Metal-Free Cyanation of gem-Difluoroalkenes via Azide-Mediated C-C Double Bond Fragmentation.

Activation and cleavage of C-C double bonds are long-standing challenges in synthetic chemistry. Herein, we report an unprecedented azide-mediated C-C double bond fragmentation of gem-difluoroalkenes under mild and metal-free conditions, enabling the efficient synthesis of structurally diverse aromatic nitriles in moderate to good yields. This protocol is also amenable to the cyanation of gem-dichloro and dibromo alkenes. This reaction features simple operation and good functional group compatibility and can be implemented at a gram scale.

Characteristics and scoring method of computed tomography in open-globe injuries.

BACKGROUND: Open-globe injuries (OGIs) remain the important cause of visual impairment and loss in all ages. Computed Tomography (CT) is a useful and common tool in the evaluation of the injuries of the eyeball. Prognostic value of CT scan in OGIs has been evaluated in many studies. However, there is no published consistent systematic scoring method for CT scan in OGIs. The purpose of this study was to evaluate the CT characteristics of OGIs and build a scoring method according to the CT scans which may aid the clinicians in management of OGIs. METHODS: Retrospective chart review of inpatients with clinical diagnosis of OGIs between 2017 and 2021 at Department of Ophthalmology, Henan Eye Institute, Henan Eye Hospital, Henan provincial People's Hospital (Zhengzhou, China). RESULTS: There were 1120 eyes from 1117 patients included in our study. The mean age was 35.7 ± 21.9 years with the range from 1 to 91 years. Significant male predominance was noted (889, 79.6%). CT scans of the OGIs were evaluated. Abnormality of anterior segment, posterior segment, and globe contour and volume were graded respectively. The most serious abnormality of anterior segment, posterior segment, and globe contour and volume were grade 3, 4 and 3 respectively and score 3, 4 and 3 respectively. Score of the CT scans of an open-injured globe ranged from 0 to 10. The correlation coefficient between the score and wound length was 0.798. The correlation coefficient between the score and final visual acuity was 0.799. In 78 eyes with 0 score, 70 eyes (89.7%) gained final visual acuity of 0.3 or better. In 31 eyes with 10 score, 20 eyes (64.5%) underwent evisceration of the eye globe and 10 eyes got visual acuity of no light perception and 1 eye lost to follow-up. CONCLUSIONS: CT scans is a useful tool in evaluating the severity of an open-injured globe. Scoring of the CT scans of an open-injured globe is a meaningful attempt and it may provide useful prognostic information regarding the outcome of an open-injured globe.

Organo-cyanamides: convenient reagents for catalytic amidation of carboxylic acids.

An unprecedented DMAP-catalysed amidation of aryl and alkyl carboxylic acids with organo-cyanamides has been developed. Unlike the use of N-cyano-N-phenyl-p-methylbenzenesulfonamide (NCTS) as an electrophilic cyanating reagent, an unusual desulfonylation/decyanation reaction model has been disclosed for the first time. Remarkable features of this reaction include readily available substrates, simple operation and broad scope, enabling the efficient synthesis of structurally diverse amides. The synthetic utility of this protocol was demonstrated by the late-stage amidation of bioactive carboxylic acids and a scale-up reaction.

Porphyrin derivative-based tandem response nanochannels triggered by Zn2+ and NO.

We describe tandem response solid nanochannels tailored with a porphyrin derivative that show Zn2+ and NO gating behaviors with good selectivity, stability, and reversibility. EXAFS and fluorescence experiments showed that zinc coordinated with the porphyrin derivative as the ratio of 1 : 1 with the binding constant for 3.39 × 105 M-1. These studies are beneficial for simulating the physiological functions of ion/gas in organisms and have the potential for designing complicated logic circuits and fabricating novel biosensors.

Rhomboidal Pt(II) Metallacycle-Based Hybrid Viral Nanoparticles for Cell Imaging.

Supramolecular coordination complexes (SCCs) have emerged as anticancer agents. Tracking the movement of these metallic anticancer agents plays an important role in the field of biomedicines. Herein, we describe a method for tracking the movement of a rhomboidal Pt(II) metallacycle agent using the quantum dots encapsidation in vitro self-assembly system of viral proteins. When incubated with living Vero cells, self-assembly of hybrid viral nanoparticles were employed for simultaneous cell imaging and visual transmission of the Pt(II) metallacycle agent. Considering these results, we believe that the multifunctional biomaterials consisting of a supramolecular coordination complex and quantum dots provide a new alternative for probing of the delivery of Pt(II) metallacycle drugs.

A Randomized Noninferiority Trial of Wearing Adjustable Glasses versus Standard and Ready-made Spectacles among Chinese Schoolchildren: Wearability and Evaluation of Adjustable Refraction III.

PURPOSE: To compare wear of standard, adjustable, and ready-made glasses among children. DESIGN: Randomized, controlled, open-label, noninferiority trial. PARTICIPANTS: Students aged 11 to 16 years with presenting visual acuity (VA) ≤6/12 in both eyes, correctable to ≥6/7.5, subjective spherical equivalent refractive error (SER) ≤-1.0 diopters (D), astigmatism and anisometropia both <2.00 D, and no other ocular abnormalities. METHODS: Participants were randomly allocated (1:1:1) to standard glasses, ready-made glasses, or adjustable glasses based on self-refraction. We recorded glasses wear on twice-weekly covert evaluation by head teachers (primary outcome), self-reported and investigator-observed wear, best-corrected visual acuity (BCVA) (not prespecified), children's satisfaction, and value attributed to glasses. MAIN OUTCOME MEASURE: Proportion of glasses wear on twice-weekly covert evaluation by head teachers over 2 months. RESULTS: Among 379 eligible participants, 127 were allocated to standard glasses (mean age, 13.7 years; standard deviation [SD], 1.0 years; 54.3% were male), 125 to ready-made (mean age, 13.6; SD, 0.83; 45.6%), and 127 to adjustable (mean age, 13.4 years; SD, 0.85; 54.3%). Mean wear proportion of adjustable glasses was significantly lower than for standard glasses (45% vs. 58%; P = 0.01), although the adjusted difference (90% confidence interval [CI], -19.0% to -3.0%) did not meet the prespecified inferiority threshold of 20%. Self-reported (90.2% vs. 84.8%, P = 0.64) and investigator-observed (44.1% vs. 33.9%, P = 0.89) wear did not differ between standard and adjustable glasses, nor did satisfaction with (P = 0.97) or value attributed to study glasses (P = 0.55) or increase in quality of life (5.53 [SD, 4.47] vs. 5.68 [SD, 4.34] on a 100-point scale, P > 0.30). Best-corrected visual acuity with adjustable glasses was better (P < 0.001) than with standard glasses. Change in power of study lenses at the end of the study (adjustable: 0.65 D, 95% CI, 0.52-0.79; standard, 0.01 D; 95% CI, -0.006 to 0.03, P < 0.001) was greater for adjustable glasses, although interobserver variation in power measurements may explain this. Lens scratches and frame damage were more common with adjustable glasses, whereas lens breakage was less common than for standard glasses. CONCLUSIONS: Proportion of wear was lower with adjustable glasses, although VA was better and measures of satisfaction and quality of life were not inferior to standard glasses.

Pilot study of a novel classroom designed to prevent myopia by increasing children's exposure to outdoor light.

We sought to assess light characteristics and user acceptability of a prototype Bright Classroom (BC), designed to prevent children's myopia by exposing them to light conditions resembling the outdoors. Conditions were measured throughout the school year in the glass-constructed BC, a traditional classroom (TC) and outdoors. Teachers and children completed user questionnaires, and children rated reading comfort at different light intensities. A total of 230 children (mean age 10.2 years, 57.4% boys) and 13 teachers (36.8 years, 15.4% men) completed questionnaires. The median (Inter Quartile Range) light intensity in the BC (2,540 [1,330-4,060] lux) was greater than the TC (477 [245-738] lux, P < 0.001), though less than outdoors (19,500 [8,960-36,000] lux, P < 0.001). A prominent spectral peak at 490-560 nm was present in the BC and outdoors, but less so in the TC. Teachers and children gave higher overall ratings to the BC than TC, and light intensity in the BC in summer and on sunny days (>5,000 lux) was at the upper limit of children's comfort for reading. In summary, light intensity in the BC exceeds TC, and is at the practical upper limit for routine use. Children and teachers prefer the BC.

Self-refraction, ready-made glasses and quality of life among rural myopic Chinese children: a non-inferiority randomized trial.

PURPOSE: To study, for the first time, the effect of wearing ready-made glasses and glasses with power determined by self-refraction on children's quality of life. METHODS: This is a randomized, double-masked non-inferiority trial. Children in grades 7 and 8 (age 12-15 years) in nine Chinese secondary schools, with presenting visual acuity (VA) ≤6/12 improved with refraction to ≥6/7.5 bilaterally, refractive error ≤-1.0 D and <2.0 D of anisometropia and astigmatism bilaterally, were randomized to receive ready-made spectacles (RM) or identical-appearing spectacles with power determined by: subjective cycloplegic retinoscopy by a university optometrist (U), a rural refractionist (R) or non-cycloplegic self-refraction (SR). Main study outcome was global score on the National Eye Institute Refractive Error Quality of Life-42 (NEI-RQL-42) after 2 months of wearing study glasses, comparing other groups with the U group, adjusting for baseline score. RESULTS: Only one child (0.18%) was excluded for anisometropia or astigmatism. A total of 426 eligible subjects (mean age 14.2 years, 84.5% without glasses at baseline) were allocated to U [103 (24.2%)], RM [113 (26.5%)], R [108 (25.4%)] and SR [102 (23.9%)] groups, respectively. Baseline and endline score data were available for 398 (93.4%) of subjects. In multiple regression models adjusting for baseline score, older age (p = 0.003) and baseline spectacle wear (p = 0.016), but not study group assignment, were significantly associated with lower final score. CONCLUSION: Quality of life wearing ready-mades or glasses based on self-refraction did not differ from that with cycloplegic refraction by an experienced optometrist in this non-inferiority trial.

Safety of Spectacles for Children's Vision: A Cluster-Randomized Controlled Trial.

PURPOSE: To study safety of children's glasses in rural China, where fear that glasses harm vision is an important barrier for families and policy makers. DESIGN: Exploratory analysis from a cluster-randomized, investigator-masked, controlled trial. METHODS: Among primary schools (n = 252) in western China, children were randomized by school to 1 of 3 interventions: free glasses provided in class, vouchers for free glasses at a local facility, or glasses prescriptions only (Control group). The main outcome of this analysis is uncorrected visual acuity after 8 months, adjusted for baseline acuity. RESULTS: Among 19 934 children randomly selected for screening, 5852 myopic (spherical equivalent refractive error ≤-0.5 diopters) eyes of 3001 children (14.7%, mean age 10.5 years) had VA ≤6/12 without glasses correctable to >6/12 with glasses, and were eligible. Among these, 1903 (32.5%), 1798 (30.7%), and 2151 (36.8%) were randomized to Control, Voucher, and Free Glasses, respectively. Intention-to-treat analyses were performed on all 1831 (96.2%), 1699 (94.5%), and 2007 (93.3%) eyes of children with follow-up in Control, Voucher, and Free Glasses groups. Final visual acuity for eyes of children in the treatment groups (Free Glasses and Voucher) was significantly better than for Control children, adjusting only for baseline visual acuity (difference of 0.023 logMAR units [0.23 vision chart lines, 95% CI: 0.03, 0.43]) or for other baseline factors as well (0.025 logMAR units [0.25 lines, 95% CI 0.04, 0.45]). CONCLUSION: We found no evidence that spectacles promote decline in uncorrected vision with aging among children.

Disordered sleep and myopia risk among Chinese children.

PURPOSE: Disordered sleep and myopia are increasingly prevalent among Chinese children. Similar pathways may be involved in regulation of both sleep cycles and eye growth. We therefore sought to examine the association between disordered sleep and myopia in this group. METHODS: Urban primary school children participating in a clinical trial on myopia and outdoor activity underwent automated cycloplegic refraction with subjective refinement. Parents answered questions about children's sleep duration, sleep disorders (Children's Sleep Habits Questionnaire [CSHQ]), near work and time spent outdoors. RESULTS: Among 1970 children, 1902 (96.5%, mean [standard deviation SD] age 9.80 [0.44] years, 53.1% boys) completed refraction and questionnaires. Myopia < = -0.50 Diopters was present in both eyes of 588 (30.9%) children (1329/3804 = 34.9% of eyes) and 1129 children (59.4%) had abnormal CSHQ scores (> 41). In logistic regression models by eye, odds of myopia < = -0.50D increased with worse CSHQ score (Odds Ratio [OR] 1.01 per point, 95% Confidence Interval [CI] [1.001, 1.02], P = 0.014) and more night-time sleep (OR 1.02, 95% CI [1.01, 1.04, P = 0.002], while male sex (OR 0.82, 95% CI [0.70, 0.95], P = 0.008) and time outdoors (OR = 0.97, 95% CI [0.95, 0.99], P = 0.011) were associated with less myopia. The association between sleep duration and myopia was not significant (p = 0.199) for total (night + midday) sleep. CONCLUSIONS: Myopia and disordered sleep were both common in this cohort, but we did not find consistent evidence for an association between the two. TRIAL REGISTRATION: clinicaltrials.gov NCT00848900.

Factors influencing the output of rural cataract surgical facilities in China: the SHARP study.

PURPOSE: To identify factors associated prospectively with increased cataract surgical rate (CSR) in rural Chinese hospitals. METHODS: Annual cataract surgical output was obtained at baseline and 24 months later from operating room records at 42 rural, county-level hospitals. Total local CSR (cases/million population/y), and proportion of CSR from hospital and local competitors were calculated from government records. Hospital administrators completed questionnaires providing demographic and professional information, and annual clinic and outreach screening volume. Independent cataract surgeons provided clinical information and videotapes of cases for grading by two masked experts using the Ophthalmology Surgical Competency Assessment Rubric (OSCAR). Uncorrected vision was recorded for 10 consecutive cataract cases at each facility, and 10 randomly-identified patients completed hospital satisfaction questionnaires. Total value of international nongovernmental development organization (INGDO) investment in the previous three years and demographic information on hospital catchment areas were obtained. Main outcome was 2-year percentage change in hospital CSR. RESULTS: Among the 42 hospitals (median catchment population 530,000, median hospital CSR 643), 78.6% (33/42) were receiving INGDO support. Median change in hospital CSR (interquartile range) was 33.3% (-6.25%, 72.3%). Predictors of greater increase in CSR included higher INGDO investment (P = 0.02, simple model), reducing patient dissatisfaction (P = 0.03, simple model), and more outreach patient screening (P = 0.002, simple and multiple model). CONCLUSIONS: Outreach cataract screening was the strongest predictor of increased surgical output. Government and INGDO investment in screening may be most likely to enhance output of county hospitals, a major goal of China's Blindness Prevention Plan.

Expression patterns of TRα and CRABPII genes in Chinese cashmere goat skin during prenatal development.

BACKGROUND: The physiologic characteristics of the cashmere trait and many of the differentially expressed genes relevant to hair cycling have been extensively studied, whereas genes involved in the prenatal development of hair follicles have been poorly investigated in cashmere goats. The aim of this study, therefore, was to quantify the time-course changes in the expressions of TRα and CRABPII genes in the fetal skin of Chinese cashmere goats at the multiple embryonic days (E70, E75, E80, E90, E100, E120 and E130) using real-time quantitative PCR (RT-qPCR). RESULTS: RT-qPCR showed that TRα was expressed at E70 with relatively high level and then slightly decreased (E75, E80, and E90). The highest expression of TRα mRNA was revealed at E130 (P > 0.05). The expression pattern of CRABPII mRNA showed an 'up-down-up' trend, which revealed a significantly highest expression at E75 (P < 0.05) and was down-regulated during E80 to E120 (P < 0.05) and mildly increased at E130, subsequently. CONCLUSION: This study demonstrated that TRα and CRABPII genes expressed in different levels during prenatal development of cashmere. The present study will be helpful to provide the comprehensive understanding of TRα and CRABPII genes expressions during cashmere formation and lay the ground for further studies on their roles in regulation of cashmere growth in goats.

Effect of providing free glasses on children's educational outcomes in China: cluster randomized controlled trial.

OBJECTIVE: To assess the effect of provision of free glasses on academic performance in rural Chinese children with myopia. DESIGN: Cluster randomized, investigator masked, controlled trial. SETTING: 252 primary schools in two prefectures in western China, 2012-13. PARTICIPANTS: 3177 of 19,934 children in fourth and fifth grades (mean age 10.5 years) with visual acuity <6/12 in either eye without glasses correctable to >6/12 with glasses. 3052 (96.0%) completed the study. INTERVENTIONS: Children were randomized by school (84 schools per arm) to one of three interventions at the beginning of the school year: prescription for glasses only (control group), vouchers for free glasses at a local facility, or free glasses provided in class. MAIN OUTCOME MEASURES: Spectacle wear at endline examination and end of year score on a specially designed mathematics test, adjusted for baseline score and expressed in standard deviations. RESULTS: Among 3177 eligible children, 1036 (32.6%) were randomized to control, 988 (31.1%) to vouchers, and 1153 (36.3%) to free glasses in class. All eligible children would benefit from glasses, but only 15% wore them at baseline. At closeout glasses wear was 41% (observed) and 68% (self reported) in the free glasses group, and 26% (observed) and 37% (self reported) in the controls. Effect on test score was 0.11 SD (95% confidence interval 0.01 to 0.21) when the free glasses group was compared with the control group. The adjusted effect of providing free glasses (0.10, 0.002 to 0.19) was greater than parental education (0.03, -0.04 to 0.09) or family wealth (0.01, -0.06 to 0.08). This difference between groups was significant, but was smaller than the prespecified 0.20 SD difference that the study was powered to detect. CONCLUSIONS: The provision of free glasses to Chinese children with myopia improves children's performance on mathematics testing to a statistically significant degree, despite imperfect compliance, although the observed difference between groups was smaller than the study was originally designed to detect. Myopia is common and rarely corrected in this setting.Trial Registration Current Controlled Trials ISRCTN03252665.

N-2-Hydroxybenzaldehyde acylhydrazone-Fe(III) complex: synthesis, crystal structure and its efficient and selective N-methylation.

N-Methyl-N'-2-hydroxybenzaldehyde acylhydrazones have been chemospecifically synthesized in good yield by N-methylation of the Fe(iii) complexes of N-2-hydroxybenzaldehyde acylhydrazones with methyl iodide in tetrahydrofuran. The reaction proceeds with the exclusive formation of the N-methyl derivative without any concurrent O-methylation side reactions. In addition, the N-methylation reaction occurred simultaneously with a complete deprotection step (elimination of the metal ion). As a result, the N-methyl product was obtained in excellent purity without time-consuming chromatographic workup. A free N-2-hydroxybenzaldehyde acylhydrazone ligand could not be methylated under the same conditions.

Spectacle design preferences among Chinese primary and secondary students and their parents: a qualitative and quantitative study.

PURPOSE: To identify the specific characteristics making glasses designs, particularly those compatible with adjustable glasses, more or less appealing to Chinese children and their parents. PATIENTS AND METHODS: Primary and secondary school children from urban and rural China with < = -1.00 diopters of bilateral myopia and their parents ranked four conventional-style frames identified by local optical shops as popular versus four child-specific frames compatible with adjustable spectacles. Scores based on the proportion of maximum possible ranking were computed for each style. Selected children and their parents also participated in Focus Groups (FGs) discussing spectacle design preference. Recordings were transcribed and coded by two independents reviewers using NVivo software. RESULTS: Among 136 urban primary school children (age range 9-11 years), 290 rural secondary school children (11-17 years) and 16 parents, all adjustable-style frames (scores on 0-100 scale 25.7-62.4) were ranked behind all conventional frames (63.0-87.5). For eight FGs including 12 primary children, 26 secondary children and 16 parents, average kappa values for NVivo coding were 0.81 (students) and 0.70 (parents). All groups agreed that the key changes to make adjustable designs more attractive were altering the round lenses to rectangular or oval shapes and adding curved earpieces for more stable wear. The thick frames of the adjustable designs were considered stylish, and children indicated they would wear them if the lens shape were modified. CONCLUSIONS: Current adjustable lens designs are unattractive to Chinese children and their parents, though this study identified specific modifications which would make them more appealing.

AN INVESTIGATION OF VISION PROBLEMS AND THE VISION CARE SYSTEM IN RURAL CHINA.

This paper examines the prevalence of vision problems and the accessibility to and quality of vision care in rural China. We obtained data from 4 sources: 1) the National Rural Vision Care Survey; 2) the Private Optometrists Survey; 3) the County Hospital Eye Care Survey; and 4) the Rural School Vision Care Survey. The data from each of the surveys were collected by the authors during 2012. Thirty-three percent of the rural population surveyed self-reported vision problems. Twenty-two percent of subjects surveyed had ever had a vision exam. Among those who self-reported having vision problems, 34% did not wear eyeglasses. Fifty-four percent of those with vision problems who had eyeglasses did not have a vision exam prior to receiving glasses. However, having a vision exam did not always guarantee access to quality vision care. Four channels of vision care service were assessed. The school vision examination program did not increase the usage rate of eyeglasses. Each county-hospital was staffed with three eye-doctors having one year of education beyond high school, serving more than 400,000 residents. Private optometrists often had low levels of education and professional certification. In conclusion, our findings shows that the vision care system in rural China is inadequate and ineffective in meeting the needs of the rural population sampled.

Accuracy of rural refractionists in western China.

PURPOSE: We assessed the prevalence and predictors of inaccurate refractive error among rural refractionists in western China. METHODS: A subset of primary school children with visual acuity (VA) ≤6/12 in ≥1 eye, undergoing subjective refinement by local refractionists after cycloplegic autorefraction in an ongoing population-based study, received repeat refraction by university optometrists for quality control. RESULTS: Among 502 children (mean age 10.5 years, 53.2% girls), independent predictors of poor (inaccurate by ≥1.0 diopter [D]) refraction by 21 rural practitioners (66.7% with high school or lower education) included hyperopia (odds ratio [OR], 4.2; 95% confidence interval [CI], 2.4-7.3, P < 0.001), astigmatism (OR = 3.8; 95% CI, 2.5-5.6; P < 0.001) and VA uncorrectable to >6/12 by the rural refractionist (OR = 4.7; 95% CI, 3.1-7.3; P = < 0.001). Among 201 children whose vision was uncorrectable in ≥1 eye by the rural refractionists, vision could be improved to >6/12 by the university optometrist in 110 (54.7%). We estimate vision could be so improved in 9.1% of all children refracted by these rural refractionists. A reason for inaccuracy in this setting is the erroneous tendency of rural refractionists to adjust instrument values for accommodation, even under cycloplegia. CONCLUSIONS: Rural refractionists in western China have little formal training and frequently fail to optimize VA among children, even when autorefractors are used. Training is needed emphasizing better use of automated refraction, particularly in children with astigmatism and hyperopia.