bluuebunny/crossref_metadata_2025 huggingface dataset:
Welfare Reform and the Health Insurance Coverage of Women and Children
Authors: Cawley John H , Schroeder Mathis , Simon Kosali Ilayperu
Published: April 2006

There is tremendous interest in understanding the effects of welfare reform enacted by the Personal Responsibility and Work Opportunity Reconciliation Act of 1996. Our interest lies in one possible consequence of welfare reform: the loss of health insurance.This paper advances the literature by utilizing the 1992-1996 panels of the Survey of Income and Program Participation, matching type of insurance coverage to the presence of waivers from AFDC or TANF implementation in each state in specific months. We utilize a difference in differences method. Specifically, we estimate the difference before and after welfare reform in the insurance coverage of women and children who were likely to be eligible for welfare compared to those who were likely to be ineligible for welfare.We find that AFDC waivers prior to 1996 and the implementation of TANF after 1996 raised the probability that welfare-eligible women lack health insurance coverage. Specifically, TANF implementation is associated with a 7.8 percent increase in the probability that a welfare-eligible woman was uninsured. Welfare reform had less of an impact on the health insurance coverage of children. We find no evidence that AFDC waivers increased the probability that welfare-eligible children were uninsured. However, TANF implementation was associated with a 2.8 percent increase in the probability that a welfare-eligible child lacked health insurance.
Assessing the Impacts of the Prescription Drug User Fee Acts (PDUFA) on the FDA Approval Process
Authors: Berndt Ernst R. , Gottschalk Adrian H. B. , Philipson Tomas , Strobeck Matthew W.
Published: April 2006

Congress enacted and renewed the Prescription Drug User Fee Acts (PDUFA) in 1992, and renewed it in 1997 and 2002, mandating FDA performance goals in reviewing and acting on drug applications within specified time periods. In turn, the FDA was permitted to levy user fees on drug sponsors submitting applications to the FDA. While PDUFA mandated action or review times, its ultimate impacts on actual final drug approval times are unknown. We model and quantify the impact of PDUFA-I and II on drug approval times, since these approval dates are the ones most directly related to new medicines becoming available to benefit patients.In assessing the impacts of PDUFA on drug approval times, it is noteworthy that approval times were trending downwards at 1.7% percent per year prior to implementation of PDUFA. Assuming continuation of that time trend, approval times post-PDUFA would have fallen even in the absence of PDUFA. Our principal finding is that PDUFA accelerated this downward trend so that instead of a counterfactual 6% reduction in approval times from 24.2 to 20.4 months in absence of these acts between 1991 and 2002, there was an observed decline of about 42%, from 24.2 to 14.2 months, following implementation of PDUFA. Thus, of the total observed decline in approval times between 1991 and 2002, approximately two-thirds can be attributed to PDUFA. However, much of this impact occurred in the initial years between 1992 and 1997 (PDUFA-I) rather than during the subsequent 1997-2002 time frame (PDUFA-II). We discuss implications of these findings and how future research might quantify the social value of the observed acceleration in the FDA drug approvals.
The Technology of Birth: Is It Worth It?
Authors: Cutler David M. , Meara Ellen
Published: April 2006

We evaluate the costs and benefits of increased medical spending for low-birthweight infants. Lifetime spending on low-birthweight babies increased by roughly $40,000 per birth between 1950 and 1990. The health improvements resulting from this have been substantial. Infant mortality rates fell by 72 percent over this time period, largely due to improved care for premature births. Considering both length and quality of life, we estimate the rate of return for care of low-birthweight infants at over 500 percent. Although prenatal care and influenza shots are more cost-effective than neonatal care, it is significantly more cost-effective than other recent innovations, such as coronary artery bypass surgery, treatment of severe hypertension, or routine Pap smears for women aged 20 to 74. We conclude that the answer to the question posed in this paper is a resounding yes.
How Costly Are Smokers to Other People? Longitudinal Evidence on the Near Elderly
Authors: Picone Gabriel , Sloan Frank
Published: April 2006

Many studies have estimated the cost of smoking. In recent years, such estimates have been widely used in litigation against the tobacco companies. Both longitudinal and cross-sectional methods have been used. On balance, the longitudinal approach, the one used in this study, is much preferable since one can account for the effects of smoking on the pool of eligibles rather than just conditioning expenditures on being eligible. We used data from four waves of the Health and Retirement Study to assess the impact of smoking on use of hospital and physicians services and nursing home care. The analysis was limited to utilization among persons aged 51 to 67 (near elderly ). During this phase of the life cycle, many adverse effects of smoking, measured in terms of mortality and morbidity,
The Health Care Consequences of Smoking and Its Regulation
Authors: Moore Michael J. , Hughes James W.
Published: April 2006

The literature on the health economics of smoking presents two principal facts: (1) that smoking increases health care costs and (2) that restrictions on smoking lead to reductions in smoking prevalence and intensity. Some researchers have hypothesized that these two facts, in combination, allow the inference that restricting smoking will lower health care costs. For various reasons, however, observed associations between smoking and health care use on the one hand, and regulations and smoking on the other, do not imply a causal effect of the restrictions on health care.This article extends the literature by examining whether cigarette tax increases lead to lower health care costs. Using data from the 1991 and 1993 National Health Interview Surveys, it fi
CMS Payments Necessary to Support HMO Participation in Medicare Managed Care
Authors: Cawley John , Chernew Michael , McLaughlin Catherine
Published: April 2006

In recent years, many health maintenance organizations (HMOs)have exited the market for Medicare managed care; since 1998, the number of participating plans has fallen from 346 to 174. As a result of this reduced participation by HMOs, hundreds of thousands of Medicare beneficiaries have been involuntarily disenrolled from the program at the end of each year from 1998 to 2001.This paper estimates the Centers for Medicare and Medicaid Services (CMS) capitation payments that are necessary to support the participation of various numbers of HMOs in Medicare managed care per county market. This paper does not make a normative statement about how many HMOs should be supported in this program; rather, it makes a positive statement about the levels of payment necessary to support various numbers of HMOs.The identification strategy is to observe how the number of participating HMOs varies over counties and time in response to CMS payment, while controlling for estimated costs. This paper studies the period 1993-2001 and focuses in particular on the variation in payment, independent of costs, that occurred as a result of the Balanced Budget Act of 1997, which dramatically changed the way that HMOs are paid in this program. In light of the fact that it may not be cost-effective for CMS to support HMO participation in relatively rural or unpopulated counties, the sample used in this paper is limited to the 60 percent of U.S. counties with the largest populations of Medicare beneficiaries.The ordered probit results presented in this paper indicate that, to support one Medicare HMO in 2001 in half of the counties in the sample, CMS would have to pay $682.08 per average enrollee per month in the marginal county. To support one Medicare HMO in 2001 in every county in the sample, CMS would need to pay $1,008.25 per enrollee per month in the maximum-payment county. For comparison, the maximum monthly payment paid by CMS to any county in 2001 was $833.55.This paper finds that 79.3 percent of counties in the sample received a CMS payment in 2001 that was less than what was necessary to support a single HMO in Medicare managed care. Compared to those counties that received a payment exceeding the estimated threshold for HMO participation, these counties are, on average, more rural and less populated, with citizens who are less wealthy and less educated. The relative disadvantage of rural and unpopulated counties persists three years after the Balanced Budget Act of 1997, designed in part to eliminate such disparities, took effect.
Hospital Ownership Conversions: Defining the Appropriate Public Oversight Role
Authors: Sloan Frank A.
Published: April 2006

This paper reviews recent empirical evidence on the effects of hospital ownership conversions on quality of care and provision of public goods, such as uncompensated care, and presents new results on these topics based on hospital discharge data from the Healthcare Cost and Utilization Projects (HCUP) Nationwide Inpatient Sample. My analysis of these data reveals that conversion from government or private nonprofit to for-profit ownership has no effect on in-hospital mortality, but rates of pneumonia complications increased following conversion to for-profit status. Other research, discussed in the paper, found increased mortality rates following discharge from the hospital for patients admitted to hospitals that had converted to for-profit ownership. There was no effect of such conversions on the propensity to admit uninsured or Medicaid patients. Clearly, there is considerable heterogeneity in outcomes attributable to conversions. Overall, the evidence suggests a role for public scrutiny of hospital ownership conversions.
Plant-Based Diets and Risk of Hip Fracture in Postmenopausal Women
Authors: Sotos-Prieto Mercedes , Rodriguez-Artalejo Fernando , Fung Teresa T. , Meyer Haakon E. , Hu Frank B. , Willett Walter C. , Bhupathiraju Shilpa N.
Published: February 2024

Importance

Previous research has found that vegetarian diets are associated with lower bone mineral density and higher risk of fractures, but these studies did not differentiate the quality of the plant-based foods.

Objective

To examine the association between the quality of plant-based diets (not necessarily vegan but also omnivorous) and hip fracture risk among postmenopausal women in the Nurses’ Health Study.

Design, Setting, and Participants

This cohort study analyzed data from 70 285 postmenopausal women who participated in the US Nurses’ Health Study from 1984 through 2014. Data were analyzed from January 1 to July 31, 2023.

Main outcomes and Measures

Hip fractures were self-reported on biennial questionnaires. Diet was assessed every 4 years using a validated semiquantitative food frequency questionnaire. Plant-based diet quality was assessed using 2 previously established indices: the healthful Plant-Based Diet Index (hPDI), for which healthy plant foods (whole grains, fruits, vegetables, nuts, legumes, vegetable oils, and tea or coffee) received positive scores, whereas less healthy plant foods (fruit juices, sweetened beverages, refined grains, potatoes, and sweets or desserts) and animal foods received reversed scores; and the unhealthful Plant-Based Diet Index (uPDI), for which positive scores were given to less healthy plant foods and reversed scores to healthy plant and animal foods. Quintile scores of 18 food groups were summed, with a theoretical range for both indices of 18 to 90 (highest adherence). Cox proportional hazards regression with time-varying covariates was used to compute hazard ratios (HRs) and 95% CIs for hip fracture.

Results

In total, 70 285 participants (mean [SD] age, 54.92 [4.48] years; 100% White women) were included, and 2038 cases of hip fracture were ascertained during the study and for up to 30 years of follow-up. Neither the hPDI (HR for highest vs lowest quintile, 0.97 [95% CI, 0.83-1.14]) nor the uPDI (HR for highest vs lowest quintile, 1.02 [95% CI, 0.87-1.20]) for long-term diet adherence was associated with hip fracture risk. However, when examining recent intake for the highest vs lowest quintiles, the hPDI was associated with 21% lower risk of hip fracture (HR, 0.79 [95% CI, 0.68-0.92]; P = .02 for trend), and the uPDI was associated with 28% higher risk (1.28 [95% CI, 1.09-1.51]; P = .008 for trend).

Conclusions and Relevance

Findings of this cohort study indicated that long-term adherence to healthful or unhealthful plant-based diets as assessed by hPDI and uPDI scores was not associated with hip fracture risk. Future research should clarify whether the associations observed with recent dietary intake are due to short-term effects of these dietary patterns, reverse causality, or both.
ATXN7-Related Cone-Rod Dystrophy
Authors: Nassisi Marco , Coarelli Giulia , Blanchard Benoit , Dubec-Fleury Charlotte , Drine Karima , Kitic Nicolas , Sancho Serge , Hilab Rania , Tezenas du Montcel Sophie , Junge Candice , Lane Roger , Arnold H. Moore , Durr Alexandra , Audo Isabelle
Published: February 2024

Importance

Reliable biomarkers with diagnostic and prognostic values are needed for upcoming gene therapy trials for spinocerebellar ataxias.

Objective

To identify ophthalmological biomarkers in a sample of spinocerebellar ataxia type 7 (SCA7) carriers.

Design, Setting, and Participants

This article presents baseline data from a cross-sectional natural history study conducted in Paris, France, reference centers for rare diseases from May 2020 to April 2021. Data were analyzed from September to December 2022. Fifteen adult ATXN7 pathogenic expansion carriers (9 with preataxia and 6 with ataxia) were included, all with a Scale for the Assessment and Rating of Ataxia (SARA) score of 15 of 40 or lower. Patients were recruited at the Paris Brain Institute, and all contacted patients accepted to participate in the study.

Main Outcomes and Measures

Three visits (baseline, 6 months, and 12 months) were planned, including neurological examination (SARA and Composite Cerebellar Functional Severity Score), ophthalmological examination (best-corrected visual acuity, microperimetry, full-field electroretinogram, optical coherence tomography, and fundus autofluorescence imaging), and neurofilament light chain (NfL) measurements. Here we report the baseline ophthalmic data from the cohort and determine whether there is a correlation between disease scores and ophthalmic results.

Results

Among the 15 included SCA7 carriers (median [range] age, 38 [18-60] years; 8 women and 7 men), 12 displayed cone or cone-rod dystrophy, with the number of CAG repeats correlating with disease severity (ρ, 0.73, 95% CI, 0.34 to 0.90; P < .001). Two patients with cone-rod dystrophy exhibited higher repeat numbers and greater ataxia scores (median [range] SARA score, 9 [7-15]) compared to those with only cone dystrophy (median [range] SARA score, 2 [0-5]). A correlation emerged for outer nuclear layer thickness with SARA score (ρ, −0.88; 95% CI, −0.96 to −0.59; P < .001) and NfL levels (ρ, −0.87; 95% CI, −0.86 to 0.96; P < .001). Moreover, ataxia severity was correlated with visual acuity (ρ: 0.89; 95% CI, 0.68 to 0.96; P < .001) and retinal sensitivity (ρ, −0.88; 95% CI, −0.96 to 0.59; P < .001).

Conclusions and Relevance

In this cross-sectional study, retinal abnormalities were found at preataxic stages of the disease. Most of the carriers presented with cone dystrophy and preserved rod function. The outer nuclear layer thickness correlated with SARA score and plasma NfL levels suggesting nuclear layer thickness to be a biomarker of disease severity. These findings contribute to understanding the dynamics of SCA7-related retinal dystrophy and may help lay the groundwork for future therapeutic intervention monitoring and clinical trials.

Trial Registration

ClinicalTrials.gov Identifier: NCT04288128
Stem End Rot Infection of Avocado (
Persea
Americana
)
Authors: Fostvedt Jessica E. , Dicks Lynn , Wagstaff Carol
Published: February 2024

Stem end rot (SER) is the name given to a post‐harvest rot disorder that manifests as internal browning and degradation of the tissues inside the fruit of avocado. It has commercial significance, causing up to 30% of a grower's yield to be negated. Symptom development is often only apparent when the fruit are opened by the consumer, resulting in complaints to the retailer, and consequent lost revenue along the supply chain. The disorder is proposed to be the consequence of infection by a number of pathogens including,
Colletotrichum
,
Botryosphaeria
, and
Fusarium
species and is exacerbated by orchard location, management, and environmental conditions. The exact mechanism and timing of infection is not clear although there is evidence for infection at flowering, during fruit development, and at harvest. An understanding of the infection routes of pathogens causing SER could guide effective mitigation strategies and this article explores how greater mechanistic insight into the route of infection of causative pathogens might be determined. Improvements that could be made to orchard management and at harvest/post‐harvest handling of the fruit to reduce SER development are also discussed.
Exploring the Impact of TLR‐2 Signaling on miRNA Dysregulation in Intervertebral Disc Degeneration
Authors: Cazzanelli Petra , Lamoca Mikkael , Hausmann Oliver Nic , Mesfin Addisu , Puvanesarajah Varun , Hitzl Wolfgang , Haglund Lisbet , Wuertz‐Kozak Karin
Published: February 2024

Toll‐like receptors (TLRs) are key mediators of inflammation in intervertebral disc (IVD) degeneration. TLR‐2 activation contributes to the degenerative process by increasing the expression of extracellular matrix‐degrading enzymes, pro‐inflammatory cytokines, and neurotrophins. As potent post‐transcriptional regulators, microRNAs can modulate intracellular mechanisms, and their dysregulation is known to contribute to numerous pathologies. This study aims to investigate the impact of TLR‐2 signaling on miRNA dysregulation in the context of IVD degeneration. Small‐RNA sequencing of degenerated IVD cells shows the dysregulation of ten miRNAs following TLR‐2 activation by PAM2CSK4. The miR‐155‐5p is most significantly upregulated in degenerated and non‐degenerated annulus fibrosus and nucleus pulposus cells. Sequence‐based target and pathway prediction shows the involvement of miR‐155‐5p in inflammation‐ and cell fate‐related pathways and TLR‐2‐induced miR‐155‐5p expression leads to the downregulation of its target c‐FOS. Furthermore, changes specific to the activation of TLR‐2 through fragmented fibronectin are seen in miR‐484 and miR‐487. Lastly, miR‐100‐3p, miR‐320b, and miR‐181a‐3p expression exhibit degeneration‐dependent changes. These results show that TLR‐2 signaling leads to the dysregulation of miRNAs in IVD cells as well as their possible downstream effects on inflammation and degeneration. The identified miRNAs provide important opportunities as potential therapeutic targets for IVD degeneration and low back pain.
Biomimetic and Durably Superhydrophobic Nanofibrous Membranes for High‐Performance Waterproof and Breathable Textiles
Authors: Gong Xiaobao , Ji Yu , Liu Xiaoyan , Yu Jianyong , Zhang Shichao , Ding Bin
Published: February 2024

Man‐made superhydrophobic membranes are of interest for various applications in energy, environment, and medical fields. However, simultaneously achieving durable superhydrophobicity, robust waterproofness, and high breathability of the membranes is still challenging. Herein, an efficient and powerful strategy is reported to create superhydrophobic membranes with perdurable liquid repellency and robust breathability via combining humidity‐induced electrospinning with coat‐crosslinking technology. The micro/nano rough structure is in situ constructed based on manipulating the phase separation of electrospun jets; meanwhile, the waterborne acrylic resins are bridged to the surface of nanofiber to endow the membranes with stable low surface energy via coating and crosslinking treatment. Eventually, the resultant membranes present superhydrophobicity with a water contact angle of ≈154°, good self‐cleaning and anti‐icing properties, robust waterproofness of 83.4 kPa, and high breathability of 3.71 kg m−2 d−1. More interestingly, the nanomaterials can maintain durable superhydrophobicity even after exposure to various severe conditions. The successful creation of high‐performance superhydrophobic membranes opens a new avenue for synthesizing advanced functional materials for application in a variety of fields.
Gradient‐Tuned VO4 Vacancies in BiVO4 Photoanode for Boosting Bulk Hole Transport and Oxygen Evolution Reaction Performance
Authors: Pei Hao , Peng Lingling , Jiang Zhuo , Zhang Yuexing , Li Renjie , Peng Tianyou
Published: February 2024

Although bismuth vanadate (BiVO4) photoanode has been widely used, the solar‐driven oxygen evolution reaction (OER) performance is constrained due to the substantial bulk recombination and poor mobility of charge carriers. Herein, a facile solvothermal post‐treatment approach that employs N,N‐dimethylformamide (DMF) is developed to induce a VO4 vacancy gradient from bulk to surface of BiVO4 film, which not only improves the charge diffusion but also establishes an advantageous upward band gradient to promote the bulk hole transport. Under Air Mass 1.5 Global (AM1.5G) simulated solar illumination, the optimized BiVO4 photoanode with a VO4 vacancy gradient (denoted as B(VO)1‐δ) exhibits excellent OER performance with a charge separation efficiency of 74.4% at 1.23 V versus reversible hydrogen electrode (RHE) and incident‐photon‐to‐current conversion efficiency of 30.7% at 445 nm, 1.2 and 1.4 times higher than that of the pristine BiVO4, respectively. After loading nickel‐iron hydroxyl oxide (NiFeOOH) as a cocatalyst, the photocurrent density of B(VO)1‐δ escalates to 5.92 mA cm−2 in a hole scavenger (Na2SO3) solution and 5.07 mA cm−2 in a potassium borate buffer solution at 1.23 V versus RHE, far superior to the pristine BiVO4. This work highlights that the gradient‐tuned VO4 vacancies can effectively modulate the bulk band structure and charge transfer in BiVO4 photoanode, providing a new strategy for boosting solar water splitting performance.
Flat‐Knit, Flexible, Textile Metasurfaces
Authors: Carter Michael J. , Resneck Leah , Ra'di Younes , Yu Nanfang
Published: February 2024

Lightweight, low‐cost metasurfaces and reflectarrays that are easy to stow and deploy are desirable for many terrestrial and space‐based communications and sensing applications. This work demonstrates a lightweight, flexible metasurface platform based on flat‐knit textiles operating in the cm‐wave spectral range. By using a colorwork knitting approach called float‐jacquard knitting to directly integrate an array of resonant metallic antennas into a textile, two textile reflectarray devices, a metasurface lens (metalens), and a vortex‐beam generator are realized. Operating as a receiving antenna, the metalens focuses a collimated normal‐incidence beam to a diffraction‐limited, off‐broadside focal spot. Operating as a transmitting antenna, the metalens converts the divergent emission from a horn antenna into a collimated beam with peak measured directivity, gain, and efficiency of 21.30, 15.30, and −6.00 dB (25.12%), respectively. The vortex‐beam generating metasurface produces a focused vortex beam with a topological charge of m = 1 over a wide frequency range of 4.1–5.8 GHz. Strong specular reflection is observed for the textile reflectarrays, caused by wavy yarn floats on the backside of the float‐jacquard textiles. This work demonstrates a novel approach for the scalable production of flexible metasurfaces by leveraging commercially available yarns and well‐established knitting machinery and techniques.
Reduction of 5‐Hydroxymethylfurfural to 2,5‐Bis(hydroxymethyl)Furan at High Current Density using a Ga‐Doped AgCu:Cationomer Hybrid Electrocatalyst
Authors: Tian Cong , Yu Jiaqi , Zhou Daojin , Ze Huajie , Liu Hengzhou , Chen Yuanjun , Xia Rong , Ou Pengfei , Ni Weiyan , Xie Ke , Sargent Edward H.
Published: February 2024

Hydrogenation of biomass‐derived chemicals is of interest for the production of biofuels and valorized chemicals. Thermochemical processes for biomass reduction typically employ hydrogen as the reductant at elevated temperatures and pressures. Here, the authors investigate the direct electrified reduction of 5‐hydroxymethylfurfural (HMF) to a precursor to bio‐polymers, 2,5‐bis(hydroxymethyl)furan (BHMF). Noting a limited current density in prior reports of this transformation, a hybrid catalyst consisting of ternary metal nanodendrites mixed with a cationic ionomer, the latter purposed to increase local pH and facilitate surface proton diffusion, is investigated. This approach, when implemented using Ga‐doped Ag‐Cu electrocatalysts designed for p–d orbital hybridization, steered selectivity to BHMF, achieving a faradaic efficiency (FE) of 58% at 100 mA cm−2 and a production rate of 1 mmol cm−2 h−1, the latter a doubling in rate compared to the best prior reports.
BF3 ⋅ OEt2 and Visible Light‐Controlled [3,3]‐ or [1,3]‐Rearrangement of Quinazolinone N−O Aryl Moieties
Authors: Nie Shu‐Min , Cheng Lu‐Min , Chen Chun‐Hua , Liang Cui , Pan Cheng‐Xue , Mo Dong‐Liang
Published: February 2024

We described a base‐promoted O‐arylation of N3‐hydroxyl quinazolinones with diaryliodonium salts and sequential BF3 ⋅ OEt2 and visible light‐controlled [3,3]‐ or [1,3]‐rearrangements of quinazolinone N−O aryl moieties to prepare a variety of 2‐(quinazolin‐4‐yloxy)phenols and atropisomeric 3‐(2‐hydroxyphenyl)quinazolin‐4‐ones in 44%‐75% yields and 28%‐70% yields, respectively. Mechanistic studies showed that HBF4 generated in situ from BF3 ⋅ Et2O and water served as the catalyst in this process and aryloxyquinazolinium salts are vital intermediates promoting the [3,3]‐ or [1,3]‐rearrangements. The N−O aryl moieties of aryloxyquinazolinium salts were found to undergo solely [3,3]‐rearrangement with heating whereas [1,3]‐rearrangement occurred via a radical process under irradiation of visible light. This method highlights the formation of aryloxyquinazolinium salts based on the use of BF3 ⋅ OEt2 and visible light to prompt [1,3]‐rearrangement generating atropisomeric quinazolinones.
Cleaving DNA with DNA: Cooperative Tuning of Structure and Reactivity Driven by Copper Ions
Authors: Dantu Sarath Chandra , Khalil Mahdi , Bria Marc , Saint‐Pierre Christine , Orio Maylis , Gasparutto Didier , Sicoli Giuseppe
Published: February 2024

A copper‐dependent self‐cleaving DNA (DNAzyme or deoyxyribozyme) previously isolated by in vitro selection has been analyzed by a combination of Molecular Dynamics (MD) simulations and advanced Electron Paramagnetic Resonance (Electron Spin Resonance) EPR/ESR spectroscopy, providing insights on the structural and mechanistic features of the cleavage reaction. The modeled 46‐nucleotide deoxyribozyme in MD simulations forms duplex and triplex sub‐structures that flank a highly conserved catalytic core. The DNA self‐cleaving construct can also form a bimolecular complex that has a distinct substrate and enzyme domains. The highly dynamic structure combined with an oxidative site‐specific cleavage of the substrate are two key‐aspects to elucidate. By combining EPR/ESR spectroscopy with selectively isotopically labeled nucleotides it has been possible to overcome the major drawback related to the “metal‐soup” scenario, also known as “super‐stoichiometric” ratios of cofactors versus substrate, conventionally required for the DNA cleavage reaction within those nucleic acids‐based enzymes. The focus on the endogenous paramagnetic center (Cu2+) here described paves the way for analysis on mixtures where several different cofactors are involved. Furthermore, the insertion of cleavage reaction within more complex architectures is now a realistic perspective towards the applicability of EPR/ESR spectroscopic studies.
2D Graphene Oxide Membrane Nanoreactors for Rapid Directional Flow Ring‐Opening Reactions with Dominant Same‐Configuration Products
Authors: Fu Jiangwei , Pang Shuai , Zhang Yuhui , Li Xiang , Song Bo , Peng Daoling , Zhang Xiqi , Jiang Lei
Published: February 2024

Nanoconfinement within enzymes can increase reaction rate and improve selectivity under mild conditions. However, it remains a great challenge to achieve chemical reactions imitating enzymes with directional molecular motion, short reaction time, ≈100% conversion, and chiral conversion in artificial nanoconfined systems. Here, directional flow ring‐opening reactions of styrene oxide and alcohols are demonstrated with ≈100% conversion in <120 s at 22 °C using graphene oxide membrane nanoreactors. Dominant products have the same configuration as chiral styrene oxide in confined reactions, which is dramatically opposed to bulk reactions. The unique chiral conversion mechanism is caused by spatial confinement, limiting the inversion of benzylic chiral carbon. Moreover, the enantiomeric excess of same‐configuration products increased with higher alkyl charge in confined reactions. This work provides a new route to achieve rapid flow ring‐opening reactions with specific chiral conversion within 2D nanoconfined channels, and insights into the impact of nanoconfinement on ring‐opening reaction mechanisms.
Ink‐Extrusion 3D Printing and Silicide Coating of HfNbTaTiZr Refractory High‐Entropy Alloy for Extreme Temperature Applications
Authors: Zhang Dingchang , Hsu Ya‐Chu , Dunand David C.
Published: February 2024

An oxygen‐resistant refractory high‐entropy alloy is synthesized in microlattice or bulk form by 3D ink‐extrusion printing, interdiffusion, and silicide coating. Additive manufacturing of equiatomic HfNbTaTiZr is implemented by extruding inks containing hydride powders, de‐binding under H2, and sintering under vacuum. The sequential decomposition of hydride powders (HfH2+NbH+TaH0.5+TiH2+ZrH2) is followed by in situ X‐ray diffraction. Upon sintering at 1400 °C for 18 h, a nearly fully densified, equiatomic HfNbTaTiZr alloy is synthesized; on slow cooling, both α‐HCP and β‐BCC phases are formed, but on quenching, a metastable single β‐BCC phase is obtained. Printed and sintered HfNbTaTiZr alloys with ≈1 wt.% O shows excellent mechanical properties at high temperatures. Oxidation resistance is achieved by silicide coating via pack cementation. A small‐size lattice‐core sandwich is fabricated and tested with high‐temperature flames to demonstrate the versatility of this sequential approach (printing, sintering, and siliconizing) for high‐temperature, high‐stress applications of refractory high‐entropy alloys.
Novel Biomimetic “Spider Web” Robust, Super‐Contractile Liquid Crystal Elastomer Active Yarn Soft Actuator
Authors: Wu Dingsheng , Li Xin , Zhang Yuxin , Cheng Xinyue , Long Zhiwen , Ren Lingyun , Xia Xin , Wang Qingqing , Li Jie , Lv Pengfei , Feng Quan , Wei Qufu
Published: February 2024

In nature, spider web is an interwoven network with high stability and elasticity from silk threads secreted by spider. Inspired by the structure of spider webs, light‐driven liquid crystal elastomer (LCE) active yarn is designed with super‐contractile and robust weavability. Herein, a novel biomimetic gold nanorods (AuNRs) @LCE yarn soft actuator with hierarchical structure is fabricated by a facile electrospinning and subsequent photocrosslinking strategies. Meanwhile, the inherent mechanism and actuation performances of the as‐prepared yarn actuator with interleaving network are systematically analyzed. Results demonstrate that thanks to the unique “like‐spider webs” structure between fibers, high molecular orientation within the LCE microfibers and good flexibility, they can generate super actuation strain (≈81%) and stable actuation performances. Importantly, benefit from the robust covalent bonding at the organic–inorganic interface, photopolymerizable AuNRs molecules are uniformly introduced into the polymer backbone of electrospun LCE yarn to achieve tailorable shape‐morphing under different light intensity stimulation. As a proof‐of‐concept illustration, light‐driven artificial muscles, micro swimmers, and hemostatic bandages are successfully constructed. The research disclosed herein can offer new insights into continuous production and development of LCE‐derived yarn actuator that are of paramount significance for many applications from smart fabrics to flexible wearable devices.
Upgrading Cycling Stability and Capability of Hybrid Na‐CO2 Batteries via Tailoring Reaction Environment for Efficient Conversion CO2 to HCOOH
Authors: Yang Xiecheng , Zhang Dantong , Zhao Lanqing , Peng Chao , Ren Kun , Xu Changfan , Liu Pan , Zhou Yingjie , Lei Yong , Yang Bin , Xue Dongfeng , Liang Feng
Published: February 2024

Rechargeable Na‐CO2 batteries are considered to be an effective way to address the energy crisis and greenhouse effect due to their dual functions of CO2 fixation/utilization and energy storage. However, the insolubility and irreversibility of solid discharge products lead to poor discharge capacity and poor cycle performance. Herein, a novel strategy is proposed to enhance the electrochemical performance of hybrid Na‐CO2 batteries, using water‐in‐salt electrolyte (WiSE) to establish an optimal reaction environment, regulate the CO2 reduction pathway, and ultimately convert the discharge product of the battery from Na2CO3 to formic acid (HCOOH). This strategy effectively resolves the issue of poor reversibility, allowing the battery to exhibit excellent cycle performance (over 1200 cycles at 30 °C), especially under low‐temperature conditions (2534 cycles at −20 °C). Furthermore, density functional theory (DFT) calculations and experiments indicate that by adjusting the relative concentration of H/O atoms at the electrolyte/catalyst interface, the CO2 reduction pathway in the battery can be regulated, thus effectively enhancing CO2 capture capability and consequently achieving an ultra‐high discharge specific capacity of 148.1 mAh cm−2. This work effectively promotes the practical application of hybrid Na‐CO2 batteries and shall provide a guidance for converting CO2 into products with high‐value‐added chemicals.
Synthesis of Trifluoromethyl‐Containing 2,3‐Dihydrobenzofurans via a Formal [4+1] Annulation of In‐situ Generated o‐Quinone Methides and CF3−Imidoyl Sulfoxonium Ylides
Authors: Sun Yue , Ling Sihao , Chen Zhengkai
Published: February 2024

A metal‐free [4+1] annulation of in‐situ generated ortho‐quinone methides (o‐QMs) and CF3−imidoyl sulfoxonium ylides (TFISYs) has been achieved under mild conditions, which provides a facile and straightforward access to a variety of trifluoromethyl‐containing 2,3‐dihydrobenzofurans in moderate to excellent yields.
Redesigned Nylon 6 Variants with Enhanced Recyclability, Ductility, and Transparency
Authors: Tian Jun‐Jie , Liu Xiaoyang , Ye Liwei , Zhang Zhen , Quinn Ethan C. , Shi Changxia , Broadbelt Linda J. , Marks Tobin J. , Chen Eugene Y.‐X.
Published: February 2024

Geminal (gem−) disubstitution in heterocyclic monomers is an effective strategy to enhance polymer chemical recyclability by lowering their ceiling temperatures. However, the effects of specific substitution patterns on the monomer's reactivity and the resulting polymer's properties are largely unexplored. Here we show that, by systematically installing gem‐dimethyl groups onto ϵ‐caprolactam (monomer of nylon 6) from the α to ϵ positions, both the redesigned lactam monomer's reactivity and the resulting gem‐nylon 6’s properties are highly sensitive to the substitution position, with the monomers ranging from non‐polymerizable to polymerizable and the gem‐nylon properties ranging from inferior to far superior to the parent nylon 6. Remarkably, the nylon 6 with the gem‐dimethyls substituted at the γ position is amorphous and optically transparent, with a higher Tg (by 30 °C), yield stress (by 1.5 MPa), ductility (by 3×), and lower depolymerization temperature (by 60 °C) than conventional nylon 6.
Calculated brightness temperatures of solar structures compared with ALMA and Metsähovi measurements
Authors: Matković Filip , Brajša Roman , Kuhar Matej , Benz Arnold O. , Ludwig Hans ‐G. , Selhorst Caius L. , Skokić Ivica , Sudar Davor , Hanslmeier Arnold
Published: February 2024

The Atacama Large Millimeter/submillimeter Array (ALMA) allows for solar observations in the wavelength range of 0.3–10 mm, giving us a new view of the chromosphere. The measured brightness temperature at various frequencies can be fitted with theoretical models of density and temperature versus height. We use the available ALMA and Metsähovi measurements of selected solar structures (quiet sun (QS), active regions (AR) devoid of sunspots, and coronal holes (CH)). The measured QS brightness temperature in the ALMA wavelength range agrees well with the predictions of the semiempirical Avrett–Tian–Landi–Curdt–Wülser (ATLCW) model, better than previous models such as the Avrett–Loeser (AL) or Fontenla–Avrett–Loeser model (FAL). We scaled the ATLCW model in density and temperature to fit the observations of the other structures. For ARs, the fitted models require 9%–13% higher electron densities and 9%–10% higher electron temperatures, consistent with expectations. The CH fitted models require electron densities 2%–40% lower than the QS level, while the predicted electron temperatures, although somewhat lower, do not deviate significantly from the QS model. Despite the limitations of the one‐dimensional ATLCW model, we confirm that this model and its appropriate adaptations are sufficient for describing the basic physical properties of the solar structures.
Simultaneous prediction of 16 quality attributes during protein A chromatography using machine learning based Raman spectroscopy models
Authors: Wang Jiarui , Chen Jingyi , Studts Joey , Wang Gang
Published: February 2024

Several key technologies for advancing biopharmaceutical manufacturing depend on the successful implementation of process analytical technologies that can monitor multiple product quality attributes in a continuous in‐line setting. Raman spectroscopy is an emerging technology in the biopharma industry that promises to fit this strategic need, yet its application is not widespread due to limited success for predicting a meaningful number of quality attributes. In this study, we addressed this very problem by demonstrating new capabilities for preprocessing Raman spectra using a series of Butterworth filters. The resulting increase in the number of spectral features is paired with a machine learning algorithm and laboratory automation hardware to drive the automated collection and training of a calibration model that allows for the prediction of 16 different product quality attributes in an in‐line mode. The demonstrated ability to generate these Raman‐based models for in‐process product quality monitoring is the breakthrough to increase process understanding by delivering product quality data in a continuous manner. The implementation of this multiattribute in‐line technology will create new workflows within process development, characterization, validation, and control.
Lycopodium Alkaloids from Huperzia goebelii
Authors: Gao Bei‐Bei , Jiang Shuai , Li Wen‐Yan , Ou Yu‐Fei , Zhao Qin‐Shi
Published: February 2024

One new fawcettimine‐type Lycopodium alkaloid, hupertimine F (1), together with five known (2–6) Lycopodium alkaloids were isolated from Huperzia goebelii. The structure of 1 was elucidated by 1D and 2D NMR spectra, HRESIMS, and X‐ray diffraction. Structurally, 1 represents the fourth example of Lycopodium alkaloids characterized by a 5/5/5/5/6 pentacyclic ring system with a 1‐aza‐7‐oxabicyclo[2.2.1]heptane moiety. These known compounds 2, 3, 5, and 6 were isolated from H. goebelii for the first time. Compounds 1–6 were evaluated for acetylcholinesterase, butyrylcholinesterase and monoamine oxidase B inhibitory activities in vitro.
Use of the Indigo CAT RX aspiration system during percutaneous coronary intervention
Authors: Peng Sydney , Rempakos Athanasios , Mastrodemos Olga C. , Rangan Bavana V. , Alexandrou Michaella , Allana Salman , Al‐Ogaili Ahmed , Mutlu Deniz , Karacsonyi Judit , Bergstedt Seth , Khalid Muhmmad S. , Stanberry Larissa , Brilakis Emmanouil S.
Published: February 2024

Background

The use of the Indigo CAT RX Aspiration System (Penumbra Inc.) during percutaneous coronary intervention has received limited study.

Methods

We retrospectively examined the clinical, angiographic, and procedural characteristics, outcomes, and follow‐up of patients who underwent mechanical aspiration thrombectomy with the Indigo CAT RX system (Penumbra Inc.) at a large tertiary care hospital between January 2019 and April 2023.

Results

During the study period, 83 patients (85 lesions) underwent thrombectomy with the Indigo CAT RX. Mean patient age was 64.9 ± 14.48 years and 31.2% were women. The most common presentations were ST‐segment elevation myocardial infarction (MI) (66.2%) and non‐ST‐segment elevation MI (26.5%). A final thrombolysis in MI flow grade of 3 and final myocardial blush grade of 3 were achieved in 76% and 46% of the cases, respectively. Technical success was achieved in 88.9% of the cases that included Indigo CAT RX treatment only, compared with 57.1% of the cases that also included manual aspiration. There were no device‐related serious adverse events. At 30‐day postprocedure, the incidence of major adverse cardiac events (composite of cardiovascular death, recurrent MI, cardiogenic shock, new or worsening New York Heart Association Class IV heart failure, stroke) was 8.5%: 1.3% stroke (postprocedure, in‐hospital), 1.3% MI, 6.1% cardiac death, and 7.5% developed cardiogenic shock.

Conclusions

Use of the Indigo CAT RX system is associated with high technical success and acceptable risk of complications, including stroke.
Treatment of sexual dysfunction induced by hyperprolactinemia accompanied by reduced luteinizing hormone levels: A case report
Authors: Liu Tao , Jia Chao , Li Yan
Published: February 2024

Key Clinical Message

Sexual dysfunction induced by hyperprolactinemia accompanied by reduced luteinizing hormone (LH) is common in anrology clinics. A low dose of bromocriptine is helpful for restoring penile erectile function and libido in patients.

Sexual dysfunction is closely related to hormonal disorders, of which prolactin (PRL) and luteinizing hormone (LH) disorders are common. How to treat sexual dysfunction induced by hyperprolactinemia accompanied by reduced LH levels is worth discussing. In this study, we aimed to present the case of a 35‐year‐old male patient with sexual dysfunction. The treatment process and physical and laboratory examination results were recorded. Before treatment, the PRL and LH levels in this patient were 31.27 ng/mL and 1.62 mIU/mL, respectively. The International Index of Erectile Function‐5 (IIEF‐5) score was initially 14 points. After regular treatment with low doses of bromocriptine and tadalafil, the hormonal disorder was corrected (PRL: 11.16 ng/mL and LH: 2.28 mIU/mL) and sexual function was recovered (IIEF‐5: 23 points). This case report suggested a sufficient exposure to low‐dose bromocriptine for such patients. Conversely, the exogenous supplementation of human chorionic gonadotropin may not be appropriate.
Acute gastric volvulus mimicking features of gastroenteritis in a 5‐year‐old girl
Authors: Ueshima Manami
Published: February 2024

Key Clinical Message

Acute gastric volvulus is a life‐threatening condition. Especially, a history of adjacent organ deformities in children with intermittent vomiting and abdominal pain should suggest gastric volvulus, even if the symptoms resemble gastroenteritis.
An atorvastatin‐induced positive anti‐HMGCR immune‐mediated necrotizing myopathy case
Authors: Chaisrimaneepan Nattanicha , Thongpiya Jerapas , Yingchoncharoen Pitchaporn , Saowapa Sakditad
Published: February 2024

Key Clinical Message

Statins can commonly cause myopathy. Most of the time, stopping the culprit drug should solve the problem. However, if the drug has been discontinued but muscle weakness continues to worsen, immune‐mediated myopathy should be taken into consideration.
Transition‐Metal Catalyzed C−H Alkylation Using Epoxides as Alkylating Reagents
Authors: Liu Ze‐Shui , Wang Danni , Cheng Hong‐Gang , Zhou Qianghui
Published: February 2024

The alkylation of arenes is one of the most fundamental transformations in synthetic chemistry and the transition‐metal‐catalyzed direct C−H alkylation represents a straightforward and attractive approach from both atom and step‐economy perspectives. Epoxides, the smallest three‐membered saturated O‐heterocycles that can be easily prepared in racemic or enantioenriched forms, are highly useful building blocks for the synthesis of complex organic molecules. Owing to their inherent high ring‐strain, epoxides readily undergo ring‐opening reactions and have been used as alkylating reagents for C−H alkylation catalyzed by transition metals. This review summarizes recent advances in utilizing epoxides as alkylating reagents in transition‐metal‐catalyzed C−H alkylation as well as their synthetic applications in organic synthesis.
Direct recycling of Li‐ion batteries from cell to pack level: Challenges and prospects on technology, scalability, sustainability, and economics
Authors: Roy Joseph Jegan , Phuong Do Minh , Verma Vivek , Chaudhary Richa , Carboni Michael , Meyer Daniel , Cao Bin , Srinivasan Madhavi
Published: February 2024

Direct recycling is a novel approach to overcoming the drawbacks of conventional lithium‐ion battery (LIB) recycling processes and has gained considerable attention from the academic and industrial sectors in recent years. The primary objective of directly recycling LIBs is to efficiently recover and restore the active electrode materials and other components in the solid phase while retaining electrochemical performance. This technology's advantages over traditional pyrometallurgy and hydrometallurgy are cost‐effectiveness, energy efficiency, and sustainability, and it preserves the material structure and morphology and can shorten the overall recycling path. This review extensively discusses the advancements in the direct recycling of LIBs, including battery sorting, pretreatment processes, separation of cathode and anode materials, and regeneration and quality enhancement of electrode materials. It encompasses various approaches to successfully regenerate high‐value electrode materials and streamlining the recovery process without compromising their electrochemical properties. Furthermore, we highlight key challenges in direct recycling when scaled from lab to industries in four perspectives: (1) battery design, (2) disassembling, (3) electrode delamination, and (4) commercialization and sustainability. Based on these challenges and changing market trends, a few strategies are discussed to aid direct recycling efforts, such as binders, electrolyte selection, and alternative battery designs; and recent transitions and technological advancements in the battery industry are presented.