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(1996). The Illusion of Vulnerability: American Reassessments of the Soviet Threat, 1955–1956. The International History Review: Vol. 18, No. 3, pp. 591-619.

In 3T3-L1 adipocytes, the glycosylation of the GLUT-1 transporter is altered beyond 12 h of glucose deprivation. To determine whether glycogen degradation provides substrate for normal protein glycosylation during this delay, we measured the glycogen content of 3T3-L1 adipocytes. From an initial value of 0.537 +/- 0.097 mumol glucose/10(6) cells, glycogen was depleted in a time-dependent manner in response to glucose deprivation, exhibiting a half-time of 6 h. Surprisingly, fructose did not prevent glycogen depletion. However, in such glycogen-depleted adipocytes, the alteration of GLUT-1 glycosylation in response to glucose deprivation was more rapid than in normal adipocytes. Chinese hamster ovary (CHO) cells, which synthesize abbreviated dolichol-linked oligosaccharides within minutes of glucose deprivation (J. I. Rearick, A. Chapman, and S. Kornfeld. J. Biol. Chem. 256: 6255-6261, 1981), contained only 1% of the level of glycogen found in 3T3-L1 adipocytes. Glycosylation of GLUT-1 was altered in CHO cells within 3 h of glucose deprivation. These data demonstrate that, during glucose stress, glycogen may serve as a buffer for oligosaccharide biosynthesis and provide a potential explanation for varying sensitivities of different cell types to glucose deprivation.

We tested the hypothesis that the constitutive glucose transporter (GLUT 1) in 3T3-L 1 adipocytes belongs to the family of glucose-regulated proteins which are transcriptionally regulated by glucose deprivation. Using cDNA probes for both GRP78 (BiP) and GLUT1, we show that the level of GRP78 mRNA increased by 15-fold within 24 h of glucose deprivation with little change in GLUT1 mRNA. The elevated GRP78 mRNA in turn led to a time-dependent increase in GRP78 protein. While glucose deprivation did not alter the expression of the normal glycoform of GLUT 1, a lower molecular weight glycoform accumulated with extended deprivation. Mannose and fructose, but not galactose, prevented the induction of GRP78 and accumulation of the abnormal GLUT1. Because GRP78 acts as a chaperone in other cell systems, we also sought evidence to support this activity in 3T3-L1 adipocytes. Using the technique of co-immunoprecipitation, we demonstrate that GRP78 bound several proteins unique to the glucose-deprived state. No deprivation-specific proteins could be detected in association with GLUT 1. These data lead us to conclude that GLUTl does not display characteristics of the glucose-regulated proteins, at least in 3T3-L1 adipocytes, a widely used model for differentiation, hormone action, and nutrient control. However, the mechanisms for activating traditional members of this family appear intact.

The second-order nonlinear optical response of amine and phenol/ether derivatives (1−8) has been evaluated using experimental and theoretical techniques. Electric-field-induced second-harmonic generation (EFISH) measurements establish that N-phenyl substitution of 4-nitroaniline (1) produces a greater increase in molecular hyperpolarizability than N-methyl substitution. In contrast, O-phenyl substitution of 4-nitrophenol (6) produces a smaller increase in hyperpolarizability than O-methyl substitution. Neither the enhancement of hyperpolarizability upon N-phenyl substitution nor the differential substituent effect is anticipated on the basis of qualitative arguments. Careful theoretical analysis using semiempirical sum-over-states and finite field calculations provide explanations for both observed effects.

1,3,5-Tris(1-naphthyl)benzene (1), 1,3-bis(1-naphthyl)-5-(2-naphthyl)benzene (2), and 1-(1-naphthyl)-3,5-bis(2-naphthyl)benzene (3) easily supercool and form glasses on cooling from the melt. We synthesized 1, 2, and 3 using Suzuki's conditions to effect the cross-coupling reactions of 1,3,5-tribromobenzene with 1-naphthylboronic acid and/or 2-naphthylboronic acid. Variable-temperature 13C NMR studies of 1 establish a barrier of ca. 12 kcal/mol for rotation about the aryl−aryl bond; this value displays good agreement with the barrier of 13 kcal/mol computed using molecular mechanics calculations (MM2). This relatively low rotational barrier is inconsistent with the previously held notion that 1,3,5-tris(1-naphthyl)benzene (1) exists as a mixture of noninterconverting rotational isomers (atropisomers) in solution at room temperature. Variable-temperature 13C NMR studies of 2 establish barriers of ca. 12 kcal/mol for rotation about the 1-naphthyl−aryl bond and

We examined the role of a history of sexual abuse as a predictor of child maltreatment by adolescent mothers in a prospective study of 104 mother-child dyads. Mothers were interviewed about any experienced abuse, and the mother-child dyads were observed in a teaching interaction and in the Strange Situation when the children were 1 year old. Three and a half years later, the mothers were interviewed about their Child Protective Service (CPS) contacts since the birth of their children. The percentage of mothers reporting CPS contacts for their own children was 15.4%, 38.5%, and 83.3%, respectively, for those mothers with no history of sexual abuse, a history of a single incident or brief duration of sexual abuse, and those mothers with a history of chronic sexual abuse (median 24 months duration; test of increasing trend significant atp< .000009). Mothers who reported having been chronically sexually abused as children were significantly more likely to have CPS contacts for their own children, after controlling for history of physical abuse, quality of early teaching interactions, and infant attachment security (both of which also predicted CPS contacts), race, IQ, welfare status at 1 year postpartum, and history of foster care.

The geometries and force fields of phenylcarbene (PC) and cycloheptatrienylidene (CHT) in their singlet and triplet electronic states as well as of cycloheptatetraene (CHTE) and bicyclo[4.1.0]heptatriene (BCT) and the transition states for the formation and decay of the latter were evaluated by various methods. Relative single point energies were calculated at the CCSD(T)/cc-pVDZ//BLYP/6-31G* level. Finally, the effects of extending the basis set to triple-ζ quality were estimated by (R)MP2 calculations and carried over proportionally to CCSD(T). These calculations show that CHTE which has a strongly distorted allenic structure is the most stable species on that part of the C(CH)6 surface which was examined in the present study, followed by planar 3PC. The strained BCT is found to be nearly degenerate in energy with 1PC, but the high activation energy for its formation from 1PC together with the low activation energy for ring-opening to CHTE suggests that this species cannot persist under the experimental...

Infant feeding practices generally influence infant growth, but it is unclear how introduction of specific foods affects growth across global populations. We studied 3 urban populations in the Global Exploration of Human Milk study to determine the association between infant feeding and anthropometry at 1 y of age. Three hundred sixty-five breastfeeding mother-infant pairs (120 US, 120 China, and 125 Mexico) were recruited soon after the infant’s birth. Enrollment required agreement to breastfeed ≥75% for at least 3 mo. Weekly, 24-h, food frequency data were conducted on infants for 1 y and exclusive breastfeeding (EBF) duration and timing of specific complementary food introduction were calculated. Weight and length were measured at age 1 y and anthropometry Z-scores calculated using WHO standards. Cohorts in the 3 urban populations (Shanghai, China; Cincinnati, USA; and Mexico City, Mexico) differed by median EBF duration (5, 14, and 7 wk, respectively; P < 0.001), timing of introduction of meat/eggs/legumes (4.8, 9.3, and 7.0 mo, respectively; P < 0.0001), and other feeding practices. By age 1 y, infants in Shanghai were heavier and longer than Cincinnati and Mexico City infants (P < 0.001). Adjusting for nonfeeding covariates, the only feeding variable associated with anthropometry was EBF duration, which was modestly inversely associated with weight-for-age but not length-for-age or BMI Z-scores at 1 y. Although feeding variables differed by cohort, their impact on anthropometry differences was not consistent among cohorts. Overall, across these urban, international, breast-fed cohorts, differences in specific feeding practices did not explain the significant variation in anthropometry.

Secondary ion mass spectrometry has been used to characterize translational motion in vapor-deposited glasses of indomethacin (IMC) and α,α,β-tris-naphthylbenzene (TNB). Vapor deposition onto substrates at ∼0.99 T(g) produced ordinary glasses that evolve according to fickian diffusion during annealing. The resulting self-diffusion coefficients for the supercooled liquids are in good agreement with previous reports. Deposition onto substrates at 0.85 T(g) produced highly stable glasses that transform with a propagating front mechanism. In contrast to previous reports, the liquid produced by this transformation has the same translational mobility as the ordinary supercooled liquid; we associate this result with lower impurity levels in the current samples. The front velocities for both TNB and IMC stable glasses are very similar functions of the translational self-diffusion coefficients of the supercooled liquids, consistent with view that the growth front velocity is controlled by mobility in the liquid adjacent to the stable glass.

Carbonyl diazide (1), OC(N(3))(2), is prepared by reaction of triphosgene and tetra-n-butylammonium azide in a solution of diethyl ether or dimethyl ether. The advantage of this synthetic method, relative to other procedures, is that the use of triphosgene, OC(OCCl(3))(2), mitigates the need to use highly poisonous reagents such as phosgene, OCCl(2), or chlorofluorocarbonyl, OC(Cl)F. The identity and purity of OC(N(3))(2) are established by gas-phase IR spectroscopy, which reveals the presence of both syn-syn and anti-syn conformers. Computed anharmonic vibrational frequencies and infrared intensities of carbonyl diazide (1) display excellent agreement with experiment, and reveal the presence of strong Fermi resonances.

This study tested the association between parent illicit drug use disorder (DUD) in early adulthood and observed parenting practices at ages 27-28 and examined the following 3 theoretically derived models explaining this link: (a) a disrupted parent adult functioning model,(b) a preexisting parent personality factor model, and (c) a disrupted adolescent family process model. Associations between study variables and child externalizing problems also were examined. Longitudinal data linking 2 generations were drawn from the Seattle Social Development Project (SSDP) and The SSDP Intergenerational Project (TIP), and included 167 parents and their 2- to 8-year-old child. Path modeling revealed that parent DUD in early adulthood predicted later observed low-skilled parenting, which was related to child externalizing problems. The preexisting parent personality factor model was supported. Parent negative emotionality accounted for the association between parent early adult DUD and later parenting practices. Parent negative emotionality also was related directly to child externalizing behavior. Limited support for the disrupted transition to adulthood model was found. The disrupted adolescent family process model was not supported. Results suggest that problem drug use that occurs early in adulthood may affect later parenting skills, independent of subsequent parent drug use. Findings highlight the importance of parent negative emotionality in influencing his or her own problem behavior, interactions with his or her child, and his or her child's problem behavior. Prevention and treatment programs targeting young adult substance use, poor parenting practices, and child behavior problems should address parent personality factors that may contribute to these behaviors.

A joint experimental-theoretical study has been carried out on electronic states of propadienylidene (H(2)CCC), using results from negative-ion photoelectron spectroscopy. In addition to the previously characterized X(1)A(1) electronic state, spectroscopic features are observed that belong to five additional states: the low-lying ã(3)B(1) and b(3)A(2) states, as well as two excited singlets, Ã(1)A(2) and B(1)B(1), and a higher-lying triplet, c(3)A(1). Term energies (T(0), in cm(-1)) for the excited states obtained from the data are: 10,354±11 (ã(3)B(1)); 11,950±30 (b(3)A(2)); 20,943±11 (c(3)A(1)); and 13,677±11 (Ã(1)A(2)). Strong vibronic coupling affects the Ã(1)A(2) and B(1)B(1) states as well as ã(3)B(1) and b(3)A(2) and has profound effects on the spectrum. As a result, only a weak, broadened band is observed in the energy region where the origin of the B(1)B(1) state is expected. The assignments here are supported by high-level coupled-cluster calculations and spectral simulations based on a vibronic coupling Hamiltonian. A result of astrophysical interest is that the present study supports the idea that a broad absorption band found at 5450 Å by cavity ringdown spectroscopy (and coincident with a diffuse interstellar band) is carried by the B(1)B(1) state of H(2)CCC.

At no time in American history has an understanding of the role and the art of diplomacy in international relations been more essential than it is today. Both the history of United States diplomatic relations and the current United States foreign policy in the 21st century are major topics of study and interest in America and around the world. Spanning the entire history of American diplomacy - from the first Continental Congress, to the war on terrorism, to the foreign policy goals of the 21st century - Guide to U.S. Foreign Policy traces not only the growth and development of diplomatic policies and traditions, but also the shifts in public opinion that shape diplomatic trends. This comprehensive, two-volume reference shows how the United States gained 'the strength of a giant' and also analyzes key world events that have determined the United States' changing relations with other nations. A three-part structure makes the key concepts and issues accessible to researchers: Part One features 40 topical and historical chapters, in which expert writers cover the diplomatic initiatives of the United States from colonial times through the present day. Part Two is an A to Z handbook of diplomatic terms and concepts, people, events, and issues in American foreign policy. Part Three features a collection of annotated primary source documents that support the work. This unique reference highlights the changes in U.S. diplomatic policy as government administrations and world events influenced national decisions. Topics include imperialism, economic diplomacy, environmental diplomacy, foreign aid, wartime negotiations, presidential influence, NATO and its role in the twenty-first century, and the response to terrorism. Additional featured topics include the influence of the American two-party system, the impact of U.S. elections, and the role of the United States in international organizations. Guide to U.S. Foreign Policy is the first comprehensive reference work in this field that is both historical and thematic. This work will be of immense value for researchers, students, and others studying foreign policy, international relations, and U.S history.

Prospective longitudinal studies that pertain to the stability, developmental pathways, and long-term outcome for the 2 primary forms of externalizing behavior problems (conduct problems [CP] and hyperactivity [HA]) are described. Treatment outcome studies for CP and HA with at least 1 year of follow-up data are reviewed. The implications of longitudinal research for the diagnosis, assessment, and treatment of externalizing behavior problems in children are discussed. Greater attention must be paid to issues related to comorbidity, developmentally appropriate assessments, and long-term outcome of interventions. Longitudinal-experimental investigations that serve to delineate developmental pathways as well as assess the effects of developmentally sensitive, comprehensive interventions are recommended.

The effects of ethynyl substitution on cyclobutadiene are explored via density functional theory and coupled-cluster calculations. The computed singlet-triplet gaps indicate a monotonic dependence on the degree of ethynyl substitution, which differentially stabilizes the triplet relative to the singlet ground state and reduces the gap. A series of isodesmic, homodesmotic, and hyperhomodesmotic equations are employed to quantify the stabilization upon ethynyl substitution. Analyses that rely on a simple isodesmic equation and/or B3LYP/6-31G(d) values are found to be problematic. Analyses that rely on homodesmotic or hyperhomodesmotic equations, in conjunction with CCSD/cc-pVDZ values, are more robust. Using a hyperhomodesmotic equation to assess the stabilization enthalpies of tetra-substituted singlet cyclobutadienes, our analysis predicts tetramethylcyclobutadiene (ΔH(0)(rxn) = -17.3 kcal/mol) to be more stable than tetraethynylcyclobutadiene (ΔH(0)(rxn) = -11.7 kcal/mol), which, in turn, is substantially more stable than tetracyanocyclobutadiene (ΔH(0)(rxn) = +12.7 kcal/mol).

Conformer-specific, vibrationally resolved electronic spectroscopy of benzylallene (4-phenyl-1,2-butadiene) is presented along with a detailed analysis of the products formed via its ultraviolet photoexcitation. Benzylallene is the minor product of the recombination of benzyl and propargyl radicals. The mass-selective resonant two-photon ionization spectrum of benzylallene was recorded under jet-cooled conditions, with its S(0)-S(1) origin at 37,483 cm(-1). UV-UV holeburning spectroscopy was used to show that only one conformer was present in the expansion. Rotational band contour analysis provided rotational constants and transition dipole moment direction consistent with a conformation in which the allene side chain is in the anti position, pointing away from the phenyl ring. The photochemistry of benzylallene was studied in a pump-probe geometry in which photoexcitation occurred by counter-propagating the expansion with a photoexcitation laser. The laser was timed to interact with the gas pulse in a short tube that extended the collisional region of the expansion. The products were cooled during expansion of the gas mixture into vacuum, before being interrogated using mass-selective resonant two-photon ionization. The UV-vis spectra of the photochemical products were compared to literature spectra for identification. Several wavelengths were chosen for photoexcitation, ranging from the S(0)-S(1) origin transition (266.79 nm) to 193 nm. Comparison of the product spectral intensities as a function of photoexcitation wavelength provides information on the wavelength dependence of the product yields. Photoexcitation at 266.79 nm yielded five products (benzyl radical, benzylallenyl radical, 1-phenyl-1,3-butadiene, 1,2-dihydronaphthalene, and naphthalene), with naphthalene and benzylallenyl radicals dominant. At 193 nm, the benzylallenyl radical signal was greatly reduced in intensity, while three additional C(10)H(8) isomeric products were observed. An extensive set of calculations of key stationary points on the ground state C(10)H(10) and C(10)H(9) potential energy surfaces were carried out at the DFT B3LYP/6-311G(d,p) level of theory. Mechanisms for formation of the observed products are proposed based on these potential energy surfaces, constrained by the results of cursory studies of the photochemistry of 1-phenyl-1,3-butadiene and 4-phenyl-1-butyne. A role for tunneling on the excited state surface in the formation of naphthalene is suggested by studies of partially deuterated benzylallene, which blocked naphthalene formation.

We report the 364-nm photoelectron spectrum of HC(4)N(-). We observe electron photodetachment from the bent X(2)A" state of HC(4)N(-) to both the near-linear X(3)A" and the bent ã (1)A' states of neutral HC(4)N. We observe an extended, unresolved vibrational progression corresponding to X(3)A" ← X(2)A" photodetachment, and we measure the electron affinity (EA) of the X(3)A" state of HC(4)N to be 2.05(8) eV. Photodetachment to the bent ã (1)A' state results in a single intense origin peak at a binding energy of 2.809(4) eV, from which we determine the singlet-triplet splitting (ΔE(ST)) of HC(4)N: 0.76(8) eV. For comparison and to aid in the interpretation of the HC(4)N(-) spectrum, we also report the 364-nm photoelectron spectra of HCCN(-) and DCCN(-). Improved signal-to-noise over the previous HCCN(-) and DCCN(-) photoelectron spectra allows for a more precise determination of the EAs and ΔE(ST)s of HCCN and DCCN. The EAs of HCCN and DCCN are measured to be 2.001(15) eV and 1.998(15) eV, respectively; ΔE(ST)(HCCN) is 0.510(15) eV and ΔE(ST)(DCCN) is 0.508(15) eV. These results are discussed in the context of other organic carbene chains.

Inadequate parental monitoring is widely recognized as a risk factor for the development of child and adolescent conduct problems. However, previous studies examining parental monitoring have largely measured parental knowledge and not the active methods used by parents to track the activities and behavior of their children. The seminal work of Stattin and Kerr (Child Dev 71:1072–1085, 2000; Kerr and Stattin in Dev Psychol 36:366–380, 2000) has challenged the field to reinterpret the construct of parental monitoring, focusing on the active components of this parenting behavior. As a result, this area of research has witnessed a resurgence of activity. The goal of the current paper is to review the evidence regarding the relationship between parental knowledge and monitoring and child and adolescent conduct problems that has accumulated during the past decade. Forty-seven studies published between 2000 and 2010 were identified by searching major databases and bibliographies and were included in this review. This paper will examine the following areas: (a) “parental monitoring” as “parental knowledge”; (b) parental knowledge as driven by child disclosure; (c) the relationship between parental knowledge and monitoring and child and adolescent conduct problems; (d) bidirectional associations between parental knowledge and monitoring and child and adolescent conduct problems; (e) contextual influences on parental knowledge and monitoring; (f) antecedents of parental knowledge and monitoring; (g) clinical implications of research on parental knowledge and monitoring; and (h) limitations of existing research and future directions.

Iso-polyhalomethanes are known reactive intermediates that play a pivotal role in the photochemistry of halomethanes in condensed phases. In this work, iso-bromoform (iso-CHBr(3)) and its deuterated isotopomer were characterized by matrix isolation infrared and UV/visible spectroscopy, supported by ab initio and density functional theory calculations, to further probe the structure, spectroscopy, and photochemistry of this important intermediate. Selected wavelength laser irradiation of CHBr(3) isolated in Ar or Ne matrices at ~5 K yielded iso-CHBr(3); the observed infrared and UV/visible absorptions are in excellent agreement with computational predictions, and the energies of various stationary points on the CHBr(3) potential energy surface were characterized computationally using high-level methods in combination with correlation consistent basis sets. These calculations show that, while the corresponding minima lie ~200 kJ/mol above the global CHBr(3) minimum, the isomer is bound by some 60 kJ/mol in the gas phase with respect to the CHBr(2) + Br asymptote. The photochemistry of iso-CHBr(3) was investigated by selected wavelength laser irradiation into the intense S(0) → S(3) transition, which resulted in back photoisomerization to CHBr(3). Intrinsic reaction coordinate calculations confirmed the existence of a first-order saddle point connecting the two isomers, which lies energetically below the threshold of the radical channel. Subsequently, natural bond orbital analysis and natural resonance theory were used to characterize the important resonance structures of the isomer and related stationary points, which demonstrate that the isomerization transition state represents a crossover from dominantly covalent to dominantly ionic bonding. In condensed phases, the ion-pair dominated isomerization transition state structure is preferentially stabilized, so that the barrier to isomerization is lowered.

Halogen atoms are important reactive radicals in the atmosphere. In this work, pulsed jet discharge matrix isolation spectroscopy and computational methods were used to characterize prereactive complexes of halogen atoms with simple halons. Our experiments combined matrix isolation techniques with a pulsed DC discharge nozzle, where a dilute CH(2)XBr (X = H, Cl, Br)/rare gas sample was gently discharged and the products were deposited onto a cold KBr window. The Br···BrCH(2)X (X = H, Cl, Br) complexes were characterized by infrared and electronic spectroscopy, supported by ab initio and density functional theory (DFT) calculations, which shed light on the structure of, bonding in, and binding energy of the complexes. The correlation of charge-transfer energy with donor ionization potential (Mulliken correlation) was examined, and the charge-transfer photochemistry of the complexes was explored.

In recent years, several pharmacological and psychosocial interventions have examined ways to prevent or treat weight gain in people receiving second-generation antipsychotics. While there has been some success, in general, results have not been compelling. Atomoxetine is a selective norepinepherine reuptake inhibitor found to be associated with appetite suppression. Therefore, we examined whether atomoxetine may be of benefit for those who have gained weight on either clozapine or olanzapine.The study was a double-blind, placebo-controlled trial. All participants received the same psychosocial platform: a structured support and exercise group. People with schizophrenia or schizoaffective disorder, on olanzapine or clozapine, who had gained at least 7% of their pre-clozapine or pre-olanzapine weight were eligible for a 24-week, randomized, parallel group, double-blind comparison of adjunctive atomoxetine or placebo.Thirty-seven participants (20 atomoxetine, 17 placebo) were randomized and 26 participants (14 atomoxetine, 12 placebo; 70.2%) completed the study. There were no significant group differences in baseline BMI (atomoxetine: 34.5±4.9; placebo: 35.7±7.0) or weight (atomoxetine: 102.2±15.7 kg; placebo: 104.3±17.5 kg). Both treatment groups showed modest, not significant, trends in weight loss, averaging about 2 kg. Gender or baseline antipsychotic treatment did not modify treatment effects on weight. Secondary outcomes included neuropsychological assessments, symptom assessments (BPRS, SANS) and safety assessments. Of these, only the group difference in Gordon distractibility test scores was statistically significant and favored treatment with atomoxetine.Atomoxetine is not effective for weight loss in this population, but both olanzapine and clozapine participants can lose weight with structured group support and exercise.

This longitudinal study examined processes that mediate the association between maternal depressive symptoms and peer social preference during the early school years. Three hundred and fifty six kindergarten children (182 boys) and their mothers participated in the study. During kindergarten, mothers reported their level of depressive symptomatology. In first grade, teachers rated children's emotion regulation at school and observers rated the affective quality of mother-child interactions. During second grade, children's social preference was assessed by peer nomination. Results indicated that mothers' level of depressive symptomatology negatively predicted their child's social preference 2 years later, controlling for the family SES and teacher-rated social preference during kindergarten. Among European American families, the association between maternal depressive symptoms and social preference was partially mediated by maternal warmth and the child's emotion regulation. Although the relation between maternal depressive symptoms and children peer preference was stronger among African American families than Europrean American families, its mediation by the maternal warmth and child's emotion regulation was not found in African American families. © 2010 The Author(s)., published_or_final_version, Springer Open Choice, 21 Feb 2012

Irradiation (λ>300 nm or λ=480±6 nm) of 2-naphthyldiazomethane (4), matrix-isolated in argon at 10 K, gives a mixture of 2-naphthylcarbene (1) and 2,3-benzobicyclo[4.1.0]hepta-2,4,6-triene (2). 2-Naphthylcarbene (1) is characterized by infrared, UV/visible, and ESR spectroscopy and by chemical trapping with CO. 2,3-Benzobicyclo[4.1.0]hepta-2,4,6-triene (2) is characterized by infrared and UV/visible spectroscopy. A photoequilibrium exists between carbene 1 and bicyclic compound 2. Photolysis (λ=290±6 nm) of bicyclic compound 2 results exclusively in ring-opening to carbene 1

Elevated glucose transport rates during glucose deprivation are phenomena that have been observed in several different types of cells in culture. We show here that glucose transport rates in 3T3-L1 adipocytes increased by 10-fold within 18 h in response to glucose deprivation, confirming earlier work by Van Putten and Krans (Van Putten, J. P. M., and Krans, H. M. J. (1985) J. Biol. Chem. 260, 7996-8001). Mannose and 3-O-methylglucose (a nonmetabolizable glucose analog), but not fructose or galactose, blocked the increase in transport activity. Although the increase in transport was dependent on new protein synthesis, only a small and transient increase in GLUT 1 mRNA (less than 2-fold) was observed. In addition, the level of the normal isoform of GLUT 1 (46 kDa) did not increase. A lower molecular mass isoform (37 kDa) was observed but not until 15 h after glucose removal, the appearance of which was clearly not correlated with the increase in activity. Further, the extracellular glucose concentration required to elicit accumulation of this form (p37) was 2 orders of magnitude less than that required for transport stimulation (5 microM versus 500 microM glucose; p37 accumulation and transport activation, respectively). Interestingly, p37 was seen in the presence of galactose, but not fructose, despite elevated transport activity with either sugar. The p37 isoform was slightly larger than N-glycosidase F-treated GLUT 1 (36 kDa), implying that this form is still glycosylated, albeit incompletely. It is not known if p37 is functional, but the time- and sugar-dependent appearance of the lower isoform suggests that p37 is not responsible for starvation-induced transport but potentially represents an underglycosylated precursor of the normal, 46-kDa isoform of GLUT 1.

In support of a deeper understanding of the chemistry of cyanoacetylene--a known constituent of planetary atmospheres and interstellar space--theoretical and experimental studies address the chemical mechanism of dimerization and trimerization, and provide high-resolution rotational spectra of two of the trimeric products, 1,2,3- and 1,2,4-tricyanobenzene. Analysis of the rotational spectra is particularly challenging because of quadrupolar coupling from three (14)N nuclei. The laboratory rotational spectra provide the basis for future searches for these polar aromatic compounds in interstellar space by radio astronomy.

This study investigated the predictive validity of youth callous-unemotional (CU) traits, as measured in early adolescence (Grade 7) by the Antisocial Process Screening Device (APSD; Frick & Hare, 2001), in a longitudinal sample (N = 754). Antisocial outcomes, assessed in adolescence and early adulthood, included self-reported general delinquency from 7th grade through 2 years post-high school, self-reported serious crimes through 2 years post-high school, juvenile and adult arrest records through 1 year post-high school, and antisocial personality disorder symptoms and diagnosis at 2 years post-high school. CU traits measured in 7th grade were highly predictive of 5 of the 6 antisocial outcomes-general delinquency, juvenile and adult arrests, and early adult antisocial personality disorder criterion count and diagnosis-over and above prior and concurrent conduct problem behavior (i.e., criterion counts of oppositional defiant disorder and conduct disorder) and attention-deficit/hyperactivity disorder (criterion count). Incorporating a CU traits specifier for those with a diagnosis of conduct disorder improved the positive prediction of antisocial outcomes, with a very low false-positive rate. There was minimal evidence of moderation by sex, race, or urban/rural status. Urban/rural status moderated one finding, with being from an urban area associated with stronger relations between CU traits and adult arrests. Findings clearly support the inclusion of CU traits as a specifier for the diagnosis of conduct disorder, at least with respect to predictive validity.

Triplet carbenes t-butylpentadiynylidene (t-BuC(5)H, 1a) and dimethylpentadiynylidene (MeC(5)Me, 1b) have been produced photochemically from their corresponding diazo compound precursors and studied spectroscopically in cryogenic matrices (N(2) or Ar) at 10 K. The infrared, electronic absorption, and electron paramagnetic resonance spectra of these species exhibit numerous similarities to the spectra of pentadiynylidene (HC(5)H) and methylpentadiynylidene (MeC(5)H) recorded previously. EPR spectra yield zero-field splitting parameters that are typical for triplet carbenes with axial symmetry (t-BuC(5)H, 1a: |D/hc| = 0.61 cm(-1), |E/hc| ∼ 0 cm(-1); MeC(5)Me, 1b: |D/hc| = 0.62 cm(-1), |E/hc| ∼ 0 cm(-1)). Electronic spectra are characterized by weak absorptions (T(1) ← T(0)) in the near-UV and visible region (350-430 nm) with extended vibronic progressions. The electronic transitions of several -C(5)- carbenes are compared, and an apparent dependence of the transition wavelength on the level of alkyl substitution of the carbon chain is found. Chemical trapping of triplet 1a in an O(2)-doped matrix affords carbonyl oxides derived predominantly from attack at C-3. Both t-BuC(5)H (1a) and MeC(5)Me (1b) undergo photochemical rearrangement upon UV irradiation.

Photolysis of matrix-isolated diazoethane (1a) at 8 K produces mainly ethene (4a), along with a small amount of 3-methyldiazirine (2a). ESR experiments employing a variety of irradiation conditions and matrix media (Ar, N 2 , Xe) show that triplet ethylidene (3T) is not an observable photoproduct. Similar experiments fail to reveal direct evidence for either singlet or triplet ethylidene by IR or UV-vis spectroscopy. Photolysis of nascent 3-methyldiazirine (2a) also fails to yield ethylidene. Deuterium substitution produces no detectable change in the chemistry

We describe the synthesis and Friedel-Crafts acetylation of a series of ferrocenylarylethylenes, C 15 H 5 FeC 54 =CH(C 6 H 4 -p-X), where X = NO 2 (3a), Br (3B), and NME 2 (3c). Compounds 3a-c provide a direct comparison of the reactivity of ferrocene, olefin, and aryl functionlities. The regiochemistry of substitution of these compounds depends on the nature of the aryl functionalities. Acetylation occurs predominantly at the olefin and the unsubstituted cyclopentadienyl ring; substitution does not occur at the aryl or ar the substituted cyclopentadienyl ring

Irradiation (λ>300 nm or λ=480±6 nm) of 2-naphthyldiazomethane (4), matrix-isolated in argon at 10 K, gives a mixture of 2-naphthylcarbene (1) and 2,3-benzobicyclo[4.1.0]hepta-2,4,6-triene (2). 2-Naphthylcarbene (1) is characterized by infrared, UV/visible, and ESR spectroscopy and by chemical trapping with CO. 2,3-Benzobicyclo[4.1.0]hepta-2,4,6-triene (2) is characterized by infrared and UV/visible spectroscopy. A photoequilibrium exists between carbene 1 and bicyclic compound 2. Photolysis (λ=290±6 nm) of bicyclic compound 2 results exclusively in ring-opening to carbene 1

Noncompliance (i.e., excessive disobedience to adults) is consistently reported to be the most prevalent behavior problem for clinic-referred and non-referred “normal” children alike, and is currently viewed as a keystone behavior in the development and maintenance of conduct disorders. “Helping the Noncompliant Child” (HNC) (Forehand & McMahon, 1981; McMahon & Forehand, 2003) is based on a parent training program originally developed by Hanf at the University of Oregon Medical School in the late 1960s (e.g., Hanf & Kling, 1973) to treat noncompliance in young (3–8 years of age) children with a range of developmental disabilities (see Reitman & McMahon, 2010). While several independent groups of clinical researchers have adapted Hanf’s original program, the adaptation by the current authors (Forehand & McMahon, 1981; McMahon & Forehand, 2003) is one of the most formally operationalized and evaluated versions of this approach to working with young children with conduct problems. The purpose of this chapter is to provide a description of the theoretical assumptions that underlie HNC, an overview of the program, and a summary of its empirical support. We also provide a description of a typical HNC case, and conclude with remarks concerning future directions.

A combination of experiment and theory provides insight into the structure and rearrangements of various C3H2 isomers. Photolysis of [13C]diazopropynes 6a−c under matrix isolation conditions afford...

Children of affluent parents are often excluded in psychological research as they are considered to be at “low risk”; however, research is beginning to suggest that this previously under-studied population may be at risk for developing multiple problem behaviors, including substance use and externalizing problems. The current study aimed to extend the application of Problem Behavior Theory (PBT) to a sample of affluent adolescents by examining the extent to which these behaviors co-occurred and were associated with negative outcomes. Data were collected from 1,147 high school students living in an affluent community via anonymous questionnaires regarding their engagement in various problem behaviors. PBT was supported in this sample, and youth who engaged in multiple problem behaviors reported experiencing more negative outcomes than youth who did not engage in these behaviors. The findings of this study support the generalizability of PBT and also highlight the importance of continuing to study affluent youth in addition to traditionally high-risk populations.

A series of 5,15-diphenylporphyrinatonickel(II) derivatives containing electron-releasing (Me2NC6H4C⋮C−) and -withdrawing groups [−CHO, −CHC(CN)2, −CHC(CO2Et)2, −CHCHCHO] in opposite meso positions has been synthesized through the classical formylation, halogenation, Knoevenagel condensation, and palladium-catalyzed cross-coupling reaction of porphyrins. The molecular first hyperpolarizabilities (β) of two of these push−pull porphyrins, namely 5-(2‘,2‘-dicyanoethenyl)-15-[[4‘‘-(N,N-dimethylamino)phenyl]ethynyl]-10,20-diphenylporphyrinatonickel(II) (7) and 5-formyl-15-[[4‘-(N,N-dimethylamino)phenyl]ethynyl]-10,20-diphenylporphyrinatonickel(II) (8) have been determined experimentally by electric-field-induced second-harmonic generation (EFISH) at 1907 nm and computationally by semiempirical methods (ZINDO sum-over-states). The values of βμ (124 and 66 × 10-30 cm5 esu-1, for 7 and 8, respectively) are moderate because the acceptor group is significantly tilted with respect to the porphyrin core in these comp...