Man versus machine: Automatic pedicle screw planning using registration-based techniques compared with manual screw planning for thoracolumbar fusion surgeries.

OBJECTIVE: This study evaluates the precision of a commercially available spine planning software in automatic spine labelling and screw-trajectory proposal. METHODS: The software uses automatic segmentation and registration of the vertebra to generate screw proposals. 877 trajectories were compared. Four neurosurgeons assessed suggested trajectories, performed corrections, and manually planned pedicle screws. Additionally, automatic identification/labelling was evaluated. RESULTS: Automatic labelling was correct in 89% of the cases. 92.9% of automatically planned trajectories were in accordance with G&R grade A + B. Automatic mode reduced the time spent planning screw trajectories by 7 s per screw to 20 s per vertebra. Manual mode yielded differences in screw-length between surgeons (largest distribution peak: 5 mm), automatic in contrast at 0 mm. The size of suggested pedicle screws was significantly smaller (largest peaks in difference between 0.5 and 3 mm) than the surgeon's choice. CONCLUSION: Automatic identification of vertebrae works in most cases and suggested pedicle screw trajectories are acceptable. So far, it does not substitute for an experienced surgeon's assessment.

New Insight into the Reactivity of S,S-Bis-ylide.

The present work focuses on the reactivity of S,S-bis-ylide 2, which presents a strong nucleophilic character, as evidenced by reactions with methyl iodide and CO2, affording C-methylated salts 3 and betaine 4, respectively. The derivatization of betaine 4 affords the corresponding ester derivative 6, which is fully characterized by using NMR spectroscopy and X-ray diffraction analysis. Furthermore, an original reaction with phosphenium ions leads to the formation of a transient push-pull phosphino(sulfonio)carbene 8, which rearranges to give stabilized sulfonium ylide derivative 7.

Inverting the Electronic Structure of Diylidylgermylenes by Backbone Modification.

Owing to the strong electron-donating ability of ylide substituents, diylidyltetrylenes are usually highly nucleophilic species with strong donor capacities. Here, we demonstrate that their electronic properties are in fact highly flexible and can be effectively tuned through variation of the substituent in the ylide backbone. Initial density functional theory studies showed that cyano groups are particularly capable in lowering the LUMO energy of diylidyl germylenes thus turning these usually highly nucleophilic species into electrophilic compounds. This was confirmed by experimental studies. Attempts to synthesize the germylene (YCN )2 Ge [with YCN =Ph3 P-(C)-CN] from the corresponding metalated ylide YCN K selectively led to germanide [(YCN )3 Ge)K]2 thus reflecting the electrophilic nature of the intermediate formed germylene. XRD analysis of single crystals of (YCN )2 Ge - serendipitously obtained through protonative cleavage of one ylide from the germanide - revealed a monomeric structure with rather long Ge-ylide linkages, which corroborates well with a pure single bond and no stabilization of the empty pπ orbital at germanium through π bonding. The germanide exhibits methanide-like reactivity towards chalcogens but a likewise weak Ge-C bond as demonstrated by the insertion of carbon dioxide.

Thiophosphinoyl-Tethered Ylide-Substituted Heavier Carbenes: Synthesis, Structures and Stabilities.

The synthesis and structure analysis of a series of mono and diylide-substituted tetrylenes of type YEX and Y2 E (E=Ge, Sn, Pb; X=Cl or Br) using a thiophosphinoyl-tethered metallated ylide (Y=Ph2 P(S)-C-P(pip)Ph2 with pip=piperidyl) is reported, amongst the first ylide-substituted plumbylenes. The tetrylenes feature distinct trends in the spectroscopic and structural properties of the ylide ligand with increasing atomic number of the tetrel element. For instance, an increasingly high-field shifted signal for the thiophosphinoyl group is observed in the 31 P{1 H} NMR spectrum as a consequence of the increasing polarity of the element-carbon bond, which likewise results in a shortening of the ylidic C-P bond in the solid-state structure. The diylidyltetrylenes are unstable towards transylidation forming the mono(ylide)tetrylenes when treated with the tetrel dihalides according to the stability trend: Y2 Pb

Health benefits of astaxanthin against age-related diseases of multiple organs: A comprehensive review.

Age-related diseases are associated with increased morbidity in the past few decades and the cost associated with the treatment of these age-related diseases exerts a substantial impact on social and health care expenditure. Anti-aging strategies aim to mitigate, delay and reverse aging-associated diseases, thereby improving quality of life and reducing the burden of age-related pathologies. The natural dietary antioxidant supplementation offers substantial pharmacological and therapeutic effects against various disease conditions. Astaxanthin is one such natural carotenoid with superior antioxidant activity than other carotenoids, as well as well as vitamins C and E, and additionally, it is known to exhibit a plethora of pharmacological effects. The present review summarizes the protective molecular mechanisms of actions of astaxanthin on age-related diseases of multiple organs such as Neurodegenerative diseases [Alzheimer's disease (AD), Parkinson's disease (PD), Stroke, Multiple Sclerosis (MS), Amyotrophic lateral sclerosis (ALS), and Status Epilepticus (SE)], Bone Related Diseases [Osteoarthritis (OA) and Osteoporosis], Cancers [Colon cancer, Prostate cancer, Breast cancer, and Lung Cancer], Cardiovascular disorders [Hypertension, Atherosclerosis and Myocardial infarction (MI)], Diabetes associated complications [Diabetic nephropathy (DN), Diabetic neuropathy, and Diabetic retinopathy (DR)], Eye disorders [Age related macular degeneration (AMD), Dry eye disease (DED), Cataract and Uveitis], Gastric Disorders [Gastritis, Colitis, and Functional dyspepsia], Kidney Disorders [Nephrolithiasis, Renal fibrosis, Renal Ischemia reperfusion (RIR), Acute kidney injury (AKI), and hyperuricemia], Liver Diseases [Nonalcoholic fatty liver disease (NAFLD), Alcoholic Liver Disease (AFLD), Liver fibrosis, and Hepatic Ischemia-Reperfusion (IR) Injury], Pulmonary Disorders [Pulmonary Fibrosis, Acute Lung injury (ALI), and Chronic obstructive pulmonary disease (COPD)], Muscle disorders (skeletal muscle atrophy), Skin diseases [Atopic dermatitis (ATD), Skin Photoaging, and Wound healing]. We have also briefly discussed astaxanthin's protective effects on reproductive health.

Psychological well-being and coping strategies among secondary school teachers: A cross-sectional study.

INTRODUCTION: Educators, academicians, and teachers are responsible for the development of the nation's human capital. Teacher coping methods are becoming more widely recognized as a key factor in determining teacher effectiveness. The aim of this study was to identify the various coping strategies adopted by high school teachers in Southern India. MATERIALS AND METHODS: A cross-sectional study was conducted in government, aided, and unaided schools of Udupi, a coastal district in Southern India. A self-administered questionnaire was used to collect the data from 460 high school teachers chosen based on convenience sampling. The coping strategies were identified using a modified version of Brief COPE(Coping Orientation to Problems Experienced) Inventory (Carver, 1997). Data were entered using SPSS version 15 and descriptive statistics was performed. RESULTS: The study found that teachers had moderate level of coping skills in all domains. The most popular coping techniques used by secondary school teachers were positive reframing, active coping, and planning; nevertheless, substance use was recognized as the least popular coping strategy. CONCLUSION: Positive reframing, active coping, and preparation were the most commonly used coping strategies by the teachers in the survey. Teachers are a vital resource who have received less attention than they deserve for their psychological well-being. A customized intervention program based on their perceived needs could be a good place to start.

Diverse Reactivity of Hypersilylsilylene with Boranes and Three-Component Reactions with Aldehyde and HBpin.

The recently reported hypersilylsilylene PhC(NtBu)2SiSi(SiMe3)3 (1) reacts with BH3, 9-BBN, and PhBCl2 to yield the respective Lewis acid base adducts 2-4, respectively. Compound 4 undergoes isomerization to form a ring expansion product 5. The same silylene was found to initially form an adduct with HBpin (6) and subsequently isomerized to 7 via the rupture of the B-H bond of HBpin (7), where the hydride was bound to the carbon atom of the amidinate ligand and the Bpin unit was attached to the silicon center. Surprisingly, the reaction of 1 with HBcat results in PhC(NtBu)2Bcat (8). Subsequently, we have shown that HBcat forms the same product when it reacts with related silylene PhC(NtBu)2SiN(SiMe3)3 (1'). With all of these reactions in hand, we ponder if silylene can activate two small molecules at one time. In this work, we delineate the three-component reactions of silylenes 1 and 1' with 4-fluorobenzaldehyde and HBpin, which afforded unusual coupling products, 9 and 10, respectively. Note that 9 and 10 were prepared from the cleavage of the B-H and C═O bonds by silylene in a single reaction and are the first structurally attested Si-C-O-B coupled products.

Access to diverse germylenes and a six-membered dialane with a flexible ß-diketiminate.

A nacnac-based tridentate ligand containing a picolyl group (L) was employed to isolate chlorogermylene (1). The reaction of 1 with another equivalent of GeCl2·dioxane surprisingly gave pyridylpyrrolide-based chlorogermylene (2) via C-N bond cleavage and C-C coupling, while with AlCl3, it afforded a transmetalated product, 4. The reaction of L with AlH3·NMe2Et led to an unusual cyclohexane type six-membered dialane heterocycle (5).

Phosphorus-ylides: powerful substituents for the stabilization of reactive main group compounds.

Phosphorus ylides are 1,2-dipolar compounds with a negative charge on the carbon atom. This charge is stabilized by the neighbouring onium moiety, but can also be shifted towards other substituents thus making ylides strong π donor ligands and hence ideal substituents to stabilize reactive compounds such as cations and low-valent main group species. Furthermore, the donor strength and the steric properties can easily be tuned to meet different requirements for stabilizing reactive compounds and for tailoring the properties and reactivities of the main group element. Although the use of ylide substituents in main group chemistry is still in its infancy, the first examples of isolated compounds impressively demonstrate the potential of these ligands. This review summarizes the most important discoveries also in comparison to other substituents, thus outlining avenues for future research directions.

Synthesis and Reactivity of a Hypersilylsilylene.

Stabilization of an amidinatosilylene with a bulky tris(trimethylsilyl)silyl substituent was realized with the preparation of PhC(NtBu)2Si{Si(SiMe3)3} (1) from PhC(NtBu)2SiHCl2 with K{Si(SiMe3)3} in more than 90% yield. The highly deshielded 29Si NMR resonance (δ = 76.91 ppm) can be attributed to the absence of a π-donating substituent. The molecular structure of 1 shows a trigonal-planar geometry around the SiII center with a SiII-SiIV bond length of 2.4339(13) Å. A series of reactions of 1 with Me3NO, S, Se, and Te were performed. While siloxane derivatives (2 and 3) are obtained from reactions with Me3NO, silachalcogenones (4-6) are formed with other chalcogens. The presence of Si═E (E = S, Se, and Te) bonds in 4-6 have been confirmed by single-crystal X-ray studies. Silaoxirane (7) formation was observed when 1 was treated with acetone, demonstrating the importance of the tris(trimethylsilyl)silyl group to kinetically and thermodynamically protect the silaoxirane derivative with less bulky substituents on the C atom.

Silylene induced cooperative B-H bond activation and unprecedented aldehyde C-H bond splitting with amidinate ring expansion.

The addition of HBpin to PhC(NtBu)2SiN(SiMe3)2 (1) results in the cleavage of the B-H bond in a cooperative fashion across the Si and amidinate-C sites. The reaction of 1 with benzaldehyde led to C-H bond activation with amidinate ring expansion leading to a five-membered heterocycle. In case of 4-fluorobenzaldehyde, a C-C bond coupling takes place leading to a dioxasilolane derivative as the major product.

Transition of Children with Perinatally Acquired HIV-Infection into Adulthood: Social Outcome and Quality of Life.

OBJECTIVES: In India, access to free anti-retroviral therapy has improved the survival of perinatally human immunodeficiency virus (HIV) infected children resulting in the transition of many such children to adulthood. This study aims to understand the social-outcomes and quality of life (QOL) among these adults. METHODS: This cross-sectional study was conducted in two tertiary HIV care centers in south India. Perinatally HIV-infected adults aged >18 y were enrolled after obtaining consent. Data were collected by questionnaire based interviews for social outcomes and WHO Quality of Life-BREF (WHOQOL-BREF) for QOL. The social-outcome indicators monitored pertained to family support, educational qualification and occupational, economic, and marital status. RESULTS: The mean age of 107 participants was 18·9 ± 1·1y. The school drop-out rate was 58%. Sixty-two percent were double orphans. Forty-three-percent of the participants were employed with mean per-capita monthly income of Rs.4105 ± 2979 ($65·2 ± 47·3). Fourteen-percent of the participants were married, or in a relationship, and a majority of them, 93%, were females. For QOL, the mean raw score was highest for social relationship (15·79). Relative to studying subjects, a higher proportion of school dropouts scored poorly in social relationship (42% vs.14·8%; Chi-square = 5·28; p = 0·02) and environmental QOL (46% vs.19·6%;Chi-square = 8·09; p = 0·004). The proportion of subjects with a poor physical health QOL was higher among those with a per-capita monthly income above the national average than those with below the national average (69% vs.33·3%; Chi-square = 5·27; p = 0·02). CONCLUSIONS: Though clinico-immunological disease was stable in these perinatally HIV-infected young adults, their social-outcomes pertaining to education, occupation, income, and family support were poor. Factors like education, parental care, and income of the subjects were associated with poor QOL.

The impact of a private-public partnership delivery system on the HIV continuum of care in a South Indian city.

We characterized the impact of a Private-Public Partnership (PPP) on the continuum of HIV care (e.g., treatment initiation, ART effectiveness and loss to follow-up) among adults enrolled at a private hospital/ART link center in the southern state of Karnataka, India from 2007 through 2012. Data on 2326 adults in care were compiled using an electronic database supplemented with medical chart abstraction. Survival methods with staggered entries were used to analyze time to ART initiation and loss to follow-up as well as associated factors. Mixed effects linear regression models were used to assess ART effectiveness. The mean age of adults in care was 36 years; 40% were male. The majority were married, had less than primary education, and less than 45 US dollars (3000 Indian Rupee) monthly income. The mean CD4 at presentation was 527 cells/mm3. The median time from ART eligibility to initiation was 5 and 2 months for before and after the PPP, respectively (p < 0.001). Becoming eligible after PPP was associated with more rapid treatment initiation (Hazard Ratio: [95% Confidence Interval] 1.49 [1.11, 1.99]). Moreover, among the 1639 persons lost to follow-up, more rapid loss was observed before the PPP (12.77 months) vs. after (13.37 months) (p = 0.25) and there was a significant interaction between ART status and calendar time before and after the PPP (p < 0.001). Being on treatment was associated with a lower likelihood of becoming lost before the PPP (HR: [95% CI] 0.33 [0.27, 0.42]), but this association was reversed after the PPP (HR: [95% CI] 1.77 [1.54, 2.04]), p-value for interaction <0.001. Treatment response measured by CD4 was comparable before and after the PPP (p = 0.088). Our findings suggest that PPP models of ART delivery may improve HIV treatment initiation and loss to follow-up without compromising the effectiveness of treatment. Efforts to expand these system-level interventions should be considered with on-going evaluation.

C(sp3)-F, C(sp2)-F and C(sp3)-H bond activation at silicon(ii) centers.

Silylene [PhC(NtBu)2SiN(SiMe3)2] (1) cleaves the C(sp3)-H and C-F bonds of acetophenone and 1,1,1-trifluoroacetophenone, respectively, under mild conditions. The reaction is initiated via a nucleophilic attack from the oxygen to the silicon atom followed by C-F/H bond cleavage. The scope of C-F bond activation has further been extended with C6F6 and C6F5CF3.

Metal free mild and selective aldehyde cyanosilylation by a neutral penta-coordinate silicon compound.

This study demonstrates the preparation and structural characterization of a Si(iv) hydride (PhC(NtBu)2SiH(CH3)Cl) (1) and its use as a catalyst for the cyanosilylation of a variety of aldehydes. Compound 1 represents the first neutral penta-coordinate silicon(iv) species that catalyzes cyanosilylation of aldehydes under mild conditions.

Combinatorial Labeling Method for Improving Peptide Fragmentation in Mass Spectrometry.

Annotation of peptide sequence from tandem mass spectra constitutes the central step of mass spectrometry-based proteomics. Peptide mass spectra are obtained upon gas-phase fragmentation. Identification of the protein from a set of experimental peptide spectral matches is usually referred as protein inference. Occurrence and intensity of these fragment ions in the MS/MS spectra are dependent on many factors such as amino acid composition, peptide basicity, activation mode, protease, etc. Particularly, chemical derivatizations of peptides were known to alter their fragmentation. In this study, the influence of acetylation, guanidinylation, and their combination on peptide fragmentation was assessed initially on a lipase (LipA) from Bacillus subtilis followed by a bovine six protein mix digest. The dual modification resulted in improved fragment ion occurrence and intensity changes, and this resulted in the equivalent representation of b- and y-type fragment ions in an ion trap MS/MS spectrum. The improved representation has allowed us to accurately annotate the peptide sequences de novo. Dual labeling has significantly reduced the false positive protein identifications in standard bovine six peptide digest. Our study suggests that the combinatorial labeling of peptides is a useful method to validate protein identifications for high confidence protein inference. Graphical Abstract ᅟ.

Facile access to a Ge(ii) dication stabilized by isocyanides.

Herein, we introduce isocyanide as a ligand in main group chemistry and describe the facile isolation of a Ge(ii) dication. The reaction of 2,6-dimethylphenylisocyanide with GeCl2 leads to the formation of a Ge(ii) dication with two [GeCl3](-) molecules as counter anions. The dicationic Ge(ii) center is bound to four isocyanide ligands and also holds a lone pair of electrons. DFT calculations reveal that the dication is stabilized only by σ-donation from the four isocyanide ligands. Natural population analysis gives a charge of +0.74 on the Ge(ii) center, indicating that the positive charge is shared by the isocyanide substituents.

Crystal structure of 5-benzoyl-2,4-di-phenyl-4,5-di-hydro-furan-3-carbo-nitrile.

In the title compound, C24H17NO2, the carbonyl O atom of the benzoyl group is cis with respect to the furanyl O atom, and the associated O-C-C-O torsion angle is 4.62 (19)°. The puckering of the dihydro-furan ring is close to twisted ((4) T 5), with parameters Q = 0.1856 (16) Šand φ = 313.5 (5)°. Mol-ecules are inter-connected via a C-H⋯N and a C-H⋯O hydrogen bond, leading to layers parallel to the (200) plane and characterized by R 4 (4)(28) and R 4 (4)(36) graph-set motifs. The furan O atom does not participate in inter-molecular hydrogen bonding. The crystal lattice encompasses a solvent-accessible void of 24.7 (8) Å(3).

Cations and dications of heavier group 14 elements in low oxidation states.

Cations and dications of heavier group 14 elements in their low oxidation state have received widespread attention in recent years. The journey started with the isolation of a series of cations of the composition [(C5Me5)E:](+) [E = Si-Pb], followed by the more recent isolation of a Ge(ii) dication encapsulated within a cryptand, a carbodiphosphorane stabilized [GeCl](+) monocation with a two coordinate Ge atom, Si(ii) cations and dications stabilized by N-heterocyclic carbenes (NHCs), which highlights the ongoing growth and interest in the chemistry of tetrel(ii) cations. This is presumably because the central atom (E) in these compounds contains two or three unoccupied valence orbitals as well as holds a lone pair of electrons. Such an electronic description represents ambiphilicity, which is of great interest for catalysis. The successful synthesis of divalent group 14 cations requires new synthetic strategies based on the sterically demanding neutral or monoanionic ligands, utilization of counter anions, and solvents with low nucleophilicity in order to minimize the degree of interactions with the cations. An alternative approach for the realization of divalent cations of group 14 elements is their coordination to the transition metals. This synthetic approach was successfully applied for the isolation of a range of transition metal coordinated divalent cations of group 14 elements. Apart from arousing academic interest some of these cations have found application as activators in the Ziegler-Natta polymerization of alkenes.

Crystal structure of [4-(2-meth-oxy-phen-yl)-3-methyl-1-phenyl-6-tri-fluoro-methyl-1H-pyrazolo-[3,4-b]pyridin-5-yl](thio-phen-2-yl)methanone.

The title compound, C26H18F3N3O2S, a 2-meth-oxy-substituted derivative, is closely related to its 4-methyl- and 4-chloro-substituted analogues and yet displays no structural relationships with them. The thio-phene ring is disorder free and the -CF3 group exhibits disorder, respectively, in contrast and similar to that observed in the 4-methyl- and 4-chloro-substituted derivatives. The torsion angle which defines the twist of the thio-phene ring is -69.6 (2)° (gauche) in the title compound, whereas it is anti-clinal in the 4-methyl- and 4-chloro-substituted derivatives, with respective values of 99.9 (2) and 99.3 (2)°. The absence of disorder in the thio-phene ring facilitates one of its ring C atoms to participate in the lone inter-molecular C-H⋯O hydrogen bond present in the crystal, leading to a characteristic C(5) chain graph-set motif linking mol-ecules related through glides along [010]. An intra-moleculr C-H⋯N hydrogen bond also occurs.