture), a massive amount of Web services emerge on the Internet. It is difficult for users to find the desired services from a large number of services. Thus, service recommendation becomes an effective means to improve the efficiency of using service. Considering that the users' QoS (quality of service) preferences are often unknown or uncertain, the recent QoS‐aware service recommendation methods recommend QoS‐diversified services for users to increase the probability of fulfillment of the service list with a limited number of services on users' potential QoS preferences. However, the existing QoS‐diversified service recommendation methods recommend services with a uniform diversity degree for different users, while the diversified preference requirements are not considered. To this end, this article proposes a service diversity adjustment algorithm, which selects more diversified services outside of the original service recommendation list to replace the services in the present recommendation list to approximate the QoS diversity preference of the active user. In this way, the probability of meeting the user's potential QoS preference requirements is improved. Comprehensive experimental results show that the proposed approach can not only provide personalized and diversified services but also ensure the overall accuracy of the recommendation results.
The effect of propolis extract as a valuable natural additive on the quality characteristics of toast bread
Authors: Hosseini Khabbazi Saba , Mansouripour Samar , Saremnezhad Solmaz 
Published: June 2023

AbstractThis study aimed to evaluate the effect of ethanolic propolis extract (EPE) as a natural antimicrobial and antioxidant agent on the physicochemical, microbial, and sensory characteristics of toast bread, as well as phenol content and antioxidant activity. In this regard, 0.1, 0.3, and 0.5% of EPE were used in the bread doughs and the quality characteristics of the breads were assessed. The bread with 0.5% EPE showed the highest phenolic content (24.02 mgGAE/g.d.m) and antioxidant activity (59.03%). These amounts were 12.96 mgGAE/g and 16.45% higher than those of the control (without EPE), respectively (p < .05). The hardness, fracturability, and chewiness of the bread samples were influenced by the levels of EPE on the third and fifth days of storage. EPE decreased the L* and a* of bread samples, but an increasing trend was observed in the b*, chroma, and browning index by elevating the levels of propolis. Propolis extract showed an inhibitory effect on mold growth in samples. The bread with 0.5% of EPE had the lowest mold count after 5 days of storage which was not significant compared to the first day. There was no significant difference in sensory evaluation between the overall acceptance of bread samples. Therefore, EPE has the potential to be used as a natural additive with antimicrobial and antioxidant characteristics in toast bread.