Publications

We present photometry and spectroscopy of SN2013fs and SN2013fr in the first\n100 days post-explosion. Both objects showed transient, relatively narrow\nH$\\alpha$ emission lines characteristic of SNeIIn, but later resembled normal\nSNeII-P or SNeII-L, indicative of fleeting interaction with circumstellar\nmaterial (CSM). SN2013fs was discovered within 8hr of explosion. Its light\ncurve exhibits a plateau, with spectra revealing strong CSM interaction at\nearly times. It is a less luminous version of the transitional SNIIn PTF11iqb,\nfurther demonstrating a continuum of CSM interaction intensity between SNeII-P\nand IIn. It requires dense CSM within 6.5$\\times$10$^{14}$~cm of the\nprogenitor, from a phase of advanced pre-SN mass loss shortly before explosion.\nSpectropolarimetry of SN2013fs shows little continuum polarization, but\nnoticeable line polarization during the plateau phase. SN2013fr morphed from a\nSNIIn at early times to a SNII-L. After the first epoch its narrow lines\nprobably arose from host-galaxy emission, but the bright, narrow H$\\alpha$\nemission at early times may be intrinsic. As for SN2013fs, this would point to\na short-lived phase of strong CSM interaction if proven to be intrinsic,\nsuggesting a continuum between SNeIIn and II-L. It is a low-velocity SNII-L,\nlike SN2009kr but more luminous. SN2013fr also developed an IR excess at later\ntimes, due to warm CSM dust that require a more sustained phase of strong\npre-SN mass loss.\n

Bioinspired architectures are effective in enhancing the mechanical properties of materials, yet are difficult to construct in metallic systems. The structure-property relationships of bioinspired metallic composites also remain unclear. Here, Mg-Ti composites were fabricated by pressureless infiltrating pure Mg melt into three-dimensional (3-D) printed Ti-6Al-4V scaffolds. The result was composite materials where the constituents are continuous, mutually interpenetrated in 3-D space and exhibit specific spatial arrangements with bioinspired brick-and-mortar, Bouligand, and crossed-lamellar architectures. These architectures promote effective stress transfer, delocalize damage and arrest cracking, thereby bestowing improved strength and ductility than composites with discrete reinforcements. Additionally, they activate a series of extrinsic toughening mechanisms, including crack deflection/twist and uncracked-ligament bridging, which enable crack-tip shielding from the applied stress and lead to “Γ”-shaped rising fracture resistance R-curves. Quantitative relationships were established for the stiffness and strengths of the composites by adapting classical laminate theory to incorporate their architectural characteristics.

LLM-based judges have emerged as a scalable alternative to human evaluation and are increasingly used to assess, compare, and improve models. However, the reliability of LLM-based judges themselves is rarely scrutinized. As LLMs become more advanced, their responses grow more sophisticated, requiring stronger judges to evaluate them. Existing benchmarks primarily focus on a judge's alignment with human preferences, but often fail to account for more challenging tasks where crowdsourced human preference is a poor indicator of factual and logical correctness. To address this, we propose a novel evaluation framework to objectively evaluate LLM-based judges. Based on this framework, we propose JudgeBench, a benchmark for evaluating LLM-based judges on challenging response pairs spanning knowledge, reasoning, math, and coding. JudgeBench leverages a novel pipeline for converting existing difficult datasets into challenging response pairs with preference labels reflecting objective correctness. Our comprehensive evaluation on a collection of prompted judges, fine-tuned judges, multi-agent judges, and reward models shows that JudgeBench poses a significantly greater challenge than previous benchmarks, with many strong models (e.g., GPT-4o) performing just slightly better than random guessing. Overall, JudgeBench offers a reliable platform for assessing increasingly advanced LLM-based judges. Data and code are available at https://github.com/ScalerLab/JudgeBench.

Abstract Building chemical structures of complexity and functionality approaching the level of biological systems is an ongoing challenge. A general synthetic strategy is proposed by which progressive levels of complexity are achieved through the building block approach whereby molecularly defined constructs at one level serve as constituent units of the next level, all being linked through strong bonds—”augmented reticular chemistry”. Specifically, current knowledge of linking metal complexes and organic molecules into reticular frameworks is applied here to linking the crystals of these frameworks into supercrystals (superframeworks). This strategy allows for the molecular control exercised on the molecular regime to be translated into higher augmentation levels to produce systems capable of dynamics and complex functionality far exceeding current materials.

Terpenes constitute the largest class of natural products with over 55,000 compounds with versatile applications including drugs and biofuels. Introducing structural modifications to terpenes through metabolic engineering is an efficient and sustainable way to improve their properties. Here, we report the optimization of the lepidopteran mevalonate (LMVA) pathway towards the efficient production of isopentenyl pyrophosphate (IPP) analogs as terpene precursors. First, we linked the LMVA pathway to NudB, a promiscuous phosphatase, resulting in the production of the six-carbon analog of 3-methyl-3-buten-1-ol (isoprenol), 3-ethyl-3-buten-1-ol (C6-isoprenol). Using C6-isoprenol as the final product, we then engineered the LMVA pathway by redirecting its upstream portion from a thiolase-dependent pathway to a beta-oxidation pathway. The beta-oxidation LMVA pathway transforms valeric acid, a platform chemical that can be produced from biomass, into C6-isoprenol at a titer of 110.3 mg/L, improved from 5.5 mg/L by the thiolase LMVA pathway, which used propionic acid as a feedstock. Knockout of the E. coli endogenous thiolase genes further improved the C6-isoprenol titer to 390 mg/L, implying efficient production of homo isopentenyl pyrophosphate (HIPP). The beta-oxidation LMVA-NudB pathway also converts butanoic acid and hexanoic acid into isoprenol and isoprenol's seven-carbon analog, 3-propyl-3-buten-1-ol (C7-isoprenol), respectively, suggesting the beta-oxidation LMVA pathway produces IPP and C7-IPP from the corresponding fatty acids. Fuel property tests revealed the longer chain isoprenol analogs have lower water solubilities, similar or higher energy densities, and comparable research octane number (RON) boosting effects to isopentenols. This work not only optimizes the LMVA pathway, setting the basis for homoterpene biosynthesis to expand terpene chemical space, but provides an efficient pathway to produce isoprenol analogs as next-generation biofuels from sustainable feedstocks.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

New methods for preparation of tailor-made fluorine-containing compounds are in extremely high demand in nearly every sector of chemical industry. The asymmetric construction of quaternary C-F stereogenic centers is the most synthetically challenging and, consequently, the least developed area of research. As a reflection of this apparent methodological deficit, pharmaceutical drugs featuring C-F stereogenic centers constitute less than 1% of all fluorine-containing medicines currently on the market or in clinical development. Here we provide a comprehensive review of current research activity in this area, including such general directions as asymmetric electrophilic fluorination via organocatalytic and transition-metal catalyzed reactions, asymmetric elaboration of fluorine-containing substrates via alkylations, Mannich, Michael, and aldol additions, cross-coupling reactions, and biocatalytic approaches.

Intermolecular additions of the O-H bonds of phenols and alcohols and the N-H bonds of sulfonamides and benzamide to olefins catalyzed by 1 mol % of triflic acid and studies to define the relationship between these reactions and those catalyzed by metal triflates are reported. Cyclization of an alcohol containing pendant monosubstituted and trisubstituted olefins catalyzed by either triflic acid or metal triflates form products from addition to the more substituted olefin, and additions of tosylamide catalyzed by triflic acid or metal triflates form indistinguishable ratios of the two N-alkyl sulfonamides.

The utilization of oxide frameworks as intercalation cathodes for non-aqueous Ca-ion batteries potentially unlocks a new energy storage system that delivers high energy density. However, the slow kinetics of Ca<sup>2+</sup> in oxide electrodes strongly handicaps their activity and reversibility at room temperature. Here, nanocrystals of layered MnO<sub>x</sub> containing a high concentration of atomic defects and lattice water are shown to have remarkable electrochemical activity towards Ca<sup>2+</sup>, amounting to a capacity of ~130 mAh/g at room temperature. Multimodal characterization revealed the notable degree of intercalation by probing the structural, compositional and redox changes undertaken by the defective MnO<sub>x</sub> nanocrystals. The results suggest that the existence of atomic defects and lattice water played a role in improving Ca<sup>2+</sup> diffusivity in the oxide. These outcomes reaffirm the prospects for functional Ca-ion batteries using oxide cathodes under moderate conditions.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Supplementary Figure 3 from Chemotherapy-Induced Genotoxic Stress Promotes Sensitivity to Natural Killer Cell Cytotoxicity by Enabling Missing-Self Recognition

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Checkpoint blockade immunotherapy targeting the PD-1/PD-L1 inhibitory axis has produced remarkable results in the treatment of several types of cancer. Whereas cytotoxic T cells are known to provide important antitumor effects during checkpoint blockade, certain cancers with low MHC expression are responsive to therapy, suggesting that other immune cell types may also play a role. Here, we employed several mouse models of cancer to investigate the effect of PD-1/PD-L1 blockade on NK cells, a population of cytotoxic innate lymphocytes that also mediate antitumor immunity. We discovered that PD-1 and PD-L1 blockade elicited a strong NK cell response that was indispensable for the full therapeutic effect of immunotherapy. PD-1 was expressed on NK cells within transplantable, spontaneous, and genetically induced mouse tumor models, and PD-L1 expression in cancer cells resulted in reduced NK cell responses and generation of more aggressive tumors in vivo. PD-1 expression was more abundant on NK cells with an activated and more responsive phenotype and did not mark NK cells with an exhausted phenotype. These results demonstrate the importance of the PD-1/PD-L1 axis in inhibiting NK cell responses in vivo and reveal that NK cells, in addition to T cells, mediate the effect of PD-1/PD-L1 blockade immunotherapy.